New Technologies For Electrochemical Applications-CRC Press (2020)

New Technologies for
Electrochemical Applications
New Technologies for
Edited by
Mu. Naushad, Saravanan Rajendran, and
Abdullah M. Al-Enizi
CRC Press
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Contents
Preface..............................................................................................................................................vii
Acknowledgments.............................................................................................................................ix
Editors...............................................................................................................................................xi
Contributors ................................................................................................................................... xiii
Chapter 1 Electrochemistry: Different Materials and Applications: An Overview .....................1
D. Durgalakshmi, Saravanan Rajendran, and Abdullah M. Al-Enizi
Chapter 2 Controlled Electrochemical Deposition for Materials Synthesis...............................25
T. Sivaranjani, T. A. Revathy, and A. Stephen
Chapter 3 Photovoltaic Energy Generation System: Material, Device, and Fabrication............ 49
Ananthakumar Soosaimanickam and Moorthy Babu Sridharan
Chapter 4 Role of Advanced Materials in Electrochemical Supercapacitors............................. 63
Joyita Banerjee, Kingshuk Dutta, and M. Abdul Kader
Chapter 5 Microbial Electrochemical Technologies for Fuel Cell Devices................................ 83
S. V. Sheen Mers, K. Sathish-Kumar, L. A. Sánchez-Olmos,

M. Sánchez-Cardenas, and Felipe Caballero-Briones
Chapter 6 Photoelectrochemical Process for Hydrogen Production......................................... 105
S. Devi and V. Tharmaraj
Chapter 7 Recent Trends in Chemiresistive Gas Sensing Materials......................................... 121
Baskaran Ganesh Kumar, J. Nimita Jebaranjitham, and Saravanan Rajendran
Chapter 8 Role of Innovative Material in Electrochemical Glucose Sensors........................... 135
R. Suresh, Claudio Sandoval, Eimmy Ramirez, R. V. Mangalaraja, and Jorge Yáñez
Chapter 9 Electrocatalysts for Wastewater Treatment .............................................................. 153
Prasenjit Bhunia, Kingshuk Dutta, and M. Abdul Kader
Chapter 10 Development and Characterization of A-MWCNTs/Tetra Functional Epoxy
Coatings for Corrosion and Prevention of Mild Steel .............................................. 169
D. Duraibabu, A. Gnanaprakasam, and S. Ananda Kumar
v
vi Contents
Chapter 11 Electrochemical Oxidation Reaction for the Treatment of Textile Dyes ................. 181
Eswaran Prabakaran and Kriveshini Pillay
Chapter 12 Materials Involved in Electrocoagulation Process for Industrial Effluents ............. 193
Carlos Navas-Cárdenas, Herman Murillo, Maibelin Rosales, Cesar Ron, and

Florinella Muñoz
Chapter 13 Role of Organic Materials in Electrochemical Applications ................................... 217
S. Ganesan
Chapter 14 Advanced Conducting Polymers for Electrochemical Applications ........................ 233
R. Suresh, R. V. Mangalaraja, Paola Santander, and Jorge Yáñez
Chapter 15 Electrochemical Studies for Biomedical Applications............................................. 251
Rajesh Parsanathan
Index.............................................................................................................................................. 267
Preface
A big thanks to Faraday, who gave us the beautiful laws of electrochemistry, and to so many electro
chemists who have made a contribution to enrich the foundations of electrochemistry, on which we
are laying a small pebble as a stepping stone to new technological applications using the basics of
the field. Electrochemistry is still moving from its basic principles to new innovations. One recent
notable advancement in the field was by Prof. Allen Brad, the father of modern electrochemistry,
with his works on electrochemiluminescence. Great technological advances will occur when there
is an interdisciplinary work among the branches of science and technology. Buckminster Fuller, the
inventor of fullerene carbon nanostructures, said, “You never change things by fighting the exist
ing reality. To change something, build a new model that makes the existing model obsolete.” And
hence, new changes related to affordable costs, easy handling, and almost zero pollution to the envi
ronment are greatly needed in the present scenario. The branches of electrochemistry have guided its
development from metal extraction, batteries, fuel cells, and supercapacitors to photovoltaic cells.
In this book, the chapters are organized to give readers an overview of the current field of elec
trochemical applications. Some of the contents of the first chapter give the historical timeline of the
advancements in the field of electrochemistry; most of the work in the 19th century focused on the
synthesis of metals and their alloys by the electrochemical deposition method. The second chapter
is devoted to the controlled electrochemical deposition method for material synthesis. With a view
to covering the most recent technologies and applications of electrochemistry, the topics of the
electrochemical application of materials in the fields of (i) photovoltaic energy, (ii) electrochemical
supercapacitors, (iii) microbial fuel cells, (iv) hydrogen generation, (v) electrocatalyst and electroco
agulation for wastewater treatments, and (vi) biosensors and gas sensors are emphasized in different
chapters. To support the subject of current material advancement in electrochemical applications,
chapters are devoted to the topics of organic material and conducting polymers for electrochemical
applications.
Although there have been various advances in the fields of science and technology, the alarms
related to global warming push us to think about materials with energy-related and environmental
applications. This may be the fastest-growing field for the future of electrochemistry. While moving
in this direction, one must not forget the words of Dr. Martin Luther King Jr., the youngest man to
receive the Nobel Peace Prize: “But today our very survival depends on our ability to stay awake, to
adjust to new ideas, to remain vigilant and to face the challenge of change. We must work passion
ately and indefatigably to bridge the gulf between our scientific progress and our moral progress.”
vii
Acknowledgments
Dr. Saravanan Rajendran would like to express his sincere thanks to Prof. Francisco Gracia
(DIQBT, University of Chile), Prof. Lorena Cornejo Ponce (Department of Mechanical Engineering,
Universidad de Tarapacá), and Prof. Rodrigo Palma (Director, SERC) for their constant encourage
ment and valuable support to complete the task. Further thanks is extended to financial support from
the Government of Chile (CONICYT-FONDECYT-Project No. 11170414), SERC (CONICYT/
FONDAP/15110019), and Faculty of Engineering, Department of Mechanical Engineering,
Universidad de Tarapacá, Arica, Chile.
Dr. Mu. Naushad and Dr. Abdullah M. Al-Enizi extend their appreciation to the Deanship of
Scientific Research at King Saud University, Saudi Arabia, for their support.
ix
Editors
Dr. Mu. Naushad is as an associate professor in the Department of Chemistry, College of Science,
King Saud University (KSU), Riyadh, Kingdom of Saudi Arabia. He earned his MSc and PhD in
analytical chemistry from Aligarh Muslim University, Aligarh, India, in 2002 and 2007, respec
tively. He has vast research experience in the fields of analytical chemistry, materials chemistry,
and environmental science. He holds several US patents, and has authored more than 280 articles in
international journals of repute, 20 book chapters, and several books published by renowned inter
national publishers. He has more than 9100 citations with a Google Scholar h-index of >56. He has
successfully run several research projects funded by the National Plan for Science and Technology
(NPST) and King Abdulaziz City for Science and Technology (KACST), Kingdom of Saudi Arabia.
He is the editor/editorial member of several reputed journals including Scientific Reports (Nature);
Process Safety and Environmental Protection (Elsevier); Journal of Water Process Engineering
(Elsevier); and International Journal of Environmental Research and Public Health (MDPI). He
is also the associate editor for Environmental Chemistry Letters (Springer) and Desalination and
Water Treatment (Taylor & Francis). He has been awarded the Scientist of the Year Award (2015)
from the National Environmental Science Academy, Delhi, India; Scientific Research Quality
Award (2019), King Saud University, Saudi Arabia; and Almarai Award (2017), Saudi Arabia.
Dr. Saravanan Rajendran earned his PhD in physics-material science in 2013 from the Department
of Nuclear Physics, University of Madras, Chennai, India. He was awarded the University Research
Fellowship (URF) during the years 2009–2011 by the University of Madras. After working as
an assistant professor at Dhanalakshmi College of Engineering, Chennai, India, in 2013–2014,
he was awarded the SERC and CONICYT-FONDECYT post-doctoral fellowship, University of
Chile, Santiago, in 2014–2017. He worked in the research group of Professor John Irvine, School of
Chemistry, University of St. Andrews, UK, as a postdoctoral research fellow within the framework
of a EPSRC-Global Challenges Research Fund for the removal of blue-green algae and their toxins
(2017–2018). Currently, he is a research associate in the Faculty of Engineering, Department of
Mechanical Engineering, University of Tarapacá, Arica, Chile. He is also a postdoctoral research
fellow at SERC, University of Chile, Santiago, Chile. He is associate editor for the International
Journal of Environmental Science and Technology (Springer). His research interests focus on the
areas of nanostructured functional materials, photophysics, surface chemistry, and nanocatalysts
for renewable energy and wastewater purification. He has authored papers in several international
peer-reviewed journals, five book chapters, and three books with renowned international publishers.
Dr. Abdullah M. Al‑Enizi earned his PhD in 2013 jointly from King Saud University (Kingdom
of Saudi Arabia) and University of Texas at Austin, and then joined the Department of Chemistry
of King Saud University as an assistant professor. His research interests are polymeric materials,
porous nanomaterials, catalysis, and electrochemistry. He has authored more than 62 publications
of high impact and has three US patents. His Scopus citation is 2500, and he is a leading researcher
in advanced polymers and hybrid nanomaterials. He is also a life member of international scientific
societies.
xi
Contributors
M. Abdul Kader D. Durgalakshmi
School for Advanced Research in Department of Medical Physics
Polymers (SARP) Anna University
Central Institute of Plastics Engineering and Chennai, India
Technology (CIPET)
Chennai, India A. Gnanaprakasam
Department of Chemistry
S. Ananda Kumar Anna University
Department of Chemistry Chennai, India
Anna University
Chennai, India S. Ganesan
Joyita Banerjee SRM Institute of Science and Technology
Department of Chemical Engineering Tamil Nadu, India
University of Pittsburgh
Pittsburgh, Pennsylvania Baskaran Ganesh Kumar
Prasenjit Bhunia PSR Arts and Science College
Department of Chemical Engineering
Indian Institute of Technology and
Kharagpur, India Department of Science and Humanities
PSR Engineering College
Felipe Caballero-Briones Tamil Nadu, India
Materials and Technologies for Energy, Health
and the Environment (GESMAT)
R. V. Mangalaraja
Instituto Politécnico Nacional, CICATA
Department of Materials Engineering
Altamira, México
University of Concepción
Concepción, Chile
S. Devi
Department of Inorganic Chemistry and
University of Madras
Technological Development Unit (UDT)
Chennai, India
Coronel, Chile
Kingshuk Dutta
School for Advanced Research in
Polymers (SARP) Herman Murillo
Central Institute of Plastics Engineering and Department of Chemical Engineering
Technology (CIPET) University of Santiago de Chile
Chennai, India Santiago, Chile
D. Duraibabu Florinella Muñoz

Department of Chemistry Department of Nuclear Sciences
Anna University Escuela Politécnica Nacional
Chennai, India Quito, Ecuador
xiii
xiv Contributors
Carlos Navas‑Cárdenas Maibelin Rosales

Department of Chemical Engineering, Advanced Mining Technology Center (AMTC)
Biotechnology and Materials University of Chile
University of Chile Santiago, Chile
Santiago, Chile
Paola Santander
and
Center of Biotechnology
Biomass to Resources Group University of Concepción
Amazon Regional University Ikiam Concepción, Chile
Tena, Ecuador
and
J. Nimita Jebaranjitham Millennium Nucleus on Catalytic Processes
P.G. Department of Chemistry towards Sustainable Chemistry (CSC)
Women’s Christian College Santiago, Chile
Chennai, India
M. Sánchez‑Cardenas
Rajesh Parsanathan Instituto Tecnológico El Llano Aguascalientes
Department of Pediatrics Tecnológico Nacional de México
Louisiana State University Health Sciences Aguascalientes, México
Center
Shreveport, Louisiana L. A. Sánchez‐Olmos
Universidad Politécnica de Aguascalientes
Kriveshini Pillay Aguascalientes, México
Department of Chemical Sciences
University of Johannesburg Claudio Sandoval
Johannesburg, South Africa Department of Analytical and Inorganic
Chemistry
Eswaran Prabakaran University of Concepción
Department of Chemical Sciences Concepción, Chile
University of Johannesburg
Johannesburg, South Africa K. Sathish‑Kumar
Instituto Tecnológico El Llano
Eimmy Ramírez Aguascalientes (ITEL)
Department of Analytical and Inorganic Aguascalientes, Mexico
Chemistry
and
Concepción, Chile Tecnológico Nacional de México (TecNM)
Mexico City, Mexico
T. A. Revathy
Department of Nuclear Physics S. V. Sheen Mers
University of Madras Indian Institute of Technology
Chennai, India Chennai, India
Cesar Ron T. Sivaranjani

Department of Geology & Geophysics Department of Nuclear Physics
University of Utah University of Madras
Salt Lake City, Utah Chennai, India
Contributors xv
Moorthy Babu Sridharan A. Stephen

Crystal Growth Centre Department of Nuclear Physics
Anna University University of Madras
Chennai, India Chennai, India
Ananthakumar Soosaimanickam V. Tharmaraj

Crystal Growth Centre Department of Analytical Chemistry
Anna University National Chung-Hsing University
Chennai, India Taichung, Taiwan
and
Jorge Yáñez
Institute of Materials (ICMUV) Department of Analytical and Inorganic
University of Valencia Chemistry
Valencia, Spain University of Concepción
Concepción, Chile
R. Suresh
Department of Analytical and Inorganic
Chemistry
Concepción, Chile
1 Electrochemistry: Different
Materials and Applications:
An Overview
D. Durgalakshmi, Saravanan Rajendran,
and Abdullah M. Al-Enizi
CONTENTS
1.1 Introduction to Electrochemistry: History ...............................................................................1
1.2 Oxidation and Reduction ..........................................................................................................4
1.3 Material Synthesis by Electrode Position Method ...................................................................5
1.3.1 Electrodeposition of Metals and Alloys ....................................................................... 5
1.3.2 Electrodeposition of Organic Materials...................................................................... 10
1.3.3 Electrodeposition of Metals as Sacrificial Coatings................................................... 10
1.3.4 Electrophoretic Deposition ......................................................................................... 10
1.4 Electrochemistry Application for Health, Energy, and the Environment .............................. 11
1.4.1 Hydrogen Generation.................................................................................................. 11
1.4.2 Chemiresistive Gas Sensor ......................................................................................... 12
1.4.3 Biosensor..................................................................................................................... 15
1.4.3.1 Glucose......................................................................................................... 15
1.4.3.2 H2O2 Sensor ................................................................................................. 16
1.4.4 Wastewater Treatment ................................................................................................ 17
1.5 Summary and Future Directions ............................................................................................ 17
References........................................................................................................................................ 18
1.1 INTRODUCTION TO ELECTROCHEMISTRY: HISTORY

The field of electrochemistry has received intense attention in applied and fundamental research
areas. The history of electrochemistry helps us to understand the technological applications in both
industrial production and daily life in the 21st century (Table 1.1). The important discoveries in
electrochemistry originated with Antoine Lavoisier, who is also called the “father of modern chem
istry,” from his discovery of oxygen and explanation of the oxidation chemical process during res
piration (Ihde 1984). The story of electrochemistry began at the end of the 18th century when Luigi
Galvani demonstrated that the transmission of nerve impulses was associated with an electric cur
rent (Bensaude-Vincent and Stengers 1996). Later, Alessandro Volta, to challenge Luigi Galvani’s
claims to have demonstrated that animals produce electricity, announced his invention of the vol
taic pile (Mertens 1998). The voltaic pile produced a continuous current and thus opened two new
areas of study: the chemical production of electricity and the effects of electricity on chemicals. In
May 1800, Nicholson and Carlisle modeled the first ever hydrogen production experiment by the
electrolysis of water with the help of battery power. Based on this, the theory of electrolytes and
the concept of breaking of water molecules into O and H due to the separation of charges was pro
posed by Grotthuss in 1807. Just prior to this, in 1806, Sir Humphry Davy presented the electrical
1
2 New Technologies for Electrochemical Applications
TABLE 1.1
Notable Inventors and Inventions in the History of Electrochemistry
Year/Era Inventor Invention
18th century Luigi Galvani Transmission of nerve impulses associated with an electric
current
18th century Alessandro Volta Voltaic pile—Chemical production of electricity and the
effects of electricity on chemicals
1800 Nicholson and Carlisle Electrolysis of water
1806 Humphry Davy Electrical theory of chemical affinity
1807 Theodor Grotthuss Theory of electrolytes
1821 Michael Faraday First electric motor
1831 Michael Faraday First dynamo
1834 Michael Faraday Stated first and second laws of electrolysis
1926 Henri Becquerel Hydrogen evolution electrodes
1936 John Frederic Daniell Daniell cell
1939 Sir William Grove First fuel cell
1874 Friedrich Kohlrausch Redefined the theory on the conductivity of electrolytes
1887 Svante Arrhenius Arrhenius theory on acid–base reaction
1897 Cart Bottger Development of H2 electrodes and measurement of pH
1902 Frederick Gardner Cottrell Electrode kinetics by diffusion
1905 Julius Tafel Law of electrode overpotential
1914 Thomas Edison Nickel/Iron battery
1914 Nikola Tesla Alternating current
Beginning of the 20th century John Alfred Valentine Studies on the transport of charged species and
Butler, Max Volmer, thermodynamics considerations
Heinz Gerisher, Rudolph
A. Marcus and others
Middle of the 20th century — Understanding the chemical and electronic structure of
solids–solution interfaces
Studies on in situ and ex situ spectroscopic techniques with
electrochemical experiments
1932–1942 James J. Drumm Zinc–nickel alkaline battery
1932 Francis Thomas Bacon First fuel cell device
— Mond and Langer Improved hydrogen–oxygen cell
1948 Arne Tiselius Sophisticated electrophoretic apparatus
1937 Arne Tiselius Protein electrophoresis
— Wiktor Kemula Hanging mercury drop electrode (HMDE)
1950 — Launch of modern electroanalytical chemistry in Warsaw
theory of chemical affinity (Davy 1840). Davy, of the Royal Institution in London, realized that
the production of electricity by the voltaic pile depended on the existence of chemical reactions,
not just on the contact of different types of metals. Davy’s student and successor, Michael Faraday,
followed the relationship between electricity and magnetism and invented the first electric motor
(in 1821) and the first dynamo (in 1831). He also published two laws of electrochemistry in 1834
and predicted the quantity of product that results from passing a certain amount of current through
a chemical compound or its solution, a process that he named “electrolysis” (Aftalion 2001). Based
on this method, a lot of industries produced metals in large amounts. The two-compartment battery
was proposed based on the observation of hydrogen evolution in electrodes by Becquerel in 1926
and developed by Daniell in 1936, giving birth to the Daniell cell. The reversibility of the water
Electrochemistry: Different Materials and Applications 3
electrolysis reaction was tried by Grove in 1939, which is the basis of the first fuel cell. At the end
of the 19th century, theoretical aspects of electrochemistry were refined due to the development of
the theory on conductivity of electrolytes by Kohlrausch in 1874, followed by Arrhenius’s theory
on acid–base reaction in 1887; the development of the hydrogen electrode and measurement of
pH by Bottger in 1897; electrode kinetics with mass transport by diffusion written by Cottrell in
1902, shedding a light onto many electrochemical processes; and the empirical law of electrode
overpotential discovered by Tafel in 1905. The first electrodeposition of alloys probably took place
at about the same time that cyanides were introduced into electroplating. De Ruolz is generally
credited with having been the first to deposit brass and bronze. The bronze bath that he described
in 1842 apparently was similar to the modern bath in that it contained a cyanide copper complex
and a stannate. The electrodeposition of brass apparently was the only alloy plating process that
had any commercial application up to modern times, although some mention is also made of bronze
plating in the early books on plating published before 1870 (Brenner 2013). The only other com
mercial alloy plating, other than brass plating, apparently was the deposition of gold alloys, which
was practiced to obtain different shades of gold, as is done today. The use of additions of copper
or silver to gold cyanide plating baths to obtain various shades of red, green, and green-white was
described by L. Eisner in “Die galvanische Vergoldung und Versilberung,” published in Leipzig in
1851 (Blaschko 1889). Before 1900, the knowledge of alloy plating was very limited and entirely
empirical, as no systematic or scientific research on the subject had been carried out. Probably the
first scientific work on alloy deposition was the classic work of Fritz Spitzer published in 1905,
which dealt with the cathode potentials involved in the electrodeposition of brass. The textbooks
of the period around 1910 showed very little appreciation of the factors governing alloy deposition.
Among the more satisfactory ones were Field’s text, The Principles of Electro-Deposition (Field
1911), which incorporated some of his work on brass plating, and a book by M. Schlötter, titled
Galvanostegie (Brenner 1963). In 1914, Tesla was giving a contradictory opinion to Edison on alter
nating current. In the 20th century, electrochemistry was mostly portrayed for the studies related to
charge carrier transport of materials and thermodynamic perspectives. With the pioneering work
carried out by Butler, Volmer, Gerischer, Marcus, and others, kinetic aspects of electrochemistry
have become more important in electrochemical research. These theories are the strong pillars of
electrochemistry, helping researchers understand the electrochemical concepts on new organic,
inorganic, and biological systems. In the middle of the 20th century there was much interest in
understanding the electrochemical aspects of the solid–solution interface. After 1920, research on
the electrodeposition of alloys greatly increased, and while much effort was devoted to devising
plating baths for particular alloys and to studying the variations in the composition of the alloys
with plating conditions, very little of a general theoretical nature was uncovered. The development
of new plating baths has remained empirical up to the present. These studies have been acceler
ated by the application of numerous in situ and ex situ spectroscopic techniques, which have been
combined with electrochemical experiments. Probably the most important advance of this period
was the application of X-rays to the elucidation of the structure of electrodeposited alloys. This was
first done by Nakamura in 1925 and was followed by the work of Roux and Cournot in 1928. Their
research showed that electrodeposited alloys had structures similar to those of the corresponding
thermally prepared alloys. Notable inventions are the Drumm traction battery (zinc–nickel alkaline
battery) invented by James J. Drumm, which was successfully employed to power a suburban train
in Ireland (1932–1942) (Allmand 1932). In 1932, inventions by engineer Francis Bacon resulted
in the first successful fuel cell devices, which were further improved by Mond and Langer with a
hydrogen–oxygen cell. The Nobel Prize was awarded to Arne Tiselius during 1948 for his work
on the invention of a sophisticated electrophoretic apparatus and for his work in protein electro
phoresis 1937 (Bacon 1969). In 1950, the hanging mercury drop electrode (HMDE) was developed
by Wiktor Kemula, which plays a central role in the field of modern electroanalytical chemistry
(Jindra and Heyrovský 2015). Accordingly, a huge number of research articles have been reported
in the field of amalgam electrochemistry, cyclic voltammetry, anodic and cathodic stripping of
inorganic and organic substrates, and electron transfer rate. The field of electrochemical research
provides various potential application areas, starting from qualitative analysis to quantitative analy-
sis, including batteries, fuel cells, photovoltaic devices, supercapacitors, gas sensors, biosensors,
corrosion of materials and purification of metals.
1.2 OXIDATION AND REDUCTION

The following definitions are taken from the American Standard Definitions of Electrical Terms,
which was revised in 1956 by a committee of about a dozen men representing several techni-
cal organizations. “Electrochemistry is that branch of science and technology which deals with
interrelated transformations of chemical and electric energy” (Lefrou et al. 2012). Oxidation–
reduction is a notion first introduced by Lavoisier (Roco et al. 2011) in which the reaction occurs
between the dioxygen and the chemical species and is denoted by the oxidation reaction, e.g.,
2Hg + O2 → 2HgO. The modern notion, related to electron transfer, was entrenched at the early
20th century. The formation of redox reaction (oxidation–reduction) engages altering electron
shifts at the core-level regions. When a chemical species loses one or more electrons in a reaction,
this species is known as oxidation and the reaction undergoes oxidation reaction. When the species
gains electrons, it is known as reduction reaction. The following are the overall reaction for Ox/
Red half couple reaction,
oxidation

Red
Ox + ne
−
reduction
The term Ox refers to oxidant, which means able to gain electrons, and the term Red refers to reduc-
tant, which means able to donate electrons.
The basic criterion for choosing material for electrochemistry is if it is able to conduct electricity.
Various materials are used in the field of electrochemical research including both organic and inor-
ganic materials. The direct current power supply is usually connected to the two terminals of the
electrochemical materials, which is controlled by the external devices either in the form of voltage
or current. The chemical species or electrons can be transferred from one terminal to another ter-
minal of the electrochemical material via electrolyte solution. The term electrode is generally used
in the field of electrochemistry to mean a metallic strip used as a conductive terminal of the elec-
trochemical devices. Sometimes, the word modified electrode or positive electrode is used to refer
to a metal electrode covered with a thin film of conducting material over the surfaces. Finally, the
term reference electrode will be used for an electrochemical half-cell. The anode is the electrode
material where oxidation reactions take place. The electrode material with the reduction reaction is
called the cathode (Crow 2017).
In the electrochemical system, the power supply is essential for the operation of the electro-
chemical cell, which is referred to as the electrolyzer mode. The most frequently used power
sources in the operation of electrochemical devices are current and voltage. A simple and change-
able carrier resistance can be sufficient to study an electrochemical system in the power supply
mode. While observing the current in the electrochemical system, it is termed as the intensiostatic
or galvanostatic method. This concerns when the imposed current is time-dependent, and the
subsequent measurements are called potentiometry. In this instance, the voltages in the system are
dignified, while current is executed. When the voltage is executed at the terminals, this denotes
a potentiostatic setup. If the executed voltage is time-dependent, the consequent measurements
are called amperometry. In this instance, while current is increased, the voltage in the system is
amplifed. The electrochemical experimental details can be classified into four main groups, which
are shown in Figure 1.1. A similar table could be drawn up for the usual potentiometry techniques,
apart from voltammetry, because its equivalent in potentiometry is not used.
FIGURE 1.1 Brief classification of four main amperometry experiments.
1.3 MATERIAL SYNTHESIS BY ELECTRODE POSITION METHOD

1.3.1 ElEctrodEposition of MEtals and alloys
The electrodeposition by applying a pulse signal of nanocrystalline metals like silver, gold,
nickel, cobalt, iron, platinum, and copper, ranging in size from 5 nm to 100 nm, has been
reported (Mohanty 2011). Various morphologies of electrodeposited materials can be modi
fied by choosing the parameters like desired electrolyte, applied potential, current density, pH
of the solution, pulsed signal, and duration of the electrodeposition process. For example, gold
nanoparticles were uniformly deposited on the carbon electrodes by an electrolytic bath con
sisting of sulfuric acid and gold auricchloride precursors (Toney et al. 1995; Wang et al. 2013).
Surfactants like CTAB, PVP, and TTABr will help to modify the shape of the nanoparticles
deposited on the substrates by electrodeposition techniques. Apart from the noble metal nano
materials, nanocomposites have also been prepared using electroposition with the use of noble
metals and some conducting polymers. Porous metal nanostructures were developed by elec
trodeposition onto anodic alumina disc or polycarbonate membranes with the help of shape
modifiers, such as sodium sulfate or potassium hydrogen phosphate (Tiano et al. 2010; Stine
2019). Alloys have received high interest in the technological field due to their ability to engi
neer the properties beyond the pure metals and to alter them specifically through composition
or phase selection. The preparation of alloys using electrodeposition or by thermal treatment is
more or less similar in terms of structural or crystallographic phases. In terms of application,
magnetic alloys like Ni–Fe or Fe–Co by electrodeposition show better coercivity value than the
other preparation techniques due to homogenous distribution, phase purity, and high crystalline
nature (Liu et al. 2000; Rahman et al. 2007). Some of the alloys are commercially available by
using electrodeposition techniques like Pb–Sn (Liu et al. 2008), Ni–Co, Fe–Ni (Liu et al. 2008),
and Sn–Zn (Kazimierczak and Ozga 2013). Some of the earlier reports on electrodeposition of
metals and alloys are given in Table 1.2.
6
TABLE 1.2
Earlier Reports on Electrodeposition of Metals and Alloys
Compound Alloy/Experiment Electrolyte Potential and Time Temperature Reference
Aluminum Al–Mn alloy coating on AlCl3–NaCl–KCl–MnCl2 molten salts Cathode current density (Dk) of 40 mA/cm2 170°C Zhang et al. 2009
Mg alloy for 30 min
Al–Cr and Al–Ni alloy AlCl3–NaCl–KCl molten salt containing Constant charge density at 40 C cm−2 423 K Ueda et al. 2007
CrCl2 and NiCl2 Cr deposit at −0.1 V
Ni deposit at −0.4 V
Al–Li–Mg alloy LiCl–KCl–MgCl2 molten salt Current density −1.337 A cm−2 Potential 620°C 113Ye et al. 2010
−2.38 V
Al–Pt alloy AlCl3–NaCl–KCl molten salt containing At 1.2 V pure Pt is deposited 448 K Ueda et al. 2011
PtCl2 At 1.0 V Pt, intermetallic compounds of
AlPt2, and/or AlPt3 are deposited
Lower than 0.8 V, intermetallic compounds
of AlPt2 and/or AlPt3.
Al–Sn alloy AlCl3–NaCl–KCl–SnCl2 molten salt 0.5 V 423 K Ueda et al. 2013
Deposition of Al films AlCl3–dimethyl sulfone 40 mAcm−2 1 h at 403 K Salman et al. 2019
Magnetic Fe–Si alloys KCl–NaCl–NaF–SiO2 molten salts Current density 30 mA/cm2, 1073 K under Yang et al. 2012
materials different deposition times: 2 min, 5 min, 10 argon atm
(Fe, Ni) min, 15 min, 20 min and 25 min
Fe–Pd alloy [Pd(NH3)4]2+ (0.02 M) and [Fe-Citrate]2+ −850 to −1050 mV Rezaei et al. 2018
(0.2 M)
Nanocrystalline quasi-bulk Citrate bath (sodium sulfate as a conducting At current densities ranging from Dehgahi et al. 2017
Fe–C material via salt and the small amount of citric acid) −20 mA/cm2 up to about −50 mA/cm2
electrodeposition E = −1000 to −1200 mV and 22 h
Ni–aluminide layer on Molten salt as the electrolyte 200 Am−2 for 3.6, 7.2, 10.8 and 12.6 ks 1023 K Sato et al. 2016
Nb–W and Nb–W–Mo Electrodeposition of Al at −1.4 V for 3.6 ks
alloys and Al that can be
electrodeposited
(Continued)
New Technologies for Electrochemical Applications
TABLE 1.2 (CONTINUED)

Tantalum on NiTi alloy 1-butyl-1-methyl-pyrrolidinium bis(tri −1.8 V RT El Abedin et al. 2005
fluoromethylsulfonyl)imide ([BMP]Tf2N)
containing TaF5 as a source of tantalum
Ni–Al2O3–SiC Watt’s bath containing Al2O3 and SiC Current density 1 A/dm2 RT Dehgahi et al. 2017
nanocomposite coatings are nanoparticles E = −0.22 V
electrodeposited on a steel
Zinc Al–Zn on an active ZnCl2-containing AlCl3–EMIC ionic liquid −0.2 V RT Pan et al. 2010
magnesium alloy
Metallic Zn on Mg alloy N-butyl-N-methyl-pyrrolidinium −2.5 V RT Deng et al. 2011
substrates dicyanamide (BMP-DCA) ionic liquids
containing ZnCl2 at 323 K
Zinc-cobalt alloys Zinc chloride-1-ethyl-3-methylimidazolium 0.15 V 80°C Chen and Sun 2001
chloride molten salt containing cobalt(II)
Zn–Fe multilayered alloy Solution 1: electrodeposition of Zn–1 wt% Current density 30 mA/cm2 40°C ± 2°C Panagopoulos et al.
coatings are deposited on Fe alloy layers; solution 2: Zn–10 wt% Fe 2019
Electrochemistry: Different Materials and Applications
mild steel substrates alloy layers

Copper To study the Trimethyl-n-hexylammoniumbis 5.6 V 50°C Murase et al. 2001
electrochemical behavior ((trifluoromethyl)sulfonyl)amide
of copper (TMHA-Tf2N)
Cu layer was successfully Copper chloride (CuCl2·2H2O)–1-ethyl-3 –0.70 V 28°C ± 2°C Saravanan and
electrodeposited on mild methylimidazolium chloride [EMIM] Mohan 2013
steel Cl–ethylene glycol [EG] ionic liquid
Deposition of copper 1-butyl-1-methylpyrrolidinium Current of 10 mA RT Brettholle et al. 2010
nanoparticles bis(trifluoromethylsulfonyl)amide ([Py1,4]
Tf2N) and 1-ethyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)amide ([EMIm]
Tf2N).
Copper–tin (Cu–Sn) alloy 1-butyl-3-methylimidazolium chloride Current density = 1.540 mA/cm2 RT Jie et al. 2019
([BMIM]Cl) E = –1.5 – 1.5 V
(Continued)
7
8

Rare‑earth Lanthanum 1-octyl-1-methyl-pyrrolidinium −1.5 V 25°C to 80°C Legeai et al. 2008
metals electrodeposition bis(trifluoromethylsulfonyl)imide ionic
liquid.
Electrodeposition of Phosphoniumcations with bis Potential and the cathode current density 150°C Lair et al. 2010
dysprosium (Dy) (trifluoromethylsulfonyl) amide anions were –3.8 V and –3.2 mA cm−2
Cerium oxide thin layer Mixed ionic liquid1-methyl-3 −1.4 V and −0.6 V applied for 2 h RT Lisenkov et al. 2010
was electrodeposited onto butylimidazolium
stainless steel bis(trifluoromethylsulfonyl)imide)/ethanol
solutions
Al–Ce alloy on surface of AlCl3 in 1-butyl-3-methylimidazolium −2.5 V to 2.5 V Below 80°C Tachikawa et al. 2009
Pt and AA2024 chloride (BMIM-Cl)
aluminium alloy
To study electrochemical Hydrophobic ionic liquid, 1-butyl-1 −0.44 V RT Tsuda et al. 2001
and spectroscopic methylpyrrolidinium
properties of divalent and bis(trifluoromethylsulfonyl)amide
trivalent europium species (BMPTFSA)
Electrochemical behavior LaCl3 in acidic AlCl3–1-ethyl-3 −1.95 V 298 K Kamimoto et al. 2018
of lanthanum ion studied methylimidazolium chloride
in various AlCl3–EMICl (AlCl3–EMICl)
molten salts saturated with
LaCl3
Zinc–rare-earth alloy Eutectic LiCl–KCl mixture –1.0 V 473 K for 24 h Jou et al. 2010
under vacuum
(Continued)

Nobel metals Palladium–tin alloys 1-ethyl-3-ethylimidazolium chloride– 0.8 V 120°C Jou et al. 2009
tetrafluoroborate ionic liquid
Palladium–copper alloys 1-ethyl-3-methylimidazolium chloride– −0.35 to –0.60 V 120°C Huang and Sun 2004
tetrafluoroborate ionic liquid
Pt–Zn alloys 40–60 mol% zinc chloride–1-ethyl-3- −0.20 to −0.24 V 90°C Molodkina et al.
methylimidazolium chloride ionic liquid 2019
containing PtCl2
Silver electrodeposition on Dicyanamide anions: 1-butyl-1- 0.5 to 0.5 V 23°C ± 1°C Tavakkoli et al. 2019
Pt (111), Au (111), and Au methylpyrrolidinium dicyanamide [BMP]
(100) single-crystal [DCA] and 1-butyl-3-methylimidazolium
surfaces dicyanamide [BMIm][DCA]
Gold–platinum Electrolytes with different Au:Pt ratios (best 0 and –1.5 V RT Song et al. 2010
nanoparticles deposited on response is 3:1 ratio of Au:Pt)
an indium tin oxide (ITO)
surface
Electrochemistry: Different Materials and Applications
9
1.3.2 ElEctrodEposition of organic MatErials

The electrodeposition of organic materials onto single or composite materials will help to protect
the surface or decorative purposes for potential applications like self-cleaning windows, antifoul
ing glasses, antibacterial coating on biomaterials, and antifriction in mechanical motors. The main
advantage of using organic coating by the electrodeposition technique on the surface of the alloys
or a single metal is a uniform and homogenous coating, which helps for protecting steels and alloys
from corrosion (Twite and Bierwagen 1998; Hu et al. 2007; Wu et al. 2014). The decorative appear
ance of the alloys or steels will be enhanced by electrodeposited organic materials onto it. Most
of the alloys are decoratively polished to a brighter surface than single metals, which is due to the
usage of electrodeposited organic agents. Some of the alloys like Co–Ni and Cu–Sn–Zn (Beattie
and Dahn 2005) were used to enhance not only the surface appearance but also to increase the
mechanical strength by electrodeposition by organic materials on the surfaces. Due to their diverse
properties, organic electrodeposited coatings are used as molds for making plastic utensils or as
wear-resistant agents for certain machinery alloys or improving the hardness of certain metals and
alloys. In electronic industries, low-melting-point alloys are used as soldering materials for making
electronic circuits and devices, and also used to replace the toxic metals in computer chassis.
1.3.3 ElEctrodEposition of MEtals as sacrificial coatings

The most important use of electrodeposits, whether individual metals or alloys, is as coatings to
protect other metals, such as steel, brass, and zinc, from corrosion. For this reason, the main inter
est in the chemical properties of electrodeposited alloys has centered on the corrosion and tarnish
resistance of the alloys with particular emphasis on the protection that alloy coatings afford to steel.
To show that the chemical nature of the metal alone does not determine its value as a coating, it may
be pointed out that, for the protection of steel against corrosion, metals of diametrically opposite
degrees of chemical reactivities are utilized; yet each type satisfactorily affords protection against
corrosion but in different applications. The two types of coatings that are applied to steel are des
ignated as cathodic and anodic (Brenner 2013). Cathodic coatings, of which nickel and copper are
examples, are chemically less active than steel. In a salt solution, these metals are positive (more
noble) to steel. Coatings of these metals protect steel by shielding it from corrosive environments
and are effective as long as they completely envelop the steel (Gan et al. 1994; Von Baeckmann et al.
1997). Being less reactive than steel, a given thickness of coating lasts much longer than an equiva
lent thickness of steel. However, if discontinuities extending down to the steel occur in the coating,
the corrosion of the steel is accelerated by the galvanic action that is set up between the coating as
the cathode and the steel as an anode in the presence of moisture. In contrast to the cathodic coat
ings, the anodic coatings, of which zinc and cadmium are the most important, are more active than
steel. In a salt solution, these metals are negative (less noble) to steel. Anodic coatings protect steel
from corrosion initially, just as do the cathodic coatings, by shielding it from corrosive environ
ments (Sørensen et al. 2009; Shreir 2013), but being chemically active they are attacked more rap
idly than cathodic coatings. When, or if, the steel is exposed through discontinuities in the coating,
the latter still protects the steel by virtue of galvanic action. In the presence of moisture, the coating
becomes the anode of a galvanic cell and is slowly consumed, whereas the steel being cathodic does
not corrode until the exposed area becomes so large that parts of it are too far removed from the
coated area to receive appreciable current.
1.3.4 ElEctrophorEtic dEposition

Electrophoretic deposition (EPD) has received great interest among materials scientists for the
production of novel inorganic nanostructured and nanoscale materials with various morphologies.
Recent advances have been made in the field of electrophoretic deposition and its process route
for the fabrication of different varieties of ceramic and metallic nanoparticles, carbon nanotubes,
and other nanomaterials. In the 1980s, Hamaker (Besra and Liu 2007) first developed the elec
trodeposition technique for the preparation of ceramic materials. In the process of EPD coating
by applying a direct electric field to the conductive substrate, the charged particles in the liquid
medium get attracted and coated on the conductive substrate of opposite charge. The fundamental
difference between the electrolytic and electrophoretic deposition techniques are that the deposi
tion takes place from the ionic species (salt solution), and the deposition occurs due to presence of
charged particle in the electrolytic medium, respectively. The potential applicability of electrode-
posited alloys include the fields of corrosion technology, fuel cells, antimicrobial coating, biomedi
cal implants, wear-resistant materials, load-bearing ceramics, and so on. Some areas are highly
enriched in the production of multifunctional coatings with nanostructured materials (Besra and
Liu 2007). The EPD technique also provides a unique approach for coating complex structures and
advanced ceramic coatings (Boccaccini and Zhitomirsky 2002). The deposition rate and uniformity
of the coating are monitored by the stoichiometric ratio of the coating materials. With respect to the
applied potential, the driving force of the electrophoretic deposition depends on the charge of the
coating materials and the mobility of the electrolyte. By carefully monitoring the driving force, the
coating kinetics will be drastically improved. The stability of the coating is directed by the interpar
ticle forces presented in the liquid medium. Some of the forces like repulsive force, van der Waals
interaction, and electrostatic interaction acting between the charged particles in the liquid medium
control the homogeneity and stability of the deposition. The usage of water in the electrolyte liquid
medium is still limited in the electrodeposition technique, which affects the coating process due to
oxidation and reduction reactions taking place when potential is applied to the electrodes for coat
ing. This is the major limitation of electrodeposition. All the strategies should be reviewed before
fabricating the nanostructures using electrophoretic deposition method (Corni et al. 2008; Gurrappa
and Binder 2008; Liu et al. 2015).
1.4 ELECTROCHEMISTRY APPLICATION FOR HEALTH,

ENERGY, AND THE ENVIRONMENT
1.4.1 hydrogEn gEnEration
Design and development for sustainable and renewable energy production in an ecofriendly man
ner are highly needed for the near future. Concerns about environmental problems arise from the
depletion of fossil fuels due to the production of energy sources. In order to avoid the environmental
issues developed by the creation of energy, an alternative method is badly needed. Sustainable ways
of producing alternative energies in the field of electrochemical techniques have received great
interest among material scientists. Among them, the photoelectrochemical reduction of CO2 and
the generation of hydrogen fuels provide the highest energy capacity per unit mass as well as they
are ecofriendly energy carriers because they do not create toxins during the production of hydrogen
fuels. The most abundant source of hydrogen energy is water, but the splitting of water molecules
into the oxygen and hydrogen requires high temperatures, nearly 2000°C, thus making experiments
problematic. Photocatalytic water splitting by sunlight radiation is attractive and has been exten
sively examined in the past few decades. When a photon of light energy is equal or greater than the
semiconductor bandgap absorbs, the electron in the conduction band leaves a positive hole in the
valence band. In a stipulated time period, photoexcited charge carriers hinder the recombination
and travel to the surface, where they react with adsorbed molecules causing reduction and oxidation,
respectively (Figure 1.2). These oxidation and reduction reactions occur in the water medium and
produce hydrogen and oxygen gases. Suitable semiconducting nanomaterials with transition metal
cations have d0 (Ti4+, Ta5+, and W6+) or d10 electron configurations (Ga3+, Ge4+, and Sn4+). Other
metal oxides with d orbitals, such as Zn2+ and Mo6+, are able to alter the band edge position in a
suitable manner to efficiently generate hydrogen fuel.
FIGURE 1.2 Schematic illustration of water splitting over semiconductor photocatalysts (Su et al. 2018).
FIGURE 1.3 Schematic representation of artificial direct Z-scheme photocatalyst (Maeda and Domen 2010).
An alternate approach to create hydrogen fuels is called the two-photon system, which resembles
Z-scheme photocatalysis. In this system, the flow of electrons shows the signature Z-direction in
two types of semiconductor photocatalysts. One semiconducting material acts as an oxidation reac
tant and the other one acts as a reduction reactant, and the electron can be excited by one of the
conduction band and resides at the valence band of another semiconductor. For example, an electron
donor/acceptor transport is added to two different photocatalytic sites (Figure 1.3). With the photo-
catalytic generation of hydrogen, the donor is oxidized to the acceptor by h+ and this is reduced back
to the donor at the O2 evolution site, while holes oxidize water to O2. However, at the H2 evolution
photocatalyst, the reduction of H+ to H2 and oxidation of the donor to acceptor may stop when the
concentration of the acceptor becomes high enough towards reduction of the acceptor competes
with the donor. Likewise, the rate of O2 evolution over the other photocatalyst may decrease when
backward oxidation of donor to acceptor becomes competitive.
1.4.2 chEMirEsistivE gas sEnsor

In monitoring the environment in the aspects of air quality, gas sensing technologies play a cru
cial role because air quality affects our daily lives. The first commercial metal-based sensor, a hot
platinum wire-based gas sensor produced was developed in 1923, and in 1962 Taguchi patented
the first oxide-based gas sensor. Various types of gas sensors have been developed, but resistivity-
based sensors are widely preferred owing to their inexpensive cost fabrication, smooth operation,
and possible miniaturization. In metal oxide gas sensors, research has been initiated to improve
the sensitivity, stability, and selectivity. The first work on metal oxide gas sensors was reported
by Seiyama with gas sensors made by ZnO thin films with the basic electrical circuit operating at
485°C (Seiyama et al. 1962). With the pioneering developments in the field of nanotechnology, it
has become possible for many researchers to make significant progress with oxide nanostructures,
conducting polymers, carbon nanostructures, and 2D materials. Metal oxide semiconductor-based
chemiresistive sensors have recently attracted significant attention for a wide variety of applica
tions, including food processing (Neethirajan et al. 2009), environmental monitoring (Fine et al.
2010), the agriculture industry (Lerma-García et al. 2009), and medical diagnosis. Most conven
tional metal oxide-based gas sensors normally operate at temperatures ranging from 100°C to
400°C. However, owing to an induced growth of metal oxide grains, this will lead to high power
consumption, reduced sensor stability, and shorter lifetime. Interestingly, room temperature gas
sensors produced with conducting polymers was developed. But they are affected by humidity, are
less stable in operating environment, have higher recovery time, and have poor stability. Studies on
including surface functionalization with noble metals, using oxide incorporated heterostructures
and thermal assistance with ultraviolet (UV) illumination, have been done improve sensitivity and
selectivity of these conducting polymers. The gas adoption mechanism and consequent resistance
change in a metal oxide semiconductor gas sensor mainly involves three major functions: receptor
function, transducer function, and utility factor (Simon et al. 2001; Yamazoe et al. 2003). The func
tion of the receptor is mostly ascribed to the selectivity and sensitivity of the device and response of
the device with respect to the surrounding environment (Figure 1.4a). In this stage, the amount of
oxygen adsorbed on the surface leading to the depletion of the surface mainly governs the sensing
FIGURE 1.4 Three main factors controlling semiconductor gas sensors: (a) receptor function, (b) transducer
function, and (c) utility factor (Roco et al. 2011; Nasiri and Clarke 2019).
capabilities of the device, which depends on the particle size (dp) of the sensing material. If dp >>
2δ, the sensing mechanism is determined by transferring electrons at the particle’s grain boundary
resulting in a low sensitivity. If dp > 2δ, a large portion of the bulk participates in the sensing mecha
nism leading to a moderate sensitivity (Tricoli et al. 2010; Nasiri et al. 2015). In contrast, if dp ≤ 2δ
the entire particle is an electron depleted with no mobile charge carrier, leading to significantly high
resistance with very low baseline currents.
The transducer function is an interparticle issue related to how the surface phenomenon is
transformed into a change in electrical resistance of the sensor (Dey 2018) (Figure 1.4b). The
chemical interaction of the semiconductor surface creates an electrical signal in the transducer
function, which is mainly controlled by the surface potential and potential barriers formed
between grains, trapping states in grain boundaries and defect states in the semiconductor struc
ture. Schottky barriers between two grains impede electrons transferring across the boundary.
Therefore, the boundaries between the grains act as transducers when the resistance change by
the gas adsorption is amplified. Quite a lot of studies have shown the significance of analyzing
the grain boundary for improving the transduction of the surface response (Korotcenkov et al.
2009; Nasiri et al. 2016).
Last, the utility factor (Figure 1.4c) is related to the morphological structure of the metal oxide
semiconductor and consequently the diffusion and reaction of target gas through the structure
pores (Barsan et al. 2007; Kim et al. 2017). The utility factor determines how the sensing perfor
mance is affected by the device structure, with the film porosity as the most important parameter
in achieving the highest utility factor. In a very porous structure, the target gas particles pen
etrate into the lowest layers of the film, resulting in an effective resistance variation of the sens
ing device (Nasiri et al. 2015). However, the utility factor might be meaningless for monolayer
structures such as MoS2, as the material structure is atomically thin and the gas adsorption is not
associated with the diffusion through the material. For such 2D-structured sensors, the utility
factor is already maximized, and the highest performance of the device should be achieved by
choosing proper receptors and enhancing the interaction between target gas and sensing material
(Kim et al. 2017).
FIGURE 1.5 Schematic illustration of electrochemical-based nanobiosensors (Zhu et al. 2014).

1.4.3 BiosEnsor
The biosensor is marked as the future of analytical devices one that has a major impact on our
everyday lives. It has several advantages including high sensitivity, low cost, rapid response, good
selectivity, high-throughput, real-time monitoring, easy to make, and easy to handle (Roco et al.
2011; Teles 2011). Noting these exceptional attributes, considerable attention has been dedicated
to the integration of recognition elements with electronic elements, which can be developed as
electrochemical-based biosensors. Our day-to-day lives are occupied by using various types of bio
sensors from medical diagnosis to food analysis, which extend to pathogen determination, glucose
monitoring, determination of drug residues in food such as antibiotics and growth promoters, envi
ronmental cleaning applications, homeland security, determination of levels of toxic substances in
bioremediation, routine analytical measurement of folic acid, biotin, vitamin B12 and pantothenic
acid, drug discovery, and evaluation of biological activity (Byfield and Abuknesha 1994; Patel
2002; Ahmadalinezhad and Chen 2013). With the help of nanotechnology, nanomaterial-based
electrochemical signal amplifications have been achieved with great prospective for improving
both selectivity and sensitivity. In electrochemical sensors, it is distinguished that the electrode
materials play an important part in detecting target molecules through various analytical prin
ciples. By altering the electrode materials with suitable functional nanomaterials, the catalytic
activity, conductivity, and biocompatibilitity properties of the electrode can be enhanced and leads
to accelerated signal transduction. By choosing suitable modeled signal tags such as biorecognition
agents the sensitive of biosensors were notably increased. A detailed review made by Chengzhou
et al. (2014) outlines on electrochemical sensors for small molecules, enzyme-based biosensors,
immunosensors, genosensors, and cytosensors.
1.4.3.1 Glucose
Over the past 50 years, intense development has been seen in enzymatic glucose sensors. The
developments have balanced the benefits versus disadvantages (Khan et al. 1996). Glucose bio
sensors have developed into a lot of technological advancements such as point-of-care devices,
continuous glucose monitoring systems, and noninvasive glucose monitoring systems. The first-
generation of glucose sensors developed were based on high oxygen presence, and hence have
limitations in use for commercial and practical applications (Wang 2001). The second-generation
glucose sensor was not working due to the existence of other electroactive interferences in the
sample and also its disadvantages in large-scale production (Scheller et al. 1991). The present
FIGURE 1.6 Summary of glucose electrooxidation mechanisms: presented as enzymatic (first-, second-,
and third-generation sensors) and non-enzymatic (so-called herein “fourth-generation” sensors) (Holade
et al. 2017).
shift to third-generation sensors is focusing on 3D orientation, low electron tunneling distances,

and substrate accessibility of the enzyme by glucose (Khan et al. 1996; Toghill and Compton
2010). Even with all these efforts, ensuring stability is the main issue for the commercializa
tion of analytical devices, and this seriously influences the research on the development of new
technology and new materials for electrochemical sensors. The fourth-generation glucose sensors
shift toward nonenzymatic electrodes, which are presently identified as a potential candidate for
analytical glucose oxidation. In this generation of sensors, the active noble metal nanomaterials
experience an oxidation reaction that forms a hydrous oxide layer, OHads, which arbitrates the
oxidation of the adsorbed species. These nonenzymatic materials are abiotic catalysts, which
extends their applications to the food industry and to fuel cells and batteries operating in close
biological conditions. Quality control in industrial processes is essential, and measuring the num
ber of numerous sugars to validate the quality, authenticity, maturity, and nutritional value of the
product is of substantial importance.
1.4.3.2 H2O2 Sensor

Hydrogen peroxide (H2O2) is an indispensable substance in many intermediate natural reactions,
a strong oxidizing agent, and is simply miscible with water. In addition to its many applications
in the electronic and food industries, it is an important by-product in the chemical industry, food
industry, pharmaceutical industry, clinical medicine, and environmental monitoring (Zhao et al.
2017). Hence, an accurate determination of H2O2 is of high importance (Wen et al. 2011). Due to
this importance, numerous kinds of H2O2 detection and measurement methods have been estab
lished, which include fluorometry, spectrophotometry, and electrochemical analysis (Dickinson
and Chang 2008). Among these methods, the electrochemical-based analytical technique has
been considered in a lot of industries due to its promising approach and excellent advantages
which include quick response, ease of operation, and high sensitivity. H2O2 biosensors by the
electrochemical detection method can be achieved by nonenzymatic and enzymatic methods. In
enzyme-based methods, horseradish peroxidase (HRP) and catalase (CAT) are commonly used
for H2O2 detection (Hernandez-Ruiz et al. 2001). The immobilization and stabilization protocol
of the enzyme makes it challenging to attain the direct electron transfer on a bare electrode. This
problem was rectified to an extent by the development of excellent support materials, which offer
a better environment for enzyme loading. For this, carbon-based nanomaterials, metal nanopar
ticles, and polymers have been utilized. The introduction of these nanomaterials has shown a
notable rise in the enzyme loading area and enhanced the contact area with more detectors,
which in turn enhance the electron transfer rate. The working nonenzymatic biosensor is based
on the electrocatalytic reduction, and the reaction is accomplished on the surface of the electrode.
Conventional electrodes used for electrochemical detection require higher overpotential. In order
to enhance work with lower overpotential, efforts were then devoted to using nanomaterial-based
modified electrodes. Hence, nonenzymatic biosensors with metal nanoparticle-modified elec
trodes have been chosen, as they can greatly improve the surface area, mass transport rate, and
catalytic efficiency. Many experimental results have shown valid proof that nanoelectronic medi
ums can advance the electron transfer rate and increase the anti-interference ability of biosensors.
Notably, the electrocatalytic performance toward H2O2 was efficient when choosing a transition
metal oxide, such as CuO (Gu et al. 2010), MnO2 (Bai et al. 2007) or Co3O4 (Wang et al. 2014).
Even though these nanomaterials have the advantages of low cost, and being environmentally
friendly, and easy to prepare, they have limitations in stability and sensitivity. Hence, the noble
metal-based nonenzymatic H2O2 biosensor needs more research (Zhao et al. 2017). Recently,
Shu-Xia Xu et al. reported on third-generation H2O2 sensors using tetraethoxy-silicone (TEOS)
sol–gel film for the immobilization of horseradish peroxidase on a multiwalled carbon nanotube
(MWNT)-modified glass carbon electrode (GCE) (Xu et al. 2014). Third-generation biosensors
can detect H2O2 at relatively low applied potentials, and feature the advantages of operation sim
plicity, no mediator, easy fabrication, and high sensitivity.
1.4.4 WastEWatEr trEatMEnt

The environment is polluted day-by-day due to either natural or man-made activities (Alqadami et al.
2017; Naushad 2014; Naushad et al. 2015). One of the important natural resources, water, is polluted
due to natural disaster, industrial use, and various human activities (Naushad et al. 2016; Sharma et al.
2014). By measuring certain parameters, it can be known up to what extent water is polluted. These
parameters include COD (chemical oxygen demand), BOD (biochemical oxygen demand), pH, TOC
(total organic carbon), TDS (total dissolved solids), volatile matter, nonvolatile matter, total hardness,
color, and odor. Electrolysis is one way of treating wastewater containing a high concentration of
metals. Industrial electrochemistry has participated in creating ideal processes and more ecofriendly
yield. One important breakthrough in environmental protection applications includes two oxidation
processes that help to remove the toxins in our environment (Martínez-Huitle and Panizza 2018):
1. Direct electrolysis—In this process, the reaction between the species at the sensing elec
trode is direct. The electron transfer to or from the undesired diluted pollutant occurs on
the electrode surface, which results in reduction or oxidation processes directly on the
electrode’s surface without the involvement of any intermediate substances (e.g., electron
mediators, biocidal species). This direct electrolysis process can be further subdivided into
the oxidation and reduction of organic and inorganic pollutants.
2. Indirect electrolysis—This electrolysis process involves the invention of active species at
the electrode surface and further reaction with the targeted pollutants. The resultant redox
reagent plays an intermediary role for shuttling electrons between the electrode and the
pollutant substrate. Electrolysis can be done both with reversible and irreversible electro
generated reagents. Indirect processes include electrocoagulation, electro notation, electro
occultation, and advanced oxidation. Among these electro notation is widely used because
this process involves the electrolytic production of gases (e.g., H2) that can be utilized to
attach pollutants (e.g., fats and oils) to the gas bubbles and transfer them up to the top of the
solution, which can be more effortlessly collected and separated. Indirect electrolysis can
be electrogenerated by either the cathodic or anodic process. The most popular cathodic
processes method is the electro-Fenton (EF), where H2O2 is produced at the cathode
with O2 or air feeding while an iron catalyst is also regenerated on the surface of cathode
(Panizza and Cerisola 2009) (Figure 1.7b). Recently, other emerging technologies based
on the EF method (Brillas and Martínez-Huitle 2015; Garcia-Segura et al. 2017; Ganiyu
et al. 2018), such as solar-PEF (SPEF), photo-EF (PEF), ultrasound irradiation, coagu
lation based on dissolution of iron anodes (peroxi-coagulation [PC]), dissolution of het
erogeneous catalysts that supply Fe2+ (heterogeneous-EF), and bioremediation, have also
received a great deal of consideration. This process selection depends on the experimental
conditions, nature and structure of the electrode material, and electrolyte composition.
1.5 SUMMARY AND FUTURE DIRECTIONS

This chapter is an overview of electrochemistry from its history to various applications and from
synthesis to analytical techniques. Even though most of the electrochemical concepts deal with the
electron movement in a conductive medium and the oxidation–reduction concept, the concepts of
electrochemistry is expanding day by day. During the initial days of the electrochemical concept it
was widely used by metal manufacturing industries. However, with the increase in the understand
ing of analytical chemistry and development of related devices this field has grown from coatings to
device designing. Other than industrial applications, due to the advancement in nanotechnology, the
interdisciplinary research on biomedical and electrochemistry is also growing with application in
various biosensors at low cost. In the future, a lot of low cost, miniature portable analytical devices
can be developed utilizing the concepts of electrochemistry.
FIGURE 1.7 A conceptual approach to (a) direct EO and mediated EO; (b) EF-based technologies as well
as electrochemical emerging wastewater treatments; (c) the 2.5 L pre-pilot plant; and (d) the use of renewable
energy sources together with electrochemical treatments (Martínez-Huitle and Panizza 2018).
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2 Controlled Electrochemical
Deposition for
Materials Synthesis
T. Sivaranjani, T. A. Revathy, and A. Stephen
CONTENTS
2.1 Introduction ............................................................................................................................26
2.2 Fundamentals of Electrodeposition ........................................................................................ 27
2.2.1 Thickness of the Deposition .......................................................................................28
2.2.2 Electrodes ...................................................................................................................28
2.2.3 Standard Electrode Potential ...................................................................................... 29
2.2.4 Electrolyte–Electrode Surface.................................................................................... 29
2.2.5 Mechanism of Electrodeposition ................................................................................ 29
2.2.6 Electrical Double Layer .............................................................................................. 31
2.2.6.1 Helmholtz Double Layer.............................................................................. 31
2.2.6.2 Gouy-Chapman Double Layer ..................................................................... 31
2.2.6.3 Stern Layer................................................................................................... 32
2.2.6.4 Grahame Layer ............................................................................................ 32
2.2.6.5 Bockris-Devanathan-Müller (BDM) Model ................................................ 32
2.2.6.6 Trasatti-Buzzanca Model ............................................................................. 32
2.2.6.7 Conway Model ............................................................................................. 32
2.2.6.8 Marcus Model .............................................................................................. 32
2.3 Parameters Affecting Electrodeposition................................................................................. 32
2.3.1 Effect of Current Density and Distribution ................................................................ 32
2.3.2 Effect of Bath Temperature ........................................................................................ 33
2.3.3 Effect of Bath Concentration ...................................................................................... 33
2.3.4 Complexing Agent ...................................................................................................... 33
2.3.5 Effect of pH ................................................................................................................ 33
2.3.6 Addition of Agents...................................................................................................... 33
2.3.7 Effect of Plating Time ................................................................................................ 33
2.3.8 Effect of Agitation ......................................................................................................34
2.3.9 Hydrogen Embrittlement ............................................................................................34
2.4 Tunable Properties of the Material by Electrodeposition Parameters ....................................34
2.4.1 Composition................................................................................................................ 35
2.4.2 Structure ..................................................................................................................... 37
2.4.3 Morphology ................................................................................................................40
2.5 Multilayer Coatings ................................................................................................................ 41
2.6 Composite Coatings................................................................................................................ 43
2.7 Conclusion .............................................................................................................................. 43
Acknowledgments............................................................................................................................44
References........................................................................................................................................44
25
2.1 INTRODUCTION
Electrodeposition (ED), or electrochemical deposition as the name suggests, is a chemical reduc
tion process induced by electric current. In the electrodeposition technique, electrical energy is
passed through an electrolytic cell setup, thereby transferring the energy to ions in the electrolyte
solution so as to prepare the coating of the material present in the electrolyte over the surface of
another material or substrate (cathode). In the ED method, a two-electrode or three-electrode setup
is conventionally used. In the two-electrode setup, there is a cathode and anode (anode or counter
electrode), whereas in the three-electrode system there is an additional reference electrode. The
electrodes are dipped inside the conducting electrolyte. The electrical energy is applied through
a power supply connected parallel to the electrodes. The electrolyte used in the deposition is an
important component since the conductivity of the whole circuit is based on the ions present in the
electrolytic solution. There are different types of electrolytes that are used in the electrodeposition
process such as liquid electrolytes, molten/ionic melt electrolytes, polymer electrolytes, and solid-
state electrolytes (Plieth 2008). The type of electrolyte decides the mobility and conducting mecha
nism of ions in the circuit. As stated by Arrhenius, the dissolution of the salt in water forms the
basis of electrodeposition (Arrhenius 1889). According to Arrhenius, adding a corresponding salt
of a metal to any solvent like water makes it an appropriate electrolyte for electrodeposition. The
electrolytes that are made of water or other organic solvents are branched under liquid electrolytes.
NiSO4 dissolved in water is one of the best examples for aqueous electrolytes. For example, consider
NiSO4 when dissolved in water, the ions dissociate into the ions Ni2+ and SO42−. Then, on applying
the electric current, the positive ions move toward the cathode and catch up with two electrons to
form a nickel atom on the substrate. This is a simple example to show that electrodeposition is an
atom-by-atom aligning process (Kim, Dick, and Bard 2016; Al-Osta et al. 2017). In the case of ionic
melts, ions are separated and driven toward the electrodes at suitable elevated temperatures and
depositions are made (Malyshev 2012; Endres, Abbott, and MacFarlane 2017). The polymer electro
lytes are an important class of electrolytes. On mixing the polymer with salt, the polymers help the
ionic conductance of the metal concerned. Based on the defects and disorder in the crystallographic
structure, the conductance of ions through solids is also made possible.
The choice of suitable electrode is indeed an essential aspect of electrochemistry. The electrode
material is chosen based on the deposition potential range. A suitable electrode should not lead
to the dissolution or formation of an unwanted layer or formation of any oxide over the surface of
the electrode (Brett and Brett 1993). The cathode is the one on which the deposition will occur.
The anode is to connect the positive terminal and close the circuit. There are two types of conven
tional anodes used in electrodeposition, namely, dissolvable (or sacrificial) anodes and nondissolv
able anodes. The dissolvable anodes continuously replenish metal in the bath (Erb, Palumbo, and
McCrea 2011). Nickel and silver are the best examples of sacrificial anodes. Nondissolvable anodes
do not replenish the metal in the bath, but the terminal closes the circuit, e.g., carbon-based elec
trodes like graphite. At the anode, oxidation takes place and the valence state of the metal increases.
At anode : M → M + + e − (oxidation) (2.1)
The reduction process takes place at the cathode. Electrons produced near the anode are carried
to the cathode and are consumed at the cathode surface. During the reduction process, unlike the
anodic process, the valence of the material decreases and it reaches zero state during deposition.
At cathode : M + + e − → M ( reduction ) (2.2)
The reference electrode is the one that has a standard electrode potential.
The power supplied to the electrodeposition arrangement is in the form of current/potential.
There are two different types of deposition based on the applied current/potential and they are
Controlled Electrochemical Deposition for Materials Synthesis 27
direct deposition (DC) and pulsed electrodeposition (PED). In direct current/potential plating, elec
trodeposition is performed on a plating unit that is connected to a DC source. Therefore, the average
current density equals the peak current density. In PED, the potential is alternated swiftly between
two different values. This results in a series of pulses of equal amplitude, duration, and polarity,
separated by zero current. Each pulse consists of an on-time (TON) during which the potential/cur
rent is applied, and an off-time (TOFF) during which zero current is applied. In certain cases, bipolar
power sources are also employed. Various types of wave and pulse forms are given by Morton
Schwartz (Bunshah 2001). It is possible to control the deposited film’s composition and thickness
by regulating the pulse amplitude, resulting in unique composition and microstructure. This helps
in producing various nanocrystalline metals, alloys, and composites successfully. It controls the
microstructure and composition of deposited alloys by varying the pulse potential/current on-time
(TON), the pulse current/potential off-time (TOFF), peak current density (IP), average current density
(IA), the duty cycle (θ), and pulse frequency (f):
I P TON
IA = (2.3)
TON + TOFF
TON
q= (2.4)
TON + TOFF
TON + TOFF
Pulse frequency = (2.5)
TON
The electrodeposition process starts with nucleation on a kink site and develops into a metal coat-
ing/alloy/semiconductor film (Plieth and Georgiev 2006). Hence, to synthesize a material by adopt
ing electrodeposition, the amount of electric current needs to be applied and the chemical properties
of the particular material should first be well understood. The electrodeposition mechanism follows
reduction processes by supplying electrons at the cathode terminal. Electrodeposition is a strong
method for coating on the surface. The main properties of the electrodeposited materials are coating
adhesion, hardness, abrasion resistance, and corrosion resistance. All these properties and charac
teristics can be changed by selecting one or more variables such as the bath’s concentration, current
density, temperature of the bath, pH, using the additives in electrolytic bath, time of plating (Jokar
and Aliofkhazraei 2017).
Erb and his group are pioneers in the field of electrodeposition and studied the various effects on
electrodeposits such as size, ductility, corrosion resistance, and other functional properties (Brooks
et al. 2011; Facchini et al. 2009). Their group has worked to prepare alloys and composites both at
bulk and nanolevel (Erb, Palumbo, and McCrea 2011). They have also successfully deposited hydro
phobic materials (Tam, Palumbo, and Erb 2016; Victor, Facchini, and 24Erb 2012).
2.2 FUNDAMENTALS OF ELECTRODEPOSITION

A rule that governs the amount of the substance deposited and gives a key idea on the electrode-
position process is Faraday’s first and second laws of electrolysis. Faraday’s law relates the current
flow, time, and the equivalent weight of the metal with the weight of deposit and may be stated as
follows:
(i) The amount of chemical change at an electrode is directly proportional to the quantity of
electric current passing through the solution.
(ii) The amount of different substances liberated at an electrode by a given quantity of electric
current is proportional to their chemical equivalent weights.
Faraday’s laws may be expressed quantitatively:
I .t.Eq
W= (2.6)
F
where W is weight of deposit in grams, I is current flow in amperes, t is time in seconds, Eq is

equivalent weight of deposited element, and F is Faraday’s constant (96,500 coulombs).
Atomic weight
Eq = (2.7)
Valence change
where valence change is the number of electrons involved in the reaction.
2.2.1 thicknEss of thE dEposition

The average deposit thickness (T) is calculated from Faraday’s law (Palli and Dey 2016)
M jt
T= (2.8)
nF r
where M is the molar mass, j is applied current density, t is total deposition time, n is the number
of electrons transferred in the electrode reaction, F is the Faraday constant, and ρ is density. The
synthesis mechanism of metal/alloy by electrodeposition is unique when compared to the other
electrochemical processes wherein a new solid phase is formed from liquid electrolyte.
2.2.2 ElEctrodEs
In the electrodeposition setup, the electrode should be a conducting material allowing the electric
field or electric current to flow in a closed circuit. In electrochemical processes the electrodes are
linked via the electrolyte. The electrode can be either a metal or a semiconductor material.
There are different kinds of electrodes available according to the necessity of the experiments in
which they are used. The major types of electrodes are
• Nonpolarizable electrodes
• Polarizable electrodes
The electrodes at which the transfer of electrons and ions take place are called nonpolarizable
electrodes where there is free movement of ions at the electrode–electrolyte interface. The electric
current that flows due to the charge transfer across the electrode–electrolyte boundary is called the
faradaic current. The electrodes at which no electron transfer takes place are called polarizable elec
trodes. It means that the electrons form a layer at the cathode surface. The positive ions form a layer
near the electrode surface. There is no transfer between the electrode–electrolyte surfaces. The
current that flows to maintain the electrostatic equilibrium at the electrical double layer (EDL) or
interfacial double layer on both polarizable and nonpolarizable electrodes is called the non-faradaic
current or otherwise known as the transient current.
The term polarizable means that the potential of the electrode is fixed and will not change. These
kinds of electrodes act as mere capacitors. These electrodes are not soluble in nature, for example,
platinum electrodes. The charge–transfer equilibrium is not achieved in polarizable electrodes since
there is no movement of ionic or electron species; but electrostatic equilibrium is maintained, pro
ducing charge of equal amount with opposite signs on both sides termed as the electrical double
layer. Every electrode material has a specific potential when there is no electric flow. The deviation
of potential from this specific potential is known as polarization in electrochemistry. Anodic polar
ization is termed as the shift in electrode potential from the specific potential of the electrode in
the anodic direction, and cathodic polarization means the shift of the electrode potential toward
the cathodic direction. The nonpolarizable electrodes cannot be polarized since the charge trans
fer occurs in them with a large value of electric current. In such a reaction there is no change in
electrode potential. At the nonpolarizable electrode, the electron or ion transfer reaction will be in
equilibrium. For the electrode reaction to be in equilibrium at the interface of nonpolarizable elec
trodes, an appreciable concentration of redox particles or potential determining ions must exist in
the electrolyte. In polarizable electrodes, no charge transfer (no electron or ion transfer) across the
EDL occurs, and the electrode can be readily polarized.
2.2.3 standard ElEctrodE potEntial

The electrode potential and standard electrode potential of the concerned metal(s) play a major role
in the process of electrodeposition. The metal and the standard hydrogen electrode are immersed
in the conducting electrolyte. Then the potential drop across the concerned metal and the standard
hydrogen electrode gives the standard electrode potential of that metal. The electrode potential
represents not only the electrostatic potential but also the energy of free electrons or ions in the
electrode–electrolyte system. The electron energy level in the electrode depends on the chemical
potential of electrons in the electrode, the potential between the electrode and electrolytic surface,
and the surface potential of the electrolyte solution. For a given system, i.e., the combination of
electrode–electrolyte, the chemical potential of electrons and the surface potential remain constant.
Hence, the electrode potential or real potential of the electrode depends on the interfacial potential
between the electrode and electrolytic surface. Since the electrode–electrolyte interface plays a
major role in measuring the electrode potential, study of the electrical double layer has become
prevalent.
2.2.4 ElEctrolytE–ElEctrodE surfacE

The electrolytic cell reaction is studied in two separate sets of reactions. The cathode is merely a
half-cell in the whole setup where the reduction takes place and vice versa, i.e., oxidation takes
place at the anode. The deposition potential and deposition rate of the same metal differs when a
different type of electrolytic bath is employed. In a galvanostatic setup, where the cell is controlled
by current, the electrode potential is the potential drop observed in the electrode–electrolyte inter
face. This potential drop is defined as galvanostatic potential difference, which cannot be mea
sured experimentally since this is not constant and changes from time to time. When a suitable
electrolyte and appropriate electrode is chosen, the electrode–electrolyte interface controls the
whole electrodeposition process. When a solute (e.g., salt “MA”) is added to the electrolyte, the
ions will dissociate into M+ and A.̄ The electrolyte is in liquid phase and the substrate (electrode)
is in solid phase. When exchange of M+ ions from solution to the substrate happens, the reduc
tion phenomenon will occur at the cathode by the addition of electrons produced by the negative
charge of the cathode. This step in electrodeposition is not as simple as we think. At the electrode
surface, which is in a solid and liquid heterogeneous phase, the behavior of the double layer has
local variations, which possibly affects the deposition kinetics and hence the overall reaction might
be altered.
2.2.5 MEchanisM of ElEctrodEposition

On applying electric field, the positive ions in the electrolytic bath move toward the cathode.
Chemical steps occurring near the electrode involve ion dehydration or ligand dissociation. The
movement of ions in the bulk electrolyte takes different forms as described next (Zangari 2015).
Mass transfer is defined as the movement of material in a solution from one location to another. The
different modes of mass transfer include:
• Migration—The motion of a charged particle due to an applied electric field is called migra
tion. Only those ions that are near the interfacial region are likely to undergo migration.
• Diffusion—In response to the concentration gradient, ionic motion throughout the bulk of
the solution occurs mostly by diffusion.
• Convection—The electrodeposition process is essentially due to the movement of ions that
constitute current through electrolyte and is called convection. Charge transfer causes the
formation of a charge cloud near electrodes.
At the atomic scale, three different steps occur in ED, namely, ionic migration, electron transfer,
and incorporation. These processes have been described in schematic diagrams (Figure 2.1 and
Figure 2.2). The deposition starts with the nucleation of the first atom on the kink site on the cathode
surface used. The nucleation of the metal/alloy is based on the nature and energy of the ions present
in the electrolyte (Sobha Jayakrishnan 2012).
The behavior of solvated ions in electrolyte changes especially when complexing agents are
added and they transform the ions into complex ions. The metal ions are associated with the sol
vent molecules and complexed with additives either by electrostatic attraction or by covalent bond.
Electrical energy is applied in order to transfer the metal ion out of solution to the growing crystal
lattice. In the nucleation and growth of metal/alloys at the substrate surface a great technology
is actually involved. The ions will cross the double layer and get adsorbed on the surface of the
substrate. On the substrate surface these adsorbed ions or adatoms or adions wander before they
position themselves in a kink site. More adsorbed ions combine to form clusters of the adatoms.
The clusters grow in size depending on the transfer energy and surface energy of these adatoms and
reach a critical size (Nc) (Paunovic and Schlesinger 2006):
bse 2
N c = (2.9)
zeh
FIGURE 2.1 Deposition mechanism at electrolyte–electrode surface.

FIGURE 2.2 Steps involved in electrodeposition from electrolyte.
where b is the factor relating the surface area of the nucleus to its perimeter, s is the area occupied by
one atom on the surface of the nucleus, η is the overpotential, and ɛ is the edge energy. The critical
size forms a nuclei for a new phase. This nuclei has equal probability for growth and dissolution.
2.2.6 ElEctrical douBlE layEr

A double layer (DL) or electrical double layer (EDL) is a structure that appears on the surface of
an object when it is exposed to a fluid. The object might be a solid particle, a gas bubble, a liquid
droplet, or a porous body. The DL refers to two parallel layers of opposite charges surrounding the
medium/object. The explanation about the electrical double was given by various scientists and they
were named after them.
2.2.6.1 Helmholtz Double Layer

Helmholtz was the first to give a theoretical explanation about this double layer charging effect.
He gave the simplest approximation to this double layer effect stating that the electrons form a
rigid layer in the cathode, and positive ions form another layer in the electrolyte near the electrode.
When the potential applied is not enough to decompose the layer of ions, the stored charge in EDL
is linearly dependent on the voltage applied. Once the critical potential for deposition is reached,
the surface charge on the surface of the cathode will be neutralized by the counter ions placed at a
distance from the substrate surface, thereby the surface potential is distributed to the counter ions
linearly. This idea of rigid double layer interprets the differential capacitance and thickness of EDL
but does not necessarily explain all the features of the double layer phenomenon.
2.2.6.2 Gouy-Chapman Double Layer

Gouy and Chapman independently put forth the idea of the diffuse double layer. The ideas of these
two scientists contradict Helmholtz in that the capacitance value is not constant and changes with
the applied field and composition of the electrolyte containing metallic ion species. The electro
chemical behavior of electrodes plays an important role in electrical double layer. This model sug
gested that the Maxwell-Boltzmann statistic has to be followed to calculate the charge distribution
of ions as a function of distance from the conducting surface. The approximation of Gouy-Chapman
gave a better value of interfacial potential but not accurate.
2.2.6.3 Stern Layer

Stern gave an improved and combined hypothesis of Helmholtz and Gouy-Chapman double layers.
The Stern layer assumed the ions are of finite size and a closed ion approximates the ionic radius.
The limitations of the Stern layer include (i) this theory considered the ions as point charges and
only columbic interactions are studied, and (ii) dielectric permittivity is taken as a constant.
2.2.6.4 Grahame Layer

The Grahame layer is a modified form of the Stern layer. Grahame proposed that some ions near
the electrode will lose their solvation shell and diffuse through the Stern layer. These ions, which
crossed the Stern layer, get adsorbed to the electrode surface. Most important is that the Grahame
theory gave the idea of presence of three regions, namely, inner Helmholtz plane, outer Helmholtz
plane, and diffuse layer.
2.2.6.5 Bockris-Devanathan-Müller (BDM) Model

Bockris, Devanathan, and Müller suggested that the attached molecules of the solvent to the ions,
say, water, is influenced and has a particular alignment toward the electrode surface. The orientation
of these solvated molecules is dependent on the ionic charge and applied electric field. This orienta
tion would have a great influence on the permittivity of the solvent which varies with field strength.
2.2.6.6 Trasatti-Buzzanca Model

This model gave the basic idea to understand the concept of pseudocapacitance. Trasatti and
Buzzanca demonstrated that at lower applied voltage, specific adions exhibit behavior similar to
capacitors expressing a partial charge–transfer mechanism.
2.2.6.7 Conway Model

Conway coined the term supercapacitor, which explained the increased capacitance value pos
sessed by the ions and electrode system. His supercapacitors stored electrical charge partially in
the Helmholtz double layer and partially as the result of faradaic reactions with pseudocapacitance
charge transfer of electrons and protons between the electrode and electrolyte.
2.2.6.8 Marcus Model

The Marcus theory explains the rates of electron transfer reactions—the rate at which an electron
can move from one chemical species to another. Marcus received the Nobel Prize in Chemistry in
1992 for this theory.
2.3 PARAMETERS AFFECTING ELECTRODEPOSITION

During the electrodeposition process, the preparative parameters significantly affect the structural,
morphological, and optical properties of the deposits. Some of the preparative parameters are discussed
here. These parameters can be controlled to obtain uniform, smooth, and stoichiometric electrodeposits.
2.3.1 EffEct of currEnt dEnsity and distriBution

In the electrodeposition process, the uniform coating of the specimen depends upon the current
distribution parameter. The metal ions are attached to the cathode at certain favored sites. This
condition results due to the presence of discontinuities in the form of pores, cracks, or other irregu
larities. The current density over a cathode will vary from point to point. Current density will be
more at the edges leading to changes in the average current density. Current density must be held
within the proper interval with respect to bath composition and temperature. Insufficient current
for the given specimen will result in poor coating. Increasing current density results in a decrease
in the crystallite size of the deposit. On the other hand, applying higher current density will lead to
hydrogen evolution.
2.3.2 EffEct of Bath tEMpEraturE

In general, an increase in bath temperature causes an increase in the crystallite size. Also, an
increase in bath temperature increases solubility and thereby increases the transport number, which
in turn leads to increased conductivity of the solution. It also decreases the viscosity of the solution,
thereby replenishing the double layer relatively faster. High bath temperature usually leads to less
adsorption of hydrogen on the deposits and it reduces stress and the tendency toward cracking. The
effect of temperature on electrodeposits has been studied by T. Chan et al. (2011).
2.3.3 EffEct of Bath concEntration

Bath concentration plays an important role in the plating performance. In normal plating conditions,
the increase of bath concentration will increase the concentration of metal ions in the solution.
Therefore it will increase the plating rate of the deposition process.
2.3.4 coMplExing agEnt

The complex ions react with the metal ions and form metal complexes, thereby altering the poten
tial of the metal. The electrode potential of the more noble metal gets shifted toward the negative
potential due to the formation of complex ions. In the ED technique a minor drawback in making
the film is that the coating thickness is not uniform all over the surface of deposition area. The
deposition rate is higher at the edges and corners of the substrate, whereas lower at other parts of
the substrate. To some extent, this can be avoided by adding complexing agents to the bath (Sahoo,
Das, and Davim 2017). While depositing alloys, complexing agents favor bringing in the standard
reduction potential of constituent metals of the alloy fairly close to each other.
2.3.5 EffEct of ph
Low pH causes hydrogen evolution, which penetrates the layer, and the deposited material becomes
harder, and it introduces a lot of stress to the layer. The electrodeposition process should be con
ducted at a stable pH. During electrolysis of an aqueous solution, hydrogen ions are discharged
together with the ions of the metal being deposited. The hydrogen evolved has often unfavorable
effects on the structure and properties of the electrodeposits. Change in pH value affects the current
efficiency of the electrodeposition process.
2.3.6 addition of agEnts

Additives are commonly used in plating baths to improve the adhesion and fine grain growth of
the deposits. The additives do not react with any ions in the electrolyte. The addition of agents will
induce more sites for nucleation rather than the existing growth sites. They adsorb onto the surface
and accelerate the rate of the deposition within trenches, thus enabling depositions of smooth and
bright deposits.
2.3.7 EffEct of plating tiME

According to Faraday’s law, quantity of charge flow (Q) in the solution is proportional to the
current flow (I), and also the flow time (t) as shown in the following equation (Dahotre and
Sudarshan 1999):
Q = I *t (2.10)
In general, the plating thickness increases and is directly proportionate to the plating time and
current.
2.3.8 EffEct of agitation

In general, agitation provides sufficient mixing of the individual metal salts so that the chemicals
become intimate and react with each other. Agitation of the solution replenishes metal salts at the
diffusion layer. It reduces the gas bubbles, which may otherwise cause pits. It helps in increasing
the operating current density and thereby permits a higher operating current density. These factors
influence the structure of the deposited metal ion and also increase in the concentration of the metal,
since it more rapidly compensates for the loss of the metal ions through discharge at the cathode.
Agitation promotes the deposition of the noble metal on the cathode process. In brief, an agitation
system can greatly improve the deposition performance since it provides sufficient mixing of the
metal salt for the plating solution.
2.3.9 hydrogEn EMBrittlEMEnt

The preceding elementary discussion of deposition reaction was aimed at giving the essentials of
how metal is deposited. But there is also simultaneous reduction reaction of two or more electro
active species in the electrolyte during electroplating. This arises from the fact that there is always
less metal deposited than it should be, based on Faraday’s laws. In some cases, there is almost no
deposit at all, which is mainly due to the hydrogen evolution. From a technological point of view,
one seeks to deposit a metal without wasting electrical energy on hydrogen evolution. But practi
cally, more current density is needed than the limiting current density for the deposition of the metal
to occur due to the hydrogen evolution.
In aqueous solutions, hydrogen evolution is unpreventable. If the total deposition current is
made sufficiently high, the hydrogen may come not only from H+ (of limited concentration) but
also from the water itself. The effects of hydrogen codeposition on the crystallography of metal
deposits are widespread and rather complicated. The entry of hydrogen into the structure of the
metal can lead to hydrogen embrittlement. As the hydrogen rearranges itself within the structure,
the internal stress set up are often enough to cause a part fracture with no external force being
applied. Even if the part does not fracture on its own, it may easily do so with the application of
minimal external stress. But even removal of H+ ions from the diffusion layer near the electrode
changes its properties, too; it makes the solution at the interface become more alkaline. If the
hydrogen reaction leads to production of a sufficiently alkaline solution at the interface, this would
cause precipitation of hydroxide and may contaminate the deposition. Thus, hydrogen codeposition
is usually destructive. The hydrogen evolution reaction from aqueous solution can be presented as,
in acid solutions,
2 H + + 2e − → H 2 + 2 H 2O (2.11)
2 H 2O + 2e ® H 2 + 2 OH (2.12)
And in alkaline solutions, it is only
2 H 2O + 2e ® H 2 + 2 OH (2.13)
2.4 TUNABLE PROPERTIES OF THE MATERIAL BY

ELECTRODEPOSITION PARAMETERS
The challenge in the electrochemical reduction of alloys is in choosing the optimum value of cur
rent density and appropriate bath with its additional agents. Choosing an irrelevant value of current
without considering the basic properties of materials, results in deposition of only one metal retard
ing the reduction of other metal(s) at the cathode. In the case of binary alloys, for both the metals to
be deposited simultaneously with atomic level mixing, the potential range at which each metal gets
deposited must be close to each other. If in the case when the potential is not in the closer window,
then complexing agents must be added to reduce the potential of one metal or increase the potential
range for deposition of the other. In the deposited materials, structure and morphology depend on
the thermodynamic and kinetic condition of the reaction. The availability of phase diagrams for
binary alloys help in studying the alloy systems. One can predict the resultant phase from phase
diagrams, but the electrodeposited alloys do not merely follow it in certain cases (Beattie and Dahn
2003; Bockris, Conway, and White 2013).
In almost all materials synthesis methods, the subjected material can be controlled in terms of
composition, structure, size, and morphology. There are many properties that get influenced by the
electrochemical phenomenon and parameters applied. When it comes to electrodeposition, all the
aforementioned characteristics can be tuned by simple use of variable parameters including current
density/potential, composition of the electrolytic bath, adding agents, and temperature by using a
conventional electrolytic cell setup.
2.4.1 coMposition
The composition of the material is readily tunable in electrochemical deposition. Almost all the
parameters play a significant role in the composition and phase of the sample. Most important, the
influence of current density changes the composition and hence in some cases alters the phase of
the sample.
The current density decides which material from the electrolyte has to be deposited and how
much of that same material is to be deposited. In the case of alloys and intermetallic compounds,
the electrolyte contains more than one kind of ionic substance. Hence depending upon the standard
electrode potential of the substance under study, one material might get deposited earlier and the
other metal does not have many favorable conditions to get deposited.
For example, Co–Fe alloy electrodeposited by Heydarzadeh Sohi (2012) exists at the body-
centered cubic (bcc) phase at limited current density. But as the current density is increased,
the amount of deposition of iron is increased, which induces the face-centered cubic (fcc) phase
structure. An increase in the current density increases the iron content of the substance and
follows a phase transition from bcc to fcc dominance. Hence, one can state that the change in
phase is coherently linked with the composition of the sample. With an increase in the current
density, the content of the iron increases and gets saturated at one point and decreases drasti
cally at further higher current density. This value tells us that it is important to note that there
is a working range limit for all the elements. The metals will get deposited prominently within
that range.
The composition of the precursor in the electrolyte has a direct influence on the composition of
the final product. Effect of bath composition on electrodeposited Ag–Co was reported by Santhi et
al. (2017). Ag–Co was deposited on stainless steel substrate from two bath compositions at three
different current densities. The ratio of cobalt to silver increased a lot for the alloy deposited at same
current density from a different bath composition. The reported results clearly show that the electro
lyte composition governs the atomic compositions of Ag–Co alloy. In both compositions, the cobalt
content increases with an increase in current density, reaching a maximum at 30 mA/cm 2. The bath
concentrations and the current density play a major role in determining the magnetic properties
more than the actual Co content (Santhi et al. 2017). It is clear from the results obtained that the
variations in structure, morphology, and magnetic properties of the deposits are attributable to the
electrolyte composition and the plating conditions, and especially the current density. The changes
in magnetic properties are discussed in Section 2.4.2.
The nickel–zinc alloy deposits are well known for their corrosion-resistant properties. The
phase diagram of Ni–Zn alloy evidences for phase transitions and has high stability over a wide
temperature range. In the electrodeposition of Ni–Zn, the deposition weight percentage of nickel
increases with increasing current density and duty cycle. The deposition of nickel percentage has
increased by 25% on increasing the applied current from 0.1 A to 0.3 A. In the combination of
nickel and zinc, the nonnoble zinc deposition is favored when compared to nickel. At lower current
density, anomalous behavior is observed in that the less noble zinc deposition is favored with lower
cathodic current efficiency. The effect of electrolytic pH plays an important role in determining the
basic characteristics of the deposited material. This is due to the increase in the local pH near the
electrode area, and formations of zinc hydroxides inhibit nickel deposition. Also the length of the
flakes of Ni–Zn varies with applied current density and duty cycle. Consider the formation of Ni–
Sn alloy through electrochemical synthesis. The standard reduction potential of nickel is –0.25 V
and for tin it is –0.14 V. Though the reduction potential of nickel and tin differs only by 0.11 V,
predominant deposition of Sn is found even when varying the current density and duty cycle
(Dhanapal 2016).
In cobalt electrodeposition, the hexagonal close-packed (hcp) phase is predominant and the
fcc phase vanishes with increasing pH. The impedance studies reveal that the hcp phase of
cobalt has better electrochemical properties (Ali and Salim 2013). In copper selenide deposi
tion, with an increase in the value of pH, the cathodic current efficiency of deposition decreased
and deposition does not occur at higher pH value (Ganjkhanlou et al. 2015). Proper pH for a
metal can be anywhere from acidic to neutral to alkaline, depending on the solubility of that
metal in the given solvent. Nickel and copper plating in acid baths are optimized around 3.8 to
4.2 and complications at higher pH values. For electrodeposition of metals like gold, zinc, and
chromium alkaline pH is preferred. The suitable pH was decided by electrochemical measure
ments. For example, if it is below, the Cu/In ratio declines. If it is more, the distribution is lost.
So, it will suit deposition only at the optimum pH (Yang et al. 2008). Hence, the current density,
composition, and pH play an important role during the synthesis of materials. Additionally,
some electroplating processes may benefit from the use of a buffer, such as boric acid. The
buffer ensures that pH near the cathode remains stable at the optimum level for metal plating.
The optimum pH for an electroplating process depends on the metal to be plated as well as the
solvent and any other additives.
Temperature is one of the important parameters in materials synthesis. During the deposition of
nickel from type watt bath it is concluded that the cathodic efficiency increases with temperature
and decreases with current density (Poroch-Seri et al. 2009). The increase of current density has
certain disadvantages in deposition technique. An increase in current density above a particular
value leads to the formation of hydrogen bubbles and decreases the current efficiency.
The electrodeposition of ternary alloys is rather an interesting phenomenon to discuss. In the
case of the Ni–Zn–Fe system, at moderate and high current density, nickel deposition is favored
(Abou-Krisha 2012). In the ternary system Ni–Zn–P, the effect of pH is studied between 8.5 and
10.5. In this range, upon increasing the pH, the amount of Ni content increases and at the same
time, the content of zinc and phosphorous reduces. Hence, in the given pH range, Ni deposition is
favored (Srivastava et al. 2017). In case of the ternary system of Zn–Fe–Mo it is very clear that an
increase in pH shows the hydrogen evolution peaks. This indicates that the deposition is controlled
by the electrodeposition parameters. Hence, only the lower pH favors this ternary alloy deposition
(Winiarski et al. 2016). The deposition of the copper tin selenide films was done at ambient condi
tions and the pH variation was in the small range from 1 to 1.5. At 1.5 the material has minimum
thickness with improved properties suitable for many applications (Kassim et al. 2009). The forma
tion of the compound Cu2ZnSnS4 and its phase is consistent with the amount of complexing agent
used (Pawar et al. 2010).
Oxide electrodeposition is an important phenomena in this era since the semiconducting oxides
find potential applications in various fields of development and electronic devices today. In depos
iting copper oxide films, the interfacial charging effects play an important role and pH plays an
important role in deciding that property (Kafi et al. 2018). Reports clearly show that the composition
and phase of the sample change with current density.
2.4.2 structurE
The structure of each material is unique, and the important phenomenon that decides the type and
name of the material is its phase. The materials that are used in different fields of technology are
structure dependent (Erb 2012; C. Chan et al. 2011). Hence, fabricating a material with notable
structure is an important aspect in materials science.
Stephen et al. (2008) exclusively worked on the structure of various alloys by altering the electro
deposition parameters. The Ni–Mn alloys were electrodeposited on a stainless steel substrate from
simple acidic sulfate baths at room temperature with pH of 3.0 with deposition current density of
30 mA cm−2. The deposited Ni–Mn alloys were formed within a narrow compositional range, inde
pendent of the bath composition with constant current density of 30 mA cm−2. The films of Ni3Mn
had a nanocrystalline fcc structure and 76.2 at. % Ni deposition indicating a higher degree of order
ing in the as-deposited condition. The ordering was visible for electrodeposited Ni–Mn with Ni
ranging from 70% to 85%. The alloy with 76.2 at. % Ni was the most stable with pure ferromagnetic
phase. Superlattice reflection confirmed from selected area electron diffraction (SAED) patterns
supported the L12 type of atomic ordering in Ni–Mn films (Arumainathan et al. 2008). The scanning
electron microscope (SEM) image of electrodeposited Ni78Mn22 alloy is shown in Figure 2.3a. The
transmission electron microscope (TEM) and SAED images of electrocrystals of Ni–Mn alloys are
depicted in Figure 2.3b and c, respectively. It is evident from the TEM picture that electrocrystals
can be grown from the deposition technique. The pictured electrocrystal is of 800 × 600 µm in size.
In the case of electrodeposition of Ni–Mn alloys, the change in magnetic property of the alloy
with respect to nickel composition has been studied (Stephen 1999). Figure 2.4a represents the
change in saturation magnetization value of the alloys before and after annealing. The maximum
saturation value is reached during the Ni3Mn phase evolution leading to maximum nickel ratio.
Figure 2.4b depicts the change in Curie temperature (TC) with nickel composition. There is an
FIGURE 2.3 (a) SEM image of Ni–Mn alloy. (b) HRTEM image of Ni–Mn electrocrystal. (c) SAED image
of Ni–Mn alloy.
FIGURE 2.4 Magnetic studies on Ni–Mn alloy.

exponential decrease in the Curie temperature explaining the disordering in Ni–Mn alloy. The
Curie temperature reaches a maximum of 625 K when the nickel concentration is 76.2 at. % and
below this percentage the TC reduces gradually representing the ordering of Ni3Mn grains. This
behavior is due to the manganese (Mn) composition and alloying behavior of Ni–Mn (Stephen et al.
2000; Stephen, Nagarajan, and Ananth 1998). The magnetic property is an important phenomenon
in the case of iron group metals and alloys. For the synthesis of iron group materials, electrodeposi
tion is a unique method. The magnetic properties are influenced by the electrochemical parameters
applied while synthesizing the material. Thus, it can be concluded that the change in microstructure
decides the magnetic property of the material (Encinas et al. 2002).
Santhi et al. (2012) studied the effect of bath composition and current density on an Ag–Ni
system from nontoxic gluconate bath using pulsed electrodeposition. Ag–Ni alloys were depos
ited at different current densities from two bath compositions. Though these parameters do not
have adverse effects on the atomic composition of prepared alloy, there is a notable change over
crystal structure and morphology. Alloys deposited at lower current densities from electrolytes
having lower concentration of nickel exhibit both solid solution of Ag and Ni along with Ag–Ni
alloy phase. Alloys deposited at high current densities from electrolytes having higher concen
tration of nickel form solid solution of Ag and Ni alone. Lowering of the saturation magnetiza
tion value evidences the occurrence of atomic level mixing of silver and nickel. From magnetic
thermogravimetric analysis, alloys deposited at different current densities depicted weight loss at
different temperatures due to magnetic transitions. It is concluded that the changes in weight was
due to structural and compositional variations (Santhi et al. 2012). The structural change in elec
trodeposited Ag–Fe alloy on altering the current density and bath composition has been studied
elaborately. The samples deposited from lower Fe salt concentration in the bath contain more of
an Ag-rich fcc phase along with the Fe rich bcc phase, while the samples obtained from higher
Fe salt concentration exhibit only the bcc Fe structure. Also it has been found that current density
has a considerable effect on Fe content in the sample. The Fe content in the samples is primarily
bath-concentration dependent for the lower bath concentration. But at the higher bath concentra
tion, variation due to current density is less pronounced (Santhi, Narayanan, and Arumainathan
2014). The magnetization properties of Ag–Co samples prepared from two different electrolytic
baths containing precursors of Ag and Co in the ratio of 1:7 and 1:14 at the same current density.
The magnetization of the sample deposited from 1:7 ratio bath is very poor (1.9 A-m2/kg) when
compared with the sample (40.2 A-m 2/kg) deposited from 1:14 bath. This property is due to the
orientation of the grains in that particular sample. Also, for the same system it is observed that
the magnetic properties vary, though composition of cobalt is almost the same. The magnetic
properties not only depend on the composition of the sample but also on the structural and domain
orientation (Santhi et al. 2017). This similar structure–property related to grain boundary effects
has been discussed by Gino Palumbo et al. (Palumbo et al. 2011).
Palladium alloys are well-known due to their paramount activity in catalysis and other properties.
Electrolyte composition, current density, and complexing agent of the synthesis technique has been
suitably optimized to deposit phase pure Pd–Ni alloy. At the same time, in this system the structure
remains the same even when the atomic ratio of Pd and Ni are changed following the phase diagram
(Revathy et al. 2018). In the case of the copper–indium alloy, the bath composition is varied while
keeping all other parameters constant. The change in bath composition has a direct influence of the
preferred orientation of crystallites and hence the phase of the prepared material. At 60:40 ratio of
precursors (Cu:In), dual phases of alloy exist, whereas at 40:60 ratio, one phase diminishes and the
other phase predominates in the sample (Sivaranjani et al. 2018). The copper indium selenide (CIS)
films made of electrodeposition has a tunable bandgap due to the phase formation (Karthikeyan et
al. 2017). The nickel-phosphorous has an important influence in the field of electrochemistry. The
effect of duty cycle in pulsed electrodeposition plays a major role in determining the amount of
phosphorous content in the system and in the formation of Ni3P phase. The phase and composition
of the phosphorous in turn control the saturation magnetization value. The duty cycle makes an
impression on the coercivity and saturation magnetization value. The duty cycle makes an impres
sion on the coercivity and retentivity values for the same applied current (Dhanapal, Narayanan and
Arumainathan 2015).
The formation process of CoNiFe ternary alloy is depicted in Figure 2.5. The diagram explains
that higher content of Ni is deposited with fcc structure. The higher content of Fe deposited cor
responds to mixed bcc/fcc structure and the higher ratio of Co/Fe deposits are to be bcc structured.
The same has been depicted in Figure 2.6. The same effect has been studied with influence of cur
rent density on composition by Yufang Yang (2015). The films deposited at higher current densities
are less porous and smooth. The Ni content of these coatings is increased from 10 to 17 wt%. The
Fe-rich alloy deposits obtained at low current density surface is rough, highly porous, and exhibited
a columnar appearance (Co64Ni11Fe25). With an increase in the current density, the Fe content in film
decreases with a corresponding increase in the Ni content. At current densities <5 mA/cm2, bcc is
the main phase; at 5 mA/cm2, fcc is the main phase with a small amount of bcc phase; whereas at
current densities >10 mA/cm2, fcc is the main phase. Following the transition from bcc to fcc phase
FIGURE 2.5 Structural variation in ternary alloy system with composition.
FIGURE 2.6 The change in composition of Co, Ni, and Fe elements in the CoNiFe alloy deposits with cor
responding change in current density.
with increase in current density, the grain size is decreased from 16 to 3 nm (Baskaran 2006). The
morphology of the same system is discussed in Section 2.4.3.
Studies have been made on the electrodeposited iron, and its mechanical properties are evaluated
based on the pH of the electrolyte solution. It is clear that with the increase in pH above 3.8, there is
a sudden increase in grain size of the electrodeposits (Levy and Macinnis 1968).
In case of the nickel deposition on gold film substrate, the lattice strain gradually decreased
on changing the pH from 1.4 to 2. The lattice constants also tend to decrease as the pH level is
increased (Boubatra et al. 2012). At the same time, pH of the sample prominently determines the
phase of the Co–Fe alloy. The lower pH favors the formation of fcc (gamma) phase, whereas the
higher pH leads to the formation of beta phase of Fe–Co (Lu et al. 2013). This purely indicates that
pH of the electrolytic bath plays a major role in the formation of the alloy substance. The surface
forces are the key factors in the influence of material deposition on the substrate. The effect of
additives greatly influences the pH and hence also influences the surface force of the cations. The
zeta potential of the charged particles helps predict colloidal stability and electrostatic interaction
of the particles. The zeta potential represents these repulsive forces between the particles. With an
increase in pH, the zeta potential increases negatively and the particle size decreases as in the case
of nickel-layered silicate nanocomposites. The composite deposited at pH 3 shows improved corro
sion performance (Tientong et al. 2013).
2.4.3 Morphology
Materials with interesting morphologies have been chosen for energy and catalytic applications.
Pd–Ni alloy electrodeposited using galvanostatic pulsed power supply using stainless steel substrate
was reported by Revathy et al. (2018). It has been reported that the effects of bath composition
and current density play a major role on composition and morphology. The alloys form dendritic
structures at lower current density, whereas when increasing the current density, the structure gets
distorted. On correlating the composition results and morphological analysis, it is understood that
palladium enhances dendritic growth while nickel suppresses it (Revathy et al. 2018). Silver–nickel
(Ag–Ni) alloy prepared by PED method using anodic alumina membrane (AAM) template was
reported by Dhanapal et al. (2013). Ag–Ni was deposited from gluconate bath at pH 4 with the cur
rent density of 40 mA/cm2. The commercially available Whatman anodisc of diameter 2 cm with
a porous diameter of 20 nm and depth 100 µm was used as the template. The morphology of the
Ag–Ni alloy was found to be double-dumbbell shaped. The average length of the dumbbell was
found to be 390 nm.
The morphology of CoNiFe ternary alloys is depicted in Figure 2.7. The Fe-rich alloy deposits
obtained at low current density surface are rough, highly porous, and exhibit a columnar appear
ance. The morphological change has been coherent with the structural change in the alloys, where
Figure 2.7a depicts the sample with fcc structure, and Figure 2.7b and c represent the bcc and bcc/
fcc mixed phases, respectively. NiCoFe ternary alloy rods were deposited from simple sulfate baths
at room temperature with pH of 3.0. The anodic aluminium oxide (AAO) membrane was employed
FIGURE 2.7 Morphology of CoNiFe alloys: (a) Co67Ni17Fe16. (b) Co54Ni10Fe36. (c) Co64Ni11Fe25.
FIGURE 2.8 Morphology of NiCoFe magnetic nanorods.
for deposition, whereas the other side of the membrane was masked using a silver-coated conducting
resin. PED was employed with a current density of 5 mA/cm2. The plating times were TON = 1 ms
and TOFF = 9 ms. The duty cycle is 10% with a frequency of 100 Hz. After the deposition the AAO
membrane with the NiCoFe, nanorods were rinsed with deionized water, then dried. Subsequently,
the AAO membrane is chemically etched using a mixture of 1.5 ml of sulfuric acid, 12.5 ml mono-
phosphoric acids, and 10 g of chromium trioxide. The typical SEM images of NiCoFe alloy rods are
shown in Figure 2.8 with dissipation of rods and top view of the rods.
In the presence of the ethyl vanillin, the morphology has been completely changed (Nayana and
Venkatesha 2014). The change in applied potential typically changes the morphology of Cu2O films
prepared by electrodeposition (Bijani et al. 2011). With controlled measure of pH and other addi
tives, a single layer of atoms can also be deposited by the electrodeposition method (Switzer 2012).
Gold was electrodeposited at a potential of –0.5 V such that the critical nuclei size is calculated to
be less than one atomic layer (Hussein et al. 2018). With increased application in various fields, it
has become very important to produce nanoparticles of regular arrays with shapes having more
surface area (Prida et al. 2015). Palladium arrays have been deposited on Al film (Bera et al. 2003).
2.5 MULTILAYER COATINGS

Multiple layers of coating are of great interest today because of their excellent properties in optics
and electronics owing to their two-dimensional structures. Multilayers are typically made by sput
tering, evaporation, chemical vapor deposition, molecular beam epitaxy, and other vacuum deposi
tion processes. Among the other techniques, ED can be employed to get phase pure alloy (Csik et
al. 2009; Schwarzacher and Lashmore 1996). Multilayer films are typically coatings of two different
alternating materials (Ross 1994). The combination of magnetic and nonmagnetic layers lead to
the overwhelming growth in spintronics. In the case of magnetic and nonmagnetic combination,
the magnetic property will be dependent on the applied magnetic field direction, and on the forma
tion of films the magnetic property is greatly tuned. Hence the anisotropic property will become
important. The thickness of the layers also determine the formation of perpendicular anisotropy.
The structure, growth condition, and layer composition determines the magnetic property of the
layers. The overall anisotropy in the layers is influenced by the crystallographic texture within
the layers and the degree of mixing between the layers (Masrour et al. 2010). The advancements
in giant magneto resistance (GMR) effects produced by materials prepared from electrodeposi
tion was enlisted by Schwarzacher and Lashmore (1996). Nickel bilayers and trilayers have been
fabricated and their magnetic properties explored by our group. The Ni/Pd/Ni trilayer is depicted
in Figure 2.9. The magnetic anisotropy of the Ni/Cu/Ni layer (Figure 2.10a) and Ni/Ag/Ni have
been studied by Dhanapal et al. (2014, 2017). The Ni/Ag bilayer has been depicted in Figure 2.10b.
Nickel–chromium layers were electrodeposited and tested for their hardness behavior (Etminanfar
and Heydarzadeh Sohi 2012).
The importance of the Cu–Co multilayers and other similar growth of films is because of the
giant magnetoresistance (GMR) effect shown by these structured layers on combining a nonmag
netic layer with a ferromagnetic layer. Bakonyi and Péter (2010) wrote a review about the GMR
effect produced by the electrodeposited films made of various materials and has produced a detailed
report on various parameters including homogeneity of the film. From the Central Electrochemical
Research Institute (CECRI) of India, works have been carried out to study the effect of Cu thick
ness affecting the magnetic property in Co/Cu multilayers (Rajasekaran et al. 2014; Rajasekaran
and Mohan 2012). Like every other parameter, the addition of additives has a significant influence
on the film formation. The addition of NaCl greatly influences the formation of the Co–Cu/Cu layer
(Péter et al. 2001). Deposition of multilayers upon one another leads to the formation of superlattice
FIGURE 2.9 Cross-section SEM image of Ni/Pd/Ni layers.
FIGURE 2.10 Cross-section image of (a) Ni/Cu/Ni layer and (b) Ni/Ag layer.
in some cases. The electrodeposited film on simple annealing changes its behavior from GMR to
AMR (anisotropic magnetoresistance) and then back to GMR (Schwarzacher et al. 1997).
2.6 COMPOSITE COATINGS

Surface coatings have a wide application because of their improved mechanical, corrosion, and
wear-resistance properties. Corrosion and wear behavior of pulsed electrodeposited Ni–Al2O3 nano
composite coating assisted with ultrasound shows improved wear-resistance behavior (Majidi et al.
2016; Allahyarzadeh et al. 2017). In the formation of Ni–B alloy film from optimized electrolytic
bath, the preferred orientation of nickel changes from fcc (200) to fcc (111) due to the incorpora
tion of boron elements. The boron elements are incorporated into the nickel matrix by adsorption
followed by catalytic reduction of dimethylamine borane (Krishnaveni, Tsn, and Seshadri 2003;
Krishnaveni, Sankara Narayanan, and Seshadri 2006). The zinc–zinc phosphate coatings are done
by galvanostatic electrodeposition, which is an energy efficient method for preparing coatings with
improved corrosion resistance (Kavitha et al. 2014). The nitride compounds are chemically sta
ble compounds, but they can still be electrodeposited by dispersing them in the electrolytic bath.
Ni–B–Si3N4 coatings are prepared by electrodeposition method at proper electrochemical condi
tions (Krishnaveni, Sankara Narayanan, and Seshadri 2008; Krishnaveni, Narayanan, and Seshadri
2009). Electrodeposition has its own scope in the medical field also. Hydroxyapatite is one of the
important materials present in bones, and teeth have been electrodeposited on magnesium by
Jamesh et al. (2012).
The deposition of collagen is a difficult thing since it has less conductivity toward the cathode.
Though various pH solutions have been used, it is possible only at pH 5 toward the titanium elec
trode (Kamata et al. 2011). Recent advances in the electrodeposition include the deposition of rare
earth oxides and composites (Tam, Erb, and Azimi 2018; Tam et al. 2017). Diamond compounds
and other nonconducting composites have been prepared to address the corrosion prevention at high
temperature. These composites improve the thermal and wear properties of the metal matrix mate
rials (Jun Cho et al. 2019; Jun Cho et al. 2016).
2.7 CONCLUSION
Electrodeposition is a conventional and an effective route to synthesize materials with challeng
ing and tunable physicochemical properties. It is clear that via the electrodeposition technique one
can synthesize single-oriented films, bulk and nanocrystalline metals, alloys, semiconductors, and
multilayers composites. The mechanism of electrodeposition is a quite easy procedure to follow, but
surface migration and lattice development of a particular material changes with the material and
the material’s composition. The parameters, such as current density, pH, and temperature, play a
major role in forming the final product of the reaction. And it is important to note that the pulsed
electrodeposition enhances nucleation rather than growth resulting in lower grain size. Other than
the experimental and environmental conditions the important factor that decides the deposition of a
material is its standard electrode potential. The deposition behavior is greatly influenced by addition
of complexing agents, which will shift the deposition potential for a particular material and can be
notified with the help of cyclic voltammetry. The deposited material’s composition, structure, mor
phology, and other properties are significantly varied on varying a particular parameter. It is possi
ble to produce different intermetallic phases at room temperature through electrodeposition at room
temperature. Besides all the advantages of the electrodeposition, hydrogen evolution during the
electrodeposition at the cathode paves way for hydrogen embrittlement, which is an unwanted thing
in preparing a material. All the parameters have to be optimized by a plausible number of trial-and
error experiments so as to reduce hydrogen formation and avoid the internal stress in the deposited
material. When the pulsed electrodeposition technique is followed, there is an appropriate value
of pulse frequency and the duty cycle for each material at which the composition of that material
is maximum in the deposit and the anticipated ordered phase is formed leading to tailored-made
properties for special applications. The change of pulse frequency may lead to the deterioration of
materials’ properties. The purity of the samples prepared by electrodeposition is very high and does
not need any further purification. The advancements in electrodeposition led to fabrication of mate
rials with functional properties. Novel materials including composites and multilayers synthesized
from electrodeposition has led to potential applications in the field of science and technology.
ACKNOWLEDGMENTS
The authors extend their gratitude to the University of Madras and acknowledge Dr. K. Dhanapal,
Dr. Kalavathy Santhi, and Dr. I. Baskaran for their scientific contributions.
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3 Photovoltaic Energy
Generation System: Material,
Device, and Fabrication
Ananthakumar Soosaimanickam and Moorthy Babu Sridharan
CONTENTS
3.1 Introduction............................................................................................................................ 49
3.2 Applications of Electrochemical Synthesis for Inorganic Heterojunction and

Organic Solar Cells................................................................................................................. 50
3.3 Electrochemical Synthesis of Materials for Hybrid Solar Cells............................................. 52
3.4 Electrochemical Synthesis of Materials for Dye-Sensitized Solar Cells ............................... 54
3.5 Electrochemical Synthesis of Materials for Quantum Dot-Sensitized Solar Cells ................ 56
3.6 Use of Electrochemical Synthesis in the Construction of Perovskite Solar Cells.................. 57
3.7 Conclusion and Summary....................................................................................................... 58
References........................................................................................................................................ 59
3.1 INTRODUCTION
Evolution in the development of synthesis of inorganic semiconductor nanomaterials, organic
conducting polymers, organic/organometallic dye complexes, and other organic and inorganic
components have delivered amazing results in achieving alternative energy resources for future
energy-related applications (Rui Yu et al. 2012; Nozik 2010). The contribution of organic and inor
ganic materials in the construction of future energy devices has always been attributed with novel
approaches and innovations that could be made through these materials. Use of vacuum-based
deposition approaches such as physical vapor deposition (PLD), sputtering, atomic layer deposition
(ALD), and pulsed-laser deposition (PLD) have delivered higher efficiency in terms of producing
large-scale applications (Green 2007; Kaelin et al. 2004). However, when we look from a cost point
of view, non-vacuum approaches such as spin coating, drop casting, dip coating, and the electro
chemical deposition method are widely used for the fabrication of the modern generation of solar
cells. In order to make effective harvesting of photons, the nanomaterials surface structure has to
be modified or functionalized using several approaches. Such tailored nanosurfaces act as potential
candidates for the charge transfer where the large improvement in efficiency is possible. For the
formation of nanostructures and nanohybrids on the conducting substrate, several approaches are
followed. Solution-based approaches such as spin coating, dip coating, and spray deposition are
used to deposit the nanoparticles and semiconducting polymers either separately or as a hybrid on
a conducting substrate (Habass et al. 2010). Among the other approaches, electrochemical deposi
tion of nanomaterials and polymers on the conducting substrate for solar cell application are quite
important techniques to realize high efficiency. Electrochemical deposition is an easy experimental
process and has more advantages over other methods. Also, through electrochemical deposition, we
could easily control the quality of layers through optimizing parameters such as applied voltage,
applied current density, concentration of the precursors in the medium, and nature of electrolyte
49
used for the deposition (Lincot 2005). Also, the quality of the electrochemically deposited lay
ers is equal with the vacuum-deposited layers, which requires consumption of less energy. Since
the surface plays a major role in achieving higher efficiency of fabricating solar cells, through
electrochemical deposition, it is possible to achieve highly smoothed, pinhole-free layers of active
materials (D. Wei et al. 2010). Moreover, formation of highly ordered nanostructures is essential in
order to facilitate the charge transport efficiently in the structure. Ordered growth of nanomaterials
is not only used to improve the charge transport, but also to ease the difficult process associated
with the assembly of the nanomaterials for the large-scale production. The chemical kinetics and
thermodynamics of the formation of the nanoparticles layer on the substrate is essential since active
surface sites present in the nanoparticles play a key role in the charge transfer. The other advantage
of electrochemical deposition of materials is that it can be used for large-scale applications. This
large scale of fabricating solar cells using the electrochemical method is already successfully com
missioned and several other attempts are trying to enlarge it in a different way. Adopting such a
large-scale technology for other emerging approaches such as perovskite solar cells is indeed use
ful for commercializing it for future purposes. The following sections discuss the contributions of
electrochemical deposition to each category of modern generation solar cells.
3.2 APPLICATIONS OF ELECTROCHEMICAL SYNTHESIS FOR

INORGANIC HETEROJUNCTION AND ORGANIC SOLAR CELLS
Heterojunction solar cells are made through the deposition of two organic or inorganic nanomateri
als that have different energy levels and semiconducting properties. Such solar cells are fabricated
mostly using the evaporation process through vacuum-based approaches. For the non-vacuum
based approaches, the electrochemical method has been used in most cases because of its reliability
for large-scale applications. In the case of inorganic heterojunction, usually an n-type and p-type
semiconductor layer is fabricated using the electrochemical deposition process through their pre
cursors. Nanostructures of these materials not only improve the charge generation but also lead to
fabrication on the flexible substrates. Formation of a transparent, conductive, and pinhole-free layer
is the essential condition for highly efficient photoconduction. In the heterojunction architecture,
most of the studies were oriented with the Cu2O/ZnO heterojunction. In this, Cu2O is the p-type
semiconductor with a bandgap of 2.0 eV and ZnO has a bandgap of ~3.4 eV. In the heterojunction,
Cu2O serves as the absorber layer and ZnO serves as the window layer. Fabrication of p-type Cu2O
layer through electrochemical deposition was analyzed by several researchers, and conditions for
the highly conductive Cu2O layer for the fabrication of solar cells was optimized through their
investigations (Pagare, Kanade, and Torane 2017; Brandt et al. 2017; H. M. Wei et al. 2012; Yoon
et al. 2016). However, it is important to fabricate a heterojunction and analyze the effect of it for
solar cells. When the growth of a heterojunction takes place in solution, the formation of an active
interface is quite important since the defects present in the first layer will affect the transformation
of carriers into the second layer, which is deposited to form the heterojunction. By coupling ZnO
with Cu2O, it is found that the absorption edge of the heterojunction could be extended to the vis
ible region (Lahmar et al. 2017). Kang et al. (2016) fabricated a heterojunction solar cell based on
the electrochemically deposited aluminum doped-ZnO (n-type) and copper oxide (p-type) as the
heterojunction. The authors used simple precursors such as Al(NO3)2 and Zn(NO3)2 in the medium
of dimethyl sulfoxide (DMSO) and the reaction was carried out at 85°C and by passing 0.3 C/cm2 at
–1.0 V versus Ag/AgCl. The authors observed a 20% increase of Jsc values through doping alumi
num with the zinc oxide. Though the observed efficiency is quite lower (~1%), these kinds of efforts
will be a platform for other low-cost heterojunction solar cells that could deliver higher efficiency.
Musselman et al. (2010b) fabricated this heterojunction by electrodepositing Cu2O arrays. The
Cu2O arrays were formed using a CuSO4 –lactic acid mixture in the electrochemical bath at 40°C
with pH 12.5. The arrays were deposited on free-standing ZnO nanowires (1 μm length) that were
grown by Zn seeds on the ITO–glass substrate. These arrays were found to be quite compatible with
Photovoltaic Energy Generation System 51
the already grown ZnO nanowires, and through this structure a continuous junction was produced.
The authors were able to achieve an internal photo conversion efficiency (IPCE) of about 85% with
the power conversion efficiency of 0.5%. Also, this research group has done extensive analysis of
Cu2O-based nanostructured materials along with ZnO nano heterostructures (Musselman et al.
2010a, 2012). Cui and Gibson (2010) fabricated a nanopillar of ZnO on the ZnO thin layer through
electrodeposition, which was then used to couple with the Cu2O to form a heterojunction (Figure
3.1). This nanopillar junction is typically used to improve the contact area and charge collection.
These nanopillars were grown using an equimolar solution of ZnNO3 and hexamine solution at
9°C with –2.5 V of applied potential. The observed efficiency in this case was 0.88%, which was
higher than the planar structured solar cell (0.55%). This study clearly emphasized growing such
one-dimensional structures for the large-scale processing of solar cells. A hybrid approach of grow
ing Cu2O/ZnO nanostructures is also beneficial for the construction of solar cells. Makhloufeet al.
(2017) used a hybrid approach of fabricating Cu2O/ZnO nanostructures in which growth of the ZnO
seed layer was carried out through the ALD method, and growth of ZnO nanowires with different
lengths and thicknesses, and deposition of Cu2O nanostructure was carried out through the elec
trochemical deposition method at solution pH 12.5. It was found that the increase of length of the
nanowires is attributed to the thickness of the seed layer of ZnO nanostructures.
Other than the heterojunction, electrochemical deposition has been successfully applied to
deposit compound semiconductors such as copper zinc tin sulfide (Cu2ZnSnS4) on the conductive
substrate. Ahmed et al. (2012) fabricated a solar cell structured Mo/MoS2/CZTS/CdS/i-ZnO/ITO.
Here the authors deposited a Cu2ZnSnS4 layer through the metal stacks of copper, tin, and zinc on
the molybdenum layer on soda lime glass. Under highly acidic conditions, these metals are electro
plated using direct current in the presence of an organic additive. As a final result, the authors were
able to achieve an efficiency of 7.3% with the Voc of 0.56 V.
Unlike inorganic materials, deposition of organic semiconductors using the electrochemical
method needs a lot of attention for efficient layer formation. Electrochemical deposition of polymers
had received lots of attention in the past and several findings are applying this method of deposition
under different potential currents. As usual, a three-electrode system is used to deposit a conducting
polymer in the electrochemical polymerization method. Usually, a working electrode serves as the
electrode for the deposition; the counter electrode is a metallic based one and it is typically based
on Pt or Au. In most cases, a saturated calomel electrode Ag/AgCl is generally used as the reference
electrode for the polymer deposition process. The supporting electrolyte is generally a quaternary
ammonium salt having the general formula R4NX (X = methyl, ethyl, etc. or phenyl radicals, X = Cl,
Br, I, PF6 –, ClO4 –, BF4 –, etc.). In addition to the conducting purpose, this supporting electrolyte
also serves as the dopant for the polymers. Polymers such as polyaniline, polyhexyl thiophene het
erocyclic polymers polyfuran, polypyrrole, and poly ethylenedioxythiophene (PEDOT) have been
successfully deposited and analyzed in the past years (Gurunathan et al. 1999). The schematic
FIGURE 3.1 Growth processing of ZnO nanopillars on the ZnO thin film and the current–voltage (I–V)
curve of the fabricated solar cell. (Reprinted with permission from Cui et al. Copyright 2010 American
Chemical Society.)
FIGURE 3.2 Schematic diagram of the experimental arrangement used for the electrochemical deposition of
polymers. (Reprinted from Gurunathan et al. Copyright 1999, with permission from Elsevier.)
diagram of the experimental arrangement used for the electrochemical process of polymers is
given in Figure 3.2. Zaban and Diamant (2000) first deposited crystalline organic polymer perylene
bis(phenethylimide) (PPEI) on the mesoporous titanium dioxide (TiO2) layer. A 0.4 M solution of
tetrabutylammonium chlorate (TBAClO4) was used as the electrolyte and the reaction was carried
out in the presence of four electrodes. It was found that the deposited TiO2/PPEI layer had a very
good optical density, which could be useful for the potential applications. In another report, the
same authors found that this reaction took place only if the TBAClO4 is used as an electrolyte, and
formation of PPEI ions took place at the source electrode (Diamant and Zaban 2001). The authors
further revealed that the deposition starts forming with a thin layer coated on the mesoporous sub
strate and further deposition and growth of the layer on the weak points of this thin layer.
3.3 ELECTROCHEMICAL SYNTHESIS OF MATERIALS

FOR HYBRID SOLAR CELLS
The device structure of a hybrid solar cell is adopted from the structure of an organic solar cell in
which the donor component is replaced with the semiconducting organic polymers like poly 3-hexyl
thiophene (P3HT) and poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV).
The energy level of these polymers is varied through substituting various donor/acceptor groups in
their structural moiety. When light strikes the hybrid of the polymer/nanoparticle composite, there
is an exciton generation that takes place in the nanocomposite blend. This exciton has to separate
out, and the respective charges are collected by the opposite electrodes. Preparation of nanoparticle/
polymer hybrids for energy-related applications is one of the challenging and interesting approaches
to achieving different morphologies. A reference and counter electrode is required in presence of a
suitable electrolyte to carry out such processes. Xi et al. (2008) demonstrated the growth of verti
cally grown CdS nanorod arrays (20 to 40 nm diameter, height 100 to 300 nm) using a template-
free electrochemical approach. On these nanorods, polybithiophene polymer was deposited using
in situ electrochemical polymerization. This polymerization was carried out using an Ag/AgCl
reference electrode and platinum sheet counter electrode. Here the bithiopene molecules diffuse
through electrolyte solution and get oxidized. Using this method, the authors constructed a solar cell
with an Au/CdS-polybithiophene/Ca/Al hybrid solar cell that delivered about 0.84 as Voc. Formation
of uniform films is essential to achieve successful deposition using these approaches. The other
advantage of electrochemical deposition is slow incorporation of polymers on the developed inor
ganic nanostructure is feasible. Shankar et al. (2008) developed a device structure consisting of
TiO2 nanotubes in which the polymers phenyl-C61-butyric-acid-methyl-ester (PCBM) and P3HT
are incorporated on it to make a hybrid junction (Figure 3.3). The TiO2 nanotubes are grown on the
barrier layer of the TiO2 layer, which is formed on a conducting substrate using a formamide-based
electrolyte consisting of 0.27 M of tetrabutylammonium fluoride and 5% water. Here, the authors
constructed two types of device configurations: front side and back side illumination structures.
Out of these two configurations, the device with front-side illumination resulted in high efficiency
of 4.1% under air mass (AM) 1.5 configuration. Synthesis and growth of such highly ordered TiO2
nanotubes by electrochemical methods is discussed in the next section. Formation of these kinds of
double heterostructures through the infiltration of polymer compounds is beneficial for extending
the light absorption to fabricate future generation solar cell architectures.
Yakup Hames et al. (2010) grew ZnO nanorods on the ZnO film to fabricate a hybrid solar cell.
The authors first carried out ZnO thin film through the electrochemical deposition process in the
presence of ZnCl2 (5 mM) and KCl (0.1 M) with a three-electrode system. Then by modifying the
concentration of ZnCl2 (6 mM) and KCl (7 mM) at the optimized temperature of 80°C ± 1°C and
cathodic voltage of 0.9 V, the authors were able to grow ZnO nanorods on the ITO substrate with the
radius of 250–300 nm. A solar cell was fabricated further with the configuration of ITO/ZnO (buf
fer layer)/ZnO(NRs)/P3HT:PCBM/Ag and achieved a 2.44% efficiency. Therefore, it is very clear
that for effective layer formation and synthesizing different nanoarchitectures, optimizing physical
FIGURE 3.3 Schematic diagram of device configuration of TiO2 nanotubes/P3HT/PCBM double hetero
junction with (a) front-side geometry and (b) back-side geometry. (Reprinted from Shankar et al. Copyright
2008, with permission from Elsevier.)
parameters are essential in the electrochemical deposition process. Therefore, these findings are
clearly illustrating that the electrochemical method is not only versatile for the development of
inorganic nanostructures, but also for the development of the hybrids of them, which is quite useful
for other potential applications.
3.4 ELECTROCHEMICAL SYNTHESIS OF MATERIALS

FOR DYE-SENSITIZED SOLAR CELLS
Dye-sensitized solar cells (DSSCs) belong to one of the important configurations of the modern
generation solar cell architecture. The basic structure composes a photoanode that has a thin layer
of nanocrystalline TiO2 nanoparticles deposited on a conducting substrate, and after a sensitization
process in an efficient adsorbing dye, the device structure is completed with a photocathode and the
electrolyte. The electrolyte is typically a redox system and is generally an iodide/triiodide couple.
Surface states, pore size, nature of ligands on the surface, shape, and size of the TiO2 severely
affect the performance of DSSCs, and several research articles elegantly deal with the kinetics of
the charge transfer process of DSSCs. For DSSCs, the electrochemical method is mainly used to
prepare the counter electrode to replace the costly platinum electrode and to prepare metal oxide
nanostructures. It is possible to prepare the highly aligned, vertically oriented TiO2 nanotubes using
the electrochemical anodization method. Many researchers have worked on this and succeeded in
fabricating highly efficient DSSCs. A simple experimental arrangement helps to achieve this goal.
Here usually a well-polished titanium (Ti) foil is taken as the anode, and a platinum or a graphite
electrode is fixed as the cathode. Different electrolytes and different physical parameters such as
anodization voltage, duration of anodization, and distance between the electrodes strongly influence
the growth of TiO2 nanotubes in solution. A schematic diagram of the experimental arrangement
used for the synthesis of TiO2 nanotubes is given in Figure 3.4.
The anodization process was carried out on aluminum (Al) before anodizing titanium (Ti) metal.
In the presence of an acidic etchant, the process is controlled by various physical parameters. There
are three classifications of the generation of synthesis of TiO2. The first generation growth of TiO2
nanotubes is based on hydrofluoric acid (HF) through which about 500–600 nm of thickness was
achieved (Macak et al. 2007). The second generation of TiO2 nanotubes is achieved in the presence
of NaF or NH4F, and the growth of more than 2 μm was achieved. Using water-free electrolytes,
the third generation of TiO2 nanotube growth achieved over 7 μm. Thus, it is clear that optimizing
reaction conditions and reactivity of solvents are playing a superior role in the determination of
FIGURE 3.4 Schematic diagram of the (a) solar cell structure based on the anodized TiO2 nanotubes.
(Reprinted with permission from Mor et al. Copyright 2006 American Chemical Society.) (b) Experimental
steps used for the electrochemical anodization process of TiO2. (Reprinted with permission from Lei et al.
Copyright 2010 American Chemical Society.)
well-aligned growth of the TiO2 nanotubes. The as-synthesized TiO2 nanotubes are in the amor
phous form, and to make it crystalline in nature, the nanotubes are annealed at higher temperature.
Once annealed, the nanotubes layer is then used for the sensitization of dye or quantum dots for
the fabrication of solar cells. The as-synthesized nanotubes are collectively called a membrane.
Scanning electron microscope (SEM) images of the typical anodized TiO2 nanotube membrane at
various resolutions is given in Figure 3.5.
Other than fabricating TiO2 nanotube arrays, other metal oxides such as ZnO nanostructures
are also fabricated using the electrochemical deposition method. In one case, it was observed by
Abd-Ellah et al. (2013) that the use of anions in the electrolyte strongly affects the morphology of
the ZnO nanostructure and different morphologies were obtained by carefully incorporating the
supporting electrolyte with different anions in the reaction medium. Here, the zinc source ZnCl2
is dissolved in water and then forms a hydroxide (Zn(OH)2), which ultimately forms ZnO after the
dehydration process. Interestingly, it was found that when the monovalent ions (Cl−, NO3−, ClO4−)
were used in the electrolyte, ZnO nanotubes (100–200 nm diameter) were produced, whereas for
the divalent anions (SO42−, C2O42−) ZnO nanorod formation was observed. It was also noticed that
through KCl, it was able to prepare both ZnO nanorods and ZnO nanotubes under the optimized
conditions. The structural directing ability of these kinds of ions during the growth of the nano
materials in solution is further motivating synthesis of different morphologies for fabricating high-
efficiency solar cells. The authors were also able to fabricate a DSSC using the as-synthesized
ZnO nanotubes and achieved an efficiency of 1.6%, which was found to be comparable to similar
nanotubes produced through the atomic layer deposition (ALD) method. Because of the high cost,
FIGURE 3.5 (a) Digital image of a freestanding TiO2 nanotube membrane. The lateral dimension is 1.2 ×
1.0 cm2. (b) SEM image of as-prepared freestanding TiO2 nanotube arrays (cross-sectional view, scale bar
= 50 μm). (c–f) SEM images of the freestanding TiO2 nanotube arrays after mild ultrasonication. (c) low
magnification (scale bar = 2 μm) and (d) high magnification SEM images (scale bar = 1 μm) (top view); (e)
cross-sectional view (scale bar = 1 μm); and (f) bottom view (scale bar = 1 μm). (Reproduced from Wang et al.
with permission from The Royal Society of Chemistry.)
the Pt-based counter electrode in the dye-sensitized solar cells is replaced using electrochemically
deposited materials. Because of the high surface area, graphene layers are chosen over other com
pounds on their surface and thereby formation of nanocomposites is successfully achieved. It is pos
sible to exfoliate high-quality graphene from the graphite flakes using the electrochemical method,
and in such processes, graphite foil serves as the working electrode (Belekoukia et al. 2016). Xu
et al. (2013) fabricated a counter electrode based on the negatively charged graphene oxide and
positively charged poly diallyldimethylammonium chloride through a layer-by-layer approach in the
fabrication of the dye-sensitized solar cell. Through a cyclic voltammetry oriented electrochemi
cal reduction procedure, the graphene oxide was converted to graphene. Through this process the
electrocatalytic sites present in the graphene was enhanced and the authors finally achieved 9.5%
efficiency. Liu et al. (2014) fabricated a similar kind of reduced graphene oxide (RGO) by the cyclic
voltammetry method and polypyrrole-based nanocomposites as the counter electrode and achieved
6.45% efficiency. Importantly, in this case the authors fabricated a plastic dye-sensitized solar cell
using an indium tin oxide (ITO)/poly ethylene naphthalene (PEN) substrate and achieved 4.25%
efficiency. Thus, the electrochemical deposition of materials is not only useful for nonflexible sub
strates, they perform quite well in the case of flexible substrates too and this has proven beneficial
for large-scale applications. Interestingly, these electrochemically deposited graphene/polypyrrole
nanocomposites on carbon steel through a potentiostatic technique are also shown useful for anti
corrosion applications (Li et al. 2017). This implies that through electrochemical deposition of these
kinds of layers, it is possible to extend the applications to various sectors. Along with two layers
of the graphene/polypyrrole, it is possible to deposit another polymer layer, like PEDOT, through
the electrodeposition method. Here, first the formed graphene/polypyrrole layers are annealed at
higher temperature, and finally deposition of PEDOT is carried out on these layers. Ramasamy et
al. (282015) used this approach through a one-step electrochemical deposition method of graphene/
polypyrrole layers and fabricated a counter electrode by depositing PEDOT as an additional layer
and achieved about 7.1% efficiency using these trilayer films as the counter electrode. These results
ensure that electrochemical deposition has certainly emerged as a promising technique for low-cost,
simple precursors based on deposition of layers.
3.5 ELECTROCHEMICAL SYNTHESIS OF MATERIALS FOR

QUANTUM DOT-SENSITIZED SOLAR CELLS
Quantum dots (QDs) are extremely small size nanoparticles having a size smaller than their exci
ton Bohr radius value. Because of their small size, QDs possess exciting optical properties such as
impact ionization, multiple exciton generation, high extinction coefficient values, efficient carrier
transfer in solution, and are capable of forming long-range assembly through ligand interactions.
The essential requirement of fabricating active layers using QDs by any kind of method is high
coverage of QDs on the surface. When nanoparticles are not much closer to each other or when
there is a poor deposition of nanoparticles, quantum dot-sensitized solar cells (QDSSCs) suffer
by the recombination process. This recombination process also depends on other parameters such
as size, shape, and ligand molecules attached on the QDs surface. Use of fabrication of the QDs
layer through the electrochemical method is investigated in constructing metal oxide/chalcogen
ide nanoparticle hybrid junctions. These nanostructures are mostly fabricated through either suc
cessive ionic layer adsorption and reaction (SILAR) or chemical bath deposition (CBD) methods.
Compared with single junction, heterojunction of semiconductor nanomaterials acts as the driving
force for the efficient charge transfer process. For example, through the electrochemical deposition
method, the heterojunction of TiO2/CdS and TiO2/CdSe nanoparticles can be fabricated a through
simple approach. Compared with biheterojunction, triheterojunction makes the electron transport
at a much faster rate. Xiao-Yun Yu et al. (2011) fabricated heterojunction of TiO2 hierarchical nano
structures/CdS/CdSe nanoparticles assembly through an in situ electrochemical deposition method.
Here, the hierarchical TiO2 nanostructure is screen printed on the conducting substrate, then the
electrochemical deposition process is carried out in the presence of electrolytes such as 0.02 M of
Cd(CH3COO)2 and 0.2 M of thiourea in a 1/1 v/v of DMSO/water and maintained at 9°C in a water
bath for the deposition of CdS nanoparticles and 0.02 M of Cd(CH3COO)2 and 0.04 M of ethylene
diamine tetraacetic acid (EDTA) together with 0.02 M of sodium selenosulfate (Na2SeSO3) for the
CdSe nanoparticles. While passing current through the solution, the dissociation of sulfide ions (S2−)
from thiourea and selenide (Se2−) ions from Na2SeSO3 takes place in solution, which finally convert
into nanoparticles on the substrate by combining with Cd2+ ions from the respective source. With
Jsc = 18.23 mAcm−2 and 489 mV, the authors achieved 4.81% efficiency through fabricating TiO2/
CdS/CdSe heterojunction. Though the electrochemical approach is used to synthesize QDs, a hybrid
approach of synthesizing semiconductor nanoparticles has also been demonstrated. Penner (2000)
successfully demonstrated the hybrid method, which describes use of a wet chemical/electrochemi
cal approach to synthesize semiconductor nanomaterials. Here, the formation of the nanoparticle
process consisted of three steps. First, the metal nanoparticles are deposited on the graphite sub
strate. After the oxidation process of these metal nanoparticles, the respective negative ions are
added to form metal sulfide, metal iodide, and metal oxide nanoparticles. Using hexagonal symme
try oriented (SKU-1) mesoporous silica as the template, Kim et al. (2010) synthesized cadmium sel
enide (CdSe) QDs with the potential of –0.7 eV at 5°C on the graphite basal plane. The authors used
a three-electrode cell for this process, which was SKU-1–coated graphene as the working electrode,
Ag/AgCl as the reference electrode, and Pt as the counter electrode. Using atomic force microscopy
(AFM) measurements, the authors found that the height of the CdSe deposits varied from 7 to 9 nm.
It is claimed that this method has enabled the direct contact of CdSe nanoparticles with the graphite
in order to enhance their properties. These kinds of efforts will eliminate the troubles associated
with the fabrication of a hybrid structure for the solar cells.
3.6 USE OF ELECTROCHEMICAL SYNTHESIS IN THE

CONSTRUCTION OF PEROVSKITE SOLAR CELLS
Perovskite solar cells are solar cells that have recently been demonstrated with an efficiency of
over 20% and commercialization of perovskite solar cells have just begun with seminal efforts.
The material properties, surface modifications, and fabrication using non-vacuum strategies have
been analyzed by several research groups and significant achievements have been attained. In this
scenario, according to its properties, hybrid perovskites are ambipolar and because of this intrin
sic ion-conducting feature, deposition of perovskite layers through the electrochemical method
has been highly concentrated on in recent years. Using the electrochemical method, Hong et al.
(2018) fabricated a large-area perovskite module through the electropatterning process through
which series connection is achieved by creating metal filamentary nanoelectrodes. By this
method, the authors achieved about 14% efficiency for a total area of 9.06 cm 2. Here during the
forward bias, the ionized perovskite charges are redistributed on the surface of the ITO and Ag
electrodes. This patterning was also confirmed through using techniques such as x-ray photoelec
tron spectroscopy (XPS), conductive atomic force microscopy (C-AFM), and scanning transmis
sion electron microscopy (STEM). Metal oxide nanostructures such as ZnO and TiO2 also could
be used to couple with perovskite solar cells in order to enhance the charge transport. Using trans
parent carbon nanotubes as the electrode, Xiaoyan Wang et al. (2015) fabricated a flexible solar
cell based on the TiO2 nanotubes as the scaffold and methyl ammonium iodide (CH3NH3PbI3)
as the electron conductor. The TiO2 nanotubes were grown using a one-step anodization method
and the length of the obtained TiO2 nanotubes was ~300 nm and the diameter was ~60 nm. The
carbon nanotubes served as the hole collector together with the traditionally used spiro-OMeTAD
polymer. The authors achieved 8.31% efficiency for the 25 μm TiCl4 -treated Ti foil, which is
the highest for flexible TiO2 nanotube-based solar cells. Inorganic hole-transporting layers also
could be fabricated through the electrochemical deposition method since inorganic materials are
more adoptable for the ionization process. Park et al. (2017) fabricated an NiOx hole transport
layer for constructing large-area (1 cm 2) p–i–n planar type perovskite solar cells through a three-
electrode-based electrochemical deposition process. Here the authors first deposited the nickel
hydroxide layer (Ni(OH)2) through its precursors by varying the deposition potential under differ
ent current densities in solution and while annealing the deposited Ni(OH)2 film, the authors were
able to achieve fine morphology of the NiOx layer for constructing perovskite solar cells. Other
than growing TiO2 nanostructures for perovskite solar cells, growth of ZnO nanomaterials by
electrochemical deposition also has been reported. Zhang et al. (2014) prepared a nanostructured
ZnO layer with a thickness of around 800–850 nm using zinc chloride medium, and formation of
nanowires morphology was observed with increasing deposition temperature and decreasing Zn
(II) precursor concentration. Another thin layer of n-type doped ZnO (described as i-ZnO) was
also fabricated from the solution using zinc nitrate as the reaction medium to cover the as-grown
nanowires/nanorods and the authors observed that this i-ZnO reduced the recombination between
ZnO nanostructures and perovskite material in the device, leading to the efficiency over 10%
with the Jsc ~22 mA cm−2 for a solid-state perovskite solar cell. This way of growing nanostruc
tures through the electrochemical method is always advantageous for effective carrier transport.
The main advantage is the thickness and diameter of the nanostructures can be manipulated
through optimizing voltage, current, pH, and precursor and electrolyte concentration in the reac
tion medium. Other than inorganic nanostructures, growth of organic polymers on the influence
of electrical potential was also carried out for perovskite solar cell applications. Yan et al. (2014)
carried out formation of poly-3-hexyl thiophene films on the glass/FTO substrate through the
electrochemical deposition method using a three-electrode system at the voltage of +1.30 V. Using
distilled boron trifluoride-diethyl etherate (BFEE) with 30 mM thiophene as the electrolyte, the
authors fabricated different thicknesses of P3HT films, which functioned as the hole-transport
layer, and assembled a device with the configuration of ITO/polythiophene/CH3NH3PbI3/C60/
BCP/Ag. For the optimized thickness of 18 nm, the best efficiency of 11.8% was achieved with
J sc = 16.2 mAcm −2 and Voc = 1.03 V.
3.7 CONCLUSION AND SUMMARY

From the discussion, it is clear that the electrochemical method is an important technique for the
construction of highly efficient solar cells with the use of hybrid nanostructures. Use of electro
chemical methods to synthesize TiO2 and ZnO nanostructures have indeed opened a new promising
direction to construct them for large-scale applications. However, new kinds of electrolytes and sol
vents are necessary to achieve a fine layer of deposition for the fabrication of high-efficiency solar
cells. Fabrication of these nanostructures by the electrochemical method will be quite useful not
only for solar cell applications, but also for other parallel promising technologies such as photoca
talysis and supercapacitors. Though there are different structural and morphological characteriza
tions available to execute the perfect nature of these materials for solar cell applications, still much
improvement is needed for large-scale applications. The well-organized, well-oriented layer of inor
ganic nanostructures on a conducting substrate is quite useful in absorbing a large number of pho
tons and converting them into useful ways of producing electricity. However, the limited number of
solvents and electrolytes available are creating setbacks in the development of this field. Extending
the fabrication of tandem nanoarchitectures through the electrochemical method will be more help
ful for constructing high-efficiency future generation solar cells. Also, much work has to be devoted
to developing highly efficient perovskite solar cells through the electrochemical deposition of pre
cursors. Optimization of such structures should be expanded with respect to solvent, thickness, and
other physical parameters. It is essential to form a common platform to demonstrate the overall
possible ways to produce high-quality thin films through electrochemical methods. Deposition of
pure inorganic perovskites such as cesium lead halides (CsPbX3, X = Cl, Br, I) and cesium lead-free
halides (CsMX3, where M = Sn, Ge) are to be carried out by means of electrochemical methods and
efficiency of the fabricated solar cells under various circumstances to be evaluated. Fabrication of
efficient layers of new inorganic semiconductor nanomaterials with simple precursors under the
optimized electrochemical conditions needs to be developed in order to improve them with differ
ent configurations. Though the efforts in these directions are at the initial level, it is expected in the
future that achieving these goals will create new pathways in the field.
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4 Role of Advanced Materials
in Electrochemical
Supercapacitors
Joyita Banerjee, Kingshuk Dutta, and M. Abdul Kader
CONTENTS
4.1 Introduction ............................................................................................................................ 63
4.2 General Discussion of Electrochemical Supercapacitors .......................................................64
4.2.1 Electric Double-Layer Capacitors .............................................................................. 65
4.2.2 Pseudocapacitors.........................................................................................................66
4.3 Application of Materials in the Field of Electrochemical Supercapacitors............................ 68
4.3.1 Advances in Materials for EDLC-Type Supercapacitors............................................ 68
4.3.2 Advances in Materials for Pseudocapacitors ............................................................. 69
4.4 Recent Advancements in Electrolytes for Electrochemical Reactions................................... 72
4.4.1 Aqueous Medium........................................................................................................ 73
4.4.2 Organic Solvent Medium............................................................................................ 74
4.4.3 Ionic Liquids ............................................................................................................... 74
4.5 Conclusion .............................................................................................................................. 75
References........................................................................................................................................ 75
4.1 INTRODUCTION
The fast depletion of fossil fuels and its adverse effect on the environment have led researchers to
focus on alternative and clean energy (Das, Dutta, and Rana 2018; Dutta, Das, and Kundu 2015;
Banerjee and Dutta 2017; Dutta et al. 2017; Dutta, Kundu, and Kundu 2014; Dutta 2017; Kundu and
Dutta 2018; Banerjee, Dutta, and Rana 2019). Renewable sources of energy are abundantly available
in nature; however, their intermittent nature of supply necessitated the emergence of more advanced
energy storage materials and devices to store the energy for future use. Electrical energy storage
devices help in storing electrical energy generated by different means for the purpose of future utili
zation. Electrochemical supercapacitors have widespread applications, starting from consumer elec
tronics, memory backup systems, fuel cells, and low emission hybrid electric vehicles to industrial
power and energy management. The most recent applications include emergency doors on Airbus
380 and to serve as temporary energy storage devices mainly coupled with fuel cells or primary
high-energy batteries.
Herein, an attempt has been done to give a basic idea about the working principle, design, and
application of electrochemical capacitors. In this book chapter, we tried to collate information
regarding various types of materials that have been used as electrode material for application in
supercapacitors. Moreover, an attempt has been made to discuss the present status and advance
ments made in the area of electrolytes utilized in electrochemical reactions.
63
4.2 GENERAL DISCUSSION OF ELECTROCHEMICAL SUPERCAPACITORS

Unlike capacitors, supercapacitors possess two electrodes—cathode and anode—with an electro
lyte between the two plates instead of a solid dielectric. In the case of supercapacitors, as the ion
transfer takes place through the electrolytes, it offers high-power density, high-energy efficiency,
and a long charge–discharge cycle life. These electrochemical supercapacitors can store electrical
charges in two ways: (1) thorough reversible faradaic reaction or (2) by storing opposite electrical
charges apart electrostatically. The Ragone plot in Figure 4.1 shows the plot for specific energy ver
sus specific power for various energy storage devices. It has been observed that the electrochemical
capacitors can deliver much higher power compared to batteries and fuel cells but lower than that of
capacitors. These supercapacitors have comparatively higher specific energy than batteries. In this
context, it is important to mention two parameters that dictate the performance of supercapacitors:
energy density and power density. Energy and power densities are defined as the amount of energy
stored and the rate of energy transfer per unit volume of the active materials used as electrodes for
supercapacitors.
In general, a supercapacitor consists of two electrodes, viz. cathode and anode, kept isolated from
each other by a semipermeable membrane in an ionic electrolyte placed between the electrodes, and
current collectors that collect current from the electrodes (Stoller et al. 2008; Chen, Song, and Xue
2014; Al-Osta et al. 2015). The semipermeable membrane, known as separator, is porous in nature
so that it can allow easy shuttling of ions between the oppositely charged electrodes. It also helps in
keeping the oppositely charged electrodes apart to avoid short-circuit.
Figure 4.2 depicts the schematic diagrams of the working principles of an electric double-layer
capacitor (EDLC) and a pseudocapacitor. The details regarding the working principles for EDLCs
and pseudocapacitors will be discussed in the later sections. The basic difference between pseu
docapacitors and EDLCs is in the charge storage mechanism. Pseudocapacitors involve fast and
reversible reaction along with charge storage near the surface or in the bulk of the electrode, which
infers that these types of capacitors have higher energy density than the EDLC types. However, the
kinetics of charge transfer is faster in case of EDLCs.
Based on the type of materials used for the cathode and anode, supercapacitors can be further
divided into two groups, namely, symmetric and asymmetric. Symmetric supercapacitors consist
of electrodes of the same materials (C1 = C2), such that the total capacitance becomes half of either
electrode. On the other hand, asymmetric supercapacitors consist of electrodes of different materials
FIGURE 4.1 Specific energy versus specific power plot for various energy storage devices. (Reproduced
from www.cap-xx.com/resource/energy-storage-technologies/, © CAP-XX 2019, accessed on March 9, 2019.)
Role of Advanced Materials in Electrochemical Supercapacitors 65
FIGURE 4.2 Schematic diagram of (a) EDLC type and (b) pseudocapacitor type. (Reproduced with permis
sion from Vangari, Pryor, and Jiang 2013, © American Society of Civil Engineers.)
with different capacitance (C1 > C2), exhibiting lower capacitance. Usually, the unique design of an
asymmetric supercapacitor comprises a battery-like faradaic electrode and a carbon-based capaci
tive electrode. By merely adjusting the operating voltage window of the electrodes constituting the
device, the capacitance of the asymmetric supercapacitors can be improved.
4.2.1 ElEctric douBlE-layEr capacitors

Conventional capacitors are able to store little energy due to geometrical constraints (limited sur
face area) imposed by a dielectric material between the two electrodes. In this case, the opposite
charges are stored on the surface of the two electrodes (separated at a comparatively large distance
by a solid dielectric) with minuscule capacity to store the charge. EDLC stores electrical charge by
electrical double layer mechanism on the two oppositely charged electrodes, which is similar to
the mechanism of capacitors (Banerjee, Dutta, Kader et al. 2019). However, the major difference is
that, instead of dielectric solid material, it consists of an electrolyte between the two electrodes. The
crucial parameters that determine the performance of the EDLCs are the type of electrolytes, the
chemical affinity between the adsorbed ions and electrode surface, electrical field applied across
the electrodes, pore size, and specific surface area of the electrodes.
The capacitance (CDL) of the EDLC-based supercapacitors can be presented as
C DL = e0 er * A /D (4.1)
where ε0 and εr represent permittivity of free space and dielectric constant (or relative permittiv
ity) of the material between the plates, respectively; A represents the area of each electrode; and
D represents the distance between the electrodes. In brief, EDLC stores charge through the “elec
trical double layer” model, which involves an adsorbed layer on the metal electrode adjacent to
the electrolyte known as the inner Helmholtz plane (IHP), followed by an outer Helmholtz plane
(OHP) with loosely attached oppositely charged ions. These types of supercapacitors resemble con
ventional capacitors and this model is valid for 1 nm from the electrode with a very high electric
field. According to this model, there exists a constant differential capacitance across the double
layer adjacent to the surface of the electrode. The outer diffuse layer of the ions in the electrolyte
extends from the inner adsorbed layer to the bulk solution (You et al. 2018). On the other hand, the
Gouy–Chapman model is applicable for a distance of 20 nm from the electrode, and in this case the
electric potential decreases exponentially from the surface of the electrode. Last, the Stern model is
applicable for highly charged double layer systems (Stern 1924), and basically it is a combination of
the electrical double layer model and the Gouy–Chapman model. For the Stern model, the adsorbed
ion layer defines the inner Stern layer (as in the Helmholtz model) and the diffuse ion layer forms
the Gouy-Chapman diffuse layer. Apart from these models, there exists several other models that
can explicitly describe the behavior of ions at the electrode–electrolyte interface.
As in this case, the charge is accumulated and stored on the surface of the plates. It is considered
to be a purely physical process; and thus, EDLCs exhibit high rate capability but limited capacitance
compared to a battery (Wang et al. 2017a). Hence, at this point, a new concept of storage of charge
through redox reaction comes into existence.
4.2.2 psEudocapacitors
The very concept of charge storage through redox reaction between the electrodes and electrolyte
was discovered in 1971 (Conway 1991). The value of capacitance of the pseudocapacitors is basi
cally proportional to the charge transferred in the whole process, and it is given as
C pc = q ( dq / dv ) (4.2)
where dθ represents the change in fractional coverage of the surface, dv represents the potential
change, and q represents the faradaic charge. However, it has been observed that for pseudocapaci
tors, the term dθ/dv does not vary linearly with its specific capacitance. The faradaic reaction is
responsible for the pseudocapacitors to achieve much higher specific capacitance than EDLCs.
The faradaic process for pseudocapacitors mainly stems from three mechanisms: (1) underpo
tential deposition (Figure 4.3a), (2) redox pseudocapacitance (Figure 4.3b), and (3) intercalation
pseudocapacitance (Figure 4.3c). In the first case, the monolayer deposition of one metal ion from
solution on another metal surface and the redox pseudocapacitance involves storage of charge in
the surface through electrochemical redox reaction via adsorption/desorption of ions between the
solution and the electrode. In intercalation pseudocapacitance, the pseudocapacitance arises from
the intercalation of active ions between the crystallographic layers of the electrode without chang
ing the crystal structure of the electrode material. For a long time, the word “pseudocapacitor”
has been used for electrode materials like Ni(II) hydroxide [Ni(OH)2] and several other materials
(Kandalkar, Gunjakar, and Lokhande 2008; Senthilkumar et al. 2014; Gaikar et al. 2017), which
had exhibited purely battery-like behavior (Hu et al. 2011a; Wang et al. 2013). However, there exists
several electrode materials like transition metal oxides (TMOs), sulfides, hydroxides, carbides,
FIGURE 4.3 Different types of reversible redox mechanisms that give rise to pseudocapacitance (a) under-
potential deposition, (b) redox pseudocapacitance, and (c) intercalation pseudocapacitance. (Reproduced from
Augustyn, Simon, and Dunn 2014 with permission from The Royal Society of Chemistry.)
nitrides, and even conducting polymers that show properties of both a purely capacitive system as
well as of a faradaic system (Gogotsi and Penner 2018). These particular class of electrode materials
has been increasingly popular for their extraordinary electrochemical properties. Simon, Gogotsi,
and Dunn (2014) have given a new identity to the word “pseudocapacitor” signifying the electrode
material that can exhibit behavior tending to capacitors. In the case of EDLC, the capacitance arises
from the potential-dependence of the electrostatically stored charges on the surface of the electrode
(i.e., non-faradaically). However, a completely different charge storage mechanism is involved for
pseudocapacitors. Pseudocapacitors involve charge storage at the interface between the electrode
and the electrolyte, but the mechanism is different from EDLCs (Brousse, Bélanger, and Long
2015). The charge storage takes place through faradaic reaction (like battery) and the charge trans
fer takes place through the double layer (like EDLC). On the other hand, electrode materials like
Ni(OH)2 and cobalt oxides in potassium hydroxide (KOH) electrolyte have shown pronounced fara
daic peaks in cyclic voltammetric (CV) curves, which is typically a battery behavior (Costentin,
Porter, and Savéant 2017). Further, Shukla, Sampath, and Vijayamohanan (2000) postulated that
the EDLC operates through charge–discharge of the interfacial double layer; and in the case of
pseudocapacitors, the transfer of electrons occurs without any bulk phase transformation. It was
further speculated that the electrons involved in electrical double layer are contributed from the
conduction band and the electrons from the valence band are involved in Faradaic reaction. In fact,
the pseudocapacitance is given by
Oad + ne − → Rad (4.3)
where Oad and Rad represent the adsorbed oxidants and reductants, respectively; and n represents
the number of electrons involved in the faradaic reaction. The main characteristic of pseudocapaci
tance stems from absorption and desorption of Oad/Rad on the surface of the electrode, which can be
explained by the Frumkin model.
It is evident from the preceding discussion that EDLC possesses high power density but lacks
energy density. Therefore, in order to improve the charge density of the electrode, researchers have
focused on hybrid supercapacitors. The hybrid supercapacitors have been found to possess a better
combination of electrochemical properties compared to either EDLCs or pseudocapacitors (Zhou
et al. 2014). These hybrid supercapacitors are the amalgamation of two completely diverse electrodes
FIGURE 4.4 Cyclic voltammogram of PbO2 and carbon-based hybrid (asymmetric) supercapacitor.
(Reproduced from Brousse, Bélanger, and Long 2015, © the authors.)
of a battery-type material and a capacitor-type material (Li, Cheng, and Xia 2005). The battery-type
materials undergo faradaic reaction for charge transfer, whereas the capacitor-type materials form
electrical double layers for electron storage (Lota, Fic, and Frackowiak 2011). Figure 4.4 shows the
cyclic voltammogram of a hybrid asymmetric supercapacitor composed of carbon electrode as the
cathode and PbO2 as the anode (Pell and Conway 2004; Zheng 2003). It was observed that a full cell
supercapacitor with two electrodes working in complimentary potential windows have shown much
capacitance due to wide operating window potential (Béguin and Frackowiak 2013).
4.3 APPLICATION OF MATERIALS IN THE FIELD OF

ELECTROCHEMICAL SUPERCAPACITORS
4.3.1 advancEs in MatErials for Edlc-typE supErcapacitors
Unlike conventional capacitors, EDLCs possess two electrodes—cathode and anode— separated
by an electrolyte with a very small gap. In this case, no faradaic reaction takes place, and the ions
or the electrons shuttle between the electrodes through the electrolyte. EDLCs can be charged or
discharged within a short time span with high power density. In order to fulfill the requirement for
an EDLC electrode, the active material is supposed to have good electrical conductivity, porosity,
and high surface area.
Electrodes based on activated carbon fiber cloth obtained from polyacrylonitrile (PAN) by opti
mizing the carbonization had been found to possess a high capacitance value of 208 F g–1, upon
using a 6 M KOH aqueous solution (Xu et al. 2007). Zhao et al. (2008) had also studied the excellent
electrochemical properties of mesoporous or macroporous carbon formed by using Pluronic F127
and SiO2 opal as templates. Nanostructured graphene nanoparticles prepared by ball-milling at four
different conditions exhibited specific capacitance values of 3 µF cm–2 (per surface area) for 4 h and
12 F g–1 (per weight) for 8 h of milling (Gomibuchi et al. 2006). Electrode material based on freestand
ing mats of entangled multiwalled carbon nanotubes (MWCNTs) along with sulfuric acid (H2SO4)
electrolyte has exhibited high capacitance (Niu et al. 1997). Earlier, the effect of vertically aligned
and random carbon nanotubes (CNTs) on the specific capacitance of the supercapacitor electrodes
have also been extensively investigated (An et al. 2001; Futaba et al. 2006). Gold (Au)–manganese
dioxide (MnO2)/CNT coaxial electrodes, prepared by a complex process, exhibited an energy density
value of 4.5 Wh kg–1 and a specific capacitance value of 68 F g–1 in an aqueous electrolyte (Reddy
et al. 2010). Yi et al. (2011) had reported CNTs-implanted mesoporous carbon spheres as a potential
electrode material for supercapacitors with additional porosity and improved electrical conductivity.
These mesoporous carbon spheres possessed a diameter of approximately 0.5 μm to 1.0 μm, an aver
age pore size of 3.9 nm, and a specific surface area of 284 m2 g–1. This electrode produced an equiva
lent series resistance (ESR) value of 0.83 V cm–2, a maximum specific capacitance value of 189 F g–1
and a power density value of 8.7 kW kg–1 at an energy density value of 6.6 Wh kg–1. Electrodes based
on random single-walled carbon nanotubes (SWCNTs) networks exhibited a specific capacitance of
180 F g–1 in presence of KOH electrolyte, a power density of 20 kW kg–1, and an energy density of 10
Wh kg–1 (Chen and Dai 2013). Jin et al. (2017) had reported that phosphorus and nitrogen codoped
exfoliated carbon nanosheets exhibited a considerably high capacitance of 265 F g–1 at a current den
sity of 0.5 A g–1 with excellent capacity retention (84% after 5000 cycles).
Recently, flexible electrodes have accrued immense attention due to their low cost, fast charging
and discharging capabilities, high power per volume, portability, and good electrochemical proper
ties. These flexible electrodes find application from health care and flexible display to wearable energy
storage devices (Jost et al. 2015; Tang et al. 2016; Vlad et al. 2015; Xue et al. 2017). So, it is clear that
flexible supercapacitors have opened a completely new plethora of advanced materials as emergent
energy storage devices. Hence, the increasing demand for flexible electronics boosted the devel
opment of supercapacitors, both yarn/fiber-shaped and planar ones, with excellent electrochemical
performances (Choi et al. 2016; Wang et al. 2017b). Also, 3D-porous flexible graphene foam-based
supercapacitors have shown magnificent electrochemical properties (Manjakkal et al. 2018). The
graphene–Ag conductive epoxy-graphene foam exhibited an aerial capacitance of 38 mF cm–2 at a
current density of 0.67 mA cm–2, upon using phosphoric acid (H3PO4) as the electrolyte. Purkait et
al. (2018) had reported the performance of porous electrochemically grown reduced graphene oxide
(pErGO) networks on copper wire as a potential electrode for flexible supercapacitor applications.
The pErGO-based supercapacitor showed a specific capacitance of 81 ± 3 F g–1 at a current density
of 0.5 A g–1, using polyvinyl alcohol (PVA)/H3PO4 as the electrolyte. Flexible supercapacitors based
on carbon fibers are also studied. Electrodes based on vertically aligned CNTs forest and carbon
nanopetals grown on unidirectional carbon fibers by chemical vapor deposition have shown excellent
electrochemical performances (Cherusseri and Kar 2015a; Cherusseri and Kar 2015b).
4.3.2 advancEs in MatErials for psEudocapacitors
TMOs and conducting polymers are the most investigated electrode material for pseudocapacitors.
Metal oxides possess several attracting properties that help them in securing a position for their
use as electrode material for supercapacitors. These metal oxides show pseudocapacitance along
with double layer capacitance, with wide charge/discharge potential range. However, they possess
limited surface area with low conductivity and stability, high cost, and toxicity. Many TMOs have
been investigated for their capabilities as supercapacitor electrodes. However, the high cost of the
ruthenium oxide that exhibits the highest capacitance values restricts its commercialization. This
paved the way for combinations of ruthenium oxide with other metal oxides, as well as, mixed
metal oxides. Stannic oxide (SnO2)/vanadium pentoxide (V2O5), formed by hydrothermal synthesis,
in combination with CNTs have shown a specific capacitance value of 121.4 F g–1, at a scan rate of
100 mV s–1 in 0.1 M potassium chloride (KCl) solution (Jayalakshmi et al. 2007).
Recently, mixed transition metal oxides (MTMOs) have been highly investigated as they have
superior properties than that of the TMOs. MTMOs have been denoted as AxB3–xO4 (where A, B =
Co, Ni, Zn, Mn, Fe, and so on) with stoichiometric or even nonstoichiometric compositions (Yuan
et al. 2014). These MTMOs are composed of single phases of two ternary transition metal oxides with
two different metal cations but not a binary mixture of two metal oxides (Teh et al. 2011; Zhang et al.
2012a; Zhou, Zhao, and Lou 2012). Due to their complex spinel structure, they exhibit multiple oxida
tion states possessed by different transition metals in a single compound. This significantly increases
their capacitance due to a synergistic effect as compared to single TMOs. Moreover, MTMOs have
higher electrical conductivity in comparison to that of TMOs, due to lower activation energies of
electron transfers between cations. Typical examples of MTMOs are CuV2O6 (Ma et al. 2008; Xiao
et al. 2009), FeVO4 (Sim et al. 2012), Li3VO4 (Li et al. 2013; Mei et al. 2014), ZnV2O6 (Sun et al. 2012),
Zn3V2O8 (Gan et al. 2014), Co3V2O8·n H2O (Wu et al. 2015b), and Co2V2O7 hexagonal microplatelets
(Wu et al. 2015a). These compounds have already found profound application in lithium-ion batteries.
However, in recent times, these MTMOs have also shown good pseudocapacitive behavior.
It was reported by Dar, Moonoosawmy, and Es-Souni (2013) that the pseudocapacitance of the
metal oxides depends on the morphology developed during the synthesis of metal oxide nanopar
ticles. It was observed that the electrodes of nickel(II) oxide (NiO) nanotubes produced much higher
capacitance value (i.e., 2093 F g–1) compared to that produced by NiO nanorods (i.e., 797 F g–1). It
has been shown in another study that cobalt tetraoxide (Co3O4) possessed a very high theoretical
capacitance of 3560 F g–1 and low environmental toxicity. Hence, it has been used extensively as an
electrode material for electrochemical capacitors. As a reason behind this high capacitance value,
it was said that both the pseudocapacitive and battery-type behavior leads to such high capacitance
(Yuan et al. 2011; Lee, Chin, and Sow 2014).
Battery-type behavior : Co3O 4 + OH − + H 2O ↔ 3MOOH + e − (4.4)
Pseudocapacitive-type behavior : CoOOH + OH − ↔ CoO2 + H 2O + e − (4.5)

Vanadium oxides are also examples of such important transition metal oxides that have been
studied extensively for their use as electrode materials for supercapacitors. They exhibit multiple
valences, such as +5, +4, +3, and +2. Among these the most investigated forms of vanadium oxides
are V2O5, V2O3, and VO2. Lee and Goodenough (1999) reported the electrochemical properties
of the amorphous V2O5·nH2O, which showed a capacitance value of 350 F g–1 along with good
cyclability.
A MnO2-based nanocomposite, formed by electrophoretic deposition of exfoliated CNTs on
nickel foam followed by deposition of nanoparticles like platinum (Pt), palladium (Pd), or Au,
has been observed to exhibit a specific capacitance value of 559.1 F g–1 (Zhao et al. 2013). This
3D porous structure electrode showed extremely good conducting due to ease in electrolyte pen
etration and ion delivery in the presence of ionic liquid (IL) (i.e., 1-butyl-3-methylimidazolium
hexafluorophosphate/N, N-dimethylformamide) electrolyte.
Supercapacitors based on functionalized freestanding CNTs as the positive electrode and free
standing CNT/MoO3–x as the negative electrode have shown a high volumetric capacitance value of
3.0 F cm–3 and high power and energy densities of 4.2 W cm–3 and 1.5 mWh cm–3 (Xiao et al. 2014),
respectively. Highly ordered V2O5–TiO2 prepared by self-organization of Ti–V alloys, with vana
dium (up to 18%), had shown specific capacitance of 220 F g–1 along with energy density of 19.56
Wh kg–1 (Yang et al. 2011). An asymmetric supercapacitor based on α-Fe2O3 on Fe foil as the nega
tive electrode and ZnCo2O4@MnO2 core-shell nanotube arrays on Ni foam as the positive electrode
exhibited a specific capacitance of 161 F g–1 along with an energy density of 37.8 Wh kg–1 (Ma et al.
2015). It was realized that most of the metal oxides, like NiCo2O4, NiO, and Co3O4, are considered
to behave like p-type semiconductors with band gap varying between 2.2 eV and 3.6 eV (Choi and
Im 2005; Hu et al. 2011b; Kumar, Diamant, and Gedanken 2000).
Figure 4.5 illustrates a schematic diagram of the synthetic procedure of mesoporous NiO/
NiCo2O4/Co3O4 composites by the sol–gel process, followed by calcination at 250°C (Liu et al.
2012). These NiO/NiCo2O4/Co3O4 composites showed a specific capacitance value of 1717 F g–1
with 94.9% retention after 1000 cycles. Hierarchical MnMoO4 –CoMoO4 nanowires disclosed a
capacitance value of 187.1 F g–1 at a current density value of 1 A g–1, along with higher stability,
which was higher than that of the electrodes composed of MnMoO4 and CoMoO4 individually
(Mai et al. 2011). CoMoO4 –NiMoO4·xH2O bundles, synthesized by chemical coprecipitation, have
manifested 1039 F g–1 capacitance at a current density of 1 A g–1 along with excellent rate capability
(Senthilkumar et al. 2013). Hierarchical nanosheet-based CoMoO4 –NiMoO4 nanotubes, formed by
the hydrothermal process, have also shown excellent pseudocapacitance (Yin et al. 2015). Zhang
et al. (2014b) reported that Co3V2O8 thin nanoplates prepared by hydrothermal reaction have shown
good electrochemical properties. These electrodes exhibited a high capacitance of 739 F g–1 at
FIGURE 4.5 A schematic diagram of the synthetic process involved in the production of mesoporous
NiCo2O4/NiO/Co3O4 composite. (Reprinted with permission from Liu et al. 2012. © 2012 American Chemical
Society.)
a current density of 0.5 A g–1, along with retention of the capacitance value of 704 F g–1 after 2000
cycles in the presence of aqueous 3 M KOH solution. Table 4.1 provides a short description of sev
eral other metal oxides that find potential application as electrodes for supercapacitors.
As mentioned earlier, flexible electronics are promising materials that have several advantages.
Pseudocapacitive materials have also been used in flexible-materials-based electronics. Huang et al.
(2018) had recently reported the capacitance of a cathode based on aluminum-doped cobalt sulfide
nanosheet anchored on nickel foam along with carbon cloth to be 2434 F g–1 at a current density of
TABLE 4.1
List of Metal Oxides That Find Potential Application as Electrodes for Supercapacitors
Specific
Electrode Materials Method of Synthesis Capacitance (F g−1) Reference
Manganese oxide nanostructure Anodic deposition 432 Shi et al. 2017
grown on nanoporous gold film
Mn3O4/graphene Hydrothermal 367 Lee et al. 2015
RuO2 thin film Chemical bath deposition 73 Patil et al. 2011
Ni(OH)2/rGO Solvothermal 1886 Zang et al. 2017
Nitrogen-doped mesoporous carbon/ Microwave 2498 Xu et al. 2016
nickel cobalt layered double
hydroxide
Carbon nanofiber/MnO2 Electrospinning 311 Zhi et al. 2012
NiO/rGO Electrodeposition 950 Zhao et al. 2016
NiO nanoflake/carbon cloth Chemical bath deposition 660 Zhang et al. 2014a
Nickel oxide coated graphene/PAni Hydrothermal and in situ 1409 Wu et al. 2016
chemical oxidative
polymerization
NiO nanomaterial Hydrothermal 1337 Pei et al. 2016
Manganese oxide film Sol–gel method 360 Sarkar et al. 2015
Co3O4–MnO2–NiO nanotubes Electrodeposition 2525 Singh et al. 2016
Cobalt–manganese layered double Electrodeposition 1062 Jagadale et al.
hydroxide 2016
Porous nickel oxide/mesoporous Chemical precipitation method 2570 Zhang et al. 2010
carbon
NiO nanosheets on Ni foam Hydrothermal 674 Tahmasebi
et al. 2016
Nickel oxide quantum dots embedded Alternating voltage approach 1181 Zhao et al. 2016
with graphene
Manganese oxide decorated graphene Sacrificial reaction 280 Wang et al. 2012b
nanosheets
PAni–RuO2 Successive ionic layer adsorption 664 Chen et al. 2016
and reaction (SILAR)
Ni(OH)2/MnO2/rGO Hydrothermal 1985 Wang et al. 2012a
Mn–Ni oxide Anodic deposition 250 Yang et al. 2012
NiCo2O4 single-wall carbon Controlled hydrolysis process 1642 Wang et al. 2012b
nanotubes (SWCNT)
Manganese oxide/multiwalled carbon Sol–gel method 339 Chen et al. 2016
nanotubes (MWCNT)
Co3O4 Sol–gel method followedby 742.3 Wang et al. 2012a
freeze-drying
NiO Hydrothermal method 1700 Yang et al. 2012
CoMoO4 Hydrothermal method 286 Liu et al. 2013
CoMoO4 nanoplate arrays Hydrothermal method 1558 Guo et al. 2013
1 A g–1. The reported value was quite high and the asymmetric supercapacitor showed an energy
density of 65.7 Wh kg–1 with good cyclability. For flexible supercapacitors, the current collector
plays a pivotal role, and it needs to be both flexible and conductive in nature. However, the quantity
of the active material that needs to be used is restricted by the current collector; thus, it is important
to develop a new advanced current collector. Recently, Ko et al. (2017) studied a novel approach that
involved the conversion of cellulose paper using a ligand-mediated layer-by-layer assembly of metal
nanoparticles to a highly porous and flexible current collector.
4.4 RECENT ADVANCEMENTS IN ELECTROLYTES

FOR ELECTROCHEMICAL REACTIONS
Electrolytes are integral parts of electrochemical supercapacitors, which help in shuttling of ions
between the two electrodes. Mainly, the electrolytes for supercapacitors can be divided into three
types: aqueous medium, organic solvents, and ILs. However, there are other types of electrolytes,
like redox-type electrolytes and solid or semisolid electrolytes, that have been explored in the past.
For an efficient electrochemical supercapacitor, the electrolyte needs to be nontoxic, possess a wide
voltage window, exhibit high conductivity, be environmentally friendly, possess self-discharge capa
bility, have low cost, and be electrochemically stable with a wide temperature range of applicability.
Each category of electrolyte has its own pros and con. Besides the electrolyte operating window, the
performance of electrochemical capacitors also depends on the interaction between the electrodes
and the electrolytes. In this context, it is important to mention here that the matching of pore size of
the carbon-based electrode and ion size of the electrolyte helps in improving the performance of the
supercapacitors. It has further been realized that the internal resistance of the supercapacitors also
gets influenced by the ionic conductivity of the electrolyte, mainly for ILs and organic electrolytes.
In addition, parameters like viscosity, freezing point, boiling point, and degradation temperature
greatly influence the thermal stability as well as the operating potential window of the electrolyte.
Figure 4.6 illustrates the effect rendered by electrolytes on several performance parameters of
electrochemical supercapacitors. It has been observed that decomposition of electrolytes may lead
FIGURE 4.6 Effects of electrolytes on electrochemical supercapacitor performance. (Reproduced from

Zhong et al. 2015 with permission from The Royal Society of Chemistry.)
FIGURE 4.7 Classification of electrolytes for electrochemical supercapacitors. (Reproduced from Zhong
et al. 2015 with permission from The Royal Society of Chemistry.)
to severe damage of electrochemical supercapacitors. Figure 4.7 depicts the broad classification of
electrolytes that are used in supercapacitors.
Recently, redox-type electrolytes have gained focus owing to their good performance as electro
lytes for supercapacitors. These redox-type electrolytes also possess additional pseudocapacitance
from redox reactions taking place at the electrode–electrolyte interface.
The specific energy density (in Wh kg–1) is given by
Specific energy density = ½Cs ( ΔV ) = ½C /m ( ΔV )

2 2
(4.6)
where m represents the active mass, and Cs and C represent the specific capacitance and total capaci
tance of the supercapacitor, respectively. It has been observed that the energy density of supercapac
itors is directly proportional to the potential window range. Hence, the working potential window of
the electrolytes plays a pivotal role in dictating the performance of the supercapacitors. It has been
reported in various studies that organic electrolytes and ILs possess wider potential window (higher
energy density) than aqueous electrolytes. In this respect it should be kept in mind that although
organic solvents and ILs can operate at a wider potential window, they exhibit high resistances
toward ion transport. This factor limits the power density of the supercapacitors.
4.4.1 aquEous MEdiuM

Although aqueous medium electrolytes enjoy low cost fabrication as well as rapid ion transfer with
demonstration of high power and energy densities, they exhibit a narrower voltage window. It has
been reported that if the voltage of the supercapacitors is increased above 1.23 V, it evokes water
decomposition that leads to oxygen/hydrogen evolution. The evolution of gases builds enormous
pressure on the electrodes, resulting in tampering of electrodes. This affects the usage of aqueous
media for commercial applications in aqueous-based supercapacitors. Nevertheless, among all the
types of electrolytes that are used for electrochemical supercapacitors, the aqueous-based superca
pacitors have demonstrated high conductivity, which is much higher than that of other electrolytes
(approximately a conductivity value of 0.8 S cm–1 for 1 M H2SO4 at 25°C). Furthermore, the aque
ous-based electrolytes can be further subdivided into three categories based on its pH value: acidic,
basic, or neutral. In order to select the electrolyte for electrochemical capacitors, it is important to
take certain parameters into account, such as size of bare and hydrated ions and even mobility of the
ions. Moreover, the degree of corrosion and the electrochemical potential window play an important
role in selecting the pH of the electrolyte. The high conductivity of the aqueous medium helps in
decreasing the ESR of the electrolyte, and thus, improves the power density of the electrochemical
capacitors. It has been observed that for an aqueous solution of H2SO4, the conductivity depends
on the concentration of H2SO4. Low and high concentration of H2SO4 in aqueous medium might
not have the same conductivity. It was observed that 1 M H2SO4 in aqueous medium possesses the
highest conductivity value. Therefore, in most cases for aqueous-based electrochemical capacitors,
it is being used. Torchała, Kierzek, and Machnikowski (2012) reported that the specific capaci
tance of activated carbon increased with an increase in electrolyte concentration and conductivity.
Moreover, it was postulated that the acid-based aqueous medium showed much higher conductiv
ity than the neutral medium (Wu et al. 2013; Zhang et al. 2012b). Recent reports on carbon-based
electrodes have revealed that EDLC-based carbon electrodes also undergo redox reaction, which
added some sort of pseudocapacitance to the total capacitance of the electrode (Conway 1999). This
redox reaction was attributed to the presence of oxygenated carbon on the surface of the electrode.
The interaction between the electrolyte and the electrode was observed to be very specific. It has
also been observed that metal sulfides (like CoSx and NiS) exhibited low pseudocapacitance value
as compared to Co(OH)2 and Ni(OH)2 in KOH electrolyte, as well as higher conductivity than any
other bases (Hou et al. 2011; Yuan et al. 2009). In this context, it is also necessary to mention that
the size of the ions plays a crucial role in dictating the electrochemical properties of the supercapaci
tors. Researchers have reported that MnO2 showed higher capacitance in lithium hydroxide (LiOH)
as compared to KOH or sodium hydroxide (NaOH) electrolyte, which is due to the smaller size of
Li+ ions that help in easy intercalation (Misnon et al. 2014; Yuan and Zhang 2006). A similar obser
vation was reported for NiO (Inamdar et al. 2011), which demonstrated higher capacitance value in
NaOH as compared to KOH.
4.4.2 organic solvEnt MEdiuM

Numerous research works have been focused on aqueous electrolyte in the last few decades.
However, due to the inherent drawbacks of aqueous-based electrolytes, recently more attention
has been given to organic electrolytes for their versatile properties. Supercapacitors with organic
electrolytes possess wide operating voltage potential, and thus, help in improving the power and
energy densities of the supercapacitors. However, the decomposition of organic electrolytes blocks
the pores of the electrode, which affects the capacitance and cycling behavior of the electrochemi
cal capacitors. Moreover, organic electrolytes exhibit environmental hazards and are also toxic in
nature. Nevertheless, in the case of organic electrolytes, cheaper materials can be used for current
collectors and packages compared to aqueous electrolytes. Generally, it is considered that organic
electrolytes consist of conductive salts, for example, tetraethylammonium tetrafluoroborate, dis
solved in acetonitrile or propylene carbonate solvents.
4.4.3 ionic liquids

ILs are low melting salts that do not crystallize at room temperature. They have accrued immense
attention because of their versatile properties. ILs are liquid at temperatures below 100°C. These
types of electrolytes have electrostatic interactions at long ranges, which contribute to Debye
screening and also to charge ordering effects (Hansen and McDonald 2013). On the other hand,
fluids only consist of neutral particles that have distinguished characteristics from that of ILs. In
fact, in the case of ILs, the two ions (cations and anions) have different ionic sizes with low degree of
symmetry, leading to reduced lattice energy that results in their lower melting points. The outstand
ing properties possessed by ILs include:
• Excellent ionic conductivity at room temperature

• Ease and flexibility in processing
• Environmentally benign
• Possess ions for conductivity
• Acceptable viscosity
• Wide working potential window
• Molten salts that are liquids at low temperatures
ILs consist of highly charged organic molecules; therefore, it is important to purify them before
use, since they are prone to contamination. In fact, ILs need to be used in pure form, otherwise a
small quantity of moisture may reduce the potential window. Usually, ILs may consist of only one
component; however, in some cases, they may consist of multiple components.
4.5 CONCLUSION
Electrochemical capacitors possess much higher charge storage capability compared to conven
tional capacitors. Although their working principle is somewhat different from that of the battery,
they are advantageous in advanced applications. The quest for higher energy and power capabilities
for advanced energy storage systems led to improvements in supercapacitors. The performance of
electrochemical capacitors is mainly dictated by the type and size of nanoparticles, along with the
method of fabrication of the electrodes. Innovation of new functional nanomaterials, along with
their intricate design, helps in developing advanced electrode materials. In this chapter, we have
summarized the several advanced materials that have been used as electrode materials in the last
few years. As mentioned earlier, the fabrication of electrode nanomaterials plays an important role
in improving the performance of electrochemical capacitors. Amongst all the fabrication methods,
electrospinning has gained immense attention for the development of electrodes due to better con
trol over the fiber morphology developed during the processing. Electrospinning is a facile process
producing nanofibers with good heterogeneity and porosity, which are beneficial for application
in supercapacitors. Electrochemical capacitors are mostly used in case of applications where high
power density and charge storage are required, like memory backup power systems, portable elec
tronic fuses, and pulse power sources for smart weapons. These devices are likely to help society to
indulge in production of new and more advanced energy storage devices on a global scale.
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5 Microbial Electrochemical
Technologies for Fuel
Cell Devices
S. V. Sheen Mers, K. Sathish-Kumar, L. A. Sánchez-Olmos,

M. Sánchez-Cardenas, and Felipe Caballero-Briones
CONTENTS
5.1 Introduction to Microbial Electrochemical Technologies ......................................................84
5.1.1 Components of MFCs................................................................................................. 86
5.1.1.1 Electrodes..................................................................................................... 86
5.1.1.2 Electrolyte.................................................................................................... 86
5.1.1.3 Separators..................................................................................................... 86
5.1.1.4 Microorganisms ........................................................................................... 87
5.1.2 Various Parameters Used in MFC Treatment............................................................. 87
5.1.2.1 Power............................................................................................................ 87
5.1.2.2 Hydraulic Retention Time (HRT)................................................................ 87
5.1.2.3 Specific Energy Consumption (µ)................................................................ 88
5.1.2.4 Chemical Oxygen Demand.......................................................................... 88
5.1.2.5 Coulombic Efficiency (CE).......................................................................... 88
5.1.2.6 Normalized Energy Recovery (NER).......................................................... 88
5.2 Opportunities and Thermodynamic/Electromotive Force Constraint of Microbial
Fuel Cell Technologies ........................................................................................................... 88
5.2.1 Thermodynamics of the MFC .................................................................................... 89
5.2.2 Potential Losses .......................................................................................................... 91
5.2.3 Activation Losses........................................................................................................92
5.2.4 Concentration Losses.................................................................................................. 93
5.2.5 Biocatalyst Metabolic Losses ..................................................................................... 93
5.2.6 Ohmic Losses ............................................................................................................. 93
5.3 Microbial Conversion of Organic Material into Electricity Production Prototypes ..............94
5.4 Microbial Conversion of Organic Matters into Fuel ..............................................................97
5.5 Microbial Electrochemical Technology Limitations..............................................................97
5.5.1 Biochemical Constraints............................................................................................. 98
5.5.2 Functional Materials Constraints ...............................................................................99
5.5.3 Economic Constraints.................................................................................................99
5.6 Future Direction of Microbial Electrochemical Technologies ............................................. 100
5.7 Conclusions........................................................................................................................... 100
References...................................................................................................................................... 101
83
5.1 INTRODUCTION TO MICROBIAL ELECTROCHEMICAL TECHNOLOGIES

The depletion of fossil fuels alarms the increased demand for seeking alternate technologies that
utilize renewable sources (solar energy, wind, hydro energy, geothermal energy, and biomass) to
meet the growing demand for energy. Among them, energy production through fuel cells seems
promising since it is clean, meaning that it is free of contaminating by-products. Various types of
fuel cells are in practice, and distinguished among them is the microbial fuel cell (MFC) that can
work collaboratively as an electricity generator, a sensor, and a wastewater/bioremediation unit.
The knowledge about the basic structure and the further advancement of MFC design that influence
the performance of MFCs should be analyzed and brought together for determining the barriers to
develop new prototypes. It is a promising field that has more scope for research and will be more
innovative when chemists, material scientists, engineers, and microbiologists collaborate. Due to
the lack of studies for a deeper understanding of the mechanism behind the microbial activity and
drop in researching MFC parameter values (chemical oxygen demand [COD], biochemical oxygen
demand [BOD], power and current densities, voltage, or coulombic efficiency) to the expected level,
there are still miles to go for taking MFCs to the next level of practical applications. In this chapter,
we discuss the basic principles of MFCs, various prototypes proposed for the conversion of waste
materials either to fuel or energy, and their future prospects. This chapter will provide readers
access to information in a simplified form for better understanding.
A microbial fuel cell comprises a simple electrochemical setup whereby biocatalyst (microbes)
functions lead to reactions at the anode. An MFC serves the dual purpose as a power generator and
as a wastewater/bioremediation unit through the removal of organic residues/contamination from
the environment. MFC technology is a century-old technique, and the number of publications and
patents in this field has shown rapid growth during the last few decades. (Schröder 2012; Figure 5.1).
The advancement in modern technology ensures the increasing demand for energy and utilization
of alternative renewable energy, thus methods like MFC technology are in high need. It should be
noted that we still depend on nonrenewable fossil fuels for 70% of our energy needs (Ieropoulos et al.,
2013). However, fossil fuels are depleting year by year, and we are aware that it will take millions of
years for them to replace themselves. Suitable alternative, renewable clean energy production can be
made real through fuel cells. Although various forms of fuel cells like polymer electrolyte membrane
fuel cells (PEMs), solid oxide fuel cells (SOFCs), alkaline fuel cells (AFCs), phosphoric acid fuel
cells (PAFCs), and molten carbonate fuel cells (MCFCs) are available, MFCs are advantageous since
they require a simple setup, comparatively low-cost components, and are more convenient to use
(Wang et al. 2011). A major limitation of this technique is that it still lacks commercialization due to
the inadequacy in performance and high fabrication cost and design when applied for practical use.
The MFC setup is composed of minimal components usually possessing an anodic chamber con
taining microorganisms (biocatalyst) and wastewater, while an oxidant at the cathode is connected
FIGURE 5.1 Number of (a) publications and (b) patents from 1962 to 2018 using the search word “microbial
fuel cell.” (Data taken from Scopus, March 2019.)
Microbial Electrochemical Technologies for Fuel Cell Devices 85
to an external circuit to generate electricity. Different cell configurations were developed to elimi
nate certain charge transfer constraints like voltage drop due to internal resistance (arising due to
highly populated organic residues in wastewater), interelectrode distance, separator problems, and
undesirable side reactions. The various prototypes recently proposed and the comparison of their
efficiencies are given in Sections 5.3 and 5.4.
Now let us have a look into different conditions under which MFCs operate and the resultant
changes in terms of chemical products. MFCs can be operated in two ways:
1. Mediated
2. Nonmediated
In MFCs, the organic residues are digested by microorganisms to produce protons and electrons. The
protons diffuse through the separator and get reduced at the cathode. The electrons produced dur
ing this process can be transferred directly to an anodic current collector if exoelectrogenic bacteria
are used, and the process is said to be nonmediated. It facilitates direct electron transfer from the
bacterial cell wall through the cytochromes to the electrode surface (Adebule et al. 2018; Schröder
2012; Inamuddin et al. 2016). In the other case, mediators like potassium ferric cyanide, thionine, or
neutral red are used to receive an electron (redox shuttle) from the bacteria to the electrode surface.
Moreover, the use of a mediator is not advisable for the sustainable operation of MFCs. The atmo
spheric condition at which the MFC operates, either in aerobic or anaerobic condition, or the impact
of oxygen present in the air could adaptably create better performances. For a more straightforward
understanding, this can be explained by taking glucose and acetate as model analytes in the MFC and
varying the atmospheric conditions (Moqsud et al. 2013). In the anode compartment, glucose is oxi
dized to CO2 and H2O under aerobic conditions, while in anaerobic conditions it is oxidized to CO2,
protons, and electrons. On the other hand, the cathode consumes atmospheric oxygen and converts
them into the water. In this way, electricity can be produced in MFCs only under anaerobic condi
tions. The corresponding anodic and cathodic reactions are given as follows (Santiago et al. 2016):
Anodic reaction:
C6H12O6 + 6H 2O → 6CO2 + 24H + + 24e − (anaerobic condition )
Cathode reaction:
O2 + 4H + + 4e − → 2H 2O
Hence, it is an environmentally friendly approach since bacteria and wastewater form the electrolyte
and carbon-based materials are used as electrodes (both for anode and cathode). The productivity
of MFCs can be enhanced through the choice of suitable electrolytes and approaches such as the
integrated active sludge method and by the addition of buffers. Buffers (>7 mS cm−1) possess better
conductivity than that of wastewater (~1 mS cm−1) and hence the improved activity (Ahn et al. 2014).
However, in terms of practical applications, the addition of buffers is not a good idea as it is eco
nomically less plausible and active sludge being an independent technique will be an additional step
during MFC operation. Hence, the main focus should be in reducing internal resistance to obtain
the increased electrical output. In this aspect, miniaturization of MFC is a feasible design generally
known as mini microbial electrolysis cell (mini-MEC) where the geometry considerably influences
the power output in the cell having a cross-sectional area of 2 cm2 and volume 1.2 cm3 (Ringeisen
et al. 2006). Before going into the existing technologies for efficient power production using MFCs,
the basic structure of MFCs needs to be understood. A microbial electrolytic cell (MEC) is one of
the bioelectrochemical technologies where an external voltage is applied for the reduction of pro
tons to form hydrogen or the formation of any other gaseous products that can be able to produce
an electric current.
5.1.1 coMponEnts of Mfcs

The schematic diagram of a typical MFC is shown in Figure 5.1. It is composed of three primary
components as seen in a normal electrochemical cell: anode, cathode, and electrolyte along with a
separator (Figure 5.2).
5.1.1.1 Electrodes
Carbon-based materials are usually used as the anode and cathode. Some of the materials include
graphite rod, carbon cloth, and graphite brush (Ahn et al. 2014; Nam et al. 2010). In MECs, a noble
metal catalyst like platinum is coated on the cathode to enhance the oxygen reduction reaction. A
few alternatives, like activated carbon and transition metal oxides, can be used for enhancing the
power output. Another way to enhance the cathodic activity is to increase the surface area twice
that of the anode. Among various anodes, carbon brushes are found to show supreme behavior since
they possess high surface area, high conductivity, and its peculiar bristles prevent the electrode from
fouling (Lanas et al. 2014). The maximum power density of an MFC is proportional to the logarithm
of the surface area of the electrodes (Oliveir et al. 2013):
Power density = −0.0369 × ln (surface area ) + 0.3371)
5.1.1.2 Electrolyte
Waste effluents like food wastes, artificial wastes and industrial wastes are used as the anolyte.
MFCs operating in an acidic medium are found to be more active. In the cathode side, the elec
trodes will be exposed to air, or an electron acceptor containing solution is taken as the catholyte.
To enhance the MFC performance, sometimes phosphate buffers are added. This approach has its
limitations due to economic feasibility, which adds to the operating cost when used for real-time
applications (Nam et al. 2010). More recently, it was shown that CO2 can also be used as the catho
lyte, as it forms carbonic acid in alkaline solution and acts as a buffer (Fornero et al. 2010).
5.1.1.3 Separators
The role of the separator is to keep the anode and cathode close without coming into contact with
each other and transfer the specific ions (anion or cation). Even though separators offer internal ionic
FIGURE 5.2 Schematic diagram showing a simple microbial fuel cell system.
resistance toward the electrolyte, a systematic study comparing MFCs operated using refinery waste
with and without operators showed that the power output of a separator electrode assembly (SEA) is
found to be ~30 mW/m2 more than a spaced electrode assembly (SPA) and the separators offer only
very low resistance (Zhang et al. 2014a). In some cases, it was found that if separators are not used,
the evolved H+ will interfere with anode reactions and undesirable side products will be formed.
5.1.1.4 Microorganisms
Bacteria like Oscillibacter, Chitinophagaceae, and Acidobacteria are composed of organic constituents
such as cellulose and chitin, and exoelectrogenic species like Clostridium butyricum EG3, Arcobacter,
Desulfobulbus, Desulfovibrio, and Geobacter are some of the known bacteria used for MFC applica
tions (Wang et al. 2013). The role of bacteria in energy production is very crucial. It digests the organic
residues and converts them to electricity. Also, this process will remove inorganic N, P, and K constitu
ents from water, as they are essential for the new cell formation (Ieropoulos et al. 2013). Some bacteria
possess specially designed pili, which are forms of a certain type of cytochrome that transfer the elec
trons to the electrode surface (Kumar et al. 2016). In such cases, there is no need for mediators for the
metabolically produced electrons to reach the anode surface. The cathode surface can also be modi
fied with certain types of the bacterial consortium to accept electrons. The microorganisms will either
reduce oxygen or act as redox mediators in the oxygen reduction reaction (Schröder 2012). Recently
Cahoon et al. (2018) found that an extracellular electron transfer (EET) mechanism is responsible for
electron transfer to metals after proceeding through a series of electron transfer phenomenon through
NADH oxidation, quinone reduction in lipids, and proteins containing heme groups.
5.1.2 various paraMEtErs usEd in Mfc trEatMEnt

5.1.2.1 Power
The output of MFC is measured in terms of voltage concerning time, which is then converted to
current (I) using Ohm’s law:
I = V/R
where V is the voltage and R is the resistance.

The required value for power output is then obtained by taking the product of current and voltage:
P = I × V
Combining the preceding equations we get
P = V2 /R (5.1)
Power is measured in W/m2 (Umachagi et al. 2017).
5.1.2.2 Hydraulic Retention Time (HRT)

HRT is the duration at which the wastewater remains within the MFC cell. The unit of HRT is in
hours and can be calculated using the formula (Umachagi et al. 2017)
V1
HRT= (5.2)
Q
where
V1 is the volume of the cell in m3
Q is the low rate in m3/h.
5.1.2.3 Specific Energy Consumption (µ)

Specific energy consumption (µ) is defined as the amount of current produced per unit of COD
removal. Further, it measured in kWh/kg COD and can be calculated using the following equation
(Yan et al. 2016):
Ew
m= (5.3)
1000M o
where Ew is the electricity consumed for water treatment (kWh) and Mo is the mass of organic matter
removed (ton).
5.1.2.4 Chemical Oxygen Demand

Chemical oxygen demand (COD) is the parameter used to measure the amount of organic matter
removed from wastewater. It defines the amount of oxygen required to convert organic constituents
in wastewater into CO2 and H2O. It is measured in mg/L (McCarty et al. 2011).
5.1.2.5 Coulombic Efficiency (CE)

Coulombic efficiency is defined as the ratio of the total coulombs of current transferred to the anode
through the digestion of organic residue to the maximum coulombs that can be produced through
the process. It is measured using the formula (Umachagi et al. 2017)
Ct
CE = ×100 (5.3)
Cp
Ct = Average current (A) × Time (s)
F × n × Δs( g) × v( L )
Cp =
M
where F is Faraday’s constant in coulombs, n is the number of electrons exchanged per mole of
oxygen, M is the molecular weight of oxygen, Δs is the change in COD concerning time, and v is the
volume of electrolyte taken in the anode chamber.
5.1.2.6 Normalized Energy Recovery (NER)

The normalized energy density is a newly introduced term to quantify energy and is given by the
equation (He 2017)
Power × Time(t)
NER =
Volume of waste water in anode compartment
(5.4)
Powerr
=
Waste water flow rate
The unit of NER is kWh m−3.
5.2 OPPORTUNITIES AND THERMODYNAMIC/ELECTROMOTIVE FORCE

CONSTRAINT OF MICROBIAL FUEL CELL TECHNOLOGIES
The overall reaction for producing electrochemical energy is thermodynamically favorable, which
can be evaluated in terms of Gibbs free energy. Gibbs free energy is a measure of the maximum
work that can be derived from the chemical reactions (Bard et al. 1985; Newman 1973) calculated as
ΔGr = ΔGr0 + RT ln ( Π ) (5.5)
where ΔGr (J mol−1) is the Gibbs free energy for the specific conditions, ΔGr0 (J mol−1) is the Gibbs
free energy under standard conditions (T = 298.15 K, concentration = 1 mol L−1, and P = 1 atm), R
is the universal gas constant (8.31447 J mol−1 K−1), T(K) is the temperature, and (П) is the reaction
quotient calculated as the activities of the products divided by those of the reactants, each raised to
the power of its stoichiometric coefficient. The standard Gibbs free energy reaction can be calcu
lated from the tabulated energy formation of organic compounds in water.
Nevertheless, thermodynamics in electrochemical systems are evaluated in terms of the elec
tromotive force (Eemf ). In the case of negative Gibbs free energy, the reaction is spontaneous and
occurs without external energy input. An MFC is an energy-producing bioelectrochemical system
and has negative Gibbs free energy (Eemf > 0), whereas an MEC system is a nonspontaneous reac
tion (Eemf < 0) and it requires an external energy input to drive the reactions. The relation between
ΔG and Eemf can be expressed by the following equation:
ΔGr
Eemf = − (5.6)
nF
where Eemf is the electron motive force, n is the number of moles of electrons transferred in the reac
tion (per mole of reactant or product), and F is the Faraday’s constant (96485 C/mol e−). Furthermore,
Eemf is calculated as the difference between the theoretical cathodic and anodic potentials. Thus, the
cathodic potential is higher than the anodic potential in the case of a spontaneous reaction.
Eemf = ECathode − EAnode (5.7)
where ECathode (V) and EAnode (V) are the theoretical equilibrium potential of cathodic and anodic
potentials at specific conditions (concentration, pH, and temperature).
5.2.1 thErModynaMics of thE Mfc

MFC is appropriate to evaluate the reaction by the electromotive force (Eemf ) of overall cell reaction,
as mentioned in Equation 5.7. Eemf is related to the work, W (joule, J), done by the fuel cell:
W = Eemf Q = −ΔGr (5.8)

where
Q = nF (5.9)
It represents the charge transferred in the reaction, expressed in coulombs (C), which is deter
mined by the number of electrons exchanged in the reaction, n is number of electrons per reaction
mol, and F is Faraday’s constant (96485 C/mole). Merging these two equations (Equation 5.8 and
Equation 5.9) yields
ΔGr
Eemf = − (5.10)
nF
If all the reactions are evaluated at standard conditions, П = 1, then
ΔGr0
0
Eemf =− (5.11)
nF
0
where Eemf (V) is the standard cell electromotive force.
Therefore, we can use the preceding equations to express the overall reaction in terms of potential as
RT
Eemf = Eemf
0
− ln Π (5.12)
nF
This equation is positive for a favorable reaction and directly produces a value of the emf for the
reaction. The Nernst equation expresses the emf of a cell in terms of activities of products and
reactants taking place in the cell reaction. The Nernst equation relates the potential of an electro
chemical cell (half-cell or full-cell reaction) containing a reversible system with fast kinetics, and
it is valid only at equilibrium and at the surface of the electrode. These would help to evaluate the
potential of the cell under nonstandard conditions (i.e., Equation 5.12) and can be used to calculate
the reduction potential at various pHs, temperatures, and concentrations of product/reactant. The
reaction quotient (П) is the ratio of the activities of the products divided by the reactants raised to
their respective stoichiometric coefficients:
Π=
[ products]p (5.13)
[ reactants]r
In the IUPAC convention, all the chemical reactions are written in the chemical reduction direc
tion. Thus, the products are always the reduced species, and the reactants are the oxidized species
(i.e., oxidized species + e− → reduced species). Likewise, as a standard condition, a temperature
of 298 K and chemical concentrations of 1 M for liquids and 1 bar for gases (1 bar = 0.9869 atm =
100 kPa) by the IUPAC convention. The values of E 0 are calculated concerning that of hydrogen
under standard conditions. These are defined to be E 0 (H2) = 0, referred to as the “normal hydrogen
electrode” (NHE). Hence, the standard potentials for all the chemical reactions are obtained with
П = 1 relative to a hydrogen electrode.
The half-cell reactions at the anode and cathode of an MFC with acetate as an electron donor and
the air as an electron acceptor are
Anode:
CH 3COOO − + 4H 2O → 2HCO3− + 9H + + 8e − E 0 = 0.187 V vs SHE
Cathode:
O2 + 4H + + 4e − → 2H 2O E 0 = 1.229 V vs SHE
In anodic theoretical reduction potential of acetate is oxidized at the specific conditions and can be
calculated as follows:
RT ⎡CH 3COO − ⎤
EAn = EAn
0
− ln ⎣ 2
⎦
9 (5.14)
8F ⎡HCO3− ⎤ ⎡H + ⎤
⎣ ⎦ ⎣ ⎦
where the standard potential of acetate, E 0 = 0.187 V, with the concentration of 1 g/L (16.9 mM)
and under conditions of neutral pH = 7 and alkalinity set by the bicarbonate concentration of
HCO3− = 5 mM,
⎛ J ⎞
⎜⎝ 8.31 mol K ⎟⎠ ( 298.15 K ) [0..0169]
EAn = 0.187 − ln
⎛ C ⎞ [0.005]2 [10 −7 M]9
(8) ⎜ 9.65 × 10 4
⎝ mol ⎟⎠
E An = −0.300 V
The cathodic reduction potential of air cathode at the specific conditions can be calculated as
RT 1
ECat = ECat
0
− ln 1 (5.15)
2F
[O2 ] [H + ]2
2
where the standard potential of oxygen reduction E 0 = 1.229 V, pH = 7, and pO2 = 0.2
⎛ J ⎞
⎜⎝ 8.31 mol K ⎟⎠ ( 298.15 K ) 1
ECat = 1.229 − ln
⎛ C ⎞ 1
(2) ⎜ 9.65 ×10 4 [0.2] 2 [107 M]2
⎝ mol ⎟⎠
ECat = 0.805 V
However, the potential with oxygen is much less in practical application than the predicted.
Thus, for an air-cathode MFC maximum cell potential:
EMFC = ECat − EAn
EMFC = 0.805 − ( −0.300 ) V
EMFC = 1.105 V
This calculated cell potential of MFC provides a maximum limit for the whole cell voltage. However,
the actual potential derived from MFC would be lower (≤0.600 to 0.800 V), due to various potential
losses. This potential loss is often referred to as overpotential or the difference between the potential
under equilibrium conditions and the actual potential.
With the aid of thermodynamic calculations, it can identify the nature of energy losses and range
of size.
5.2.2 potEntial lossEs

The experimental voltage in an MFC can be expressed as follows (Logan et al., 2006):
ECell = Eemf − hCathode − hAnode − hOhm (5.16)
where ECell (V) is the experimental voltage of an MFC; hAnode (V) and hCathode (V) are the overpotential
of the anode and cathode, respectively; and hOhm (V) is the ohmic overpotential.
The overpotential of both the anode and cathode can be calculated as the difference between
the experimental electrode potential and the theoretical reduction potential at specific conditions:
hAnode = EAnode − EAnode

theory
(5.17)
hCathode = ECathode − ECathode

theory
(5.18)
theory theory
where EAnode and ECathode are the theoretical electrode potential of the anode and cathode respectively.
Moreover, overpotentials are the sum of activation, concentration, and biocatalyst metabolic
losses. Thus, the following can be stated:
hAnode = hAct,An + hCon,An + hMet,Biocat (5.19)
hCathode = hAct,Ca + hCon,Ca (5.20)
where hAct,An and hAct,Ca are the activation losses for the anode and cathode, respectively; hCon,An
and hCon,Ca are the concentration losses for the anode and cathode, respectively; and hMet,Biocat is the
metabolic loss of the biocatalyst.
5.2.3 activation lossEs

The activation losses represent the overpotential required to overcome the activation energy of an
electrochemical reaction on a catalyst surface, i.e., the voltage loss required to initiate a reaction.
It depends on the catalyst used. The better catalyst reduces the activation energy, and as a result,
lowers the activation losses. The electrochemical kinetic equation of Butler-Volmer describes the
relationship between the activation losses and the current intensity. The oxygen reduction reaction
of the Butler-Volmer equation is
⎡⎛ C * ⎞ ⎛ C * ⎞ 4 ⎛ −abO 2 F hAct,C ⎞ ⎛ (1 − a ) bO2 F hAct,C ⎞ ⎤

I = I O,c ⎢⎜ OB2 ⎟ ⎜ HB + ⎟ exp ⎜ ⎟ − exp ⎜ ⎟⎥ (5.21)
⎢⎝ CO2 ⎠ ⎝ C H + ⎠ ⎝ RT ⎠ ⎝ RT ⎠ ⎥⎦
⎣
where I (A) is the current intensity, I O2 (A) is the current exchange intensity (background current or
current intensity at zero overpotential), C * (mol L−1) stands for the concentration at the catalyst sur
face, C B (mol L−1) is the concentration at the bulk solution, and α is the transfer coefficient. Equally
I O,c and α are the parameters related to the catalyst activity and should be determined for each
specific case. High activation energy exhibits at the low exchange current intensity (Freguia et al.
2007). In MFC cathodes, a concentration gradient of oxygen from the bulk solution to the catalyst
surface can be neglected. Hence, limitations from oxygen transport occur at very high intensities.
This condition is not yet achieved in MFCs (Popat et al., 2012; Wang et al., 2001). Thus, the term
⎛ CO*2 ⎞
⎜⎝ C B ⎟⎠ in Equation 5.21 could be eliminated.
O2
Biocatalysts serve as catalysts in the anode of MFCs, therefore to reduce the activation losses
of the oxidation reaction, the biocatalyst could effectively transfer the electron to the electrode by
the adaptation/stress conditions. Moreover, the anode reaction is governed by both the enzymatic
kinetics (i.e., conversion of the substrate [organic] into the product [carbon dioxide, protons, and
electrons]) and the electron transfer kinetics (i.e., direct/indirect electron transfer from biocatalyst
to anode).
The Nernst-Monod model considers the anode as a final electron acceptor and is a modified version
of the Monod model (Torres et al., 2008). Therefore, it describes the bio-anode kinetics as a function
of the substrate concentration and the anode potential. The Nernst-Monod model is as follows:
⎛ ⎞
1
I = I max ⎜ F
⎟ (5.22)
⎜⎝ − ( EAnode − EKA ) ⎟
⎠
1+ e RT
where I max (A) is the maximum current intensity determined by the enzymatic reaction, EKA(V) and
K s (mol L−1) are the anode potential and the substrate concentration at which the current intensity is
half the I max , respectively; and Cs is the substrate concentration (mol L−1).
⎛ −
F
hAnode ⎞
⎜ 1 − e RT ⎟
I = I max ⎜ F ⎛ Ks ⎞ ⎟
(5.23)
F
⎜⎝ K .e − (1− a) RT hAnode + K .e RT Anode ⎜⎝ Cs ⎠⎟ ⎟⎠
− h + + 1
1 2
where hAnode is the anodic overpotential (V), K1 is a lumped parameter describing the ratio between
the biochemical and the electrochemical reaction rates, and K 2 is a lumped parameter describing the
ratio between the forward and the backward biochemical rate constants. The anodic overpotential
( hAnode ) is used in the Butler-Volmer-Monod equation instead of the anodic activation losses ( hAct,An ),
which means that the different anodic overpotentials are considered in this model. The experiments
for fitting the model were conducted by avoiding mass transfer limitations and therefore the anodic
concentration losses ( hCon,An ) could be neglected.
5.2.4 concEntration lossEs

The concentration losses ( hCon ) affect the thermodynamics of a reaction. It is caused by the reactant
or product diffusion limitation between the bulk solution and the electrode surface. hCon can be esti
mated as the difference between the theoretical reduction potential calculated at the bulk solution
concentrations (E eq ) and at the local electrode concentrations (note by the superscript asterisk [*]).
hCon,An = EAnode
eq
− EAnode
*
(5.24)
hCon,Ca = ECathode
eq
− ECathode
*
(5.25)
As previously mentioned, in the cathodes of MFC concentration, overpotentials related to oxygen

can be neglected. Hence, the concentration losses are associated with protons.
4
RT ⎛ C B+ ⎞
hCon,Ca = ln ⎜ H* ⎟ (5.26)
bO2 F ⎝ CH+ ⎠
The maximum attainable voltage was hindered by an increase in the cathodic surface area of
MFC. Further, in the anodic reaction hCon,An can be associated with either reactant (glucose or
acetate) or proton (products) mass transfer limitations. In the case of proton transfer, limitations
are reflected in the pH decrease in the biofilm that affects the bioanodes kinetics using thermody
namics reaction.
5.2.5 Biocatalyst MEtaBolic lossEs

Biocatalyst metabolic energy (ATP and NADH) is generated by transporting electrons from a sub
strate (glucose, acetate, etc.,) to the final terminal electron acceptors (oxygen, sulfites, nitrates, etc.).
The metabolic energy gain of the biocatalyst will be determined by the difference between the
potential of the anode and the substrate redox potential.
5.2.6 ohMic lossEs

The resistance to the flow of ions in the electrolyte and through the separators (membrane) and the
resistance to flow of electrons through electrodes (anode and cathode) and interconnections exhibit
the ohmic overpotential. Ohm’s law can be used to calculate this loss:
hOhm = I .Rint
where Rint (Ω) is the internal resistance of MFCs.

5.3 MICROBIAL CONVERSION OF ORGANIC MATERIAL

INTO ELECTRICITY PRODUCTION PROTOTYPES
The following are some of the prototypes fabricated in our laboratory.
1. An efficient electrochemically active sodic–saline inoculum was enriched through electri

cal stress, and it exhibited superior performance in the single chamber microbial fuel cells
(Sathish-Kumar et al. 2012a; Sathish-Kumar et al. 2012b). The prototype thus developed
was used to power an LED and a calculator (Sathish-Kumar 2014) (Figure 5.3).
2. Our group has developed the novel vertical integrated MFC design exploitation of natural
composite materials such as lignocellulose and clay (Figure 5.4a to g) (Sathish-Kumar
et al. 2015a). This type of new design will diminish the cumbersome design of the MFC
scale-up process by inserting the vertical integrated MFC in the existing wastewater treat
ment process that will accelerate the removal of DQO and meanwhile generate electrical
energy to achieve the sustainable treatment. Moreover, with the use of natural materials
like clay and softwood, we can replace the cost-effective commercial membranes (Nafion,
etc.). Further, we have extracted the MnOx catalyst from used alkaline batteries since we
aimed at avoiding the usage of noble metals in the cathodes (Angel Rodrigo et al. 2015).
FIGURE 5.3 Electrical stress directed enriched inoculum seeded in a single-chamber MFC prototype pow
ered LED and calculator.
FIGURE 5.4 (a–c) Novel clay tube integrated MFCs prototypes lab scale-up (120 ml to 20 L). (d–g) Novel
Softwood integrated MFC prototypes lab scale-up (120 ml to 1.5 L). (h, i) Clay-cup-modified dual-chamber
MFC prototypes. (j) Clay-cup-modified air cathode MFC prototypes. (k) Brick-modified MFC prototypes.
The surface of the clay was modified with the aid of acrylic varnish, which will improve
the performance of MFCs. This setup was then used to digest the biomass effluent from
a Nopal biogas plant. The control experiment without applied varnish did not show a sta
ble potential, supporting the idea that the acryloyl group in varnish could favor the per
formance. Finally, a four-digit clock was powered with the two serial connected MFCs
(Figure 5.4h) (Sathish-Kumar et al. 2015b; Sathish-Kumar et al. 2019).
3. Reuse of materials is attractive for their sustainable environmental and economic benefits.
At this context, we have extracted the graphite rod (GR) from a spent battery and used
it as electrode materials in a dual-chamber MFC for treating wastewater. Interestingly,
the surface of the graphite rod was fractured/irradiated by laser ablation to increase the
superficial of the electrode, and as a result this improved the volumetric power production
(2210.55 mW/m3) 15 times higher than the control electrode. The power generated from
this system was used to power the LED (Figure 5.4i) (Ochoa et al. 2017).
4. Another prototype, a clay cup modified MFC, was designed that used the MnOx from the
spent battery as the air catalyst. Two of the clay cup MFCs connected in serial were able to
power the digital clock (Figure 5.4j) (Bárcenas Durón et al. 2017). The brick was modified
into MFC by placing the electrode on the two sides (on the internal side the anode, and on
the external side the cathode). It was inoculated with the wastewater acting as the medium
of treatment and inoculum. This type of MFC was easily scalable and would have potential
for real-world application. We demonstrated the brick-MFCs prototype to power digital
clocks (Figure 5.4k) (Sathish-Kumar et al. 2018).
5. A paper-cup-based integrated microbial fuel cell (PC-MFC) was produced for instant
power production (Figure 5.5). In this, a cellulose-based paper material can act as a separa
tor to facilitate the air cathodic reaction by a Pt/carbon cloth wrapped on the paper cup out
side as the standard cell. Standard PC-MFC shows the maximum volumetric power density
of 231.56 mW/m3. Further, we applied the used b1attery material as a cathode for the
different catalyst loading rates of 1, 2 and 3 grams per cm2 to avoid the usage of Pt and to
prepare the cost-effective real-time electronic applications. Remarkably, the used battery
material cathode of 3-PC-MFC exhibited 3 times higher volumetric power density than the
Pt cathode. Moreover increasing the catalyst loading could significantly improve the power
in PC-MFCs. This work demonstrates the potential realization of practical applications
where we can generate instant electricity directly from the wastewater with the aid of used/
dead batteries (Figure 5.4) (María Catalina et al. 2015).
6. We extended our novel vertical integrated MFCs intermediated by the plants to generate
electrical energy from the growing plants. We applied different plants such as Philodendron
scandens, green grass, and cactus plants. These would have potential applications in the
FIGURE 5.5 Biodegradable paper-cup-based MFC prototype.

green roof—to reduce the temperature of the buildings and give lighting to the surround
ing and vertical garden hanging on the roadside bridges—to reduce the emission of green
house gases, for lighting roads, and in sustainable agriculture systems (Sathish-Kumar et
al. 2017).
The maximum voltage that can be obtained using a single stack MFC is approximately 1 V, and in
most of the cases, it will be reduced to half of its value and even lower due to poor bacterial metab
olism, weak electrode activity, and high internal resistance. (Kim et al. 2012). Several prototypes
have been used during the last decades for improving the efficiencies of MFC toward organic matter
FIGURE 5.6 Plant-intermitted MFC prototypes.
FIGURE 5.7 Pathways for current production and gaseous products in microbial fuel cell.
conversion and for the production of electricity. The main requirements for improving MFC perfor
mance are (1) increasing the surface area of the anode for bacterial inoculation, (2) identification of
anaerobic microbes responsible for electron transfer, and (3) establishing favorable cell conditions for
bacterial growth. One of the noteworthy innovations in MFC is the utilization of urine samples for
energy production. Since urine possesses the major organic component, urea, and contains N, P, and
K, it works as an ideal setup for bacterial growth, electricity generation, and water treatment. The
usage of urine as the anolyte is a suitable preference for usage in remote areas and a preferable solution
for the wastage of water in urinals and lavatories. A Samsung mobile phone was charged for 2 h using
the power developed from this urine containing MFC setup, producing 5 min of talk time (Walter
et al. 2016). Tender et al. (2008) implemented an MFC setup in the marine environment where MFC-
friendly microorganisms like the Geobacteraceae family of bacteria (eliminated the use of mediators),
Clostridium (production of acetate from organic matter), and Desulfobulbus or Desulfocapsa genera
(conversion of elemental sulfur to sulfate) are present. Arrays of graphite anodes were used, and it is
found that the power production was stable for 2 years and can be used for operating marine-deployed
scientific instruments. MFCs have been executed in other environments like river sediments and soil
substrates, typically near the roots of plants (Ewing et al. 2014; Kouzuma et al. 2014).
Cha et al. (2010) combined the single-chambered MFC technique with the active sludge method
and found that the cell performance increased linearly with the amount of oxygen purging. This
particular MFC prototype functioning using graphite felt anode had shown a power density of
16.7 Wm−3 and minimal internal resistance of 17 Ω. A comparison of the power outputs using the
various techniques discussed above is given in Table 5.1.
5.4 MICROBIAL CONVERSION OF ORGANIC MATTERS INTO FUEL

A microbial electrolysis cell (MEC) is a modified form of MFCs where the main motive is the conver
sion of organic matter into value-added products like hydrogen, methane, acetate, and hydrogen per
oxide from which electricity can be produced indirectly (Kumar et al. 2017). The difference between
a microbial fuel cell and a microbial electrolytic cell is depicted graphically in Figure 5.7. Of these
value-added products, hydrogen evolution is more desirable as it can be directly used for electricity
production. Usually, in MFCs, the protons produced due to anode reaction are reduced in the cathodic
compartment to produce hydrogen gas. For the reduction of protons, platinum is found to be highly
active and is generally used as the cathode. Several challenges are there regarding the production of
hydrogen from such a setup. The methanogenic bacteria compete with the electroactive bacteria that
are present within the wastewater. The methanogenic bacteria consume the produced hydrogen from
the cathode and convert them into methane. Loss of hydrogen yield will also happen when no mem
brane is used during the cell operation. The reduced hydrogen gas reaches the anode, and again, it
will be converted to protons (Rozendal et al. 2008; Patil et al. 2015). Moreover, various studies show
that activated carbon is a suitable alternative for the high-cost cathode material, Pt (Ge et al. 2015).
Another form of an MFC, a microbial desalination cell (MDC), works with the aim of desalinat
ing water to emanate hydrogen gas (Aghababaie et al. 2015). Interestingly, high-temperature opera
tion of the MECs (at 30°C) using Pt-decorated carbon cloth enhances the evolution of hydrogen
(Cusick et al. 2011). Heat shock is applied to retard the growth of methanogenesis that restricts the
evolution of hydrogen. The heat treatment was between 75°C and 121°C, and some of the hydro
gen evolution-friendly bacteria are Bacillus sp., Clostridium sp., and Desulfitobacterium hafniense
(Butti et al. 2016).
5.5 MICROBIAL ELECTROCHEMICAL TECHNOLOGY LIMITATIONS

As previously stated, MFCs struggle to meet the essential energy requirement due to increasing
demand as a result of increased usage of electronic devices. It is successful in providing power to
operate small devices, which requires low power values. Some of the constraints that will retard
TABLE 5.1
Comparison of Power Outputs Using Various Techniques
Type of Maximum
Method of Wastewater Power Output
Operation Cathode Anode Separator Reference Used (mW/m2)
1 Dual cathode mode Graphite fiber Activated carbon Plastic, He et al. Raw 1100 (steel)
on stainless steel polycarbonate, (2015) domestic
painted steel wire wastewater
2 Multiple unit cells Graphite felt, Platinum Nafion N424 Kim et al. Brewery 1184.80 (unshared)
connected in series (A) (2012) wastewater 282.63 (shared
anolyte)
3 MFC in series Carbon cloth Platinum grid — Oliot et al. Acetate 0.9
(2017)
4 SEA, SPA Graphite fiber Platinum Textile separator Ahn et al. Domestic 328 (SEA)
(46% cellulose and (2014) wastewater 282 (SPA)
54% polyester)
5 Fed-batch method Non-wet- Pt on wet-proofed — Nam et al. Activated 410
proofed carbon cloth (2010) sludge
carbon cloth
6 Single-chamber MFC NH3-treated Pt on carbon cloth — Cheng et al. Acetate 1260
graphite fiber (2011)
7 Stacked microbial Graphite fiber Pt with Nafion 5 CEM and 6 AEM Shehab et al. Brackish 650
electrodeionization (2014) water,
cell seawater
8 PF-MFC Carbon fiber Pt/C — Karra et al. University 281.74
stack (2013) wastewater
CM-MFC Granular 239.56
activated
carbon
9 Single-chamber MFC Graphite Graphite Nafion 117 Goud et al. Synthetic 309
(2013) wastewater
10 Single-chamber MFC Graphite Pt/C Nafion 117 Liu et al. Domestic 26
(2004) wastewater
SEA, separator electrode assembly; SPA, closely spaced electrode assembly; CEM, cation exchange membrane; AEM, anion
exchange membrane; PF-MFC, plug flow MFC; CM-MFC, complete mixing MFC.
better implementation of MFCs for practical applications are microorganisms, electrode materials,
and separator cost. How it affects the overall performance and feasibility of this technique is in the
following sections.
5.5.1 BiochEMical constraints

The efficiency of an MFC is determined in terms of COD removal and current production. There
are situations where the COD removal is found to be superior while the current efficiency is poor.
The reason is that in real samples, various types of bacteria are present in which the nonelectrogenic
bacteria process the organic matters and supply the electrons for the metabolic activities of microor
ganisms (Karra et al. 2013). Some of the exogenous compounds used are potassium ferric cyanide,
thionine, and neutral red, which produce a toxic environment to bacterial growth (Adebule et al.
2018), whereas bacteria Shewanella putrefaciens, Geobacter sulfurreducens, Geobacter metalli
reducens and Rhodoferax ferrireducens act as self mediators and improve the efficiency of MFCs
(Min et al. 2004).
It is advisable to keep the pH stable without fluctuation, and one such effort is through the addi
tion of buffers. These will favor better growth of microorganisms. In real samples, it is difficult to
buffer the wastewater, and the growth of microorganisms is thus constrained (Nam et al. 2010).
One of the known hydrogen-producing bacteria, acidophilic bacteria, prefers to inoculate at acidic
pH (~6). Simultaneously, the acidic pH condition inhibits the growth of methanogenic bacteria,
thus improving efficiency (Mohan et al. 2008). Since it is well known that the bacteria will produce
current only under anaerobic conditions, the usage of substrates containing dissolved oxygen is
restricted (Min et al. 2004). It is also likely possible that dissolved oxygen will diffuse from the
cathode side to the anode compartment where bacteria consume it and reduce the efficiency (Ahn
et al. 2014). However, genetic engineering of bacteria is sure to increase productivity (Choudery
et al. 2014). Still, the problem of additional labor requirement and the cost for programming bac
terial genes will be a concern. Another constraint regarding bacterial growth is the temperature.
Bacteria require optimum temperature for its inoculation. Usually, bacteria requires an optimum
temperature for carrying out anodic microbial activity. Michie et al. (2010) showed that only psy
chotolerant bacteria can be used for MFCs operating at 10°C and mesophilic bacteria can alone be
used at 35°C.
5.5.2 functional MatErials constraints

In MFCs, the electrodes are predominantly made of carbon-based materials such as carbon felt,
(Wang et al. 2013), carbon cloth, and activated carbon (Karra et al. 2013; Zhang et al. 2014b).
Regarding the activity of MFCs, the voltage loss occurs due to the emergence of internal resistance,
which is associated with solution resistance and resistance offered by electrode materials (Karra et
al. 2013; Wang et al. 2013). This ohmic loss can be compensated by designing morphologically sig
nificant electrode materials and through regulating the flux of substrates near the electrode surface
(Karra et al. 2013). So far, two types of MFC configurations were followed: (1) connecting MFCs in
series and (2) insertion of multiple electrodes in a single unit cell (Kim et al. 2012). Considering the
whole MFC configuration, the voltage drop will predominantly occur in the cathode side. A cathode
with low surface area cannot compensate with the electron flow from the anode.
To accelerate the electron accepting phenomena, either the cathode material should possess higher
surface area than the anode, or the cathode should be modified with a kinetically favorable high-elec
tron-accepting bacteria. Usually, graphene felts are used as cathodes and anodes in the manufacture
of MFCs as they provide high surface area and a constructive environment for bacterial inoculation.
Another important component of MFC is the proton exchange membrane, which is usually made of
Nafion. One of the drawbacks of Nafion is that it will peel off easily when the electrolyte flows in
high pressure. Similarly, the salinity of the anolyte is also known to affect bacterial growth due to the
diffusion of Cl− ions from the cathode to neutralize the charge (Shehab et al. 2014).
5.5.3 EconoMic constraints

While using MFCs for electricity production, the setup is simple and cost-effective since graphite
rods are used as anodes and cathodes. But in case of the microbial electrolytic cell, for the reduction
of protons to form hydrogen, the cathode should be made of platinum. It will increase the cost of the
whole MFC setup. Another scenario is the large-scale production of electricity or fuel using real-
time wastewater. Most of the prototypes proposed are in the lab scale, and when trying to explore
for practical use, they suffer from economic feasibility and technical issues. Generally, in lab-scale
studies, the electrode area taken is 35–40 cm2, but to be applied in the practical scenario it requires
hundreds of meters. Usage of platinum for such large areas is highly impossible in terms of cost.
Another constraint is the use of selective loading of genetically modified bacteria, which requires
an additional process that requires huge time and expense (Choudery et al. 2017). Activated carbon,
carbon fiber, and cobalt-based materials are alternatives for platinum to carry out reduction reaction
but the cost is still high for activated carbon and cobalt is a toxic material (He et al. 2015; Logan
et al. 2014; Ghasemi et al. 2011). Also, since the resistivity of carbon fiber increases with surface
area, it cannot confer the efficiency provided by platinum (Ieropoulos et al. 2010). The pH of the
solution between 6 to 9 is also known to have a huge impact on the growth of microorganisms
typically and hence buffering is a proven way to improve the MFC performance. But buffering
such a large pool of wastewater is not cost effective and not a feasible method for real applications.
In certain prototypes, to enhance bioelectricity, air should be purged in the cathode compartment,
which will further increase the cost of operating MFCs (Cha et al. 2010).
The maintenance cost of electric generators is further costly, and the evolved biogas from the
cathode side requires a purification step for the removal of hydrogen sulfide. The energy losses
happening due to microbial and functional material constraints also contribute to the high cost
of the setup (Ge et al. 2013). When connected in series, separate batteries should be used for
each MFC and that too adds to the cost (Kim et al. 2012). The prominent constraint of practical
applications is that the domestic water possesses poor electronic conductivity, which is less than
5 mS cm−1, and the neutral pH provides constraint for microorganisms toward efficiency (Stoll
et al. 2016).
5.6 FUTURE DIRECTION OF MICROBIAL ELECTROCHEMICAL TECHNOLOGIES

Future development of microbial electrochemical technologies should rely on ideas that can scale
up MFCs for production. Serially connected MFCs are expected to satisfy this requirement, but
in practice, the theoretical output cannot be obtained due to a phenomenon called ion-short cir
cuit within the electrolyte (Oliota et al. 2017). People have come up with the microbe sprinkle
technique to enhance COD removal, and after that the performance was found to be better. The
COD removal, which is directly related to power output, can be achieved by improving the treat
ment efficiency and proper cell configuration, which in turn reduces the cost of MFC operation.
Concerning practical use, MFCs are by far the best method of obtaining the essential energy
output. In short, design of electrode materials possessing essential characteristics like high sur
face area, a nontoxic environment for bacterial growth, good conductivity, and a mechanically
strong membrane separator that will allow only proton transfer and the better electrode align
ment that will prevent ohmic losses are the primary elements where alterations can be made for
enhancing the operation of an MFC. The voltage loss in MFCs connected in series is due to ionic
short-circuiting, which can be decreased by keeping the anodes and cathodes closer and keeping
MFCs apart. In these ways, it is possible to obtain at least 80% of the theoretical voltage output
value (Kim et al. 2012). Even though MFCs lag in producing desirable power output, it is grow
ing in terms of technical aspects. The growing technical aspects and the research for practical
implementations of MFCs show that this field is expected to be improved in the coming years in
terms of excellent power output without fluctuation and low capital investment with cheap raw
materials for cell fabrication.
5.7 CONCLUSIONS
This chapter explains the whole aspect of MFCs from the cell design to the recent advancements in
the field. MFCs are a promising technology for energy production since it can be operated without
any external voltage. The focus on the design of suitable prototypes is the primary requirement for
the enhancement of productivity. Apart from this, there are still voids in the understanding of bac
terial activity especially regarding their metabolism. Thus, the collaborative analysis of biological
and electrochemical influences will definitely help in the prediction of MFC output. Another issue
to be noted is that current technologies are in the laboratory scale and practical use is far beyond the
required level, which requires a lot of understanding regarding basic chemistry and finding the limi
tations offered by substrates, electrode materials, separators and cell design to tune up the voltage/
power output. Moreover, the data about the various constraints related to microbial activity, func
tional materials, and the economy will help researchers to resolve the issues. In the practical sense,
this can be achieved through the modification of the electrode surface and inoculation of specific
bacterial types. In this way, we hope this chapter provides a review of core concepts in condensed
form that will support further innovation.
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6 Photoelectrochemical Process
for Hydrogen Production
S. Devi and V. Tharmaraj
CONTENTS
6.1 Introduction .......................................................................................................................... 105
6.2 Hydrogen (H2) and Solar Energy.......................................................................................... 106
6.3 Photoelectrochemical Process .............................................................................................. 106
6.3.1 Experimental Setup .................................................................................................. 107
6.3.2 General Mechanism of PEC ..................................................................................... 107
6.3.3 Calculations in PEC Process .................................................................................... 108
6.4 Metal Oxide as Photoelectrode in PEC Water Splitting....................................................... 109
6.4.1 Titanium-Dioxide-Based Electrodes ........................................................................ 109
6.4.2 Zinc-Oxide-Based Electrodes .................................................................................. 109
6.4.3 Iron-Oxide-Based Electrodes ................................................................................... 110
6.4.4 Copper-Oxide-Based Electrodes .............................................................................. 110
6.5 Nonmetal Oxide as Photoelectrode in PEC Water Splitting ................................................ 110
6.5.1 Nitride in PEC .......................................................................................................... 110
6.5.2 Phosphide in PEC ..................................................................................................... 112
6.5.3 Oxynitride in PEC .................................................................................................... 113
6.5.4 Sulfide in PEC .......................................................................................................... 113
6.6 Quantum-Dot-Based Photoelectrode.................................................................................... 113
6.7 Hydrogen Production from Biomass and Water ................................................................... 113
6.8 Conclusions........................................................................................................................... 116
References...................................................................................................................................... 116
6.1 INTRODUCTION
Recently, increases in both population and standards of living have caused an increase in energy
demand worldwide. The demand for energy has been increasing continuously in highly populated
countries (e.g., India and China). Around 85% of the energy has been supplied by fossil fuels for
transportation and electricity generation. However, the use of fossil fuels for energy leads to envi
ronmental pollution due to the emission of greenhouse gases (CO2) during their combustion that is
accountable for global warming. Fossil fuels are also considered as a nonrenewable energy source
because of their slow formation, nonhomogeneous distribution, rapid depletion, and limited nature
(Fulcheri and Schwob 1995). Hence, it is essential to explore an alternative clean energy system
for the sustainable development of the environment. The clean energy system is sustainable when
it gives (1) better energy security, (2) better design and analysis, (3) better resource utilization,
(4) better cost efficiency, (5) better effectiveness, and (6) a non-polluted environment.
105
6.2 HYDROGEN (H2) AND SOLAR ENERGY

In recent years, the development of clean energy systems has attracted great attention for solving
the increasing energy demand without polluting the environment and depleting energy sources that
already exist in nature. Solar energy is considered a suitable resource for supplying the energy
needed for the future that could replace the use of fossil fuels. For example, direct sunlight irradia
tion of earth surface for 30 min can produce the worldwide consumption of energy for one year.
Solar energy is inexhaustible in nature and also the end product is nonpolluting to the environment.
However, the quantity of sunlight reaching the Earth’s surface can be influenced by the intermit
tent and fluctuating (day/night) character of solar energy. Hence, a medium is needed to store solar
energy for its continuous supply. Conversion of solar energy into easily storable chemical fuel has
recently attracted considerable attention as a strategic technology to provide clean energy. The solar
energy can be converted into a chemical fuel, namely hydrogen, through the dissociation of water or
renewable biomass thus providing a green environment (Turner 2004). Among the reported chemi
cal elements, the lightest and plentiful element in the universe is H2. It mainly exists with other ele
ments, for example, it is combined with oxygen in water and also combined with nitrogen, carbon,
and oxygen in living things. In a fuel cell, H2 can be converted into electricity by producing water
as a byproduct. H2 can also produce liquid fuels by the reduction of carbon dioxide. The methods
involving the production of H2 are classified based on solar energy (Figure 6.1) (Saraswat, Rodene,
and Gupta 2018; Dincer and Acar 2015; Veras et al. 2016). Most of the methods are not well recog
nized and also convert solar energy to H2 with low efficiency. The techno-economic analyses of H2
production by different methods are studied (Shaner et al. 2016).
The reasons for choosing H2 as an energy carrier are (1) it is easily generated from the renew
able energy source and water without producing greenhouse gases like CO2 resulting in a green
environment; (2) it can be stored in various phase such as solid, liquid, or gas; (3) it is abundant in
nature with other elements; (4) it is an easily transportable fuel with minimum loss and also has
good energy storage densities.
6.3 PHOTOELECTROCHEMICAL PROCESS

The photoelectrochemical (PEC) process, also known as “artificial photosynthesis,” is the more suit
able route for the direct conversion of solar energy into H2 through water splitting. The advantages
of the PEC process are (a) easy fabrication of chemically modified electrode materials, (b) no post
FIGURE 6.1 Types of hydrogen production methods using solar energy. (Adopted from Saraswat 2018 with
permission.)
Photoelectrochemical Process for Hydrogen Production 107
separation of evolved H2 gas, (c) low temperature process, (d) environmentally safe, and (e) poten
tial for combination with conventional photovoltaics (Walter et al. 2010; McKone, Lewis and Gray
2013; Lewis and Nocera 2006). Here, a photon in the visible range of solar spectrum with energies
in the range 1 to 3 eV was enough for generating H2 through splitting of water. H2 was also generated
from biomass and fossil hydrocarbons via the photoelectrochemical process. In some cases, the by-
products obtained via water dissociation were converted into useful industrial products like sodium
hydroxide and chlorine (Rabbani, Dincer, and Naterer 2016).
6.3.1 ExpEriMEntal sEtup

A PEC cell consists of three electrodes, namely reference, working or photo, and counter electrodes.
All the electrodes were immersed in an electrolyte solution. Mostly, Ag/AgCl or standard calomel
electrode (SCE) and Pt were used as reference and counter electrodes. The working electrodes
should be an n-type (anode) or p-type (cathode) semiconductor material that plays an important role
in the absorption of light, generation of electron–hole pairs, and charge transfer in PEC cell. The
applied bias and photocurrent (Iph) density as a function of counter electrode potential (VCE) can be
measured from the potential difference between working and counter electrodes. The PEC cell was
constructed in such a way to collect the produced gases. Most PEC processes involved simulated
sunlight (air mass [AM] 1.5G) as the light source that was obtained from a commercially available
solar simulator. An attached potentiostat and gas chromatography analyzer with PEC cell were
employed to determine the photoelectrochemical properties and the composition of evolved gases.
In some cases, two electrode PEC cells, namely photoelectrode and counter electrode without refer
ence electrode, were used for the photoelectrochemical water splitting. Both working and counter
electrodes were connected using a metal wire. A membrane or a divider was used to collect and
separate the gases produced in the PEC process and also for preventing the recombination of water.
In most of the PECs the electrolyte medium is water but acid/alkaline solution can also be used.
6.3.2 gEnEral MEchanisM of pEc

At first, an excited electron was generated on the semiconductor (photoanode) by the absorption of
photonic energy. The excited electrons were jumped from the valence band (VB) to the conduction
band (CB) of the semiconductor thereby creating electron–hole pairs in the photoanode. The holes
were used to oxidize water on the photoelectrode surface with subsequent reduction of water into H2
at the counter electrode (cathode) by the migration of electrons toward the cathode side.
The overall water splitting reaction was written as follows.
1. hJ → e − + hole +
2. At cathode: 4hole + + 2H 2O → O2 ↑ + 4H +
3. At anode: 2H + + 2e − → H 2 ↑
4. The overall water splitting reaction is 4hJ + 2H 2O→ O2 ↑ +2H 2 ↑
Fujishima and Honda first reported the PEC H2 production under irradiation of visible light using
TiO2 as the photoelectrode without applied electrical bias (1972). They achieved a PEC device with
very low solar to hydrogen (STH) efficiency. Currently, the research is focusing on the develop
ment of more cost-effective photoelectrodes with improved light harvesting efficiency. The STH
efficiency can be improved by applying external bias. STH conversion efficiency directly depends
on the quantity of light absorbed by the semiconductor. A semiconductor with suitable bandgap
or photosensitizer or H2-forming catalyst as the photoelectrode was used to improve the STH effi
ciency by efficient light harvesting and reducing the electron–hole recombination. The minimum
voltage required for water splitting is 1.23 V. The ideal semiconductor photoelectrodes have to meet
the following requirements: (1) narrow bandgap to absorb the entire solar spectral region, (2) highly
durable; (3) easy charge transport, and (4) suitable band alignment that straddle with redox potential
of water splitting.
6.3.3 calculations in pEc procEss

The following formulas are used to assess the performance of PEC devices.
1. The bandgap of the new material was obtained from the absorption spectrum using the
Tauc formula:
1
ln (1 − R|T ) ; ahJ = b ( hJ − Eg )
n
a=
d
where
α = optical absorption coefficient
T = transmittance
d = film thickness
R = reflectance
h = Planck’s constant
n – 2 or ½ for the direct and indirect allowed transition
2. STH (η) is the ratio between the power used for splitting of water and the input light power:
hPEC = i
(E °
rev − Vbias )
I0
where
i = photocurrent density (mA/cm2)
E°rev = standard water splitting reaction potential with respect to the normal hydrogen
electrode (NHE)
Io = light intensity (mW/cm2)
Vbias = applied external potential with respect to the reversible hydrogen electrode (RHE)
3. The incident photon to current conversion efficiency (IPCE) is also employed for evaluat
ing PEC materials:
IPCE =
(1240 × I )
l × Plight
where
I = measured photocurrent density in mA cm–2 at a specific wavelength
λ = incident light wavelength in nm
Plight = power density of monochromatic light at a specific wavelength in mW cm−2
4. Applied bias photon to current efficiency (ABPE):
(
ABPE (%) = i ph mA/cm 2 × ) (V −Vb )(V )
redox
⎛ mW ⎞
1.5 G ×100 (%)
Plight ⎜ AM
⎝ cm 2 ⎟⎠
where
iph = photocurrent density (mA cm−2) at applied bias Vb
Vredox = redox potential for hydrogen production (0 V)
Vb = externally applied bias potential
Plight = intensity of the incident light for AM 1.5G condition (~100 mW/cm2)
5. H2 generation rate was calculated from the photocurrent as follows:

Q × hF h 1800 × I ph × hF
hH2 = ; uH2 = H2 =
2F t ×S e ×NA
where
Q = quantity of electricity
Iph = photocurrent density in mA/cm2
ηF = faradic efficiency
e = electronic charge
NA = Avogadro constant
In the following section, we report on the literature on PEC hydrogen production with special
emphasis on different metal oxides, sulfides, nitrides, silicon metal, carbides, oxynitrides, phos
phides, and nanostructures materials.
6.4 METAL OXIDE AS PHOTOELECTRODE IN PEC WATER SPLITTING

6.4.1 titaniuM-dioxidE-BasEd ElEctrodEs
Since 1972, titanium dioxide (TiO2) is one of the popular semiconductors for PEC water splitting
due to its extraordinary properties such as high stability, high photocatalytic activity, nontoxicity,
low cost, resistance to corrosion, and abundance. However, TiO2 only absorbs light in the ultravio
let (UV) region due to its large bandgap (3.2 eV) and also the fast electron–hole recombination,
resulting in low STH efficiency. The bandgap of TiO2 can be diminished by doping with elements,
surface modification, construction of the heterostructure, synthesis in the form of nanostructures,
and sensitization with dye.
Even though TiO2 nanoparticles (NPs) have high surface-to-volume ratio, the use of TiO2
nanoparticles in PEC was limited due to the reflection of light on the surface of TiO2 that leads
to poor photon absorption. As compared with NPs, one-dimensional (1D) nanostructures such as
nanorods (NRs) (Zheng et al. 2015), nanowires (NWs), and nanotubes (NTs) (Zhang, Hossain, and
Takahashi 2010) enhanced the charge separation between electron–hole pairs and absorbed the light
efficiently while the kinetics of water oxidation was sluggish.
Morita et al. (2017) modified a mesoporous TiO2 electrode using platinum porphyrin as the cata
lyst to achieve the H2 production from water. The mesoporous TiO2 thin film was fabricated on the
conductive fluorine-doped tin oxide (FTO) glass through screen printing and the sintering method
followed by modification with porphyrin via an immersion method. The absorption spectra were
used to evaluate the amount of porphyrin deposited on TiO2. PEC measurements was performed
in three electrodes containing PEC cell using 0.1 M aqueous phosphate buffer (PBS) containing
0.1 M Na2SO4 as the supporting electrolyte. The total amount of H2 at –0.80 V vs. standard calomel
electrode (SCE) generated was found to be 34 μmol. This electrode has high stability and longtime
durability and can serve as a potential electrode in dye-sensitized solar cells.
6.4.2 Zinc-oxidE-BasEd ElEctrodEs

Zinc oxide (ZnO) (bandgap 3.37 eV) has similar characteristic properties to TiO2 except it pos
sesses high electron mobility. The fast recombination of photogenerated electron and hole pairs in
ZnO decreased the efficiency in H2 production. It can be improved by fabricating a heterostructure
with ZnS. Sánchez-Tovar et al. (2016) synthesized a heterostructure based on ZnO/ZnS for study
ing photoelectrochemical water splitting using solar energy. Nitrogen-doped ZnO nanowire as the
photoanode was also used for the generation of H2 through water splitting (Yang et al. 2009). The
photoanode was synthesized via hydrothermal and thermal annealing methods.
6.4.3 iron-oxidE-BasEd ElEctrodEs

Hematite was considered as a promising material in PEC water splitting due to its advantages of
easier synthesis; visible light absorption; stability in neutral, acid, and alkaline solutions; nontoxic
ity; cheapness; narrow bandgap (2 eV); and abundance. However, its drawbacks such as low conduc
tivity, short excited lifetime, low electron mobility due to the small hole diffusion length, and rapid
recombination inhibited its applications in PEC. The performance of hematite can be improved by
elemental doping. Titanium was doped on hematite (α-Fe2O3) by electrodeposition followed by ther
mal annealing methods (Kalamaras et al. 2016). Ti/hematite was used for generating H2 in the pres
ence of ethanol as a sacrificial agent. The PEC measurements at 0.9 V vs. RHE indicated that the
photocurrent of hematite was increased by increasing the loading of Ti on hematite, which further
increased by using ethanol. This was due to trapping of photogenerated holes by ethanol that result
in the separation of electron and holes for longer time. At this time, a greater number of hydrogen
ions are reduced into hydrogen by the electrons at the cathode, thereby increasing the amount of
hydrogen evolved. The obtained photocurrent was stable up to 16 h.
6.4.4 coppEr-oxidE-BasEd ElEctrodEs

A p-type semiconductor, Cu2O, has a narrow bandgap of 1.9 to 2.2 eV. The Cu2O NP was used to
modify the wide bandgap semiconductors such as TiO2 and ZnO to improve the STH conversion
efficiencies. Fan et al. (2016) fabricated a heterostructure based on semiconductor metal oxides
and reduced graphene oxide (rGO). Herein, rGO plays a role in optimizing the interfacial area
between different semiconductors, which influences the separation between electron and hole pairs.
The TiO2/rGO/Cu2O was fabricated on FTO conductive glass via hydrothermal, spin coating, and
chemical solution deposition. PEC measurements were performed in the three-electrode PEC cell
using 0.5 M Na2SO4 as the supporting electrolyte and a 150 W xenon lamp with intensity of 47 mW/
cm2 as the light source. The higher H2 production rate for the heterostructure was attributed to the
inhibition of electron–hole pair recombination and improved charge transfer efficiency. The stabil
ity test indicated that there was an increase in photocurrent after irradiation for 4 h. This was due to
the change in morphology of Cu2O. During PEC reaction, the photogenerated holes can oxidize Cu
(I) to Cu (II) that was suppressed by adding the sacrificial reagent such as methanol. The pure elec
trodeposited Cu2O on stainless steel plate was employed for the PEC hydrogen production (Bicer
and Dincer 2017). The produced H2 can be used to synthesize ammonia by attaching the relevant
reactor. The same group also investigated the effect of H2 production using copper oxide deposited
on various substances at different experimental conditions (Bicer, Chehade, and Dincer 2017). A
Cu2O/CuO bilayer composite was also used for the production of H2 (Yang et al. 2016).
6.5 NONMETAL OXIDE AS PHOTOELECTRODE IN PEC WATER SPLITTING

6.5.1 nitridE in pEc
Metal nitrides have received considerable attention in PEC cell for the production of H2 through
water splitting. Metal nitrides compared with metal oxides have many advantages such as increas
ing STH conversion efficiency, resistance to corrosion in acid/alkaline aqueous solution, and a band-
gap that covers the full solar spectrum region (Wu 2009; Moses and Van de Walle 2010; Huygens,
Strubbe, and Gomes 2000). Gallium nitride (GaN) and Si-doped GaN were used as a photoelec
trode for generating H2 through the photoelectrochemical process (Alotaibi et al. 2013a). The dop
ing on GaN was achieved by using radio-frequency plasma assisted molecular beam epitaxy. The
doped GaN has reduced surface depletion region with increased current conduction. Hydrogen bro
mide and potassium bromide were used separately as electrolytes. H2 can be produced without any
applied bias. If the bias was applied, the photocurrent varied depending on the dopant in GaN. The
charge properties and surface band structure of GaN can also be influenced by the incorporation of
dopant. IPCE of Si-GaN NW in HBr under ∼350 nm light irradiation was ∼18%. An Xe lamp was
used as the light source. The H2 production rate and IPCE value can be increased by altering the
density and length of nanowire or by introducing a co-catalyst like NiOx (Yotsuhashi et al. 2012), or
by combining with other nanowire structures such as InGaN (Alotaibi et al. 2013b).
Figure 6.2a shows the variation of photocurrent density with an applied voltage under dark illu
mination, light irradiation at wavelength of 375 nm, and AM 1.5G simulated sunlight. The pho
tocurrent density was increased up to ~23% under illumination from dark to simulated sunlight.
The higher value of core–shell nanostructures was attributed to excellent charge carrier transport
properties, upward surface band bending that enhances charge separation, and defect free structure.
Figure 6.2b shows the IPCE value at different wavelengths. The IPCE value was increased with a
decrease in the wavelength, which was related to the spectra absorbance of InGaN. The maximum
IPCE value of 27.6% was observed at 350 nm due to the activated GaN and InGaN. There is the for
mation of strong ionic bonds between different III-nitride semiconductors that increased the stabil
ity of n-type InGaN/GaN nanowire for a period of time. GaN also protected InGaN from corrosion
and oxidation, additional reasons for the stability of the core–shell structure. A NiO nanoparticle
deposited InGaN/GaN nanorod array was also used for solar H2 production through PEC (Benton,
Bai, and Wang 2013a). The PEC measurements were performed using NaOH electrolyte medium
under the illumination of sunlight using LOT-Oriel solar simulator. The photocurrent was increased
as compared with that of InGaN/GaN nanorod without NiO NPs that was attributed to the overlap
of NiO NPs bandgap with nitride nanorod array that leads to an increase in the separation of elec
tron–hole pairs. The use of NiO NPs also inhibited photoelectrochemical etching.
Graphitic carbon nitride (g-C3N4), (Eg 2.7 eV), a metal-free semiconductor, has attracted consid
erable attention in fabricating photoelectronic devices such as light-emitting diodes, solar cells, and
PEC cells. Su et al. (2015) studied the PEC performance of H2 production using phosphorus-doped
g-C3N4 modified TiO2 nanotube array. g-C3N4 makes efficient charge transfer and separation due to
the higher conduction band potential. This array was synthesized using electrochemical anodiza
tion, wet dipping, and thermal polymerization. The photocurrent density of array was 3 times higher
than that of TiO2 NT in 0.1 M NaOH solution as electrolyte. The rate of H2 evolution for P-g-C3N4/
TiO2 NT under simulated sunlight was found to be 36.6 µmol h−1 cm−2 at 1.0 V vs. RHE, which was
higher than that for TiO2 NT. To enhance the performance of P-g-C3N4/TiO2 NT for H2 generation
was attributed to the increase in light absorption in the visible region and increased the photogen
erated electron and hole separation.
A multilayer tantalum nitride (Ta3N5) hollow sphere nanofilm with a bandgap of 2.1 eV was
used as photoelectrodes for PEC H2 production (Gao et al. 2014). The performance of PEC depends
on the number of layers formed in Ta3N5. This electrode was fabricated using oil–water interfacial
FIGURE 6.2 (a) The plot of current density vs. applied voltage (vs. Ag/AgCl) (scan rate 20 mV/S).
(b) Measurement of IPCE for InGaN/GaN nanowire photoelectrodes (electrolyte, 1 mol/L HBr; applied bias,
1 V). (Adopted from Alotaibi 2013 with permission.)
self-assembly and sol–gel methods. The PEC properties were investigated by modifying the elec
trodes with IrO2 acting as the co-catalyst that reduces the overpotential related to the redox reaction
and increases the charge separation. The highest photocurrent for monolayer and Ta3N5 with four
layers was found to be 6.1 mA·cm−2 and 17.9 mA cm−2 at 0.65 V vs. Ag/AgCl. This indicated that the
increase in the number of layers will increase the photocurrent density due to the increases in light
absorption. If the layer was further increased, the decrease in the photocurrent was observed due to
the decrease in electric field and increase in film resistance that results in electron–hole recombina
tion. IPCE for Ta3N5 containing four layers at 1.23 V was estimated to be 43.5% under the illumina
tion of light at wavelength of 470 nm.
6.5.2 phosphidE in pEc

A solar fuel based on molecular catalyst (cobaloxime) immobilized semiconductor was synthesized
(Beiler et al. 2016). Here, III-V semiconductor, gallium phosphide (GaP) with the indirect bandgap
of 2.26 eV was used. The two faces of GaP (100) and (111) were easily exposed to oxidation and
corrosion. This can be avoided by stabilizing GaP with polyvinylimidazole (PVI) polymer. This
material was used as the photocathode in PEC H2 generation. The light source used for PEC stud
ies was AM 1.5 filters equipped 100 W Oriel Solar Simulator. Phosphate buffer (PBS) with pH 7
and 100 mV/s was used as the supporting electrolyte and scan rate, respectively. Figure 6.3 shows
the linear sweep voltammogram of photoelectrodes with and without cobaloxime-modified GaP.
As compared with unmodified electrodes, the photocurrent density of the modified electrode was
greater at 0 V vs. RHE. The Iph of PVI-GaP electrodes was 0.32 ± 0.04 and 0.30 ± 0.08 mA cm−2.
The Iph of Co-PVI-GaP electrodes was 0.89 ± 0.02 and 0.89 ± 0.03 mA cm−2 for the A- and B-faces,
respectively. Thus, it shows that the electrodes with both A- and B-faces have identical current and
voltage response. This photocurrent was also stable for 1 h.
Nann et al. (2010) discovered robust photoelectrode comprised of an inorganic light absorber
and earth abundant element containing electrocatalyst for the production of H2. Both materials are
nontoxic and inexpensive. First, a layer-by-layer assembly method was used for constructing a cross
linked indium phosphide (InP) nanocrystal array followed by the incorporation of an iron–sulfur
electrocatalyst, namely [Fe2S2(CO)6]. The InP was bound with electrocatalyst through the sulfide
bridges present in the electrocatalyst. This InP-[Fe2S2(CO)6] system on gold substrate was used as
the photocathode for the production of H2 using 0.1m aqueous NaBF4 as electrolyte in neutral pH.
More than 60% efficiency was achieved under the illumination of light at wavelength of 395 nm.
The indium-phosphide-based core shell nanorod structure (InP-CdS and InP-ZnTe) was also inves
tigated for PEC H2 production (Yu et al. 2005).
FIGURE 6.3 LSV of (a) GaP(111)A and (b) GaP(111)B; polyvinylimidazole grafting (blue) and cobaloxime
attachment (red). The data was observed in the dark (dashed-dotted lines) or under 100 mW cm−2 illumination
(solid lines) in neutral pH. (Adopted from Beiler 2016 with permission.)
6.5.3 oxynitridE in pEc

Tantalum oxynitride (TaON) is an n-type semiconductor with a bandgap of 2.5 eV. Even though it
is nontoxic, the poor stability and low electron mobility offer the synthesis of nanostructure oxy
nitrides. p-Cu2O/n-TaON heterojunction nanorod array as photoanodes was discovered for photo-
electrochemical water splitting after passivating with ultrathin carbon sheath (Hou et al. 2014). The
passivation was achieved by a solution based process for protecting the surface of oxynitrides. Due
to the shape anisotropy and p-n heterojunction structure, the photocurrent density of carbon–Cu2O/
TaON heterojunction nanorod arrays reached 3.06 mA cm−2 under AM 1.5G simulated sunlight
at 1.0 V vs. RHE with a maximum IPCE of 59% at 400 nm. The photocurrent remained at about
87.3% of the initial activity after 60 min irradiation, exhibiting that not only the onset potential is
negatively shifted but also the photocurrent and photostability are significantly improved in com
parison to that of TaON and Cu2O/TaON that was due to the high built-in potential in the protective
p-n heterojunction device encapsulated in an ultrathin graphitic carbon sheath from the electrolyte.
6.5.4 sulfidE in pEc

Molybdenum disulfide (MoS2) has attracted considerable attention due to its low cost and high elec
trocatalytic activity. Jang et al. (2016) fabricated carbon and molybdenum sulfide (MoS2) modified
zinc telluride (ZnTe) as photocathode for the production of H2 from solar energy and water by the
photoelectrochemical process. This electrode was fabricated via carbonization and annealing. The
PEC measurements were performed in 0.5 M Na2SO4 as the electrolyte under simulated sunlight. The
photocurrent density and ABPE of C-MoS2/ZnTe were found to be −1.48 mA cm−2 and 0.12%, respec
tively. Rabbani and coworkers (2016) developed a new photoelectrocatalytic reactor using zinc sulfide
as a photocatalyst for the production of hydrogen along with chlorine and sodium hydroxide from salt
water. They studied the influence of different parameters, namely applied voltage, amount of catalyst,
and light intensity, on solar-to-hydrogen conversion efficiency. They reported that the increase in light
intensity will increase the production of hydrogen but decrease the efficiency of the process.
Carbide-like tungsten carbides were also used as photoelectrode for the generation of H2 through
the PEC process (Gong et al. 2016).
6.6 QUANTUM-DOT-BASED PHOTOELECTRODE

Quantum-dot-based photoelectrodes have garnered much attention for PEC hydrogen generation
due to their extraordinary physical properties such as tunable light absorption, excellent photostabil
ity, easy surface binding, and high extinction coefficient. Hydrogen can be produced through pho
toelectrochemical water splitting using giant core–shell quantum-dot-sensitized mesoporous TiO2
nanoparticles as the photoanode (Adhikari et al. 2016). Herein, a thin film of Cu2S nanoflakes was
used as counter electrodes instead of standard Pt film without affecting the PEC performance. This
quantum dot (QD) was synthesized via successive ionic layer adsorption reaction and sensitization
with TiO2 films was achieved by electrophoretic deposition. Two different QDs were synthesized
with different core sizes and the photoelectrochemical properties were studied. Lv et al. (2017) also
employed CdSe QD-sensitized NiO-coated indium tin oxide photoelectrodes for hydrogen produc
tion under light irradiation. Herein, QD acted as the photocathode. The electrode was synthesized
through the spin coating method. They fabricated a rainbow-like QD electrode by layering coatings
of different sized QDs.
6.7 HYDROGEN PRODUCTION FROM BIOMASS AND WATER

PEC H2 production from renewable biomass such as alcohols, organic acids, and saccharides and
water was more efficient as compared with that from water splitting. There is a formation of CO2
during the H2 production that was retransformed into carbohydrates through natural photosynthesis
114
TABLE 6.1
Various Semiconductors Used for PEC H2 Production
Iph or STH or IPCE or H2 Production
Photoelectrode Material Electrolyte Light Source Rate or ABPE Reference
GaN nanorod array HCl LOT-Oriel solar simulator −1 −1 2
Rate 0.73 m h cm ; STH 0.26% Benton, Bai and, Wang 2013b
Ta3N5 nanorod array/Co(OH)x NPs 1 M NaOH Simulated sunlight Iph 2.8 mA cm−2; IPCE 37.8%; Zhen et al. 2013
rate 274.6 mmol h−1 m−2
WO3 nanowire array 0.5 M H2SO4 Simulated solar light IPCE 85%; ABPE ~0.33% Chakrapani, Thangala, and
Sunkara 2009
WN3 0.5 M H2SO4 Simulated solar light ABPE ~0.4% Chakrapani, Thangala, and
Sunkara 2009
Branched TiO2 nanorod 1 M KOH Xenon lamp Iph 0.83 mA cm−2; IPCE 67%; ABPE –0.49% Cho et al. 2011
p-Si/NiCoSex core/shell nanopillar 0.5 M H2SO4 Simulated sunlight Iph –37.5 mA cm−2 Zhang et al. 2016
array photocathode
CQD/TiO2 NT 0.25 M Na2S and 0.35 M Na2SO3 Simulated sunlight Rate 14.1 mmol h−1; Iph 1.0 mA cm−2 Zhang et al. 2013
aqueous solutions
Polymeric CN-CuInS2 0.1 M H2SO4 (pH 1) Simulated sunlight Iph 50 mA cm−2 Yang et al. 2013
H:TiO2 NW 1 M NaOH Simulated sunlight Iph ∼2.5 mA cm−2; STH 1.63%: rate 0.47 mLh−1; Wang et al. 2011
IPCE 95%
CNQDs/TiO2 NTAs 0.1 M Na2SO4 (pH = 6.0) Simulated solar light Rate 22.0 μmol h−1 cm−2; Iph 1.34 mA cm−2; Su, Zhu and Chen. 2016
IPCE 6.8%
Ta3N5:Mg+Zr 0.1 M Na2SO4 Simulated solar light Iph 2.3 mA cm−2; IPCE 9%–18%; STH 0.59% Seo et al. 2015
CN-rGO Triethanolamine in 0.1 M KOH Simulated solar light Iph 660 µA cm−2; rate 0.8 mol h−1 g−1; IPCE 63.2% Peng et al. 2018
Co-phosphate/Ba-Ta3N5 nanorods 0.5 M K2HPO4 Simulated solar light Iph 6.7 mA cm−2; STH 1%; rate 130 mmol cm−2 Li et al. 2013
Heterostructures of chemically 0.5 M H2SO4 Simulated solar light Iph 17.6 mA cm−2 Ding et al. 2014
exfoliated metallic 1T-MoS2 and
planar p-type Si
(Continued)
Various Semiconductors Used for PEC H2 Production
Iph or STH or IPCE or H2 Production

Photoelectrode Material Electrolyte Light Source Rate or ABPE Reference
Zn0.956Co0.044O 0.2 M KNO3 Xe lamp Iph 55 µAcm−2; IPCE 0.04% Jaramillo et al. 2005
Cu2ZnSnS4/Mo-mesh thin-film 0.1 M NaOH 300 W Xe lamp STH 6.7%; IPCE 15.5% Ma et al. 2011
Porous CdS/Nafion 0.25 M Na2S(pH 12) Simulated sunlight Iph 5.68 mA cm−2; IPCE 75%; Zheng et al. 2016
rate 98 µmol h−1 cm−2
Monoclinic WO3 nanomultilayers 0.1 M Na2SO4 Simulated sunlight Iph 1.62 mA cm−2; IPCE 40%; rate 3 μmol h−1 cm−2 Zheng et al. 2015
TNTs-CdS@Sb2S3 3 M aq. KCl 100 W Xe-arc lamp Rate 10.23 mmol h−1 Carrera-Crespo et al. 2017
NiP2 0.5 M H2SO4 Simulated sunlight Iph 12 mA cm−2; STH-2.6% Chen et al. 2016
p-Si wire 0.5 M H2SO4 Simulated sunlight Iph ~1.45 mA·cm−2 Choi et al. 2017
arrays and NiMoZn heterojunction
SnO2/TiO2/CdS multi- 0.25 M Na2S and Simulated sunlight Iph 8.75 mA cm−2; rate 163.24 mmol h−1 cm−2 Gao et al. 2015
heterojunction structure 0.35 M Na2SO3 aqueous solution
nano-CdSe thin film Na2SO3 solution Simulated sunlight Iph 4.4 mA cm−2; STH 4.31%; rate 82.7 mmol h−1 Guo et al. 2016
cm−2
150 W xenon lamp Liu et al. 2016
Photoelectrochemical Process for Hydrogen Production
Bi2S3 nanowire @ TiO2 nanorod 0.35 M Na2SO3 and 0.25 M Na2S Iph 2.4 mA cm−2; rate 35.97 mol cm−2 h−1
(pH 11.5)
Bi2S3/BiVO4 nanostructure 0.1 M Na2S/0.02 M Na2SO3 Simulated sunlight Iph 3.3 mA cm−2; rate ~417 µmol cm−2 h−1 Mahadik et al. 2018
115
(Ampelli et al. 2011). As compared with other processes such as fast pyrolysis, steam gasification,
and supercritical conversion, the PEC process offers the use of sunlight under ambient conditions
that leads to fabrication of low-cost PEC devices. Like, PEC water splitting, the production of H2
from biomass and water uses the same experimental setup. The properties of photoelectrodes, par
ticularly photoanodes, decided the H2 production rate and the decomposition of biomass derivatives.
The ideal photoanode for PEC H2 production from biomass and water should meet criteria similar
for PEC water splitting. The biomass materials can be oxidized easier than water due to its more
negative redox potential. At first, Kawai and Sakata (1980) generated H2 from biomass containing
glucose backbone and water using RuO2/TiO2/Pt photocatalysts. However, the PEC method was
more efficient than photocatalysis.
Various metal oxides such as Fe2O3, TiO2, and WO3 have been employed for PEC production
from biomass and water. The metal oxide sensitized quantum dots were more suitable for the pro
duction of hydrogen from biomass and water with improved PEC efficiency rather than the use of
metal oxides alone. This was due to the consumption of holes produced after absorption of light
irradiation by the biomass acting as the hole scavenger that stabilizes the QDs. If methanol is used as
the biomass in solar H2 production, the oxidation of methanol gives CO2 and H2 with the formation
of formaldehyde or formic acid. The oxidation of methanol varied for different pH. The oxidation
of ethanol produced acetic acid or CO2 with the formation of H2. Mesoporous tungsten oxide (WO3)
was employed for the production of H2 from ethanol and water achieving 100% IPCE (Barczuk et
al. 2009). Lu et al. (2014) reviewed the photoelectrochemical H2 production from biomass and water
with their reaction mechanisms. Some recent reports for various semiconductors used for PEC H2
production are listed in the Table 6.1.
6.8 CONCLUSIONS
Incredible growth in the development of efficient photoelectrochemical methods for production of
hydrogen employing metal oxide, nonmetal oxide, nanomaterials, and biomass has been made over
the past several years. In this chapter, we mainly discussed the development of a more efficient
energy conversion photoelectrochemical cell in terms of reliability and durability for the production
of hydrogen. However, many of the oxides, such as TiO2, ZnO2, iron-based oxides, sulfides, nitrides,
and quantum dots, were used as photoelectrodes in the direct splitting of water using sunlight.
Fabrications of semiconductor-materials-based photoelectrochemical cells are more efficient for
energy conversion for the production of hydrogen. The attractive design and fabrication of nanoma
terials-based photoelectrochemical cells can offer a high efficiency and increased durability for the
production of hydrogen. Photoelectrodes produce hydrogen from the direct splitting of water using
sunlight, which provides clean fuel for a green environment.
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7 Recent Trends in
Chemiresistive Gas
Sensing Materials
Baskaran Ganesh Kumar, J. Nimita Jebaranjitham,
and Saravanan Rajendran
CONTENTS
7.1 Introduction and Motivation ................................................................................................. 121
7.2 Chemiresistive Sensors......................................................................................................... 122
7.3 Device Design and Mechanism ............................................................................................ 122
7.4 Analytes................................................................................................................................ 124
7.5 Sensing Material ................................................................................................................... 124
7.5.1 Metal Oxide Sensors................................................................................................. 126
7.5.2 Polymers ................................................................................................................... 126
7.5.3 Composites................................................................................................................ 126
7.5.4 Complexes................................................................................................................. 127
7.5.5 Nanoparticles ............................................................................................................ 127
7.5.6 MOFs ........................................................................................................................ 128
7.6 Sensing Platform................................................................................................................... 129
7.7 Important Parameters ........................................................................................................... 129
7.8 Summary .............................................................................................................................. 130
7.9 Chemiresistive Gas Sensing Materials: Future Directions................................................... 130
References...................................................................................................................................... 131
7.1 INTRODUCTION AND MOTIVATION

The emergence and demise of economically powerful nations depend on technological advances.
Electronics are the central heart of any novel technological invention. We are now living in the age
of electronic components and they influence every aspect of life from cooking to aircraft. In our
increasingly electronics-reliant society, sensors play a major role in our daily lives. By definition,
a sensor is a functional device that responds to any type of stimulus and generates the function
ally related output (Joo and Brown 2008). Any digital action starts with sensing, and sensors are
expected to be involved in every scientific and technological discipline in the near future (Patolsky
et al. 2006). Another important contribution of sensors is sensing the harmful chemicals in the
air and environment (Zhang et al. 2017b). Our atmosphere contains various toxic substances from
cars, explosives, industrial toxic vapors, and biowar chemicals. These toxic substances are harmful
to people and affect masses, animals, and plants. These chemical species should be identified and
removed. Sensors are ideal for gas sensing, and toxic substances can be effectively controlled to
a desired toxic limit. Hence, sensors are exciting and very relevant to all aspects of life including
safety, monitoring, health devices, microorganism detection, the perfume industry, security, and
surveillance. So many improvements and advancements in technology have moved the world, which
121
depends completely on sensors. The sensing can originate from mechanical, electrical, thermal,
electrical, magnetic, or radiant, as well as chemical change. The scientific community uses many
terms to describe sensors, namely, “sensors,” “electronic noses,” and “transducer,” throughout the
literature (Amjadi et al. 2016; Fratoddi et al. 2015; Joshi et al. 2018; Pandey 2016; Timmer et al.
2005). Here, we are going to discuss chemiresistive sensors exclusively (Baruah and Dutta 2009; Di
Natale et al. 2014; Fratoddi et al. 2015; Joo and Brown 2008; Joshi et al. 2018; Kumar et al. 2015;
Lieberzeit and Dickert 2007; Llobet 2013; Mahadeva et al. 2015; Pandey 2016; Pandey et al. 2013;
Timmer et al. 2005; Wang et al. 2013). Overall, chemiresistive sensing is important technology and
an indispensable tool for next-generation electronic devices.
Throughout the chapter, we discuss the device design, mechanism, innovative materials, and fac
tors influencing sensing activity. Along with many research efforts, we describe prospective materi
als and conventional analytes for chemiresistive sensing. At the end, we discuss next directions, key
challenges, prospects for commercialization, and opportunities for next-generation chemiresistive
sensors.
7.2 CHEMIRESISTIVE SENSORS

In 1962, Seiyama et al. reported the first ZnO-based gas sensor using chemiresistive sensing tech
nology. Since then, chemiresistive sensing has been widely adopted and its performance is continu
ously being increased by researchers. The chemiresistive sensor produces the modified signal to a
specific measurand (or analyte) (Fennell Jr. et al. 2016). Simply, the chemiresistive sensor uses elec
trical detection for identifying analyte molecules. The modified signal in our case is change in resis
tance. The chemiresistive sensors are generally used to identify the gases and volatile compounds
by monitoring the voltage drop due to resistance changes. Chemiresistive sensors offer simple and
low-cost technologies for detecting and identifying gases and volatile organic compounds. The
ideal chemiresistive sensor is expected to exhibit accuracy, physical stability, chemical stability,
high selectivity, high sensitivity, high resolution, linearity, dynamic range, and better repeatability.
The simplest sensing mechanism facilitates low energy consumption that would lead to simple pos
sible technology for sensing application, which is ideal for commercialization. Due to its simplicity,
the scientific community exploited it to various real-world applications (Table 7.1). The real-world
applications include diabetics monitoring, water quality analyses, explosive sensing, and homeland
security. This chapter discusses the operating principles, common materials, and nexus of opportu
nities with various disciplines.
7.3 DEVICE DESIGN AND MECHANISM

Chemiresistive sensors are based on the simple change in resistance in response to the binding of
analytes. The ideal simple sensor design contains active materials as the thin film, substrate, and
an electrical setup (Figure 7.1) (Fennell Jr. et al. 2016; Liu et al. 2015b; Wang et al. 2008). If the
device exhibits change in resistance, this indicates the presence of an analyte. The conductance
is proportional to amount of analyte present. The active materials of chemiresistive can be any
material type such as metal oxides, polymers, composites, and nanoparticles. The active materi
als are generally prepared as thin film on the substrate. The substrate of the sensors can be glass,
polymer, textile, paper, or any flexible substrate. Simply, the sensor senses gases producing mean
ingful resistance-change as the signal. The sensed gas molecules are called analytes and they can
be small gas molecules like oxygen or large molecules such as DNA. Various researchers have
exploited the device design and have sensed many types of organic matter in various medium
including air, water, and land (Di Natale et al. 2014; Llobet 2013). The mechanism is that the
binding analyte creates interference and creates a new conducting path, which then induces con
ductivity change. The performance of the device is based on the partition coefficients between the
substrate-active substance and analyte vapor (Ancona et al. 2006). The sensitivity is completely
Recent Trends in Chemiresistive Gas Sensing Materials 123
TABLE 7.1
Real-World Applications of Chemiresistive Sensors
Real-World Sensing
Applications Sensing Materials Reference
Spoilage of meat Single-walled carbon nanotubes with cobalt meso-aryl Liu et al. 2015b
porphyrin complexes
Public safety Enzyme alcohol oxidase Mitsubayashi et al. 1994
Fuel diagnosis Poly[(2-bromo-5-hexyloxy-1,4-phenylenevinylene)-Co-(1,4 Benvenho et al. 2009
phenylenevinylene)] (BHPPV-co-PPV) copolymer
Water quality Phenyl-capped aniline tetramer to dope single-walled carbon Hsu et al. 2015
nanotubes
Explosive sensing Single-walled carbon nanotubes coated with a Zhang et al. 2015
carbazolylethynylene
Medical diagnosis Polypyrrole nanowire immune sensor Shirale et al. 2010
Diabetics monitoring Guar gum and gold nano composite Pandey and Nanda 2015
Homeland security Polythiphene-carbon nanotube based sensors Wang et al. 2008
Environmental protection Poly(ethyleneimine) functionalized polyaniline nanothin film Srinives et al. 2015
Detection of nerve agent Carbon black/poly(ethylene oxide) Hopkins and Lewis 2001
simulants drugs
Fish freshness detection Tin-oxide film Hammond et al. 2002
Plant pathogen detection Polypyrrole nanoribbon Chartuprayoon et al. 2013
Breath sensors Hierarchical SnO2 fibers Shin et al. 2013
DNA fingerprint sensing ZnS nanocrystals decorated single-walled carbon nanotube Rajesh et al. 2011
Human rheumatic heart Single-walled carbon nanotubes with Streptococcus pyogenes Singh et al. 2014
disease detection gene
Plant fungus infection Poly(9,9-dioctyl-2,7-fluorenyleneethylene) Gruber et al. 2013
Ovarian cancer Gold nanoparticles Kahn et al. 2015
FIGURE 7.1 (a) Device design and sensing of chemiresistive sensors. (b) The circuit diagram of an ideal
chemiresistive sensor.
based on resistivity or on conductivity impedance. The interaction zone (between the analyte and
active substance) over the cross-sectional area of the device controls the electrical properties of
the device (Zhang et al. 2008). The electrical resistance changes of the sensor array are measured
by exposing them to various concentrations of different analytes. It is to be mentioned that the
analytes also increase the conductivity instead of decreasing it by facilitating charge transfer,
lowering barriers, or charge-injection by accidental doping.
Three influencing factors, namely, the receptor, transducer, and utility, control the device per
formance (Yamazoe 2005). First, the receptor is present in the sensor, which is responsible for the
interaction between the analyte and active layer. The receptor generally binds functional groups
to anchor the target analyte. Second, the transducer is responsible for interaction-led conductivity
change. The utility generally means effective use of the surface to the observed signal. The nature of
the material surface decides the degree of diffusion/interaction of the analyte on the surface of the
sensor and it leads to better kinetics of the sensing. Generally, sensor response (S) is explained by
Equation 7.1. It can be defined as the ratio of resistance change (Rg – Ra) due to exposure of analyte
to the resistance (Ra is baseline resistance) (Pandey 2016). Since the device design is simple it has
several advantages including easy operation, quick troubleshooting, reproducibility, fast response,
portability, and low cost. Overall, the purpose the design is to sense the analyte, quantify the ana
lytes, and display the resistive values of analytes.
Rg Ra
S= ´100% (7.1)
Rg
7.4 ANALYTES
The analyte is a chemical that is to be sensed by chemiresistive sensors. Analytes are various types
of chemicals and carry information about various environments, the body, and many other organic
systems (Figure 7.2). The analytes in the air (explosives, biowar fares, toxic substances) provide
broad information about environments. Similarly, analytes in the body or biological system pro
vide warning information possible dangers and disease detection. The analytes can be either solid,
liquid, or gas. Based on the structure, the analytes can be classified broadly to small and large mol
ecules. The small molecules are normally gases and small size structured molecules (e.g., ammo
nia). The second category is large molecules, which are generally biological molecules (e.g., DNA).
A comprehensive but not exhaustive list of analytes is shown in Figure 7.2. The analytes’ structure,
physical state, functional groups, vapor pressure, concentration, binding kinetics, and binding/inter
acting nature with substrate greatly influence the sensor performance. To get a social perspective
on real-time application, an alcohol test to assess for drunk driving involves sensing of ethanol and
aldehyde from the breath (Di Natale et al. 2014).
7.5 SENSING MATERIAL

Sensing materials are the heart of chemiresistive sensors and they interact and sense the analyte and
produce the response. In 1985, the best chemiresistive application was from copper phthalocyanine
complex (Wohltjen et al. 1985). Later similar smarter materials such as metal oxides, nanoparticles,
metal organic frameworks (MOFs), and composites were developed (Table 7.2). The chemical purity
FIGURE 7.2 Classification of analytes based on the physical structure.

of the sensitive material is critical and affects every performance parameter. The choice of active
material is based on various parameters such as ease of preparation, coordinating nature with the
analyte, ease of film formation, thermodynamic stability, adsorption kinetics of analytes, tunable
conductivity, and material compatibility with the system. Generally, active materials are solid sur
faces or amorphous polymers. Herein, we classify the sensing material based on the composition
as well as properties. In the following are representative examples for each type of sensing material
with a focus on their merits and demerits (Mutkule et al. 2016).
TABLE 7.2
Types of Chemiresistive Sensing Materials
Sensing Material Target Gas Detection Limit Reference
Metal Oxides
(i) WO3 NOx 75 ppm Marquis and Vetelino 2001
(ii) SnO2 H2 0.1–10 ppm Katoch et al. 2016
(iii) CoO3 Ethanol 1 ppm Balouria et al. 2013
(iv) ZnO TNT 8 ppb Chen et al. 2010
(v) Ga2O3 NH3 0.5 ppm Pandeeswari and Jeyaprakash 2014
Polymers
(i) Polyaniline HCl and NH3 100 ppm Huang et al. 2003
(ii) PEDOT:PSS Ethanol 325 ppm Kriván et al. 2000
(iii) Polythiophene Benzoic acid 10 ppm Chang et al. 2006
(iv) PANI fibers Ammonia 0.5 ppm Sutar et al. 2007
(v) PEDOT NO2 200 ppb Le Ouay et al. 2016
Composites
(i) Gold nanoparticle/dendrimer 1-Propanol 100 ppm Krasteva et al. 2002
(ii) rGO/polymer NO2 0.28 ppm Yun et al. 2014
(iii) SnO2/grapheme LPG 50 ppm Nemade and Waghuley 2014
(iv) Pd/PEDOT-TAA Toluene 2 ppm Vaddiraju and Gleason 2010
(v) CNT/DNA Propionic acid 150 ppm Staii et al. 2005
Complexes
(i) Pd-porphyrine complex NH3 100 ppm Wang et al. 2011
(ii) Iron (II) phthalocyanine NO 100 ppm Shu et al. 2010
(iii) Cobalt phthalocyanine O2 15 ppb Bohrer et al. 2007
(iv) Cu3(hexaiminotriphenylene)2 NH3 1 ppm Campbell et al. 2015
(v) Re-thiyl radical Ethylene 1 ppm Chauhan et al. 2014
Nanoparticles
(i) PbS H 2S 50 ppm Liu et al. 2015a
(ii) Si nanowire TNT 1 ppb Engel et al. 2010
(iii) ZnS H2S 50 ppm Zhang et al. 2017a
(iv) Cu2O NO2 100 ppb Zhou et al. 2017
(v) CdSe CHCl3 100 ppm Mondal et al. 2012
MOFs
(i) Cu3(HHTP)2 NH3 100 ppm Yao et al. 2017
(ii) ZnO@ZIF-CoZn Acetone 10 ppm Yao et al. 2016
(iii) Cobalt imidazolate Trimethylamine 2 ppm Chen et al. 2014
(iv) [Zn4O]6+ terephthalic acid Formaldehyde 5 ppm Iswarya et al. 2012
(v) Co zeolitic imidazolate Toluene 5 ppm Jo et al. 2018
7.5.1 MEtal oxidE sEnsors

Metal-oxide-based sensors are the first and foremost choice for chemiresistive sensing due to their
exceptional stability over atmosphere (Afzal et al. 2012). Other metal oxides include SnO2, ZnO,
TiO2, In2O3, CuO, and V2O5 (Afzal et al. 2012; DMello et al. 2018; Hammond et al. 2002; Joshi et al.
2018; Li et al. 2012; Marquis and Vetelino 2001). The sensing mechanism depends upon the redox
reaction involved during the sensing, and the concentration of gases is monitored by varying resis
tance. The performance of the device can be enhanced by the crystal structure and morphology. Even
though metal oxides have various advantages, they suffer from selectivity. Metal-oxide-based sensors
normally sense similar types of analytes present in a gas atmosphere but lack selectivity. As a result,
metal-oxide-based sensors have interfering noise signals (Joshi et al. 2018). Various reports demon
strated that oxides of nitrogen (NOx) are ideal analytes for metal-oxide-based sensors. Additionally,
the metal oxide sensor exhibits peak performance at high temperatures instead of room temperature.
For example, we will discuss the sensing of TNT using ZnO-based chemiresistive sensors (Chen et
al. 2010). The sensors exhibited 8 ppm detection limit of TNT. Chen et al. explained that NO2 mol
ecules are strongly electron-withdrawing and thus reduced conductance for ZnO substrates. Hence
NO2 increased the hole concentration in the devices. The ZnO-based sensor enabled the electronic
nose for explosive materials. Li et al. (2012) reported on a CuO-based H2S sensor with the detec
tion limit of 10 ppb. The high sensitivity is due to binding kinetics, temperature dependence, and
resistance change. Joshi et al. (2014) demonstrated the polycarbazole films for the detection of H2S
with the detection of 10 ppm. The chemiresistive sensors were made with the Langmuir-Blodgett
technique. They improved the performance of the device by surface modification using a gold layer.
7.5.2 polyMErs
Polymers are the second foremost explored chemiresistive sensor material after metal oxides (Pandey
2016; Song and Choi 2013). The polymers conduct with an alternative single and double bond and
hence have better conductivity. The polymers are explored due to their film-forming properties,
controllable thickness, chemical stability, and tunable conductance. The film-forming property and
mechanical property of polymers attracted many researchers to adapt polymers for chemiresistive
sensing. One of the main disadvantages of polymers is their instability toward different pHs and that
they work properly only in neutral environments. One other drawback is the slow response time of
polymers due to analyte doping. In polymer-based chemiresistive sensors, the analyte HCl gas was
doped with polymer films during sensing. Polypyrrole was one of the first conducting polymers uti
lized for chemiresistive sensing applications (Kriván et al. 2000). As an example, we will describe
the PEDOT-based chemiresistive sensor for NO2 analyte detection (Le Ouay et al. 2016). PEDOT is
p-type semiconductor and its Fermi level can be tuned by oxidizing analytes. Hence, a strongly elec
tron-withdrawing group NO2 is used for analyzing the device performance. Le Ouay et al. observed
that the conductivity of the sensor is increased when subjected to three NO2 gas streams. The response
time was 30 s and the detection limit was 200 ppb. Kwon et al. (2012) described the polypyrrole based
highly sensitized and selective chemiresistive sensor for detection of ammonia. The sensor was pre
pared using the polydimethylsiloxane (PDMS) substrate using a dry-transfer method. The sensor had
the ability to discriminate ammonia when the detection limit of the sensors is 0.1 ppm. Li et al. (2008)
reported on poly(4-hexyloxy-2,5-biphenyleneethylene)-based chemiresistive sensing of 1,2-dichloro
ethane and other chlorinated compounds. The polymer is hydrophobic and has the advantage of water
insensitivity and conduction was not perturbed by the humidity in the atmosphere.
7.5.3 coMpositEs
Composites-based chemiresistive sensors are evolving in recent times based on the fact that com
bining two high-performing materials provides peak performance (Pandey 2016). The popular
combinations are metal/polymer, metal oxide/polymer, nanoparticle/polymer, polymer/polymer,
CNT/polymer, graphene/quantum dots, graphene/polymer, and metal complex/polymer. Mostly,

polymers are used as a second composite material because of their film-forming properties, envi
ronmental stability, mechanical bending and conductivity, and ease of device fabrication. The
polymer association could help the metal oxide sensors become flexible and conform to any type
of surface. The main advantage is room temperature performance of the polymer and hence the
device, whereas metal oxides alone exhibit peak performance at high temperatures. Throughout
research literature polythiophene, polyaniline, and polypyrrole were used as co-composite mate
rials. These composites are sometimes called hybrid of metal or metal oxides. The mechanism
for sensing is similar to the simple metal oxide sensors. But the first adsorption process is a little
different. During the sensing process, the vapor molecules of analyte approach and attach to the
polymer surface and then react with the metal oxides (Meng et al. 2015). Synergistically, the elec
tronic perturbation occurs in the polymer and then the perturbation transfers to the metal through
the polymer. An example of a composite is the SnO2/graphene-based chemiresistive sensor for LPG
sensing (Nemade and Waghuley 2014). Due to high surface-to-volume ratio, the sensor receives
and oxidizes the analyte gas, which in turn leads to change in the chemical conductivity. Fu et al.
(2013) explored the unusual gold–DNA composite for detecting methanol and other volatile organic
compounds. The DNA composite gives the gold–alkanethiol properties of sensitivity and detection
limit. Such rare combinations are interesting, but the cost and complexity of DNA compositing
mean it has not gained wild popularity among researchers.
7.5.4 coMplExEs
Complexes were attempted for chemiresistive sensing because of their binding/anchoring proper
ties with gas molecules (Wang et al. 2011). Since the synthesis of complexes is easy and existed
vastly in literature, various examples of the chemiresistive sensors were reported. The complexes
have the advantage of having a single molecule containing both organic and inorganic parts. The
organic part contributes to the solubility and film-forming nature. The inorganic part provides
good intrinsic electrical conductivity and adsorption with gas molecules. The metal centers are the
coordination site for analytes, and the analytes may create a weak bond with the organic region
(ligand) due to weak hydrophobic interaction. The sensing mechanism is similar to the metal oxide
semiconductor sensing mechanism. During binding with the oxidizing gases (NOx), the metal sites
gained hole concentration and conductivity of devices. Conversely, with the reducing gases (NH3),
electrons are injected and trapped with the complexes and decreased conductivity was observed in
sensing devices. The phthalocyanine-based complexes are the dominant form of sensing and exist
throughout literature. Bohrer et al. (2007) studied the cobalt-phthalocyanine complex for oxygen
sensing. They reported that analyte could be considered the ligand or base that could bind to the
central metal atom by a weak coordination bond. The device had a detection limit of O2 as low
as 15 ppb. Since the analyte is considered as the base, the conductivity can be directly correlated
with the Lewis basicity. Similarly, the sensor response and recovery were also directly related with
Lewis basicity. At the high concentration of the analyte, chemisorption (ligand binding) dominates.
However, at low concentration of analyte, sensitivity responded well to transition from physisorp
tion from chemisorption. Wang et al. (2012) reported on lead phthalocyanine-based sensors for the
detection of NH3 with the detection limit of 0.15 ppm. They enhanced the performance of the device
using CNTs by anchoring phthalocyanine. The hybrid complex device structure provided higher
response and sensitivity.
7.5.5 nanoparticlEs
Nanoparticles revived old sensing materials with the perspective of nanoscale. Nanodimensional
materials are often considered as next-generation materials for sensing applications (Liu et al.
2014). Nanoparticles with diameters that range from 10 to 100 nm are considered to be nanoscale.
The nanoscale materials have a high surface-to-volume ratio when compared to bulk and provide
new properties and new opportunities. Nanoscale materials provide a unique surface, crystal fac
ets, which lead to new electronic and optical properties. Nanoscale materials include quantum
dots, nanowires, nanosheets, nanorings, nanohelixes, nanoflowers, and nanoporous materials.
Nanoparticles have many advantages such as high surface-to-volume ratio, a large surface area
to adsorb, fewer defects, and precise chemical composition. Hence, the performance of existing
compounds can be increased to the next level as well as the performance of rejected materials can
also be revived to the optimum level. Additionally, quantum dots have various handles to control
chemiresistive sensing such as size, shape, morphology, composition, and crystal structure. The
mechanism that is similar to bulk oxides is the conductivity change in the device during the analyte
binding to the quantum dots (Gurlo 2011). After binding, the analyte is ionized and charge carriers
created. The minor disadvantage of nanoscale chemiresistive sensors is irreproducible surfaces and
the surfaces generate an irreproducible electronic signal (Gurlo 2011). Nanoparticles exhibit n-type
response with the electron donating analytes and exhibiting p-type response with the electron with
drawing analytes. Liu et al. (2015a) described a PbS-based nano chemiresistive sensor for detection
of H2S gas. The sensors had an exemplary detection limit of 50 ppm and with the switching of both
p-type and n-type conduction. The chemiresistive sensors showed good sensitivity and recoverable
response during sensing. Ibañez et al. (2006) demonstrated the detection of toluene using gold
monolayers-based chemiresistive sensors. The gold nanoparticles had the advantage of the tuning
conductivity by cluster-to-cluster distance. Penza et al. (2008) studied Pd–Pt nanoclusters for the
detection of CO with the detection limit of 1 ppm. They enhanced performance of the chemiresis
tive sensor by using carbon nanotubes. The incorporation of Pd–Pt on carbon nanotubes gave better
sensitivity, reversibility, and very low limit of ppb detection.
7.5.6 Mofs
Metal organic frameworks (MOFs) are improved counterparts of metal complex materials and often
considered as alternative to zeolites. In MOFs, the metal part is called the node and ligands are
called linkers. MOFs’ unprecedented tunability, porosity, and structural diversity provided a new
perspective to metal complexes. MOFs have extensive combination possibilities for making new
materials such as organic parts, metal ions, and structural motifs. As a postsynthetic modification,
MOFs have the possibility of structural modification and tuning. The porosity of MOFs has the nat
ural ability of concentrating the gas (analyte) inside. Hence, MOFs are natural gas sensors with very
good selectivity based on structure of and size of analyte (to fit in pores). One disadvantage is that
the conductivity of MOFs suffer due to the large amount of organic contribution in their composi
tion. Additionally, the synthesis demands serious expertise from researchers, preventing scalability
and wide adoption by industries and researchers. Hence, MOF-based chemiresistive sensors are
moderately developed. The mechanism is slightly different from the conventional mechanism. In
MOFs the analyte passes through the MOFs and interact with linkers creating the analyte-induced
electrical perturbation. The change in the conductivity arises from formation of surface states by
chemisorption of oxidizing/reducing gases at the gas–solid interface. Normally, sensitivity is often
high because the analyte spends more time inside the cavity compared to other materials. As an
example, there is the cobalt-imidazolate-based metal–organic framework for sensing of trimeth
ylamine (Chen et al. 2014). Trimethylamine evolves during the decomposition of fish and is used
to identify its freshness. The concentration level of trimethylamine released from fish gradually
increases with a decrease in freshness. Hence, the degradation has a linear relation with the increase
in the concentration of trimethylamine. The peak detection of trimethylamine was at low operating
temperature (75°C) with the detection limit of 2 ppm. Mello et al. (2018) made ZIF-67 MOF for
the detection of CO2 gas sensing and provided an attractive perspective. When the MOF was used
with SnO2, the performance of the device was multiplied. The device had a response of 16.5% with
a detection limit of 5000 ppm.
7.6 SENSING PLATFORM

The scientific community used glass and silicon as a substrate for a chemiresistive sensor without
any notion of possible end uses or applications. The sensors are in every part of living and nonliv
ing system. Normally, the human body requires a conformational or curvilinear sensor for better
integration. At the same time, disposable or one-time-use sensors are required for disease detection.
Conventional platforms suffer from rigidity and nonconformity. Nowadays, electronics are moving in
the direction of wearable electronics, smartwatches, smart glasses, wearable cameras, e-textiles, and
smart packaging (packed in any space and shape) (Briand et al. 2011). Hence, the pool of substrate
should be extended to meet demand. Novel platforms include paper, textile, flexible plastic, transpar
ent plastic, and self-healing plastic. The new platforms offer folding, stretching, conformation, rolla
ble, twistable ergonomics and easy destruction (paper-burning). Kumar et al. (2015) demonstrated the
fabrication of a graphene chemiresistive sensor on a paper platform for NO2 detection with a stunning
detection limit of 300 parts per trillion. Surprisingly, the performance of the device is retained even
after making with paper. Huynh and Haick (2016) demonstrated a sh-crl-PU self-healing polymer for
the detection of hexane with the detection limit of 120 ppb. The self-healing sh-crl-PU platform can
conform and regain its original shape by itself. The healing efficiency of the polymer is very high,
and the chemiresistive sensor survived even after cutting several times at random positions. There
is some real interest among researchers to achieve a flexible chemiresistive sensor for its versatility,
and the mechanical properties are increasingly becoming a consideration for device design. The next
level challenge will be designing flexible chemiresistive sensors without losing performance.
7.7 IMPORTANT PARAMETERS

It is worth mentioning here the important parameters and key words used in the chemiresistive sen
sor research (Fennell Jr. et al. 2016).
• Limit of detection (LOD)—It is the minimum amount of analyte that can be identified by
chemiresistive sensors. It is expressed in terms of parts per million (ppm). The industrial
standard is about parts per million but in a few cases parts per trillion is also observed
(Kumar et al. 2015).
• Dynamic range—It is the range in which the minimum and maximum amount of ana
lyte can be detected by chemiresistive sensors. The standard dynamic range frequently
reported in literature is 1–100 ppm.
• Sensitivity—It is a ratio of the analyte of interest and interfering gases, e.g., analyte ethyl
alcohol can be interfered by moisture present in the atmosphere. A typical sensor should
be sensitive to the measurand and insensitive to any other analyte.
• Stability—It is defined as how much time the device can produce the same peak output.
Stability is of great importance for commercialization.
• Drift—It is the stimuli-independent change of an observed output over a period of time.
The drift in the device can generate uncertain results and false alarm during the device
operation.
• Response time—The amount of time required to achieve 90% of intensity after analyte
binding.
• Dead time—The amount of time required to reach 10% of intensity after signal observation.
• Reversibility—It is about the ability of a sensor to restore the initial state of the signal after
observation.
• Recovery time—The time taken by the device to reach the baseline before the next mea
surement of analyte.
• Selectivity—The same sensor can sense various types of chemicals. But it should be selec
tive toward a particular gas, which is called selectivity. Sensitivity without selectivity is
described as just noise. A chemiresistive sensor should respond strongly only to desired
analytes. The selectivity of chemiresistive sensor to a specific gas is necessary for the suc
cess of the sensor.
• Accuracy—It is about how exactly the chemiresistive sensor reflects the amount of analyte
present. The accuracy can be affected by preparation standards of chemicals as well as
sensors, operation conditions, and concentration of analyte.
• Linear response—This is the concentration of gases and the change in resistance expected
to be linear. The linear response helps the sensor to be easily calibrated.
7.8 SUMMARY
Chemiresistive sensors are popular among other sensing technologies due to their simplicity, selec
tivity, fast response time, and high sensitivity. Chemiresistive sensors have the potential to replace
any other type of existing sensor (e.g., capacitive). With the current knowledge of chemiresistive
sensing, all the possible directions are explored. Currently, tailoring the sensor to specific industrial
applications is being carried out by various research groups. Chemiresistive sensors are mostly
designed on a trial-and-error combinatorial basis using physics and chemistry as the interdisciplin
ary approaches. Chemiresistive sensing includes various processes such as carrier transport, chemi
cal synthesis, thin film formation, material gas–solid interaction, electrical measurements, static,
and portable packing. All the processes are intertwined and need expertise from many research
fields. Hence, serious interdisciplinary approaches considering the adsorption process, gas chem
istry, electronics, synthetic chemistry, device fabrication, mechanics and device physics should
be carried out collaboratively. The number of disciplines involved in the research and design of
chemiresistive sensors has increased drastically. The interdisciplinary approach moves the cur
rent conventional research (chasing sensitivity or new materials detection) into a new, innovative
direction. The challenge is hard but the potential of chemiresistive sensors continues to motivate
researchers. In summary, to study the chemiresistive sensor, researchers should understand the
application and end use for next-generation sensing.
7.9 CHEMIRESISTIVE GAS SENSING MATERIALS: FUTURE DIRECTIONS

Chemiresistive sensors reached the sensitivity required to commercialize as gas sensors and are
expected to become real-time sensors. The next logical directions are described as follows:
(1) The scope of sensor applications should be increased. Sensors could be used in practically
any feedback system and they are key elements in every electronic product. Hence new
avenues like robotics should be identified for better outreach. The application pool can be
extended by identifying sensing needs and targeting the required physical properties.
(2) Sensors are expected to solve growing practical problems. For example, for body integra
tion for preventive detection of diseases can be realized in flexible sensors for real-time
applications in biological, human, robotics, process control, medical, sports, and rehabili
tation fields. The sensor would conform to the skin or any curved-linear surface to inte
grate in any type of working system.
(3) Chemiresistive sensors should be stand-alone devices free from the energy source along
with a wide dynamic range. This is possible through wireless technologies and could
lead to very different applications such as one-time-use sensors for health and military
applications.
(4) From a technological point of view, sensors are central for many electronic devices and
machinery. Recent efforts have been toward taking technologies to third-world countries
like Somalia at minimal cost or almost cost free. Hence, cost-effective chemiresistive sen
sors should be developed.
(5) Sensors are normally designed to collect the data. But the future sensor design should not
only consider data collection but also data analysis and decision-making.
(6) Sensitivity of sensors should be increased above the state of the art to take advantage of
new nanoscale materials. This would create compactness and allow easy integration with
any system. By using nanoscale applications, better values can be achieved.
(7) There are a number of minor issues with existing chemiresistive sensors (e.g., poor sen
sitivity and peak performance at high temperature). By addressing the minor issues, we
should be able to achieve the ideal commercially viable product.
(8) The usable chemicals of sensors should be extended to new types of chemicals, e.g., qua
ternary compounds, carbon nano types, and MOFs.
(9) An empirical and simple theoretical approach should be developed to identify viable
chemical sensors. This unified approach could expand the chemical library, optimizations,
and be used to customize applications (such as biofriendly magnesium-based sensors for
inside the human body).
(10) For commercial viability, the chemicals should be synthesized at larger quantities. Hence,
automated synthesis for chemicals used in sensors should be developed with the required
quality and quantity.
(11) The toxicity of the chemicals used in chemiresistive sensors contaminates water, land,
animals, and plants. Hence, the materials used in these sensors should be biofriendly and
biodegradable.
(12) Challenges in the field of chemiresistive sensors are still many, and the fact that carriers
(electrons or holes) have intrinsic charge and can give large interfering signals from a vari
ety of polar and ionic species are general issues this community continues to confront.
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8 Role of Innovative Material
in Electrochemical
Glucose Sensors
R. Suresh, Claudio Sandoval, Eimmy Ramírez,
R. V. Mangalaraja, and Jorge Yáñez
CONTENTS
8.1 Introduction .......................................................................................................................... 135
8.2 Enzymatic Glucose Sensor ................................................................................................... 136
8.3 Innovative Materials as Nonenzymatic Glucose Sensors..................................................... 137
8.3.1 Metal Nanoparticles.................................................................................................. 137
8.3.2 Metal Oxides............................................................................................................. 138
8.3.3 Conducting Polymers................................................................................................ 140
8.3.4 Other Metal Compounds .......................................................................................... 140
8.4 Improving Strategy in Nonenzymatic Glucose Sensors ....................................................... 142
8.4.1 Functionalization ...................................................................................................... 142
8.4.2 Alloying .................................................................................................................... 142
8.4.3 Morphology .............................................................................................................. 144
8.4.4 Doping ...................................................................................................................... 145
8.4.5 Nanocomposites........................................................................................................ 145
8.5 Conclusions........................................................................................................................... 146
Acknowledgments.......................................................................................................................... 147
References...................................................................................................................................... 147
8.1 INTRODUCTION
D-glucose acts as an energy source in living organisms. Also, it plays a major role in metabolic
homeostasis (Wang and Lee 2015). Maintenance of the optimum glucose level in blood is necessary.
An abnormal glucose level in blood causes diabetes, a chronic health disorder affecting millions of
people worldwide (Ogurtsova et al. 2017). Diabetes is caused by malfunctioning of beta (β) cells of
the pancreas, which is responsible for production of insulin, a hormone. Insulin controls the glucose
level in the blood. A high blood glucose level can lead to blindness; heart problems; kidney failure;
and renal, cerebral, and peripheral vascular diseases in diabetic patients. To avoid these complica
tions of diabetes, the glucose level of diabetes patients must be analyzed. To achieve accurate and
rapid glucose blood sugar detection, researchers developed several glucose sensing methods.
The available glucose sensing methods are colorimetry (Kim et al 2017), chemiluminesence
(Petersson 1989), microdialysis (Tholance et al. 2011), fluorescence (Chen et al. 2018), field effect
transistors (Bhat et al. 2017), photoelectrochemical (Wang et al. 2019a), reverse iontophoresis (Liu et
al. 2011), electrochemiluminescence (Wang et al. 2019b), and near-infrared spectroscopy (Mouazen
and Walaan 2014). However, these methodologies suffer from complicated principles, matrix
interference, tedious fabrication process, high cost, and low reproducibility. On the other hand, an
electrochemical method for detection of glucose enjoys high potential due to greater sensitivity,
135
accuracy, specificity, rapidity, simplicity, low cost, easy operation, lower detection limit, real-time
detection, stability, biocompatibility, and construction for portable glucose sensing devices (Tian,
Prestgard, and Tiwari 2014). The redox property of glucose makes it possible to detect electro
chemically (Equation 8.1):
H OH H OH
H O H OH
HO HO + 2H+ + 2e
HO H HO
H
OH (8.1)
H OH OH
H OH H O
D-Glucose D-Gluconic acid

Bare working electrodes, carbon paste electrode (CPE), graphite electrode, glassy carbon elec
trode (GCE), gold (Au) disc, platinum (Pt) disc, silicon (Si) wafer, copper (Cu) foam, stainless
steel, nickel (Ni) foam, platinum–iridium (Pt-Ir) wire, indium tin oxide (ITO), F-doped tin oxide
(FTO), gold-coated glass, and B-doped diamond electrode were used to detect glucose in solution.
However, they have three major drawbacks (Bond 2012; Tian, Prestgard, and Tiwari 2014). They are
1. Poor sensitivity—Kinetics of glucose oxidation at a smooth electrode surface is too slow

resulting in poor sensitivity.
2. Poor selectivity—Interfering species are also oxidized in the potential range similar to the
oxidation of glucose, resulting in poor selectivity.
3. Electrode fouling—The electroactivity of bare electrodes is strongly affected by adsorp
tion of glucose electrooxidation intermediate compounds and chloride ions.
Hence, modification of electroactive materials on the surface of bare electrodes is mandatory. The suit
able electroactive material may be enzymes or engineered nanomaterials. Based on these materials,
modified electrodes as electrochemical glucose sensors are classified into two types. They are enzymatic
and nonenzymatic sensors. In the first category, the electrode surface is modified with glucose-sensitive
enzymes, which reduce oxygen to hydrogen peroxide. The generated hydrogen peroxide is monitored
electrochemically. In nonenzymatic sensors, the direct electrooxidation of glucose on electroactive
nanomaterials-modified bare electrode surface is measured. So far, metallic nanoparticles, metal oxides,
sulfide, selenide, tungstate, nitrides, phosphides, carbon-based materials, and conducting polymers are
widely used as the modifying layer on the bare electrodes. Each and every nanomaterial exhibits its own
advantages and disadvantages in glucose detection. To improve the sensing performances of nanomate
rials-based glucose sensors, different improving strategies have also been proposed.
In this chapter, a concise review of innovative nanomaterials as electrochemical glucose sensors
is outlined.
8.2 ENZYMATIC GLUCOSE SENSOR

In 1962, Clark and Lyons (1962) fabricated the first electrochemical sensor for the detection of glu
cose concentration. The principle of this method is based on glucose oxidase (GOx) catalyzed glu
cose oxidation, which was monitored by using an oxygen anode and platinum cathode (Equations
8.2 and 8.3):
(8.2)
Role of Innovative Material in Electrochemical Glucose Sensors 137
O2 + 4H + + 4e ® H 2O (8.3)
In 1973 (Guilbault and Lubrano 1973), amperometric determination of glucose concentration based
on hydrogen peroxide monitoring was developed (Equation 8.4):
H 2O2 ® O2 + 2H + 2e (8.4)
Apart from GOx, glucose dehydrogenase (GDH) was also used in enzyme-based electrochemi
cal glucose sensors (Iwasa et al. 2018). These enzyme-based sensors show good sensitivity and
sufficient selectivity. Nevertheless, several drawbacks of enzyme-modified electrodes (Hwang et
al. 2018) were also identified. They are (a) enzymes are much costlier; (b) the activity of enzymes
depends on the experimental condition, for example, GOx exhibits its activity in the pH range of
only 2–8; (c) enzymes have poor stability, for example, GOx will be denatured at above 40 °C;
(d) the sensitivity of enzyme-modified electrodes is severely affected by interfering species, for
instance, GDH–pyrroloquinoline quinone is affected by high concentrations of maltose or galac
tose; (e) an acute operational environmental condition is required to be maintained, for example,
GOx-based sensors are seriously influenced by unstable humidity content and hence its level should
be constantly maintained; (f) these enzymes are inefficient to transfer electrons to the electrode sur
face, however, this drawback could be eliminated by immobilizing the enzyme on suitable support
materials (Lad, Kale, and Bryaskova 2013). Nanostructured metal oxides, including TiO2, γFe2O3,
ZnO, MnO2, and ZrO2, are used as support for enzyme immobilization. Conducting polymers like
poly(sulfobetaine-3,4-ethylenedioxythiophene), and organic molecules such as benzoquinone and
ubiquinone have also been used as support for enzyme-based glucose sensors. For instance, GOx
was immobilized on graphene/chitosan composite modified GCE, which exhibits much higher sen
sitivity. The presence of graphene promotes electron transfer from the redox enzyme to the surface
of the electrode.
However, enzyme immobilization is a tedious process and thus creating doubt about the repro
ducibility of the sensor. Hence, there is a demand for the construction of enzyme-free glucose sen
sors with high sensibility, stability, and reproducibility.
8.3 INNOVATIVE MATERIALS AS NONENZYMATIC GLUCOSE SENSORS

8.3.1 MEtal nanoparticlEs
The noble metal nanoparticles such as platinum and gold have larger active surface areas and excel
lent electronic conductivity. These behaviors make them appropriate to enhance the electron trans
fer rate between the electrode surface and glucose. The glucose sensing performances of a few
nanostructured metal electrodes are given in Table 8.1. The electrochemical detection of glucose
TABLE 8.1
Glucose Sensing Performance of Some Metallic Electrodes
Linear Sensitivity Limit of
Sensor Range (mM) (mA mM−1 cm−2) detection (μM) Reference
Au 0–8 0.16 0.5 Kurniawan, Tsakova,
and Mirsky 2006
Pt 0.2–3.2 0.1377 5 Cao et al. 2007
Ni 0.05–7.35 — 2.2 Lu et al. 2013
Cu 0–4.711 2.432 0.19 Guo et al. 2015
FIGURE 8.1 Electrochemical oxidation of glucose at metallic electrode. M is metal.
by metallic electrodes is explained as follows: (a) The adsorption of glucose onto active sites of the
electrode takes place. The factors such as oxidation states and unfilled d-orbitals of metal centers
affect the adsorption of glucose. (b) The adsorbed glucose molecule undergoes oxidation and forms
gluconic acid through various reaction pathways. During electrocatalysis, the surface-bound reac
tive hydroxide species (OHads) are generated. They are also involved in the oxidation of glucose
molecules (Figure 8.1). (c) When the oxidation state of the redox center is changed, the interaction
between the glucose oxidation product and electrode weakens, leading to desorption of the product
from the electrode surface.
It is important to mention that the aforementioned model is generally assumed for noble metal
electrodes. Therefore, this mechanism is not fully applicable to numerous transition metals or metal-
oxide-based electrodes. Instead, the redox behavior of the transition metal centers can explain the
glucose oxidation on metallic electrodes.
The advantages of metal electrodes are as follows: (a) metals are free from interfering species
like ascorbic acid and uric acid, (b) they are relatively stable under detection conditions, and (c) they
have ultrahigh sensitivity. At the same time, there are some disadvantages of metal electrodes as
glucose sensors: (a) They are prone to chloride poisoning, and (b) Pt and Au electrodes are expen
sive. Even though the cost of other transition metals like Cu and Ni electrodes are less expensive,
they are unstable in neutral or acidic pH condition, (c) they have insufficient selectivity, and (d) they
are active in alkaline media, and thus cannot be used in blood samples directly.
8.3.2 MEtal oxidEs

The investigation of metal oxides as electrochemical sensors for glucose has gained considerable
attention. This is because of their redox behavior, high stability, low cost compared to noble metals,
high sensitivity, and rapid response to analytes. Various transition metal oxide nanostructures were
studied as electrochemical glucose sensors (Table 8.2). For instance, the glucose sensing behavior of
nanostructured NiO electrode has been reported (Heyser, Schrebler, and Grez 2019). At alkaline pH
conditions, the electrooxidation of glucose occurs through the Ni(OH)2/NiOOH redox couple. The
NiO converts to β-Ni(OH)2, which undergoes oxidation to form β-NiOOH. Then, glucose undergoes
oxidation by NiOOH and forms gluconolactone and Ni(OH)2 (Equations 8.5–8.7):
NiO + OH ® Ni ( OH )2 (8.5)
TABLE 8.2
Glucose Sensing Performance of Electrochemical Sensors Based on
Metal Oxide Nanostructures
Linear Sensitivity (μA Limit of
Metal Oxide Rage (mM) mM–1 cm–2) Detection (μM) Reference
CuO 0.006–2.5 431.3 0.8 Wang et al. 2009
ZnO 0.01–10 5.6 0.5 Dar et al. 2011
Fe2O3 0.015–8 726 6.0 Cao and Wang 2011
Co3O4 2.04 36.25 0.97 Ding et al. 2010
TiO2 0.01–0.2 201.5 — He et al. 2018
NiO 0.1–10 206.9 1.16 Heyser, Schrebler,
and Grez, 2019
Ag2O 0.2–3.2 — 10 Fang et al. 2009
Ni ( OH )2 ® NiOOH + e – (8.6)
NiOOH + C6H12O6 ® C6H10O6 + Ni(OH)2 (8.7)
Copper oxide is one of the most extensively studied metal oxides for electrochemical glucose sens
ing applications. The mechanism of glucose detection (Xu et al. 2015) is based on the following
reaction. In a CuO electrode, the Cu(II)/Cu(III) redox couple is responsible for glucose determina
tion (Equations 8.8 and 8.9):
Cu(II)O + H 2O + OH → Cu(III) ( OH )4 + e −
−
(8.8)
Cu(III) ( OH )4 + e − + C6H12O6 → C6H10O6 + Cu(II)O

−
(8.9)
The Co3O4-modified GCE also detects glucose concentration through the Co(III)/Co(IV) redox
couple (Equation 8.10), i.e., in an alkaline solution, Co3O4 converts as CoO2, which oxidizes glucose
into gluconolactone (Ding et al. 2010).
2CoO2 + C6H12O6 ® 2CoOOH + C6H10O6 (8.10)
Zinc oxide is also an important candidate in the field of sensors owing to its high stability, high
isoelectronic point, biocompatibility, and piezoelectric property. Unlike NiO and CuO electrodes,
the glucose sensing mechanism of ZnO electrode follows Equations 8.11–8.13 (Dar et al. 2011). This
sensor has a detection limit of 0.5 µM.
(
O2ads ( ZnO ) + 2e − ( ZnO ) ↔ 2e −ads O − /O2− ) (8.11)
Glucose + O − → Glucanolactone + 2e − (8.12)
Glucanolactone ¾Hydrolysis
¾¾¾® Glucanoic acid (8.13)
8.3.3 conducting polyMErs

Conducting polymers are promising materials in electrochemical sensors due to their excellent elec
tronic conductivity, redox behavior, tunable morphology, and easy deposition on the electrode sur
face. However, it should be mentioned that reports on pure conducting-polymer-modified electrodes
for glucose quantification are very few. In 2013, a sensor based on poly(3-aminophenylboronic
acid-co-3-octylthiophene)-modified (Figure 8.2a) GCE was reported (Nia et al. 2015) with a detec
tion limit of 0.5 mM. Moreover, this sensor was not interfered with by dopamine, uric, and ascorbic
acids.
Later, a poly(hydroxymethyl-3-4-ethylendioxythiphene) glucose sensor was developed
(Figure 8.2b). This sensor showed responses in the range of 1–9 mM with good selectivity, which is
comparable to commercial glucose sensors. The reason for the excellent sensing performance of this
sensor was attributed to the structure of the polymer, which favors activation of the hydroxyl group
and promotes oxidation of glucose molecules (Hocevar et al. 2016).
Recently (Kailasa et al. 2019), a polyaniline nanosheets-based screen-printed electrode was fab
ricated and applied for glucose monitoring with better selectivity. The glucose sensing mechanism
is shown in Equations 8.14 and 8.15:
PANI + SO 4 2 ® PANI 2+ -SO 4 2– + 2e – (8.14)
PANI 2+ -SO 4 2 + C6H12O6 ® PANI + + C6H10O6 (8.15)
8.3.4 othEr MEtal coMpounds

Apart from metals, metal oxides, and conducting polymers, various metal compounds such as metal
hydroxide, sulfide, phosphate, tungstate, hydroxide, nitride, phosphides, and tellurides have also
been used for glucose determination (Figure 8.3). For example, a β-Ni(OH)2 nanowire sensor with a
sensitivity of 60.5 A mM–1 cm–2 was reported. It showed a linear response in the range of 20 μM–0.5
mM glucose solution with a sensitivity of 60.5l A mM–1 cm–2. The mechanism of glucose oxidation
at β-Ni(OH)2 electrode is similar to Ni or NiO electrodes (Luo et al. 2012), i.e., the Ni(II)/Ni(III)
redox couple involved in the glucose oxidation.
FIGURE 8.2 Structure of (a) poly(3-aminophenylboronic acid-co-3-octylthiophene) and (b) poly

(hydroxymethyl-3-4-ethylendioxythiphene).
FIGURE 8.3 Different kinds of metal compounds used as electrochemical glucose sensors.
Metal tellurides have garnered significant attention in sensors because of their enhanced metallic
behavior, i.e., electronegativity of Te is lower than oxygen (O) atom and thus they possess a greater
metallic property. This property offers enhanced electronic transmittability. In this view, porous
nickel telluride (NiTe2) nanosheets synthesized by the hydrothermal method with excellent electro
catalytic activity toward glucose oxidation have been reported. This sensor showed good response
to glucose in solution as well as blood serum and fruit juices (Li et al. 2018).
The Ni3(PO4)2 nanoflakes synthesized by the hydrothermal method were coated on nickel foam
electrode and used as a glucose sensor (Padmanathan, Shao, and Razeeb 2018). This sensor shows
a very low detection limit of 97 nM with high sensitivity (24.39 mA mM–1 cm–2). The proposed
mechanism of glucose oxidation at Ni3(PO4)2 electrode is given by Equations 8.16 and 8.17:
-P-O-Ni-O-P-+OH − → -P-O-Ni ( OH ) -O-P- + e − (8.16)
-P-O-Ni ( OH ) -O-P- + C6H12O6 → -P-O-Ni ( OH ) -O-P- + C6H10O6 (8.17)
Binary metal sulfides are remarkable electrocatalysts due to their redox nature, a synergistic
effect between two metal centers, and easier electron transportation property. For example, the
nickel cobalt sulfide (NiCo2S4) nanoflowers, synthesized by electrochemical method, are explored
as excellent electrochemical glucose sensors in alkaline media with a detection limit of 50 nM.
The reason for observed enhanced performance is due to the redox active sites, synergistic effect
between Co4+ and Ni3+, and rapid electron transportation tuned with the substitution of sulfur
(Justice Babu et al. 2018).
Transition metal phosphides having excellent electrical conductivity and thus could perform well
as electrocatalysts. For instance, nickel phosphide (Ni2P) nanoparticles coated on carbon cloth was
fabricated and used for glucose determination in alkaline condition (Chen et al. 2016). The Ni2P
sensor showed a sensitivity of 7792 μA mM–1 cm–2 with satisfactory selectivity and reproducibility.
The CuI nanoplates, covered with teeth-like tips, showed structure-dependent sensitive detec
tion of glucose with a wide linear range (Khan et al. 2018). The glucose oxidation process at a CuI
electrode follows Equations 8.18 and 8.19. Further it was found that Cu(III) ions are the main source
for electron transfer from glucose to current collector.
Cu(I)/Cu(II) ® Cu(II)/Cu(III) + e (8.18)
Cu(II)/Cu(III) + C6H12O6 ® Cu(I)/Cu(II) + C6H10O6 (8.19)
As an example of metal nitride, copper nitride (Wang et al. 2017) also acts as a superior glucose
sensor with a sensitivity of 7600 μA mM–1 cm–2 and a detection limit of 8.9 nM.
A metal azolate framework is a kind of metal–organic framework. It also acts as a good alterna
tive for conventional metal–organic frameworks owing to its high stability and reproducibility. The
existence of hydrophobic liners offers high stability to the metal azolate framework. For instance,
(MAF-4-Co) Co(2-methylimidazole), a Co-based azolate-framework-based glucose sensor has
been reported (Equation 8.20 and 8.21). The oxidation of glucose to gluconolactone takes place via
the MAF-4-Co(II)/MAF-4-Co(III) redox couple (Lopa et al. 2019).
MAF-4-Co(II) ® MAF-4-Co(III) + e (8.20)
MAF-4-Co(III) + C6H12O6 ® MAF-4-Co(II) + C6H10O6 (8.21)
Metal tungstates have much attention as electrode materials due to their unique properties.
For example, the CoWO 4 nanospheres act as excellent glucose sensors with high sensitivity of
1416.2 μA mM –1 cm –2 (Sivakumar et al. 2016).
8.4 IMPROVING STRATEGY IN NONENZYMATIC GLUCOSE SENSORS

Unlike glucose biosensors, pure electroactive nanomaterials do not satisfactorily performed in the
detection of femto- or picomolar concentrations of glucose in solutions. Hence, to improve their
sensing performance further the following strategies have been developed.
8.4.1 functionaliZation
The glucose sensing performance of conducting polymers and carbon materials can be significantly
enhanced by the functionalization of a suitable moiety. In general, phenylboronic acid is selected for
functionalization, because boronic acid can reversibly bind with cis-1,2-diols or cis-1,3-diols to form
cyclic boronate ester. At pH > 8, boronic acid converts into boronate ester, which further improves
its affinity to diols. Therefore, boronic acid group functionalized material could act as a sensing
probe for detection of glucose. For example, pure poly(3,4-ethylenedioxythiophene) functionalized
by phenylboronic acid (Figure 8.4a) modified gold chip electrode has been used for detection of
glucose. The detection limit is found to be 50 µM (Huang et al. 2018). Similarly, N-phenylboronic
acid functionalized polypyrrole (Figure 8.4b) deposited Pt disk electrode was fabricated and was
examined for its glucose sensing property. At pH 12.0, this functionalized polypyrrole effectively
binds with glucose and thus acts as a good glucose sensor (Aytac et al. 2011).
8.4.2 alloying
The shortcomings of pure metallic electrodes as glucose sensors can be overcome by making alloy
nanostructures. The success of alloy-based sensors depends on two important factors. One is the
choice of suitable metals. Generally, Pt-based alloys are widely synthesized and used for glucose
determination (Figure 8.5). The choice of other metals in Pt alloys is based on biocompatibility,
enhancement of active sites, and durability. The 3d-transition metals such as Cu, Ni, Bi, and Cd are
FIGURE 8.4 Structures of (a) poly(3,4-ethylenedioxythiophene) functionalized by phenylboronic acid and

(b) N-phenylboronic acid functionalized polypyrrole.
FIGURE 8.5 Pt-based alloys for glucose detection.
used as counter metallic parts in Pt alloys. These Pt alloys generally afford rapid response, good
stability, and high electrocatalytic efficiency toward glucose molecules. On the other hand, the opti
mum composition of metals has also played a vital role in glucose detection. For example, Pt75Cu25
alloy is sensitive (135 μA mM–1 cm–2) and selective for glucose detection rather than Pt88Cu12 and
Pt50Cu50 alloys (Cao et al. 2013).
In addition to Pt alloys, transition-metal-based alloys are also explored as excellent glucose sen
sors. For example, Cu/Co alloy (Noh et al. 2012) electrode detects glucose efficiently, mainly due to
Co(II) ions while Cu(I) ions provide limited assistance in the glucose oxidation. On the other hand,
CuNi dentric nanostructures, synthesized by the electrochemical method also showed enhanced
glucose oxidation in alkaline conditions (Qiu et al. 2007). For more clarity, a few metal alloy elec
trodes with their glucose detection limits are given in Figure 8.6.
FIGURE 8.6 The NiFe (Bao et al. 2019), NiCo (Ranjani et al. 2015), PdCr (Zhao et al. 2014), CuCo (Noh
et al. 2012), and PdCu (Yang et al. 2017) alloy electrodes with their glucose detection limits values.
8.4.3 Morphology
It is known that the bulk material couldn’t offer excellent glucose detection due to its lack of active
centers. However, nanoparticles have larger surface area and thus will provide larger active sites
for glucose oxidation. Furthermore, electrocatalytic activity of nanomaterials also depends on their
morphology. This is because the multidimensional nanostructures may have larger surface areas,
which offer more channels for electron transfer within the nanoparticles. Also those materials are
good for accessibility of glucose molecules. For a better impression, comparisons of electrochemi
cal glucose sensing performances of CuO with various morphologies along with their synthesis
methods and working electrodes are given in Table 8.3.
TABLE 8.3
Glucose Sensing Performances of CuO with Different Morphologies
Synthesis Working Sensitivity Limit of
Morphology Method Electrode (μA mM–1 cm–2) Detection Reference
Microfibers Electrospinning FTO 2321 2.2 nm Cao, Gong 2012
Nanoflowers Template-assisted — 2217 0.96 μM Kong et al. 2018
Nanoplatelets Template-free process Cu foil 3490.7 0.50 μM Wang and Zhang 2011
Nanorods Electrochemical GCE 1523.5 1 μM Kim et al. 2019
Nanosheets Electrochemical Cu foam 33.95 mA cm–1 cm–2 330 nM Zhang et al. 2019
Nanowires Wet-chemical Cu foam 32330 20 nM Liu et al. 2017
Nanopetals Wet-chemical GCE 7546.37 0.259 μM Wang et al. 2018
Nanorose Hydrothermal Silver electrode 4.640 0.39 mM Kim, Umar, and
Hwang 2015
Nano needle Hydrothermal GCE 637 1.7 μM Ma et al. 2017
Nanodisk Microwave Carbon 627.3 0.2 μM Jagadeesan et al. 2019
Nano urchins Templated growth GCE 1634 1.97 μM Sun et al. 2013
Dandelion Electrochemical Cu foil 5368 1.2 μM Li et al. 2014
8.4.4 doping
In general, metal ion doping in semiconductor metal oxides can induce structural defects that
increase electronic conductivity. The materials with greater conductivity could exhibit enhanced
electrochemical sensing performances. Hence, metal ion doping in transition metal oxides is also
an important strategy to improve glucose sensors. For example, it was found that doping of Cu2+
ions in Co3O4 significantly improves its glucose sensing property (Harry et al. 2019). Similarly
Zn2+ ion doping in Ni(OH)2 also enhances the sensitivity, selectivity, and long-term stability toward
glucose detection (Nguyen, Bach, and Bui 2019). Also, Li+-ion doped NiO nanofibers also showed
greater glucose sensing features than pure NiO nanofibers (Luo et al. 2015). Mahmoud et al. (2019)
have reported that when compared to pure ZnO, copper-doped ZnO exhibits superior glucose sens
ing properties. The reasons for obtaining improved performances of Cu-doped ZnO are due to
high surface area, large number of available electroactive sites for glucose oxidation and greater
conductivity.
8.4.5 nanocoMpositEs
Nanocomposites have wide interest in many fields, including glucose sensors. This is due to inte
gration of desired properties by combination of various kinds of materials. The materials generally
used for making composites are metals, metal compounds, carbon-based materials, and organic
molecules with selective binding to glucose molecules. According to the number of constituent
materials, nanocomposites are classified as binary and ternary nanocomposites. In binary com
posites, two kinds of materials are coupled. Generally, binary composites will be metal–metal,
metal–metal compound, metal compound–metal compound, metal–conducting polymer, metal–
carbonaceous material, metal compound–conducting polymer, or metal compound–carbonaceous
material. It has been reported that binary compounds exhibit better sensing performances than their
constituent materials. Binary nanocomposite based electrodes with their glucose sensing perfor
mances are given in Table 8.4.
On the other hand, ternary composites are designed by coupling three different nanomaterials.
Many researchers have found that ternary-composite-based glucose sensors are pronounced due to
their relatively high conductivity, large active surface area, and fast electron transfer rate. Hence,
TABLE 8.4
Performance of Binary-Composite-Based Electrochemical Glucose Sensors
Linear Sensitivity Limit of
Composite Sensora Range (mM) (μA mM–1 cm–2) Detection (μM) Reference
Pt/Polyaniline 0.01 to 8 96.1 0.7. Zhai et al. 2013
Pd−SWNTs 0.5−17 160 0.2 ± 0.05 Meng et al. 2009
Ag–CuO 100 to 1000 μM 2528.6 1.5 Felix, Kollu, and Grace 2019
PSAC/Co3O4 — 34.2 mA mM–1 cm–2 21 nM Madhu et al. 2015
CuO-ZnO 8.00 × 10−7 to 463.7 0.126 Wu and Yin 2013
3.88 × 10−3 M
Cu–Cu2S 2 μM–8.1 mM 361.58 0.1 Zhang et al 2012
SDCNs/ Ni(OH)2 0.0001–10.22 — 28 Karikalan et al. 2016
nM
Ni2P/Graphene 5 μM to 1.4 mM — 0.44 Zhang et al. 2018
Co–CoOOH Up to 0.5 967 10.9 Lee et al. 2012
a SWNTs, single-walled nanotubes; PSAC, pongam-seed-shells-derived activated carbon; SDCNs, sulfur-doped carbon
nanoparticles.
they show good response in wide linear range, very low detection limit, and high sensitivity and
selectivity. The electrochemical activity of a few ternary-nanocomposite-based glucose sensors
with their results is given in Table 8.5.
8.5 CONCLUSIONS
Based on the necessity of glucose determination, researchers have developed many quantification
methods. Among those methods, the electrochemical method has attention worldwide due to its
simplicity, sensitivity, portability, and cost effectiveness. The advantages and disadvantages of
enzymatic and nonenzymatic electrochemical methods were discussed in this chapter. Major draw
backs of enzymatic sensors are poor stability, high cost, and stringent experimental conditions.
Hence, focus on nonenzymatic sensors has been given by researchers worldwide. Early, nonenzy
matic glucose sensors were fabricated by using nanostructured noble metals like Pt, Au, and Ag.
Then, other transition metals like Ni and Cu electrode were also utilized as sensors. A mechanism
of glucose oxidation at metallic electrodes was highlighted. Later, much effort has been given to
NiO, Cu2O/CuO, Co3O4, Fe2O3/Fe3O4, Ag2O, and RuO2. Reports on pure conducting polymer elec
trodes for glucose determination are also available. Various metal compounds like metal hydroxide,
telluride, tungstate, nitride, phosphate, and phosphide were also examined for their electrocatalytic
activity toward glucose determination. Nanomaterial-based glucose sensors offer high conductiv
ity, active surface area, selective binding ability, and easy synthesis. Hence, their glucose sens
ing performances are quite appreciable. However, these sensors also have some drawbacks such
as unsatisfactory performance in pico- or femtomolar concentration of glucose solution and the
effect of interfering species. In order to further improve performances of nanomaterials, strategies
such as functionalization, alloys, morphology tuning, and doping of metal ions have been adopted.
Furthermore, the fabrication of nanocomposites by using various metals and/or metal compounds,
conducting polymers, and carbon materials has been explored for their promising electrochemical
glucose sensing properties.
TABLE 8.5
Performance of Ternary-Composite-Based Electrochemical Glucose Sensors
Linear Range Sensitivity Detection Limit
Composite Sensora (mM) (μA mM–1 cm–2) (μM) Reference
TiO2/PAPBA–Au 0.5 and 11 66.8 mA cm mM−2 −1 9.3 Muthuchamy et al. 2018
Cu/graphene-resorcinol 0.30–30.0 μM — — Khalid, Meng, and
benzaldehyde Cao (2015)
CuO/NiO-Carbon 100 nM-4.5 mM 586.7 37 nM Archana et al. 2019
NiO/Fe3O4-SH/para-amino 0.1–10.0 μM and — 0.13 Baghayeri et al. 2018
hippuric acid 10.0–300.0 μM
Ag-CuO/rGO 0.01–28  214.37  0.76 Xu et al. 2018
NiO/CuO/PANI 20–2500 μM — 2.0 Ghanbari and Babaei 2016
Cu/Cu2O/CuO — 8726  0.39 Lin et al. 2018
Cu@Cu2O/Pd 0.00–10 1.157 mA cm−2 mM−1 742 nM Ji et al. 2017
Ni/Co/Fe3O4 1 μM–11 mM 2171 0.19 Vennila et al. 2017
PtxCo1-x/C 0.10 to 14.20 73.60 — Sheng et al. 2015
a PAPBA, poly(3-aminophenyl boronic acid); rGO, reduced graphene oxide; PANI, polyaniline
ACKNOWLEDGMENTS
The authors acknowledge the National Commission for Scientific and Technological Research
(CONICYT), Santiago, Chile, for financial assistance in the form of FONDECYT Post-Doctoral
projects Nos. 3160499 and 3190534 and CONICYT Doctoral Fellowship 21180934.
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9 Electrocatalysts for
Wastewater Treatment
Prasenjit Bhunia, Kingshuk Dutta, and M. Abdul Kader
CONTENTS
9.1 Introduction .......................................................................................................................... 153
9.2 Fundamentals of Electrocatalytic Oxidation........................................................................ 154
9.2.1 Configuration of Electrocatalytic Reactor................................................................ 155
9.2.2 Mechanism of Electrocatalytic Oxidation................................................................ 156
9.2.2.1 Direct Oxidation ........................................................................................ 158
9.2.2.2 Indirect Oxidation...................................................................................... 159
9.2.3 Categorization of Electrocatalytic Anode Material.................................................. 160
9.3 Recent Advances in Electrocatalysts for the Decontamination of Wastewater.................... 161
9.4 Superiorities and Inferiorities of Electrocatalytic Approach................................................ 163
9.5 Conclusion ............................................................................................................................ 164
References...................................................................................................................................... 164
9.1 INTRODUCTION
In recent years, pollution of the aquatic environment is a major emerging problem caused by the
discharged organic and inorganic chemicals from municipal and industrial sources (Albadarin
et al. 2017; Daneshvar et al. 2017). Especially, industries are continuously engaged with the pro
duction of enormous volumes of wastewater containing organic and inorganic contaminants, which
are extremely detrimental for the aquatic environment. The poor biodegradability of the discharged
chemicals from the industries has been demonstrated bearing a high degree of pollutants, such as
high dissolved solids, chemical oxygen demand (COD), color, and chloride content (Bisschops and
Spanjers 2003, Kim et al. 2003, Ölmez, Kabdaşlı, and Tünay 2007). Therefore, untreated industrial
effluent causes severe damage to the aquatic environment. These issues have led to a number of sci
entific studies and development of industrial techniques with increasing awareness of the potential
risk of contaminants present in industrial effluents. Generally, the decontamination techniques are
selected depending on the nature and concentration of the contaminants. Due to the extreme diverse
features of the industrial wastewater, which usually carries a complicated mixture of organic as well
as inorganic contaminants, decontamination techniques are urgently required (Woisetschläger et al.
2013; Sirés et al. 2014). After a thorough investigation, several decontamination techniques, includ
ing biological processes, adsorption, membrane processes, and chemical coagulation, have been
developed for the treatment of industrial wastewater (Dutta and De 2017a,b; Dutta and Rana 2019;
Naushad et al. 2016). However, the critical drawbacks of the aforementioned processes are expensive
chemical coagulants and adsorbents, membrane fouling, and generation of secondary pollutants,
which limit their scale-up applications (Kaur, Sangal, and Kushwaha 2015; Georgiou, Melidis, and
Aivasidis 2002; Cañizares et al. 2006; Kaur, Kushwaha, and Sangal 2018). Although the biological
processes are more favorable in terms of cost-effective, long-term treatment and environment friend
liness, the limited range of operational pH of the microorganisms with extremely toxic contaminants,
nonbiodegradability of the synthetic dyes, or reappearance of the refractory by-products are the major
153
disadvantages. Similarly, a high concentration of contaminants can be eliminated through incinera

tion and chemical oxidation, but serious emission problems and generation of toxic by-products set
them back (Sirés et al. 2014). In this regard, electrocatalytic oxidation (EO), which involves degrada
tion through the interaction of electrocatalysts and contaminants, is attracting enormous attention for
the decontamination of industrial effluents nowadays. The essence of EO as an encouraging alterna
tive technique, due to its wide application for the decontamination of effluents, was elucidated long
back in 1970s (Martínez-Huitle et al. 2015). This technique is recognized as being environmentally
benign, because of its deep involvement of very clean reagent—“the electron.” Of course, there are
other advantages related to its versatility, viz. high energy efficiency, amenability to automation, and
safety owing to its mild operation conditions (Rajeshwar, Ibanez, and Swain 1994). In practice, there
are several hurdles to be faced to attain high conversion efficiencies. Consequently, several strategies,
such as the use of suitable electrocatalysts, the promotion of turbulent regimes, preconcentration, and
use of multistage systems, need to be adopted (Rajeshwar and Ibanez 1997).
As the wastewater can either be reused for other purposes or recycled through proper manage
ment, “wastewater” can be reconsidered as “a used resource” rather than “a waste.” It should be men
tioned here that the nutrients can be recovered from wastewater electrochemically through sustainable
decontamination of detrimental chemicals or recovery of some essential chemicals (Yoshino, Cong,
and Sakakibara 2013; Lahav et al. 2013). The versatility of the EO technique has been investigated
with effluents containing several contaminants/ingredients, including dyes and dye effluents, pesti
cides and herbicides, phenolic compounds, pharmaceuticals, and personal care products (Wu, Huang,
and Lim 2014). In addition, conventional water quality parameters, such as COD, biochemical oxygen
demand (BOD), suspended solids (SS), and nutrients (nitrogen, phosphorus, and phosphate), are also
evaluated through application of the EO technique. A large number of electrocatalytic anodes, includ
ing metal oxides (MOx) such as ruthenium dioxide (RuO2) (Kim et al. 2010; Arikawa, Murakami, and
Takasu 1998; Feng and Li 2003; Ardizzone, Fregonara, and Trasatti 1990), iridium dioxide (IrO2) (Li
et al. 2009; Chen, Chen, and Yue 2001), tantalum-doped iridium dioxide (Ta-IrO2) (Ren et al. 2015);
antimony-doped tin oxide (Sb-SnO2) (Shao et al. 2014; Yang et al. 2012; Borras et al. 2007; Yang, Kim,
and Park 2014; Yang, Choi, and Park 2015), lead dioxide (PbO2) (Panizza and Cerisola 2007; Iniesta
et al. 2002) and bismuth-doped titanium oxide (Bi-TiO2) (Park, Vecitis, and Hoffmann 2008, 2009;
Park et al. 2008, 2012; Ji et al. 2009; Kim et al. 2013; Cho and Hoffmann 2014), and nonoxides such as
platinum (Pt) (Li et al. 2009; Iniesta et al. 2002), carbon (Kuramitz et al. 2002; Haque, Cho, and Kwon
2014) and boron-doped diamond (BDD) (Cañizares et al. 2002), have been examined for the electro
catalytic decontamination of wastewater (Cong et al. 2016). Mostly the metal oxides are coated on Ti
foil. Depending on the onset potential as well as the catalytic efficiency for single or multiple electron
transfer kinetics, the catalysts are segregated as either low or high oxygen evaluation potential anodes
(Panizza and Cerisola 2009). It should be noted here that the strong oxidizing intermediates, including
hydroxyl radical (∙OH) (H2O/∙OH, +2.80 V vs. SHE), ozone (O3) (O2/O3, +2.07 V vs. SHE), perox
odisulfate (S2O82−) (SO42−/S2O82−, +2.01 V vs. SHE), and chloride radical (∙Cl) (Cl−/ClO2−, +1.57 V vs.
SHE), are generally corresponded to decompose organic contaminants in electrocatalytic advance
oxidation processes (EAOPs) (Chen 2004; Martínez-Huitle and Andrade 2011). The most attractive
features of EAOPs for the treatment of wastewater are high treatment performances, accumulation of
less toxic by-products, and finally its environmentally benign technology. This chapter does not intend
to cover all the literature, but to focus on the fundamentals of EO and to demonstrate an overview
regarding the electrocatalysts employed in the technique for decontamination of wastewater, so as to
offer to the readers an easy grasp and integral view of the field.
9.2 FUNDAMENTALS OF ELECTROCATALYTIC OXIDATION

Electrochemistry has a significant role in the EO technique, and the efficiency of the electrolytic cell
depends on a number of parameters. The efficiency of the EO technology has focused on the con
figuration of the electrolytic cell through the proper modification of electrodes and electrocatalysts.
Electrocatalysts for Wastewater Treatment 155
9.2.1 configuration of ElEctrocatalytic rEactor

A conceptual configuration of an electrocatalytic reactor (Figure 9.1) for the decontamination of
wastewater through electrooxidation includes a current supply, a cathode, an anode, and the elec
trolyte (the wastewater under investigation). The representative reactions involved at the respective
electrodes are also displayed in Figure 9.1 (Cong et al. 2016; Martínez-Huitle and Andrade 2011).
More precisely, the anode/cathode couple is dipped in the supporting electrolyte, which usually is
the effluent under investigation. A direct current (DC) power supply is used to maintain a constant
cell voltage or current in between the anode/cathode couple. Therefore, the treatment of effluents
as well as the development of new techniques or the less harmful by-products through EO is often
mentioned as the process-integrated environmental protection. Generally, the EO technique deliv
ers two functions during decontamination with the aim of oxidizing the contaminants, not only to
CO2 and water (also called electrochemical combustion or mineralization) but also to biodegradable
products (Martínez-Huitle and Ferro 2006).
As the electrocatalytic reaction takes place on the electrode surfaces, the most important chal
lenge in the cell configuration is to maintain high mass transfer rates. Thus, common techniques,
such as high fluid velocity, gas purging, introduction of several types of turbulence promot
ers, and use of baffles, are applied to improve the mass transfer to the surface of the electrode.
Sonoelectrochemical processes may also be employed to assist the mass transfer (Chen 2004).
The cell should be constructed in such a way that all the components are easily accessible and
exchangeable to the electrolyte/effluent. In this regard, two types of electrodes, mainly two-
dimensional and three-dimensional, are known to exist. Obviously, the latter electrode ensures
a high value of electrode surface-to-volume ratio. Again, the electrodes can be divided into two
types, namely static and moving electrodes. Due to turbulence promotion, the latter type of elec
trode leads to improved values of the mass transport coefficient. In recent trends in reactors for
EO, the static parallel and cylindrical electrodes are designed and employed in two-dimensional
electrodes for the decontamination of wastewater. For scale-up cell designs, the parallel plate
geometry in a filter press arrangement is widely used to obtain a larger electrode size through the
use of either more electrode pairs or an increased number of stacked cells (Rajeshwar and Ibanez
1997). It should be mentioned here that during the design of the reactor, the configuration of the
FIGURE 9.1 Speculative fundamental structure of an electrocatalytic reactor with representative reactions
on the respective electrode surfaces.
cell, i.e., either divided or undivided, must be considered. Especially, in case of divided cells,
a porous diaphragm or an ion-conducting membrane must be deployed to separate the anolyte
and the catholyte. As the separators are expensive and reduce the electrode distance, the use of
divided cells should be avoided as much as possible. Besides, they encounter a host of mechanical
and corrosion problems (Wendt and Kreysa 1999). Finally, the limiting hydrodynamic behavior,
including plug flow and perfect mixing, should be considered to maintain the flow characteristics
in a reactor.
9.2.2 MEchanisM of ElEctrocatalytic oxidation

In 1990, the mechanism of oxidation of organic contaminants was first proposed by Feng and
Johnson (1990). According to their investigation, a reactive oxygenated intermediate was generated
at high potential during oxygen evaluation reaction (OER). During water discharge, the anodic oxy
gen from H2O was transferred to the organic contaminants through the adsorbed hydroxyl radicals
(∙OH) according to the following reactions:
MO x [] + H 2O ® MO x [iOH] + H + + e (9.1)
MO x [ iOH ] + R ® MO x [] + R Ox + H + + e (9.2)
where, MOx[] represents the adsorption sites on the surface of MOx electrocatalysts for the sorption
of the ∙OH intermediates and R represents the organic contaminants present in wastewater. In addi
tion to these reactions, due to the oxidation of water through OER, an undesirable and inevitable
reaction may also occur:
MO x [ iOH ] + H 2O ® MO x [] + O2 + 3H + + 3e (9.3)
However, the oxidation of organic contaminants may also take place directly on the surface of the
anode, according to the tentative indication by Feng and Johnson (1990).
In principle, the generated reactive intermediates, for instance ∙OH, adsorbed on the MOx elec
trode surfaces, are responsible for the initiation of the electrocatalytic anodic reactions. The inter
mediates are consumed through the surface reactions with the aqueous contaminants (Panizza and
Cerisola 2009; Chen 2004; Kesselman et al. 1997; Lee 2015). Also, some mobile reactive interme
diates, such as Cl2− and HOCl/OCl−, directly get produced from the supporting electrolytes, which
are responsible for the reaction in the bulk (Park, Vecitis, and Hoffmann 2008; Park et al. 2008).
Usually, high energy is consumed for the generation of these reactive species due to oxidation of
supporting ions and water via a single electron. Based on the catalytic activities of the MOxs for
single-electron and multielectron transfer kinetics as well as their onset potential, they are differ
entiated into two categories, namely low and high oxygen evolution potential (Panizza and Cerisola
2009). For instance, due to higher oxygen evolution potential of Sb-SnO2 anode compared to dimen
sionally stable anodes RuO2 and IrO2, it manifests high electrocatalytic activities toward phenol
degradation in sulfate electrolyte. This may be due to the efficient generation of surface-adsorbed
∙OH according to Reactions 9.1 and 9.2 (Kim et al. 2010). However, indistinguishable electrocata
lytic activities have been observed for RuO2 and Sb-SnO2 anodes in chloride electrolyte, due to
superficial generation of ∙Cl according to Reaction 9.4a (Kim et al. 2010). Finally, various species,
such as hypochlorous acid (HOCl), chlorine (Cl2), dichloride anions (Cl2−), and high-valent chlorine
species (ClO4−, ClO3−, and ClO2), are converted from the fugitive ∙Cl according to Reactions 9.4b
to 9.4d. Concomitantly, the molecular oxygen (O2) is usually evolved in both electrolytes, following
Reaction 9.5.
MO x [ iOH ] + Cl ® MO x [ iCl ] + OH (9.4a)
2MO x [ iCl ] ® 2MO x [] + Cl 2 (9.4b)
MO x [ iCl ] + Cl- ® MO x [] + Cl 2 (9.4c)
Cl 2 + H 2O ® HOCl + Cl + H + (9.4d)
MO x [ iOH ] ® MO x [] + ½O2 + H + + e (9.5)
Meanwhile, with the application of various anode materials (e.g., Ti/SnO2, Ti/IrO2, and Pt), the
electrocatalytic combustion and conversion of organic contaminants along with parallel oxygen
evolution were studied. Based on the generation of a considerable quantity of ∙OH at the anode
surfaces and, consequently, their reaction with the pollutants, Comninellis (1994) suggested the cor
responding inceptive mechanism of electrocatalytic oxidation. The proposed pathway was evident
through the recognition of ∙OH created by water discharge at the anodes manipulated by electron
spin resonance through spin trapping. The investigation transparently demonstrated that the SnO2
anode surface accumulates a much higher concentration of ∙OH, whereas the surfaces of the Pt
and IrO2 anodes manifest almost zero concentration. However, the surface concentration of ∙OH
intermediates is governed through the intermediate step of oxidation reaction as well as the inter
action between metal ions and oxygen. In 1996, Comninellis and Battisti reported new evidence
of electrocatalytic oxidation pathways depending on the aforementioned observation. Hence, rely
ing on the suggested pathways by Feng and Johnson (1990), Comninellis (1994), and Comninellis
and De Battisti (1996), the EO for decomposing organic contaminants approaches through two
different pathways. Firstly, the contaminants are degraded at the surface of the anode, known as
direct anodic oxidation (Figure 9.2), and, secondly, an electrochemically formed intermediary (e.g.
H2S2O8, HClO, H2O2, etc.) conducts the oxidation, called indirect oxidation (Figure 9.3). They are
elaborated in the forthcoming sections. It should be noted here that the two pathways may synchro
nize during electrooxidation of aqueous contaminants (Chiang, Chang, and Wen 1995).
FIGURE 9.2 A conceptual scheme of direct electrolytic decontamination.

FIGURE 9.3 A conceptual scheme of indirect electrolytic decontamination.
9.2.2.1 Direct Oxidation

In this pathway, either the generated chemisorbed “active oxygen” (incorporated oxygen atom in
the metal oxide crystal lattice, i.e., MOx + 1) or the physisorbed “active oxygen” (∙OH) are highly
responsible for the EO of contaminants (Martínez-Huitle and Ferro 2006; Kuhn 1971). The method
is also named “anodic oxidation” or “direct oxidation,” which propagates in two steps: (1) diffusion
of the contaminants from the bulk to the surface of the anode and (2) oxidation thereof. Practically,
the highly active electrodes, for instance, graphite, boron-doped diamond (BDD), or Ebonex, have
been effectively employed for the investigation. It is highly significant to mention here that the fun
damental model suggested by Comninellis is the clearest mechanistic pathway to express and com
prehend the electrolytic reactions through the EO approach. The simplified mechanism conceives
the characteristics of the electrode material as well as the sensibility of the ∙OH and is represented
in Scheme 9.1. The ∙OH gets generated from the discharge of H2O (or OH−) adsorbed on the MOx
anode in the first step of the mechanism, according to Reaction 9.6a:
MO x + H 2O ® MO x ( iOH ) + H + + e (9.6a)
MO x ( iOH ) ® MO x+1 + H + + e (9.6b)
The surface-adsorbed ∙OH interfere with the oxygen atom of the MOx in the second step, result
ing in a pretended higher oxide MOx + 1 as displayed in Reaction 9.6b. This may be possible when
the MOx anode contained a higher oxidation state whose standard potential is higher compared to
that of oxygen evolution. Nevertheless, both states of “active oxygen,” namely chemisorbed “active
oxygen” (MOx + 1) and physisorbed “active oxygen” (∙OH), coexist on the anode surface. Henceforth,
two scenarios may arise, namely (1) absence of oxidizable organics, which are transformed into
molecular oxygen by the physisorbed and chemisorbed “active oxygen” according to Reactions 9.6c
SCHEME 9.1 Schematic representation of the mechanism of electrocatalytic oxidation of contaminants with
concomitant evaluation of oxygen. Gradual changes are as follows: (a) generation of •OH on the catalyst sur
face, (b) reorganization of oxygen atom from •OH to the metal oxide lattice, (c and d) evaluation of molecular
oxygen due to lack of oxidizable organic contaminants in the electrolyte, (e) electrocatalytic degradation of
organic contaminants via generated •OH, and (f) electrocatalytic transformation of organic pollutants (R).
(Reproduced with permission from Comninellis 1994, © Elsevier).
and 9.6d; and (2) presence of oxidizable organics (R), in which the organic contaminants are com
pletely mineralized according to Reactions 9.6e and 9.6f.
MO x ( iOH ) ® MO x + ½O2 + H + + e (9.6c)
MO x+1 ® MO x + ½O2 (9.6d)
R + MO x ( iOH )z ® MO x + CO2 + zH + + ze (9.6e)
R + MO x+1 ® MO x + RO (9.6f)
It is clear from the reactions that most of the organic pollutants are degraded to CO2 by the ∙OH
through the transfer of generated electrons to the surface of the anode (Reaction 9.6e and Figure 9.2).
Contrarily, the RO can be formed from the organic contaminants (R) with simultaneous conversion
of the electrode into its original form MOx. Thus, the physisorbed ∙OH effectively mineralizes
the organic contaminants to CO2, H2O, and inorganic ions through electrochemical incineration
(Comninellis 1994; Comninellis and Battisti 1996), whereas, the chemisorbed “active oxygen”
selectively converts the refractory organics into biodegradable by-products (Brillas and Martínez-
Huitle 2015). However, this oxidation pathway results in very poor decontamination of pollutants.
9.2.2.2 Indirect Oxidation

In this pathway, the contaminants are decomposed in the bulk solution through the electrochemi
cal formation of a robust oxidizing agent at the surface of the anode (Anglada, Urtiaga, and Ortiz
2009). The electro-generated oxidant plays the role of a mediator, which conducts the total or partial
decontamination process (Figure 9.3). It is presumed that due to enough availability of chloride
ions in wastewater, the chlorine is the most familiar electrogenerated oxidant at the anode surface.
However, the function of active chlorine in the indirect oxidation process is not clear and is still
under investigation. Peroxodisulfuric acid (H2S2O8), hydrogen peroxide (H2O2), and ozone (O3) are
the other familiar electrogenerated oxidants. For instance, the H2O2 mediator is formed through the
indirect consumption (i.e., dimerization) of surface-adsorbed ∙OH:
2MO x ( iOH ) ® 2MO x + H 2O2 (9.7)
Alternatively, for the formation of ∙OH, metal ion catalysts, such as Ag2+, Co3+, and Fe3+, may also
be used as the external mediators. Of course, the remediation techniques are required to recover the
metallic intermediates, as they result in more toxic effluent compared to the initial one (Martínez-
Huitle and Ferro 2006).
9.2.3 catEgoriZation of ElEctrocatalytic anodE MatErial

The efficiency and selectivity of the electrocatalytic oxidation method are strictly directed by the
nature of the electrode material. In the meantime, the BDD electrode was found to be highly reac
tive toward electrooxidation of organic contaminants. The organic incineration with high current
efficiency indicated that the electrogenerated ∙OH at the surface of the BDD anode were found to
be unusually reactive compared to the other conventional electrode materials. Based on the afore
mentioned observation on BDD electrode, Comninellis (1994) suggested the conclusive mechanism.
The predictions in the model were nicely fitted with the obtained data. Depending upon the oxi
dation capability, the electrocatalysts as anode material are classified in two different categories:
active and nonactive anodes. However, in the suggested model, it is presumed that the oxidation of
H2O molecules resulting in the generation of physisorbed ∙OH, i.e., MOx(∙OH), is considered to be
the instigative reaction in both categories of anodes (Reaction 9.6a).
In the active anodes, the oxygen evolution overpotential of the electrocatalysts is low, which is
suitable for oxygen evolution reaction (OER); and as a result, they oxidize the organic contami
nants selectively. These anodes assemble with the electrogenerated ∙OH in a comparatively stron
ger way to form a higher oxide or super oxide (MOx + 1) (Reaction 9.6b). Carbon, graphite, IrO2,
RuO2, and platinum-based anodes are common examples of this category. It should be mentioned
here that the redox couple MOx + 1/MOx functions as the mediator during the oxidation of organic
contaminants (Reaction 9.6f) along with the competitive OER as a subsidiary reaction (Reaction
9.6d).
In contrast, due to the high oxygen evolution overpotential of the nonactive anodes, they are rela
tively poor electrocatalysts for OER and are expected to perform direct electrochemical oxidation.
The nonactive anode surfaces interact with ∙OH so feebly that MOx(∙OH) favors the direct reaction
with the organic contaminants to produce CO2 (Reaction 9.6e), leading to complete combustion
reactions. Only SnO2 and PbO2 are considered to be the nonactive anodes, and obviously are the
most suitable for complete electrochemical incineration reactions. Similarly, the generated surface
redox couple MOx + 1/MOx (Reaction 9.6f) by oxidative reaction is more exciting compared to the
mineralization reaction (Reaction 9.6e) via the physisorbed ∙OH. The surface-adsorbed ∙OH, i.e.,
MOx(∙OH), also competes with either the direct oxidation to O2 (Reaction 9.6d) or through dimer
ization to hydrogen peroxide (Reaction 9.7) via indirect consumption along with the mineralization
reaction. Although a nonactive electrode neither supplies any active catalytic site nor participates in
the direct anodic reaction of organic contaminants, it functions as an electron sink and an inert sub
strate. The distinctive overpotential values applying to the most extensively studied anode materials,
along with the generated typical oxidants for OER in acidic medium, are listed elsewhere in the
literature in order to gain better understanding of the performance (Martínez-Huitle and Andrade
2011). As the MOx–∙OH interaction is the governing factor for the electrochemical activity and the
chemical reactivity; the BDD anode is found to be the best nonactive electrode for the degradation
of organic contaminants (Martínez-Huitle and Andrade 2011). Thus, the oxidation pathways can be
tuned through proper selection of the anode materials.
9.3 RECENT ADVANCES IN ELECTROCATALYSTS FOR THE

DECONTAMINATION OF WASTEWATER
According to the aforementioned information, it is clear that the selectivity and the efficiency of an
electrocatalytic process for the oxidation of organic contaminants entirely depend upon the nature
of the electrocatalysts. So, in order to find a suitable electrocatalyst for the decontamination of
wastewater, a thorough literature survey will be needed. In this regard, a number of electrocatalytic
anode materials applied to various toxic contaminants are enlisted in Table 9.1. The table summa
rizes the important parameters, namely the applied electrocatalysts, the initial concentration of the
contaminants (C0), and removal efficiency (RE).
Some of the MOx anodes, for instance, PbO2, IrO2, SnO2, and RuO2, have been extensively
employed for the decontamination of a wide range of pollutants. It has been observed that for the
contaminants, such as tannin, methyl red, and 4-chloropheneol, RE of almost 100% was obtained
applying PbO2 coating on titanium substrate anode (Ti/PbO2) (Panizza and Cerisola 2004; Panizza
and Cerisola 2008; Duan, Ma, and Chang 2012). A significant enhancement in conductivity and sta
bility of the MOx electrode has been noticed after coating on titanium substrate. Concomitantly, the
generation of ∙OH on the electrode surface is responsible for the remarkable degradation of tannin:
PbO2 + H 2O ® PbO2 ( iOH ) + H + + e (9.8)
C27H 22 O 9 + PbO 2( iOH ) ® PbO2 + degraded products (9.9)
As discussed in the preceding section, the large oxygen evolution overpotential of PbO2 elec
trode enhanced the complete degradation of tannin through formation of electroactive chloride
ions. Selective electrocatalytic degradation of tetracycline in raw cow milk and oxytetracycline in
Na2SO4 and NaCl electrolyte, respectively, through the application of Ti/IrO2 anode were reported
by Kitazono et al. (2012). Also, packed-bed granular platinum anode has been demonstrated for
the phenolic compound degradation with nominal energy consumption at a high RE (Sakakibara,
Kounoike, and Kashimura 2010). Although titanium-based electrode, namely Ebonex (Ti4O7), has
been reported by Zaky and Chaplin (2014) for the removal of phenol derivatives, the RE was very
poor (~30.2%). Not only have metal or metal oxide electrodes, but also some nonmetal electrodes
have been demonstrated for the decontamination process. A thin layer of carbon nanotube (CNT)–
Prussian blue (PB) nanocomposite was employed by Nossol et al. (2013) for decontamination of
methyl orange with high RE of 96% to 98%. It is to be mentioned here that the BDD electrodes
exhibited excellent conversion efficiency of 99% and significantly higher removal performance in
chloride-free solution. This is because of the weak sorption affinity of the ∙OH toward the BDD
electrode surface, resulting in outstanding chemical reactivity for the decomposition of organic pol
lutants (Costa et al. 2010). It also exhibited complete removal of β-estradiol, oxalic/oxamic acid, and
bisphenol A in 0.05 M to 0.1 M Na2SO4 electrolyte. For the selective decontamination of toxic con
taminants, Cong, Iwaya, and Sakakibara (2014) demonstrated a granular glassy carbon electrode.
In this decontamination technique, the synthetic and natural estrogen in wastewater was eliminated
through electropolymerization. Especially, the Sb-SnO2 anode is uncommon due to its lower toxic
ity, whereas PbO2 has large oxygen evolution potential compared to RuO2 and IrO2. The BDD and Pt
electrodes are highly expensive to apply in the field. Therefore, because of the efficient generation of
∙OH on Sb-SnO2 anodes, it manifests remarkably high electrocatalytic activities for the decontami
nation of phenol derivatives in sulfate electrolyte (Niu et al. 2013). Although the Bi-TiO2 electrode is
not included in the table, it is known to be an efficient electrocatalyst in a chloride electrolyte (Ahn
et al. 2017). Based on the survey, it has been found that remarkable improvement has been achieved
through the application of mixed-metal oxides on recalcitrant pollutants in wastewater, which are
extremely hard to remove through the conventional techniques (Wu, Huang, and Lim 2014).
TABLE 9.1
Electrocatalysts for the Treatment of Wastewater
Initial concentration
Electrode Pollutant (C0) (mg L−1) RE (%) Reference
Modified Metal Oxide Electrode, Dimensionally Stable Electrode, Ti Substrate
PbO2 Textile wastewater COD: 470, PhOH: 0.11 59, 70 Mukimin, Vistanty, and
Real textile wastewater COD: 550 95 Zen 2015
4-chlorophenol 10–90 100 Aquino et al. 2014
Methyl red COD: 220 ≈100 Duan, Ma, and Chang 2012
Tannin Tannin: 1500, COD: 6000 100 Panizza and Cerisola 2008
Panizza and Cerisola 2004
IrO2 Oxytetracycline 100 83 Kitazono et al. 2012
Tetracycline 100 99.4 Miyata et al. 2011
SnO2 17-alpha-ethinylestradiol 0.5–10 96.5 Feng et al. 2010
RuO2 Tannin 1500 100 Panizza and Cerisola 2004
Real textile wastewater COD: 1156 81 Kaur, Kushwaha, and
Highly acidic wastewater COD: 6,43,000 41.83 Sangal 2017
Goyal and Srivastava 2017
SnO2-Sb Pentachlorophenol 100 99.8 Niu et al. 2013
Ru0.3Ti0.7O2 Atrazine 20 100 Malpass et al. 2006
Sn-Sb-Ni-O 4-chlorophenol 1028 100 Wang et al. 2006
RuIrO2 Real batik printing wastewater COD: 253 66.4 Mukimin et al. 2017
Other Electrode Materials
Graphite carbon Bisphenol-A 500 78.3 Govindaraj et al. 2013

Bovine serum albumin 2500 91.02 Sundarapandiyan
et al. 2010
Boron-doped Oxalic/oxamic acid 2.08 mM ≈100 Garcia-Segura and
diamond (BDD) Tannery wastewater COD: 2370 70–90 Brillas 2011
Chlorobenzene 50 94.3 Costa et al. 2010
17β-Estradiol 0.5 100 Liu et al. 2009
Bisphenol A 20 100 Yoshihara and
Murugananthan 2009
Murugananthan et al. 2007
CNT/Prussian blue Methyl orange 2.5 × 10−7 M 96–98 Nossol et al. 2013
Ebonex Ti4O7 P-substituted phenol 2.5 mM p-nitrophenol 30.2 Zaky and Chaplin 2014
Pt Chlorobenzene 50 85.2 Liu et al. 2009
17β-Estradiol, bisphenol A 0.08–0.14 96 Sakakibara et al. 2006
Reactive orange 91/red 184/ 5 × 10−4 M (each dye) 94.4 Sakalis et al. 2005
Blue 182/black 5
Glassy carbon Estrone, allylamine 0.01 mmol L−1, 10 mmol L−1 93 Cong, Iwaya, and
Sakakibara 2014;
Bardini et al. 2013
In principle, the property of the polymers has to be remarkably different from the conventional
polymers for the decontamination through electrocatalytic reduction. Accordingly, the polymers
have to be conductive enough for the passage of electrons and have a large surface area as well
as exceptional stability (Yang et al. 2014). Although the application of polymer in electrocatalytic
water treatment is limited, some conductive polymers such as polyaniline (PAni) and polypyrrole
(PPy), either functionalized or unfunctionalized, have been employed for the decontamination of
hexavalent chromium (Cr6+), bromate (BrO3−), azo dyes, etc. Because of the reversible conductiv
ity, by changing the oxidation state PAni can be transformed to be the appropriate catalyst for the
electroreduction of contaminants from water (Ruotolo, Santos-Júnior, and Gubulin 2006; Ding et al.
2010). In this regard, Ding et al. (2010) reported a PAni-film-modified electrode for the electrocata
lytic reduction of bromate ion. Accordingly, the decontamination of bromate ion was investigated
through electrochemical treatment and the BrO3− removal efficiency in 0.10 mol L−1 Na2SO4 sup
porting electrolyte was 99% at pH 7 in 25 min. In addition, a graphene-functionalized PAni was also
reported in order to improve the catalytic efficiency (Ji et al. 2015; Yang et al. 2014). Accordingly,
the Cr6+ reduction efficiency was found to be more than 99%, and graphene sheets enhanced the
effective electron transfer rate. Furthermore, Haque, Smith, and Wong (2015) explored PPy films for
the decontamination of azo dyes from textile industry effluent through electrochemical treatment.
Thus, in green technology, conducting PPy films can potentially be applied for industrial effluent
treatment.
9.4 SUPERIORITIES AND INFERIORITIES OF ELECTROCATALYTIC APPROACH

Of course, the EO technique has advantages as well as disadvantages, and both of them are elabo
rated herewith. In order to discuss the superiority of the EO approach for the treatment and avoidance
of pollution complications, it should be mentioned here that since this technique employs a clean
reagent—“the electron”—it is environmentally compatible. Simultaneously, the use of detrimental
chemicals can be avoided in the process, leading to mild operation and straightforward equip
ment. Likewise, the technique is also recognized through its versatility, cost-effectiveness, ease
of automation, and remarkable efficiency. In addition, the process can be operated through renew
able energy from solar sources and wind. A wide variety of effluents has been examined for the
decontamination of wastewater through this technique by several groups of researchers (Anglada,
Urtiaga, and Ortiz 2009). For instance, (a) urban and domestic wastewater; (b) effluents from chemi
cal factories, such as paper and pulp, petrochemical, textile, fine chemical industry, pharmaceutical,
food industry, and tannery industry; and (c) the agro-industry, namely dairy, manure, and olive oil,
have also been investigated (Anglada, Urtiaga, and Ortiz 2009). Nevertheless, the scale-up appli
cation of the technique is found to be challenging because of the operational restrictions for the
competent applicability of the EO approach exceedingly regulating the involved pathways. More
precisely, the advantages of the process can be shown by the following points:
• Controllable automation—The electrical parameters applied in the methods (particularly,

current [I] and voltage [V]) convenient for boosting data process automation, acquisition,
and control can be regulated.
• Robustness—In very short time the degradation reactions can be either restarted or termi
nated through turning off the power supply.
• Mild operation condition—As this process is operated in lower pressure and temperature
compared to nonelectrochemical techniques (e.g., super critical oxidation, incineration),
discharge of unreacted wastes and volatilization of toxic components can be overridden.
• Adaptability—A wide variety of industrial and domestic wastewater can be decontami
nated from microliters to millions of liters through this technique.
Even after having such superiorities, the EO approach also has several inferiorities. The foremost
demerits are summarized in the following:
• Extrinsic limitations—Under certain circumstances the current efficiency is low and some
electrodes are expensive and/or possess a short life span. In addition, the potential or cur
rent distribution, exhibition of unwanted reactions, influence of pH, type and concentration
of contaminants, design of the electrocatalytic reactors, and arrangement of electrodes on
the efficiency of the technique are still not completely resolved. Moreover, because of the
adherence of the by-products on the surface, electrode fouling may take place.
• Intrinsic limitations—Until now, low surface-to-volume ratio, low space–time yield, grad
ual temperature enhancement, and mass transport limitations have not been adequately
elucidated. Also, the electrical conductivity of the effluent is an unavoidable condition;
however, all waste streams are not conductive enough for the applicability of the technol
ogy. Thus, the addition of external electrolyte may complicate the process.
9.5 CONCLUSION
In this chapter, fundamental principles, recent progress, and superiorities of EO technology for
wastewater decontamination have been described for better understanding of the readers. A wide
variety of effluents can be treated efficiently through this process, manifesting its versatility. With
the remarkable advancement of material science, a wide variety of electrocatalytic electrode mate
rial, including metal, metal oxides, mixed-metal oxides, carbon, and BDD, have been developed
ensuring future suitability for the decontamination technique. Among them, superior contribution
of diamond electrodes for their capability of treating high volumes of effluent ensured the scale
up application of the EO process. Also, this process indicated its capability for decontamination
of specific pollutants in a complicated matrix. Before scale-up implementation of the process, the
principal barriers, such as evolution-stable and efficient electrocatalysts as well as operating cost
reduction, must be addressed and should be other major areas for future research. It is needless to
mention that evaluation of efficient electrocatalysts, innovative electrocatalytic reactors, and uncon
ventional design of the pilot plant will be more supportive of fruitful industrial implementation.
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10 Development and
Characterization of
A-MWCNTs/Tetra Functional
Epoxy Coatings for Corrosion
and Prevention of Mild Steel
D. Duraibabu, A. Gnanaprakasam, and S. Ananda Kumar
CONTENTS
10.1 Introduction .......................................................................................................................... 169
10.2 Experimental Details ........................................................................................................... 172
10.2.1 Synthesis of N,N,N′N″-Tetrakis(2,3-Epoxypropyl)-4,4′

(1,4-Phenylenedioxy) Dianiline ................................................................................ 172
10.2.2 Synthesis of Amine Functionalized Carbon Nanotubes (A-CNTs).......................... 172
10.2.3 Surface Preparation of the Mild Steel Specimens.................................................... 172
10.2.4 Sample Preparation................................................................................................... 173
10.3 Results and Discussion ......................................................................................................... 174
10.3.1 Thermal Properties .................................................................................................. 175
10.3.2 Electrochemical Impedance Study .......................................................................... 176
10.3.3 Morphology Studies ................................................................................................. 176
10.4 Conclusion ........................................................................................................................... 177
Bibliography .................................................................................................................................. 178
10.1 INTRODUCTION
Mild steel is low cost and can be widely used in various fields such as chemical processing, mining,
construction, production, and marine applications (Nayak and Mohana 2018; Duraibabu et al. 2014).
The main drawback is corrosion of mild steel on the metal surface, which leads to structural dam
age and decreases the chemical properties, mechanical properties, vessels, and pipelines (Kadhum
et al. 2014; Zhang et al. 2016). Moreover, mild steel is remarkably sensitive toward corrosion, such
as to diffusive chloride ions in saltwater (Manjumeena et al. 2016; Hernandez et al. 2012). In order
to overcome the issue, various methods, such as protective coatings like coating the metal substrate,
chemical vapor deposition, polymer coating, and electroplating have been developed (Deyab et al.
2016; Raotole et al. 2015). In the last decades, organic coatings are most commonly used for cor
rosion protection in metallic structures and act as a physical barrier to corrosive agents. However,
these coatings do not have long-term corrosion resistance against corrosive ions (Mohammadi et al.
2019; Sørensen et al. 2009). Current coatings research mainly focuses on long-term corrosion resis
tance performance, among them epoxy resin is one of the outstanding protective coatings in terms
169
of corrosion protection, good quality insulating properties, saltwater resistance, strong affinity and
adhesion for heterogeneous materials, great adherence to many substrates, and chemical resistance
(Wei et al. 2007; Dhanapal et al. 2015). A general structure of commercially available DGEBA
epoxy resin is shown in Figure 10.1. Epoxy coatings are osmotic to corrosive species related to
water, oxygen, and ions. The corrosion mechanism is as follows: the hydroxyl ions (OH) generate at
the cathode and increase the pH of the coating. This may reduce the adhesion properties and accel
erate corrosion of the metal underneath the coating (Ramezanzadeh and Attar 2011; Wu et al. 2014).
Consequently, the adhesion of epoxy coating properties can be improved by the incorporation of
inorganic nanoparticles such as Al2O3, ZnO, SiO2, CaCo3, TiO2, and organoclay (Afzal et al. 2013;
Behzadnasab et al. 2011). These inorganic particles display better mechanical, optical, and chemi
cal properties (Bhattacharya and Gupta 2005). Generally, the addition of inorganic nanofillers into
the polymer matrix is a challenging task due to the accumulation of inorganic fillers, which leads
to reduced coating performance (Toorani et al. 2017; Neisiany et al. 2018). At present, carbon-based
materials like carbon nanotubes (CNTs) and graphene oxide (GO) possess greater chemical stability,
thermal, electrical, and mechanical properties (Lee et al. 2017; Moitra et al. 2016). The reinforcement
of CNTs into the polymer improves the strength, thermal properties, radiation sources, electrical
properties, and corrosion protection properties. Over the past years a number of different techniques
for coatings have been developed and are summarized in Table 10.1. Moreover, CNTs are difficult to
disperse in the polymer; it could be because the high specific surface area CNTs tend to aggregate
and enhance the van der Waals π–π interactions (Park and Ruoff 2009; Tasis et al. 2006). The surface
functionalization of CNTs can be avoided with the disaggregation of the polymer in a homogeneous
coating. Kumar et al. (2017) studied the homogeneous cluster-free dispersion of carbon nanotubes
in the polymer matrix. The authors reported a systematic method to achieve a better dispersion in
multiwalled carbon nanotubes (MWCNTs) in epoxy by implementing ultrasonic waves and generat
ing shear force in the flow of axial impeller. Field emission scanning electron microscopy (FESEM)
results showed that cluster-free uniform dispersion of MWCNTs in the epoxy matrix can lead to the
enhancement of toughness by 53%, tensile strength by 35%, and storage modulus by 35% by loading
of 0.75 wt% of MWCNTs in epoxy. Likewise, Kumar et al. (2018) analyzed the properties of mechan
ical and anticorrosion in epoxy MWCNT/TiO2 hybrid nanofiller toward the high-performance epoxy
composite using transmission electron microscopy (TEM). The results of the MWCNT/TiO2 hybrid
epoxy nanocomposite exhibited greater mechanical performance and anticorrosion than the nano
composites. The tensile storage modulus and tensile strength of epoxy increased up to 43% and 61%,
respectively, by implementing MWCNT/TiO2 hybrid nanofiller. Additionally, from these studies, the
corrosion rate decreased to 2.5 × 10 –3 MPY and 0.87 × 10 –3 MPY from 16.81 MPY (Kumar et al.
2018) and the protection efficiency increased to 99.99% by a process of coated MWCNT/TiO2 hybrid
epoxy nanocomposite on mild steel. Enhancement of the epoxy adhesion observed between the steel
plates by treatment method and CNT/short-fiber reinforcement was studied by Wang et al. (2016).
The shear strength of the epoxy adhesive improved 50% using the treatment method. The results
further observed enhanced shear strength by incorporating MWCNTs and short Kevlar fibers into
the adhesive joints, the reinforcing mechanisms along with the interfacial zone, and the toughening
mechanisms within the composite adhesive joints. Yeole et al. (2016) analyzed the corrosion protec
tion of prone metals like iron and aluminum. These metals are utilized for anticorrosive coatings for
a large number of applications. Nanocontainers have the capability of encapsulating large amounts
of guest molecules to aid in the self-healing abilities of the coating to provide active protection. The
process involves the deposition of the CNT layer-by-layer process, inhibitor, and polyelectrolytes
to enhance the corrosion protection on mild steel (MS) plates. The surface charge, thickness of the
FIGURE 10.1 Chemical structure of epoxy (DGEBA) resin.

A-MWCNT Epoxy Coatings 171
TABLE 10.1
Summary of Various Coating Systems Used for Anticorrosive Applications
Resin Technique Used Application Reference
Epoxy resin Spin coating Corrosion resistance Nayak and Mohana 2018
DGEBA epoxy resin Solution process Corrosion resistance Kadhum et al. 2014
(Epon 1001)
DGEBA epoxy resin Bar-coater Anticorrosion and Manjumeena et al. 2016
(GY250) antimicrobial
Epoxy resin Film applicator coating Anticorrosion Mohammadi et al. 2019
(Epon Shell 1001)
Epoxy resin Spray coating Anticorrosion Kumar et al. 2017
(Cam coat 2071)
Fusion bonded epoxy Electrostatic spraying coating Anticorrosion Ramezanzadeh et al. 2019
(FBE)
NANYA epoxy resin Brushing coating Corrosion resistance Hosseini and Aboutalebi 2019
(NPEL-127)
Epoxy resin Film applicator coating Anticorrosion Yeganeha et al. 2019
(Shell)
Epoxy resin Spray coating Anticorrosion Lou et al. 2019
(E-51)
Epoxy resin Film applicator Anticorrosion Ramezanzadeh et al. 2019
(EPONTM 828)
Epoxy resin Film applicator Anticorrosion Yeganeh et al. 2019
(1001)
Epoxy ester resin Film applicator Corrosion resistant Sanaei et al 2018
(EE-430CS)
DGEBA epoxy resin Doctor blade film applicator Anticorrosion Kabeb et al. 2019
(BE-188)
DGEBA epoxy resin Dip coating Anticorrosion Pour et al. 2018
(Epiran 6)
Epoxy resin Spray coating Anticorrosion Sambyal et al. 2018
Epoxy ester resin Film applicator Anticorrosion Sanaei et al 2017
(EE-430CS)
DGEBA epoxy resin Bar-coater Anticorrosion and antifouling Palanivelu et al 2017
(GY250)
Epoxy resin Air spray Anticorrosion Wang et al. 2015
(AR555)
Epoxy resin Film applicator Anticorrosion Majd et al. 2019
(GZ 7071)
Epoxy resin Bar-coater Anticorrosion Qiu et al 2017
(E44)
Epoxy resin Dip coating Anticorrosion Khodair et al. 2018
Epoxy resin Film applicator Anticorrosion Vakili et al. 2015
(GZ 7071)
Silicone-epoxy resin Air spray Anticorrosion Yuan et al. 2015
(SILIKOPON EF)
layer, and functional groups on each layer were determined using various analytical techniques such
as particle size distribution, Fourier transform infrared (FTIR) spectroscopy, zeta potential analysis,
and X-ray diffractograms analyses of CNT. These modified CNT techniques were performed to
examine the crystallographic properties. From the results, Yeole et al. (2016) concluded that mor
phology and particle size clearly indicate the development of a nanocontainer. Further, the corrosion
rate analysis of nanocontainer epoxy coatings on MS panels was measured by DC polarization and
salt spray. In addition to that, the corrosion resistance measured the immersion of the coated samples
into the alkali solution.
In this work, a TGBAPB epoxy resin with an ether linkage through the intermediates 1,4′-bis(4
nitrophenoxy) benzene BHPB and 1,4′-bis(4-aminephenoxy)-benzene BAPB was developed. The
intermediates and TGBAPB epoxy resin were characterized by means of FTIR and nuclear mag
netic resonance (NMR) spectroscopic studies. The TGBAPB epoxy resin was coated in sandblasted
mild steel specimens using a room temperature curing agent HY 951 in the presence and in the
absence of an amine functionalized carbon nanotube (A-MWCNTs) to a thickness of 100 microns
by brush. The anticorrosive behavior of these coated specimens was examined by electrochemical
impedance studies (EIS) and the results are discussed in the following.
10.2 EXPERIMENTAL DETAILS

10.2.1 synthEsis of n,n,n′n″-tEtrakis(2,3-Epoxypropyl)-4,4′
(1,4-phEnylEnEdioxy) dianilinE
The ether linked tetrafunctional epoxy resin, N,N,N′N″-tetrakis(2,3-epoxypropyl)-4,4′-(1,4-pheny
lenedioxy) dianiline, was analyzed from 4,4′-(1,4-phenylenedioxy) dianiline according to the
method reported in the literature (Duraibabu et al. 2014) (Figure 10.2).
10.2.2 synthEsis of aMinE functionaliZEd carBon nanotuBEs (a-cnts)

A-MWCNTs were formed via acid functionalized MWCNTs. MWCNTs were treated with a mix
ture of 3:1 (concentrated sulfuric and nitric acid) by stirring at temperature of 40°C for 4 hours.
The amine MWCNTs mixture was filtered and washed with deionized water. Further, the acid-
MWCNTs were dried at 100°C for 12 hours in a vacuum oven. Furthermore, the 1 gram of acid-
MWCNTs was dispersed in ethyl alcohol solvent using an ultrasonic generator for 10 minutes. Also,
0.2 grams of dodecylamine solution was added into the amine MWCNTs mixture, and the reaction
was carried out at 80°C for 24 hours. Then the residue of reaction output was washed with ethanol
solvent to remove unreacted organic compounds. The amine functionalized carbon nanotubes were
dried at 100°C for 12 hours in a vacuum oven (Jin et al. 2011) (Scheme 10.1).
10.2.3 surfacE prEparation of thE Mild stEEl spEciMEns

Mild steel specimens (Si-0.01%; C-0.04%; P-0.002%; Mn-0.17%; S-0.005%; Mo-0.03%; Ni-1.31%;
Cr-0.04%; Fe-balance) were used for our study. The specimens were degreased with acetone to
remove stain from the steel substrate and to condition before use (Saravanan et al. 2018).
FIGURE 10.2 Preparation of TGBAPB epoxy resin.

SCHEME 10.1 Surface functionalization of multiwalled carbon nanotubes (A-MWCNTs).
10.2.4 saMplE prEparation

The TGBAPB epoxy resin was mixed individually with MWCNTs and A-MWCNTs at a tempera
ture of 80°C for l hour and further ultrasonic analysis for 30 minutes. After that, the stoichiometric
amount of curing agent was added to HY951 at room temperature (Table 10.2). Then the formula
tion was applied on the mild steel with the range of thickness of about 100 m using a bar coater
technique (Figure 10.3 and Figure 10.4).
TABLE 10.2
Composition of Neat TGBAPB and TGBAPB/MWCNTs/A-MWCNTs
Epoxy Coatings
Coating System TGBAPB/%MWCNTs/%A-MWCNTs Room Temperature Curing Agent
a 100/0/0 HY951
b 100/0.5/0 HY951
c 100/0/0.5 HY951
FIGURE 10.3 Schematic diagram of the preparation of TGBAPB/A-MWCNTs epoxy coating.
FIGURE 10.4 TGBAPB epoxy and TGBAPB/A-MWCNTs epoxy coating system cured by HY951.
10.3 RESULTS AND DISCUSSION

The FT-IR spectrum of TGBAPB epoxy resin is presented in Figure 10.5a. The band at 913 cm–1
appears due to the presence of an oxirane ring. The appearance of bands at 2969 cm –1, 1506 cm–1,
and 1612 cm–1 corresponds to the aromatic rings of TGBAPB epoxy resin and 1372 cm–1 is due to
the C-N stretching of TGBAPB epoxy resin. After curing (HY951) with TGBAPB, epoxy resin
shows the appearance of the peak at 3449 cm–1 and disappearance of oxirane rings at 912 cm–1,
as presented in Figure 10.5b. In the 1HNMR spectrum of TGBAPB epoxy resin the chemical shift
values obtained are assigned according to the protons of their environment; δ = 6.5–7.0 ppm. This
may be due to the presence of aromatic protons (Figure 10.6). The remaining oxirane and methylene
(a)
2969
1662
1372
913
% Transmittance
(b)
1506
3449
4000 3500 3000 2500 2000 1500 1000 500

–1
Wave number (cm )
FIGURE 10.5 FT-IR spectra of (a) TGBAPB epoxy resin and (b) TGBAPB/A-MWCNTs epoxy resin cured
with HY951.
FIGURE 10.6 1HNMR spectrum of TGBAPB epoxy resin. (From Duraibabu 2014 with permission.)
protons adjacent to the oxirane ring appear at around δ = 2.8–3.8 ppm, as illustrated in Figure 10.6.
The 13CNMR spectrum of TGBAPB is presented in Figure 10.7. The appearance of signals at 46
ppm and 49.5 ppm was assigned due to the presence of –OCH2 and –CH–, respectively, of TGBAPB
epoxy resin (Duraibabu et al. 2014). The signal at 60 ppm may be due to the presence of –N–CH2
carbon. The remaining signals that appear at around 116–153 ppm may be due to the aromatic car
bon of TGBAPB (Duraibabu et al. 2014).
10.3.1 thErMal propErtiEs

The samples TGBAPB/MWCNTs, TGBAPB/A-MWCNTs, and neat TGBAPB were thermal ana
lyzed by thermogravimetric analysis (TGA). Figure 10.8 shows that the epoxy system c (TGBAPB/
A-MWCNTs) indicates the enhancement of thermal stability other than systems a (TGBAPB/
MWCNTs) and b (TGBAPB). The improvement of thermal stability of system c is attributed to the
FIGURE 10.7 13 CNMR spectrum of TGBAPB epoxy resin. (From Duraibabu 2014 with permission.)
100 a
b
c
80
Weight (%)
60
40
20
0
100 200 300 400 500 600 700 800
Temperature (°C)
FIGURE 10.8 TGA of neat TGBAPB, TGBAPB/MWCNTs, and TGBAPB/A-MWCNTs.

uniform dispersion of A-MWCNTs with the TGBAPB epoxy matrix as well as the covalent bond
between TGBAPAB epoxy/A-MWCNTs (Pourhashem et al. 2017; Dhanapal et al. 2018). In this
case system b showed fewer thermal properties when compared to neat TGBAPB epoxy (system a).
This may be due to the agglomeration of the MWNCTs inside the polymer matrix to reduce the
thermal properties (Duraibabu et al. 2016, 2014).
10.3.2 ElEctrochEMical iMpEdancE study

The Bode plots for neat TGBAPB, TGBAPB/MWCNTs, and TGBAPB epoxy reinforced with
A-MWCNTs coating systems are depicted in Figure 10.9. The obtained values of the impedance of
this coating system are between 105 and 106 ohm·cm2. It is interesting to note that the A-MWCNTs
reinforced TGBAPB epoxy coated system c specimens exhibited higher impedance values than the
TGBAPB/MWCNTs (system b) and neat TGBAPB epoxy (system a) immersion in 3.5 wt.% NaCl
solution for 7 days. This may be due to the nanostructured A-MWCNTs cross-linking between
TGBAPB epoxy, and strong interfacial interaction exhibits stable corrosion resistance of the metal
substrates (Zhou et al. 2019). TGBAPB/MWCNTs (system b) coatings show less corrosion resis
tance compared to the neat TGBAPB epoxy system a. This might be due to MWCNT particles
coming close to one another and giving rise to an appreciable decrease in impedance value. A
similar observation was made by Nayak et al. (2015) for CNT-poly sulfone nanocomposites coatings
(Manjumeena et al. 2016; Saravanan et al. 2016).
10.3.3 Morphology studiEs

The surface morphology of neat TGBAPB, TGBAPB/MWCNTs, and TGBAPB/A-MWCNTs coat
ings specimens were determined by SEM and illustrated in Figure 10.10. Figure 10.10a indicates
that the smooth surface morphology was observed in the neat TGBAPB epoxy matrix (system a).
However, the addition of nonfunctionalized MWCNTs (system b) and functionalized A-MWCNTs
(system c) showed surface roughness increases. We observe that system c (TGBAPB/A-MWCNTs)
exhibits excellent adhesion due to chemical bonding between A-MWCNTs and the TGBAPB epoxy
resin (Yoonessi et al. 2014), as presented in Figure 10.10b. This confirms that the improvement of
corrosion properties among the nonfunctionalized MWCNTs exhibited less impedance value due
TGBAPB
TGBAPB/MWCNTs
106 TGBAPB/A-MWCNTs
log (Z/ohm2)
105
104
103 104 105

log (Freq/HZ)
FIGURE 10.9 EIS Nyquist plot of neat TGBAPB, TGBAPB/MWCNTs, and TGBAPB/A-MWCNTs coated
samples immersed in 3.5 wt.% NaCl solution for 7 days.
FIGURE 10.10 SEM image of systems (a) neat TGBAPB, (b) TGBAPB/MWCNTs, and (c) TGBAPB/
A-MWCNTS epoxy coatings.
to poor dispersion of the MWCNTs within the TGBAPB epoxy matrix (Kim et al. 2016), as shown
in Figure 10.10c.
10.4 CONCLUSION
Modified TGBAPB epoxy coating for corrosion was developed using the linkage of the interme
diates 1,4′-bis(4-nitrophenoxy) benzene BHPB and 1,4′-bis(4-aminephenoxy)-benzene BAPB. The
intermediates and TGBAPB epoxy resin were characterized by means of FTIR and NMR spec
troscopic studies. The synthesized TGBAPB epoxy resin was coated on sandblasted mild steel
specimens using the room temperature curing agent HY 951 in the presence and in the absence of
an A-MWCNTs to a thickness of 100 microns by brush. The anticorrosive behavior of such coated
specimens was evaluated by electrochemical impedance studies (EIS). It was interesting to note that
the A-MWCNTs reinforced with TGBAPB epoxy coated specimens exhibited tremendous corro
sion properties when compared to MWCNTs/TGBAPB and neat TGBAPB epoxy coatings, repre
senting the good dispersion and better compatibility of A-MWCNTs with TGBAPB epoxy matrix.
The nonfunctionalized MWCNTs/TGBAPB epoxy coating system displayed lesser impedance
value than the neat TGBAPB epoxy coating system. This might be due to the continuous conduct
ing network of nanocomposites coating just starting to form with many MWCNTs particles coming
close to each other giving rise to an appreciable decrease in impedance indicating a conducting
behavior of MWCNTs/TGBAPB epoxy coating. Thus, we concluded that the development of amine
functionalized MWCNTs reinforced with TGBAPB epoxy coatings can be used for applications of
corrosion protection of mild steel substrate for enhancement of longevity performance other than
coatings systems in present usage.
ACKNOWLEDGMENTS
The authors thank facilities for operating of instruments provided by the Department of Chemistry,
Anna University, Chennai, under the projects FIST-DST and DRS-UGC.
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11 Electrochemical Oxidation
Reaction for the Treatment
of Textile Dyes
Eswaran Prabakaran and Kriveshini Pillay
CONTENTS
11.1 Introduction .......................................................................................................................... 181
11.2 Advantages of EAOP Anodes............................................................................................... 183
11.3 Types of Electrochemical Advanced Oxidation Methods .................................................... 184
11.3.1 EAOPs by Direct Method ......................................................................................... 184
11.3.2 EAOPs by Indirect Method ...................................................................................... 185
11.4 EAOPs of Textile Dyes from Wastewater............................................................................. 186
11.4.1 Electrochemical Advanced Oxidation of Methylene Blue Dye................................ 186
11.4.2 Electrochemical Advanced Oxidation of Rhodamine B Dye .................................. 188
11.4.3 Electrochemical Advanced Oxidation of Congo Red............................................... 188
11.4.4 Electrochemical Advanced Oxidation of Indigo Carmine Dye ............................... 188
11.4.5 Electrochemical Advanced Oxidation of Yellow 3 (DY3) Dye................................ 189
11.4.6 Electrochemical Advanced Oxidation of Acid Blue 113 Dye .................................. 189
11.4.7 Electrochemical Advanced Oxidation of Triphenylmethane Dye............................ 189
11.5 Conclusion ............................................................................................................................ 190
References...................................................................................................................................... 190
11.1 INTRODUCTION
Textile dyes have been used in dyeing and converting fibers into commercial substances. These pro
cesses include the dyeing of both manmade and natural fibers to produce permanent coloration for
the textile production industry. This coloration process has resulted in a massive amount of colored
wastewater with excessive pH, COD, and high temperature (Pathania et al. 2016). The color in the
wastewater cannot be easily removed and requires some energy-intensive techniques (Sharma et al.
2015). The specific conventional techniques that have been used for the treatment of fabric dyes
include biological (Paprowicz and Slodczyk 1988), adsorption (McKay 1980), coagulation (Hicham
et al. 2019), and ozonation techniques (Lin and Lin 1992). These methods have, however, demon
strated drawbacks such as low efficiency and high cost, and additionally have not been employed for
fabric dye remediation because of recalcitrant to biodegradation. The disadvantage of the adsorp
tion technique is that the adsorbent cannot be regenerated and excessive costs arise depending on
the type of adsorbent used. The other chemical strategies that have been employed have also gener
ated a lot of sludge and these are difficult to eliminate.
Textile dyes contain a whole lot of chemical compounds and therefore it is difficult to isolate and
remove the dyes and additionally these methods are not suitable (Anastasios et al. 2005). Consequently,
low cost and environmentally friendly strategies are required for the removal of fabric dyes. Superior
oxidation methods have been used for the removal of fabric dyes. These include electrochemical
181
methods, ozonation, wet oxidation, and photocatalytic oxidation. Among these, electrochemical pro
cesses have exhibited greater oxidation of textile dyes because of their lower cost and less time
consumption, and these are also less problematic to use (Lorimer et al. 2001). The electrochemical
technique is a critical analytical technique that has been used to detect poisonous pollutants, which
include inorganic and organic pollutants commonly contained in wastewater (Rajeshwar et al. 1994;
Rao and Venkatarangaiah 2014; Martınez-Huitle et al. 2015). These exclusive electrochemical meth
ods have been used to degrade toxic pollutants by electrocoagulation, electrodialysis, electroreduc
tion, electroflotation, and electrochemical oxidation with energetic oxidation. These strategies have
additionally included the electro-Fenton, photoelectro-Fenton, solar photoelectro-Fenton, and solar
photoelectrocatalysis processes (Brillas et al. 2015). Electrochemical advanced oxidation processes
(EAOPs) have been used for the degradation and removal of textile dyes from wastewater, as shown
in Figure 11.1. In recent times, electrochemical anodic oxidation has been used for the elimination of
fabric dyes and has manifested itself as a one of a kind methodology.
Electrochemical advance oxidation processes have been implemented for efficient anodic oxi
dation of textile dyes (Moreira et al. 2017). This method has the distinct advantage of not requir
ing any chemical reagents as the oxidizing agent is provided on the anodic electrode surface. The
oxidizing agents are hydroxyl radicals, which are generated by the usage of water molecules at the
anodic electrode. The hydroxyl radical is an incredible oxidizing agent for fabric dye remediation
from wastewater (Buxton et al.1988). These hydroxyl radicals are also produced from H2O2 dur
ing EAOPs. This reaction takes place on the anodic surface. This anode therefore generates a lot
of oxidizing agents and these are used for the treatment of textile dyes from contaminated water
(Cañizares et al. 2009; Lan et al. 2017; Barazesh et al. 2018; Jasper et al. 2016; Martinez-Huitle et al.
2005). The ·OH radical is reacted with chlorine Cl2 and S2O82− to give sulfate radicals (SO4·−) and
perchlorate (ClOH·−) radicals as shown in Figure 11.2. S2O8, H2O2, and Cl2 were used as oxidizing
agents for the treatment of disinfectants in wastewater and they had been applied in aquifer remedi
ation (Tsitonaki et al. 2010). S2O82− has been explored at a standard oxidation potential of E0 = 2.01 V
and H2O2 at E0 = 1.8 V and Cl2 at E0 = 1.48 V. Among them S2O82− has demonstrated extraordinary
potential as an oxidizing agent for the treatment of wastewater and as a disinfectant against bacte
rial action (Polcaro et al. 2007). The Cl·, ClOH2·, and SO42·− radicals have been proven to be high-
quality oxidants for the treatment of toxic pollutants from wastewater samples and by virtue of their
immediate electron transfer to pollutants within the water samples. The pollutants in wastewater
became directly carried out by the ·OH radicals and additional oxidants are applied to degrade the
organic textile dyes with EAOPs. However, these do not completely degrade the textile dyes and
FIGURE 11.1 Different types of EAOPs employed for the removal of organic textile dyes.
Electrochemical Oxidation for the Treatment of Textile Dyes 183
FIGURE 11.2 Mechanism of oxidant generation.
need additional anodic electrode materials for the oxidation of textile pollutants with EAOP anodes
(Carter et al. 2008; Zhuo et al. 2012; Zhuo et al. 2011).
11.2 ADVANTAGES OF EAOP ANODES

The electrochemical cell containing an anode and a cathode has been used for the electrochemical
remediation of textile dyes from wastewater samples. Both anodes and cathodes have been sepa
rated via the usage of a membrane within the electrochemical cell, which maintains the flow of liq
uids within both compartments as shown in Figure 11.3. Therefore, the current response measures
the flow of charge in the electrochemical cell while the ions are shifting among the membrane sepa
rators. The ion exchange membranes that are generally used as separators inside the electrochemical
FIGURE 11.3 General setup of EAOPs.

cells include Nafion and fluoropolymer. In these, the membrane was extensively explored in both
acidic and alkali environments with excellent selectivity of H+ ions. Despite this fact, these types
of membranes are not used within electrochemical cells for the electrochemical treatment of textile
dyes from wastewater because of excessive cost, effortless fouling, high electricity intake, exces
sive maintenance, and a reduction in overall performance (Sala et al. 2014). This results in the
oxidation of textile dyes in wastewater without any problems provided that the samples are on the
surface of the electrode, and the cathode is not affecting the anodic procedures. Electrochemical
oxidation tactics have been carried out for the remediation of textile dyes in wastewater samples.
This method can be utilized at a regular temperature. Other advantages presented by this method
include the fact that the materials used to fabricate the electrode have a long-term lifespan and have
a high resistance to acidic and basic media. The substances that constitute the anodic electrode in
the electrochemical oxidation of textile dyes have shown improved remediation of dyes (Guo et al.
2016; Yoon et al. 2013). Oppositely charged materials were used in order to constitute the anode for
the EAOPS inside the electrochemical mobile systems.
11.3 TYPES OF ELECTROCHEMICAL ADVANCED OXIDATION METHODS

A lot of these methods have been applied for the treatment of textile dyes from contaminated water
and they have also shown some disadvantages. These processes are dependent on physical, chemical,
and biological techniques. These methods also demonstrate different demerits due to the improper
discharge of waste textile dye into the environment. In this sense, the problems posed include sludge
formation, adsorbent problems, and complex dye formation. The complete mineralization of textile
dyes results in the formation of carbon dioxide, water, and other products with photocatalytic pro
cesses. Advance oxidation processes (AOPs) have demonstrated better degradation of textile dyes
from wastewater due to using powerful oxidants such as −·OH, F−, HO2, and H2O2, and these radicals
have resulted in complete mineralization of the textile dyes from wastewater samples (Oturan et al.
2014; Sires et al. 2014). EAOPs were therefore used to complete the mineralization of organic tex
tile dye pollutants by creating the hydroxyl radicals inside the supporting electrolyte. Two types of
advanced oxidation procedures, namely direct EAOPs and indirect EAOPs have been explored. In
direct EAOPs, hydroxyl radicals are produced inside the electrolyte system at the anode floor with
direct techniques. This hydroxyl radical is produced at the anode surface, which is dependent on the
anode substances, the active site of anode substances, and current density. This method has therefore
eliminated the need for external reagents for the creation of ·OH radicals (Panizza and Cerisola 2009;
Miled et al. 2010). However, the oblique technique of EAOPs has required external reagents for the
production of hydroxyl radicals together with electro-Fenton, H2O2, and ferrous iron (Fered-Fenton).
Hydrogen peroxide is used to produce cathode floor materials. The cathode surface then creates the
hydroxyl radical electrolytically with H2O2 as an external reagent, and more hydroxyl radicals are
also produced at the anode surface with ferrous iron as an external reagent (Brillas et al. 2009). The
indirect EAOP method generates hydroxyl radicals at the cathode floor and produces H2O2 radicals
and ferrous ions electrocatalytically. The EAOP is therefore an electrochemical method that offers
the advantages of flexible nature, high removal performance, operational protection, and automation
(Peralta-Hernandez et al. 2009; Jüttner et al. 2000; Anglada et al. 2009).
11.3.1 Eaops By dirEct MEthod

This EAOPs method generates the hydroxyl radicals at the anode surface of materials in electro
chemical systems without any external chemical reagents. This system also removes textile dyes
from wastewater at the anodic surface. This direct electrochemical advanced oxidation method
is therefore an important technique for generating the oxidants of hydroxyl radicals at the anode
surface (Panizza and Cerisola 2009). The hydroxyl radicals are coated on the surface of the anode
and these are actually chemisorbed on platinum (Pt) and Ti/RuO2-IrO2 DSA anodes. The formation
of these types of anodes leads to the demand for the production of hydroxyl radicals. The oxy
gen evolution and hydroxyl radical formation anodes are known as boron-doped diamond (BDD).
This anode is referred to as a thin film anode and it produces the hydroxyl radicals for the oxida
tion of textile dyes. The AO method results in the degradation of textile dyes at anodes surface
(Comninellis 1994; Scialdone 2009). Two types of organic textile dyes have been degraded by using
the AO method. The electrochemical conversion is conducted by degrading the persistent textile
dyes into biodegradable by-products such as short-chain carboxylic acids, electrochemical combus
tion and incineration (Comninellis and De Battisti 1996). AO method is defined as the direct EAOPs
in which the degradation of the organic pollutants occurs mainly by the adsorbed hydroxyl radicals
produced by water oxidation in the presence of high O2 overvoltage anodes. The organic pollutant
degradation mechanism of AO process is shown in Figure 11.4.
11.3.2 Eaops By indirEct MEthod

The manufacturing of hydroxyl radicals is accomplished with the addition of external chemicals for
degrading the organic textile pollutants. Chlorine and hypochlorite ions have been used to degrade
textile pollutants in the water medium, which may be generated by the anodic surface electrode as
shown in Figure 11.5. Those processes are suitable for the electrochemical oxidation of inorganic
FIGURE 11.4 Electrochemical advance oxidation method with direct processes.
FIGURE 11.5 Electrochemical advance oxidation method with indirect processes.

and organic pollutants from wastewater samples (Hicham et al. 2019; He et al. 2016; Ines et al. 2014;
Jalife-Jacobo et al. 2016). In this process the chlorine salts of sodium chloride and potassium chlo
ride are brought into contact with organic and inorganic wastewater for good conductivity and the
production of hypochlorite ions at the anodic surface. At the anodic surface chloride ions are also
created and these form chlorine as shown in Figure 11.6.
11.4 EAOPS OF TEXTILE DYES FROM WASTEWATER

EAOPs had been conducted on different textile dyes with different anode substances because effec
tive oxidizing agents were produced, and these include chlorine, oxygen, hydroxyl radicals, and
other oxidants. These are generated at the anodic surface and serve as materials which result in
better decolorization of the textile dyes due to the complete mineralization into carbon dioxide and
the water molecule.
11.4.1 ElEctrochEMical advancEd oxidation of MEthylEnE BluE dyE

Electrochemical oxidation of methylene blue (MB) was achieved with the electro-Fenton approach
using stainless steel mesh as an electrode. This electrode was used for MB decolorization as a func
tion of the following parameters, namely concentration of dye, pH and Fe:H2O2 reagent ratio, cur
rent density, and the diversity of the electrode. Satisfactory decolorization of MB was achieved at
pH 3 after 20 minutes and also achieved the removal of MB dye at the highest Fe2+:H2O2 ratio of 1:4.
The current density resulted in a growing oxidation rate of MB dye and fast decolorization. The size
of the mesh pores also resulted in MB dye degradation and additionally increased the proportion of
elimination of MB dye with the optimum removal of MB dye of 94.5% within 25 minutes at the two
electrodes instead of the metal plate. The metal mesh resulted in twice the rate of removal of MB
dye solution than the steel plate with decreasing power consumption. Consequently, it is advised that
steel mesh is used as an electrode for electrochemical techniques (Loloei and Rezaee 2016).
This has led to direct decolorization by the electrochemical oxidation of MB in aqueous solution
with electroactive polymers (EAPs), wherein graphite becomes the anode and stainless steel 316
grade is used as the cathode. The electrochemical oxidation of MB dyes was reduced because of
specific parameters, which include current density, electrolyte temperature, pH of the solution, and
preliminary dye concentration. As a result, the MB dye decolorization was rapidly achieved with the
graphite anode. Decolorization of MB of 99.75% and 99.60% was achieved. The energy consump
tion was increased from 2.055 to 11.714 Kw.h/m3 at the applied voltages 14.6 V and 28.5 V, respec
tively (Jawad and Najim 2018). These approaches verified that 10 mA/cm2 current density, 0.5 g/L
Na2SO4, 60 min electrolysis time, and concentrations of MB of 50 mg/L and 400 mg/L resulted in
72.51% and 77.94% removal of color at 20°C, respectively. An electrochemical oxidation approach
FIGURE 11.6 Electrochemical advance oxidation reaction on anode surface with indirect method.
is therefore useful for mineralizing methylene blue dye dissolved in water. For this reason, an
electrochemical cell was used. This includes electrodes crafted from chrome steel and graphite.
Different factors that influenced dye elimination were studied and these included current density,
treatment time, and preliminary concentrations of dye solution. The increase in dye elimination was
found to be in direct proportion with the initial dye concentration. However, the dye elimination was
found to be improved with an increase in treatment time as high as 30–40 min and a contemporary
density as high as 0.06 A cm−2. The electrochemical oxidation of methylene blue was additionally
conducted in an electrochemical cell consisting of an anode that was made of graphite and a cathode
that was made from a graphite sheet of stainless steel. Each of the electrodes had been separated
with the aid of setting a polyethylene-based membrane (Daramic 350). The cathode and anode
were filled with electrolyte and methylene blue solution, respectively. The methylene blue solution
was completely mineralized and the remaining concentration was used as a colorimetric agent in a
spectrophotometric method. After filling the respective solutions in each of the compartments, the
electrodes were linked to a DC current supply. The effect of preliminary attention, contemporary
density, and remediation was studied with reference to the percentage elimination of methylene blue
from its aqueous solution (Asghar et al. 2015). The cell was constituted of both anode and cathode
as shown in Figure 11.7.
Electrochemical treatments of MB become indirectly decolorized by using a Pt electrode under
a strong electrolyte where numerous parameters have been optimized to achieve maximum elimina
tion of MB. The entire decolorization of MB was dependent on the presence of chloride as first-order
reaction and bromide as a second-order reaction. The electrochemical oxidation of the MB decolor
ization rate was investigated as a function of various parameters, which include current density, the
effect of chloride and bromide ions, supporting electrolyte, and initial pH of the solution. Although
MB dye showed no effective decolorization with concentration, temperature, and chloride and bro
mide ions in MB solution, the electrochemical oxidation of MB was not complexly decolorized
with iodide, fluoride, chloride, and bromide either. No effective decolorization coloration was also
observed in the presence of sulfate ions in the MB solution (El Hajj Hassan and El Jamal 2012). BDD
FIGURE 11.7 Electrochemical advance oxidation of methylene blue in the electrochemical cell.
electrodes act as anodes for the electrochemical oxidation of methylene dye in aqueous solution.
In this case the level of MB dye decolorization was low because of the low rate of electrooxidation
due to mass-transfer limitation. The adsorption techniques have resulted in a decrease in the inter
est of electrochemical oxidation of MB dye. The adsorbent–adsorbate combination of sawdust and
methylene blue dye gave good results for the investigation of adsorption, kinetic rate activity, current
density and regenerated time. MB decolorization was evaluated by the usage of electrochemical oxi
dation on sawdust, and the sawdust was regenerated for the next adsorption of MB dye. This cyclic
process of adsorption and electrochemical regeneration has moved forward the decolorization of and
enhanced adsorption of MB dye solution from wastewater samples (Bouaziz et al. 2014).
11.4.2 ElEctrochEMical advancEd oxidation of rhodaMinE B dyE

Environmental pollution is the main problem that is created by surface waters contaminated with
different types of dye industrial wastewater. Dye wastewater samples have been degraded with
the electrochemical anodic oxidation method. Rhodamine B (RhB) dye was electrochemically
degraded by using Ti/RuO2-IrO2 (DSA) and SnO2 anodes. These individual electrode efficiencies
have been studied for the treatment of dye wastewater. The effect of decolorization and chemical
oxygen demand (COD) were optimized with distinctive parameters including current density, dif
ferent initial pH, and the concentration of electrolyte and temperature on the electrochemical oxida
tion. The decolorization of RhB was achieved in the presence of chloride ions with Ti/RuO2-IrO2
(DSA) and SnO2 anodes electrodes at various time intervals. DSA electrode was optimized for the
decolorization of RhB dye including pH 6.5, t = 25°C, the contemporary density of 40 mA cm−2
in NaCl 0.05 mol L−1 + Na2SO4 0.1 mol L−1 mixture of supporting electrolyte solution. As a result,
100% color removal and 61.7% chemical oxygen demand removal after 90 min of electrolysis was
achieved. The DSA anode exhibited better performance than the SnO2 anode due to efficient activ
ity and greater cost-effectiveness. The DSA anode resulted in good electrochemical anodic oxida
tion of RhB dye because of chloride ions within the mixture of electrolyte, which provided good
oxidants such as Cl2 and ClO –, and these are used to facilitate the treatment of RhB at the electrode
of Ti/RuO2-IrO2 (DSA) and SnO2 anodes (Baddouh et al. 2018).
11.4.3 ElEctrochEMical advancEd oxidation of congo rEd

The electrochemical oxidation method was also used to degrade the diazo dye Congo red (CR)
with anodic oxidation using the boron-doped diamond anode (AOx/BDD) with various support
ing electrolytes. This treatment was performed by using the BDD anode and cathode of stainless
steel (AISI-304) with exceptional current densities consisting of 7.5, 15, 30, and 50 mA/cm2 in the
3L flow reactor. EAOPs of CR dye were additionally tested with distinctive supporting electro
lytes (HClO4, NaCl, Na2SO4, and H2SO4) with a 50 mM concentration and a flow rate of 7 L/min.
The NaCl supporting electrolyte medium resulted in faster degradation of CR dye with EAOPs
BDD anode when compared to HClO4, Na2SO4, and H2SO4. The supporting electrolytes of HClO4,
Na2SO4, and H2SO4 resulted in lower oxidation of CR due to the presence of SO42− and ClO4− in the
bulk solution. EAOPs of CR degraded products have also shown evidence of mineralization with
dissolved natural carbon ((DOC) and HPLC analysis (Jalife-Jacobo et al. 2016).
11.4.4 ElEctrochEMical advancEd oxidation of indigo carMinE dyE

Electrochemical oxidation of textile dye wastewater remediation has not been directly performed
inside the temporary mathematical model of FM01-LC reactor with the continuous stirring tank
in the presence of chloride ions. IrO2-SnO2 doped with Sb2O5 was used as an anode with titanium
multiplied meshed and stainless steel elevated meshes as the cathode. This reactor was operated as
a batch recirculation system with the galvanostatic condition and current densities of 132 Am−2 and
200 Am−2; 1.0 mM of indigo carmine dye; 0.05 M of NaCl supporting electrolyte; and flow rates of
0.9 L min−1, 1.8 L min−1, 2.7 L min−1, and 3.6 L min−1. FM01-LC reactor performance was studied
with the aid of the liquid float pattern through axial dispersion coefficient (Dax), the electrooxida
tion of chloride ions within the anode side (CCl−), the electrochemical discount of chlorine oxidizing
species (Cox) under transport control in cathode, while inside the continuous stirring tank (CST) the
chemical oxidation reactions between active chlorine species and organic matter through homoge
neous second-order kinetics were considered. This had been evaluated through the consumption
of the chemical oxygen demand (COD) and the color decay (Ccol). The mathematical model was
explained properly by the experimental investigation of different chemical species together with
CCl- (kCl = (3.2 × 103 to 4.9 × 103 m3 mol−1 s−1), CCOD (1.16 × 105 to 4.7 × 105 m3 mol−1 s−1), and Ccol
(1.2 × 103 to 9.98 × 103 m3 mol−1 s−1), and these results were correlated with previous reported data
(Cruz-Díaz et al. 2018).
11.4.5 ElEctrochEMical advancEd oxidation of yElloW 3 (dy3) dyE

The electrochemical oxidation method for the degradation of the industrial textile disperse yellow 3
(DY3) dye in aqueous solutions was studied with the use of specific electrocatalytic substances, BDD,
Ti/Ru 0.3Ti 0.7O2, and Ti/Pt anodes. The various current densities of 40 mA cm−2 and 60 mA cm−2
at 40°C with diverse supporting electrolytes Na2SO4 50 mM and NaCl 50 mM under specific pH
values 2.3, 7.0, and 10.0 were employed. The best degradation results achieved were 90% (TOC) in
Na2SO4 supporting electrolyte, BDD, anode, and pH. However, the other anodic materials had simply
resulted in 50% removal of the dye in Na2SO4 supporting electrolyte. Complete mineralization was
achieved in the following order of anode usage: Ti/Ru0.3Ti0.7O2 > BDD > Ti/Pt in a NaCl electrolyte
medium. Chloride ions had been produced at the surface of Ti/Ru0.3Ti0.7O2, BDD, and Ti/P at vary
ing pHs. Active chloride oxidants were dependent on the pH and electrode substances. Ultimately,
a rate of estimation for every electrocatalytic textile dye below various experimental conditions was
realized exhibiting less energy consumption and electrolysis time in NaCl medium. Based totally
on the results acquired, the electrochemical elimination of dyes and the profile of the carboxylic by-
products depend on the nature of the material, pH, and supporting electrolyte (Salazar et al. 2018).
11.4.6 ElEctrochEMical advancEd oxidation of acid BluE 113 dyE

In one of the studies reported, the degradation of a commercial textile dye by using the electrochem
ical oxidation (EO) technique was performed in an aqueous medium. Galvanostatic electrolysis, via
the use of platinum supported on Ti (Ti/Pt), lead dioxide (Pb/PbO2), and TiO2-nanotubes decorated
with PbO2 supported on Ti (Ti/TiO2-nanotubes/PbO2) anodes, was carried out in an electrochemi
cal flow cell with 1.0 L of solution containing 250 mg dm−3 of the textile dye acid blue 113 (AB113)
using Na2SO4 as supporting electrolyte applying 20, 40, and 60 mA cm−2. Large disk electrodes of
Ti/TiO2-nanotubes/PbO2 (65 cm2 of the geometrical area) were successfully synthesized by anod
ization and electrodeposition procedures. The electrolytic process was monitored by the ultraviolet
(UV)-visible spectrometry and COD. The effects confirmed that AB113 was correctly degraded by
using hydroxyl radicals electrogenerated from water discharge on the Ti/Pt and Pb/PbO2; the Ti/
TiO2-nanotubes/PbO2 anode showed better performance at removing AB113. In comparison with
Ti/Pt and Pb/PbO2, the Ti/TiO2-nanotubes/PbO2 anode showed a higher overall performance to
recycle AB113. It provided a higher oxidation rate, higher current efficiency, and consumed less
energy than the galvanostatic electrolysis using the other electrodes (Moura et al. 2016).
11.4.7 ElEctrochEMical advancEd oxidation of triphEnylMEthanE dyE

Electrochemical degradation and decolorization of triphenylmethane dye xylenol orange (XO) on
BDD electrodes were also studied. A series of parameters, including electrode materials, current
density, initial dye concentration, and electrolyte composition, was examined to discuss the effect of
these factors in terms of COD removal, current efficiency, and decolorization rate. Complete decol
orization and mineralization of XO could be realized on BDD electrodes while the oxidation is mass
transfer controlled, and the degradation progress performs better in the case of the porous BDD
electrode compared with the flat BDD electrode. The enhancement of effectiveness is highly cor
related to the structure of the electrode material, where the porous BDD film provides more active
sites for hydroxyl radicals. The presence of Cl− in the solution promotes the COD and color removal
due to the formation of active chlorine. The porous Ti/BDD electrode presents excellent potential
in the electrochemical decolorization and mineralization of triphenylmethane dye (He et al. 2016).
11.5 CONCLUSION
Electrochemical advanced oxidation processes are an advanced oxidation method used to remove
textile dyes from wastewater. These EAOPs have exhibited superior decolorization of textile dyes
from wastewater samples. These processes have some demerits due to the cost of anodes as well
as high oxygen overpotential. Different types of Fenton methods have resulted in effective decol
orization of textile dye wastewater. EAOPs have shown varying effectiveness of different anode
materials for the treatment of textile wastewater containing different types of organic textile dyes.
The method of using different composite electrodes has been employed for the decolorization and
chemical oxygen demand in textile wastewater in the presence of other chemicals and has shown
promising potential. This book chapter focused on determining the effects of pH, inter-electrode
distance, current intensity, reaction time, and applied voltage on decolorization and COD reduction
of synthetic textile wastewater. Advanced electrochemical oxidation strategies are therefore used to
improve the chemical oxidation of textile dyes from wastewater. This method helps to enhance the
remediation of textile wastewater.
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12 Materials Involved in
Electrocoagulation Process
for Industrial Effluents

Carlos Navas-Cárdenas, Herman Murillo, Maibelin Rosales,
Cesar Ron, and Florinella Muñoz
CONTENTS
12.1 Introduction .......................................................................................................................... 193
12.2 Fundamentals of Electrocoagulation.................................................................................... 194
12.2.1 Colloidal Stability..................................................................................................... 194
12.2.2 Electrocoagulation Principle .................................................................................... 195
12.3 Effects of the Operating Parameters on the Performance of Electrocoagulation ................ 196
12.3.1 Electrode Material .................................................................................................... 196
12.3.2 Initial pH................................................................................................................... 196
12.3.3 Electrode Configuration............................................................................................ 197
12.3.4 Current Density ........................................................................................................ 198
12.3.5 Temperature .............................................................................................................. 198
12.3.6 Conductivity.............................................................................................................. 199
12.4 Materials Employed for Electrocoagulation of Industrial Wastewater ................................200
12.4.1 Textile and Tannery Industry....................................................................................200
12.4.2 Food Industry............................................................................................................200
12.4.3 Oil Industry............................................................................................................... 201
12.4.4 Pulp and Paper Industry ...........................................................................................202
12.4.5 Pharmaceutical Industry...........................................................................................202
12.4.6 Wastewater Containing Heavy Metals .....................................................................204
12.5 Future Perspectives...............................................................................................................206
12.6 Conclusions...........................................................................................................................208
References...................................................................................................................................... 210
12.1 INTRODUCTION
The scarcity of hydric resources and industrial wastewater discharging have become worldwide
threats. The environmental impact generated by industrial effluents has led to the development
of suitable strategies to remove pollution in water and reuse the wastewater. In this sense, several
wastewater treatment technologies have been proposed to reduce toxic pollutants from industrial
effluents. However, most of these technologies require large amounts of nonrenewable energy, caus-
ing considerable carbon dioxide emissions into the environment (Garcia-Segura et al. 2017; Moussa
et al. 2017).
Industrial wastewaters contain several pollutants (e.g., organic or inorganic components with
complex structures, acid or alkaline constituents, toxic and biorefractory pollutants, dyes, etc.),
193
which can cause thermal and biological impacts, scum formation, and a loss of biodiversity in the
environment (Khansorthong and Hunsom 2009; Yavuz and Ogütveren 2018). Thus, conventional
wastewater treatment methods (i.e., physical, chemical, and biological processes) have been pro
posed to eliminate toxic pollutants from industrial effluents. However, they are subjected to several
drawbacks including low efficiency, high energy consumption, long time of treatment, generation
of secondary pollutants, and high operating costs (An et al. 2017; Song et al. 2017). Therefore,
research related to developing suitable methods for industrial wastewater treatment has nowadays
intensified.
In this context, electrochemical methods such as electrocoagulation (EC), electrooxidation,
electroflotation, and photo-assisted electrochemical methods have been emerging as alternatives of
wastewater treatment, and are based on the use of electrons as the working agents to promote the pol
lutant removal (Brillas and Martínez-Huitle 2015; Moussa et al. 2017; Yavuz and Ogütveren 2018).
Among the electrochemical methods, EC is one of the most promising water treatment technologies
employed to remove refractory pollutants from industrial effluents. The EC process involves elec
trochemical reactions to lead the in situ formation of coagulating agents by the electrodissolution
of a sacrificial anode due to the applied electric field to the electrodes (Aljaberi 2018; Chen 2004;
Meas et al. 2010). The advantages of EC over conventional wastewater treatments include high
removal efficiency, use of less or no chemicals, compact treatment facilities, relatively low cost,
lower amount sludge production, and the possibility of complete automation (An et al. 2017; Jiang
et al. 2017; Kobya et al. 2011).
In this chapter, we briefly review the fundamentals of EC, the factors that affect its performance
on wastewater treatment, and the promising materials employed to treat effluents from several
industries. The last part of this chapter describes future perspectives of the use of possible combina
tions of EC with other kinds of wastewater treatments, as conventional techniques or nonconven
tional technologies (e.g., advanced oxidation processes) in order to improve the pollutant removal
performance and to exploit the properties of several materials that can be employed during the EC
process.
12.2 FUNDAMENTALS OF ELECTROCOAGULATION

Electrocoagulation is a colloidal destabilization technique based on the perturbation of particle
surface charge via applied electrical fields to the anodic–cathodic pair in order to promote coagula
tion, flocculation, and final precipitation of suspended particles (Ghernaout et al. 2011; Mollah et al.
2001; Shim et al. 2014).
12.2.1 colloidal staBility

A particle is considered as “colloidal” when its aggregation or sedimentation happens at such slow
rates that it remains suspended in solution (Vepsäläinen et al. 2011). Colloidal particles (colloids)
can be present in natural as well as in engineered systems, and typically their size ranges from ~1
nm to ~10 μm. The relatively small size of colloids leads to a very small mass-to-surface area ratio.
Given that colloid mass and size are small compared to its surface area, gravitational effects are
negligible as compared to surface phenomena (e.g., colloidal surface forces) (Ghernaout et al. 2011;
Moussa et al. 2017).
The stability of colloids depends on the balance of surface forces described, physically and math
ematically, in the classic DLVO theory (Derjaguin and Landau 1941; Verwey and Overbeek 1948).
In the DLVO theory, the total interaction between colloid surfaces can be represented as the sum of
van der Waals (vdW) and electric double layer (EDL) forces. vdW force emanates from fleeting and/
or permanent dipoles appearing in molecular bonds, is attractive for most surfaces, and is indepen
dent of solution chemistry (Gregory 1981; Israelachvili 2011). EDL force arises from electroosmotic
effects appearing when intrinsic surface charge interacts with ions present in a solution, is repulsive
Materials Involved in Electrocoagulation Process 195
for like-charged surfaces (e.g., in nature, most surfaces are negatively charged), and relates inversely
to solution ionic strength (Hogg et al. 1966; Wiese and Healy 1970).
When repulsive EDL forces overwhelm the attractive vdW forces, colloids repel each other
and form a stable dispersion. In contrast, when attractive forces overcome repulsive forces, col
loids attach and the coagulation process is triggered leading to the destabilization of a dispersion
(Moussa et al. 2017). One of the basic principles of any coagulation process is to destabilize a col
loidal dispersion by reducing or neutralizing the colloid surface charge. After the surface charge
is disturbed, EDL forces reduce allowing the colloids aggregate via vdW forces (Ghernaout et al.
2011; Vepsäläinen 2012).
In real-life systems, DLVO theory is a good starting point to understand colloidal stability, how
ever, it cannot totally explain the stabilization/destabilization phenomena. In complex systems, it
is always required to consider surface forces arising from steric, hydration and solvation effects,
hydrophobic–hydrophilic interactions, Lewis acid–base interactions, and others (Israelachvili 2011;
van Oss 2006).
12.2.2 ElEctrocoagulation principlE

In conventional coagulation processes, chemical species (coagulant agent) (e.g., metallic, ionic poly
mers, ionic surfactants) are added to the system in order to reduce or neutralize the colloid surface
charge. In EC, similar effects to conventional coagulation can be produced by promoting the gen
eration of coagulant agents (e.g., metallic cations as Fe3+, Al3+). Coagulating agents are delivered to
a to-be-treated system via dissolution of a metallic electrode after application of DC electrical fields
(Brillas and Martínez-Huitle 2015; Chen 2004; Mollah et al. 2001). Although EC is considered to be
similar to conventional coagulation techniques in terms of the colloidal destabilization mechanism,
it is still different in other aspects such as the delivery mechanism of the coagulant agent, as well
as the side reactions occurring simultaneously at the electrodes (Brillas and Martínez-Huitle 2015;
Ghernaout et al. 2011; Moussa et al. 2017).
A basic EC cell system consists of an electrolyte cell wherein anode and cathode metal electrodes
are externally connected to an electric power supply (Figure 12.1). The electrodes are immersed in
the solution to be treated. Iron (Fe) and aluminum (Al) are the most extensively used electrode
materials given their availability, reduced toxicity, and reliability (Garcia-Segura et al. 2017). The
anode corresponds to the sacrifice electrode, and it serves as a coagulant agent while it dissolves and
delivers cations (e.g., Fe3+, Al3+) to the solution (Ghernaout et al. 2011; Moussa et al. 2017).
FIGURE 12.1 Schematic representation of a basic EC unit. (From Moussa et al. 2017.)
EC is a complicated process with several mechanisms operating in a coupling mode to desta

bilize colloids from solution. A strict description of the reaction mechanisms and physiochemical
phenomena driving EC is out of the scope of this review. However, we herein provide a general
description of the basic chemical reactions occurring simultaneously in an EC unit (Figure 12.1).
In general, the EC process can be described considering the following steps (Chen 2004; Garcia-
Segura et al. 2017; Ghernaout et al. 2011; Mollah et al. 2001):
1. Anodic reactions leading to in situ generation of metal cations and production of oxygen
gas, as well as cathodic reactions producing hydrogen gas and releasing hydroxyl ions.
At the anode:
Al(s) → Al3+ (aq) + n e − (12.1)
2H 2O → 4H + (aq ) + O2 ( g ) + 4e − (12.2)
At the cathode:
3
3H 2O + 3e − → H 2 ( g ) + 3OH − (aq ) (12.3)
2
2Al (s) + 6H 2O + 2OH − (aq) → 2Al ( OH )4 (aq) + 3H 2 ( g )

−
(12.4)
2. Reduction or neutralization of the colloid surface charge via absorption of metal ions.
3. Formation of aggregates from destabilized colloids leading to coagulation and further
flocculation.
4. Removal of coagulated colloids via sedimentation by flotation. Flotation occurs as a result
of generated hydrogen and oxygen gases.
12.3 EFFECTS OF THE OPERATING PARAMETERS ON THE

PERFORMANCE OF ELECTROCOAGULATION
The removal efficiency of the EC process depends on many factors that can affect the oxidation–
reduction reactions in the system and the formation of the coagulating agents. The most important
factors to be controlled in EC are detailed next.
12.3.1 ElEctrodE MatErial

The electrode pair is the main component of an EC cell given that it will influence the overall per
formance of the EC process. In dependence of the system, both electrodes can be made of the same
or different metal. The most common electrode materials employed for the EC process are alumi
num and iron (Chen et al. 2000; Nidheesh and Singh 2017). Each electrode material exhibits dif
ferent behavior (Linares-Hernández et al. 2009) since it determines the different reactions involved
during this process (Moussa et al. 2017). Materials employed for EC process will be discussed
further in Section 12.4.
12.3.2 initial ph
Initial pH is an important parameter to be controlled in the EC process. It affects the conductivity
of the aqueous medium, final pH, zeta potential, and the solubility of metal hydroxides (Khorram
and Fallah 2018; Moussa et al. 2017; Trompette and Vergnes 2009). At an appropriate initial pH,
the metal ions can form coagulating agents that remove contaminants from wastewater either by
precipitation and adsorption of dissolved pollutants or by aggregation of suspended particles (Aoudj
et al. 2010; Brillas and Martínez-Huitle 2015).
The pH effect on the EC process has been widely studied for the treatment of industrial effluents.
The typical pH range for industrial effluents is between 5 and 7. However, it depends on the nature
of pollutants and the material electrode. For textile wastewaters, higher removal efficiencies were
found at neutral pH by using Al electrodes. On the other hand, when Fe is employed as the electrode,
higher removal efficiencies, in terms of color and chemical oxygen demand (COD), were founded at
basic pHs (Chen 2004). Different pH conditions were studied for EC treatment of industrial effluent
with toxic metals (Gatsios et al. 2015), where the optimal pH was 6 and using iron electrodes and an
applied current of 0.1 A. In addition, it has been found that an alkaline pH (between 7 to 9) can be
the optimal condition for oily wastewater treatment, using Fe as the anode at a current density of 6
mA/cm2 and a treatment time of 31 min (Zhao et al. 2014).
12.3.3 ElEctrodE configuration

The electrode connection mode affects the removal performance of an EC cell, as well as the energy
consumption and the total cost of the process. The electrode can be arranged in monopolar (in par
allel, MP-P, or in serial connection, MP-S) or in bipolar (in serial connection, BP-S) configuration
(Asselin, Drogui, Benmoussa et al. 2008; Garcia-Segura et al. 2017; Hakizimana et al. 2017). The
different electrode arrangements are shown in Figure 12.2.
In MP-P configuration, all the sacrificial electrodes are directly connected to each other and
to the power supply. The same configuration is employed for cathode electrodes. In this sense, the
applied current to the system is distributed within each anode–cathode pair, and the voltage remains
equal across the cell. In MP-S configuration, the power supply is only connected to the outermost
electrodes (anode and cathode; Figure 12.2b), while the internal electrodes of each anode–cathode
pair are connected to each other. In this case, the voltage is distributed in each anode–cathode pair
and the applied current is the same for each one, resulting in a higher potential difference compared
to the MP-P connection (Garcia-Segura et al. 2017; Moussa et al. 2017; Song et al. 2017).
On the other hand, the BS configuration can only be performed in serial connection. Here, the
outermost electrodes are directly connected to the power supply, while the inner electrodes are
not electrically connected to the external circuit. The electric current applied through the EC cell
generates the polarization of the inner electrodes, which in turn leads to different polarities in
FIGURE 12.2 Different electrode arrangements employed for EC process. (Modified from Song et al. 2017.)
the opposite faces of them (Asselin, Drogui, Kaur et al. 2008; Khandegar and Saroha 2013). It is
reported that the BP-S configuration is the most cost-effective electrode arrangement, however, the
electric current can bypass the bipolar electrodes and flow in the electrolytic solution, generating a
current loss in the system (Kobya et al. 2011; Song et al. 2017).
The choice of an appropriate electrode arrangement may be crucial in the EC process and
depends on the kind of effluent. For example, Asselin and coworkers (Asselin, Drogui, Benmoussa,
et al. 2008) analyzed the influence of electrode arrangement in the EC treatment of oily slaughter
house wastewaters. They reported a system based on the use of iron (anode and cathode) or alu
minum (anode and cathode) electrodes arranged in two different kinds of connections: MP-P and
BP-S. An 82% COD removal performance was achieved using an MP-P configuration system with
0.3 A current density. In addition, a comparison between monopolar and bipolar electrode arrange
ments during the EC process employed to remove Cr3+ from aqueous solutions has been conducted.
The optimal conditions to obtain complete Cr3+ removal were a current of 1 A, initial pH of 3.4,
and using mild steel sheets as electrodes and a BP-S electrode configuration (Golder et al. 2007a).
On the other hand, Kobya and coworkers studied the effect of different electrode connection modes
on arsenic removal from potable water by EC. They compared MP-S and MP-P electrode arrange
ments, obtaining the highest arsenic removal (94%) at a current density of 2.5 A/m2 for Al and Fe
electrodes arranged at MP-S configuration (Kobya et al. 2011).
12.3.4 currEnt dEnsity

The applied current density to the EC cell determines the number of metal ions released from the
electrodes and, therefore, the amount of resulting coagulating agents for the EC process (Brillas
and Martínez-Huitle 2015; Yavuz and Ogütveren 2018; Zodi et al. 2011). The effect of current den
sity on the treatment of wastewater from textile industries by electrocoagulation has been widely
studied. Verma (2017) investigated the pollutant removal efficiency by the EC process using Fe–Al
electrodes and varying the current density. Here, the COD and color removal efficiencies increased
when the current density increased from 5 to 25 A/m2, due to the higher coagulant dosage and
bubble generation rates during the EC process. A similar behavior was observed for the removal
of textile dye (Remazol Red 133) from industrial wastewater by EC using three-dimensional steel
wood electrodes and a cartridge-type reactor (López et al. 2017). A removal efficiency of 100% was
obtained at current densities above 3.75 mA/cm2, meanwhile 84% and 42% removal efficiencies
were obtained at 2.5 and 1.25 mA/cm2, respectively.
The current density depends on the initial concentration of pollutants in the wastewater (Hansen
et al. 2019). For example, arsenic removal from industrial effluents was performed by EC at differ
ent current densities. It has been reported that for arsenic concentrations from 1 to 440 mg/L, the
optimal current density may be between 6.5 and 50 A/m2 (Ratna Kumar et al. 2004; Song et al.
2014), and for arsenic concentrations higher than 3000 mg/L, between 170 and 250 A/m2 (Hansen
et al. 2019).
12.3.5 tEMpEraturE
The EC process is usually performed at room temperature, however, some works have reported the
effect of temperature on the removal efficiency of industrial wastewaters by EC. Higher tempera
tures o enhance the mass transport in the EC reactors, favoring a higher pollutant removal efficiency
in the treatment (Vepsäläinen et al. 2009). In addition, the conductivity of the aqueous solution
depends on the temperature. A higher temperature increases the conductivity of the wastewater,
which in turn, decreases the power consumption during the EC process (An et al. 2017).
The effect of temperature on the EC process depends on the type of wastewater. For example, the
effect of temperature on natural organic matter (NOM) removal from paper mill surface water by
EC treatment was investigated (Vepsäläinen et al. 2009). A minor effect of the temperature of EC on
the removal performance was determined using aluminum electrodes, a current density of 0.5 mA/
m2, initial pH of 5.0, and a temperature range of 2°C–22°C. At these conditions, the higher dissolved
organic carbon removal was 80% at 22°C, while at 2°C, the dissolved organic carbon removal was
76%. This slight increase in the removal efficiency has been related to the higher dissolution of elec
trodes that occurs at high temperatures, however, the effect of temperature on the removal efficiency
is minor for this type of wastewater.
On the contrary, Ulucan and coworkers (2014) reported a major effect of temperature on the
COD removal from bilge wastewater by EC. The EC process was performed using an EC reactor
with aluminum electrodes, at initial pH of water of 7.0, current density of 6 mA/m 2, and tempera
tures from 10°C to 55°C. At 10°C, the COD removal was only 38%, whereas COD removals of
c.a. 90% were observed at 25°C. Similar COD removal was found for temperatures above 25°C.
This indicates that 25°C is the optimal condition for this specific wastewater treatment. The
same trend was observed for the removal of polyvinyl alcohol (PVA) from aqueous solution by
the EC process using Fe and Al as the anode–cathode pair (Chou et al. 2010). Here, the effect of
temperature and applied voltage on removal performance were studied at 15°C, 25°C, 35°C, and
45°C, and 5, 10 and 20 V, respectively. The highest PVA removal (85%) was achieved at 35°C and
45°C, whereas poor PVA removal (48%) was registered at 15°C. The difference in the removal
performance is related to the higher destruction of iron oxide film on the anode and to the higher
generation of hydroxyl radicals, which promote PVA removal from the wastewater (El-Ashtoukhy
et al. 2009). However, it is reported that higher temperatures can increase the solubility of pre
cipitates and promote the formation of unsuitable flocs in the system, generating an opposite
effect on the removal efficiency. In this sense, it becomes necessary to determine the optimal
temperature conditions to enhance the removal efficiency and to avoid technical problems during
the EC process.
12.3.6 conductivity
Solution conductivity is an important parameter that affects the removal performance and operating
cost of EC treatment. The applied current passing through the circuit depends on the conductivity
of the wastewater at a specified applied voltage (Chou et al. 2010). A high conductivity implies a
higher generation of coagulating agents and a lower energy consumption during the EC process.
The solution conductivity can be adjusted by adding supporting electrolytes (e.g., anions), which
can also interact with the electrodes to promote the electrolytic reactions over their surface (Moussa
et al. 2017; Trompette and Vergnes 2009).
Several studies have employed sodium chloride (NaCl) or sodium sulfate (Na2SO4) to obtain an
appropriate conductivity for EC treatment of industrial effluents (Chou et al. 2010; Khandegar and
Saroha 2013). Na2SO4 was used as supporting electrolyte at different concentrations (between 1
to 7 mM) to treat industrial estate wastewaters by EC with iron electrodes, wherein the maximum
removal efficiency and the lowest power consumption were achieved at a concentration of 3 mM
(Yavuz and Ogütveren 2018).
It has been reported that the use of NaCl as the supporting electrolyte can be more efficient com
pared to Na2SO4 (Ghernaout and Ghernaout 2011). The effect of the type of electrolyte on the EC
system was analyzed for the treatment of oily effluents (Cañizarez et al. 2007). Here, higher COD
removal efficiencies were obtained by using NaCl instead of Na2SO4. This fact was studied in a con
tinuous EC reactor with Al electrodes at 25°C, at an initial pH of oily–wastewater of 8.5, and with a
concentration of supporting electrolyte of 3000 mg/L. At an electrical charge passed of 0.15 Ah/L,
ca. 90% COD removal was achieved with NaCl, whereas for Na2SO4, only ca. 60% COD removal
was obtained. This difference has been related to the formation of different aluminum species
depending on the type of supporting electrolytes. In this sense, the use of Na2SO4 can promotes the
formation of amorphous Al hydroxide precipitates, which are not effective for the treatment of this
kind of wastewater, while the chloride media (i.e., NaCl) can promote the formation of polymeric
hydroxocations, which are active sites that favor the pollutant removal in the EC process (An et al.
2017; Cañizarez et al. 2007; Khorram and Fallah 2018).
12.4 MATERIALS EMPLOYED FOR ELECTROCOAGULATION

OF INDUSTRIAL WASTEWATER
Different materials have been used as electrodes for the EC process in the treatment of industrial
wastewaters and their selection depends on the nature of pollutant to be removed. The electrochemi
cal reactions involved during EC are determined by the electrode materials employed in the process,
considering the fact that their physicochemical properties are critical factors in the removal effi
ciency. Examples of some of the most effective employed materials in the EC process for different
industrial wastewaters are discussed next.
12.4.1 tExtilE and tannEry industry

In recent years, EC technology has become an effective tool for the treatment of textile wastewaters.
High removal efficiency (>90%) has been typically obtained with the use of optimum material as
the sacrificial electrode. In general, aluminum, iron, and stainless steel (SS) electrodes can be used
as efficient electrode materials for the EC process (Brillas and Martínez-Huitle 2015; Khandegar
and Saroha 2013; Kobya et al. 2016).
Khorram and Fallah reported that 97% of dye decolorization was obtained at 30 min of EC treat
ment, using Al electrodes (Khorram and Fallah 2018). A reduction in the initial dye concentration
was obtained by Behin et al. (2015), when Fe electrodes were used as anodes in the EC process com
bined with ozonation. This improvement occurred due to the strongly oxidizing ozone that can react
with wastewater compounds or with the oxidized iron to produce hydroxyl radicals. The latter react
with organic molecules accelerating the decrease of dye concentration and consequently enhancing
the efficiency of the decolorization. Linares–Hernández et al. (2009) studied the use of aluminum,
iron, and a combination of them to decolorize textile wastewaters, and the dye removal efficiency
was reported to be higher than 83% by employing a combination of electrodes (Al and Fe). Similar
results were obtained when three different types of textile wastewaters were treated with an Fe–Al
composite electrode; the treatment showed approximately 99% dye removal efficiency. Moreover,
an anode of steel wool, also known as wire wool, was developed by A. López et al. (2017), and their
results showed 99% of efficiency for removing the dye. Wei and coworkers (2012) observed higher
color removal by employing iron plate as the anode and steel wool as the cathode. In that work, the
authors investigated the efficiency of three types of cathodes (iron plate, stainless steel plate, and
steel wool) and the results revealed higher dye removal using a steel wool cathode than by using
the iron plate or the stainless steel plate cathodes. The higher efficiency was attributed to the higher
surface area of the steel wool cathode. Finally, the literature indicates that electrocoagulation is an
efficient process for removing dye from wastewater.
12.4.2 food industry

Several contaminants are found in wastewaters from the food industry. Common characteristics of
food industry wastewater are highly degradability, nontoxic suspended solids, COD, and elevated
biological oxygen demand (BOD) (Moussa et al. 2017). Color, oil, grease, dissolved organic com
pounds (e.g., proteins, blood), fat, hair, feather, flesh, manure, and grit are characteristic pollutants of
wastewater from the meat processing industry and restaurants (Asselin et al. 2008; Chen et al. 2000).
In the following, materials and removal efficiencies in specific food industry sectors are discussed.
Early attempts in the treatment of slaughterhouse wastewater with EC were performed employ
ing Al and Fe electrodes. The process yielded 70% removal of COD, color, oil, and grease, working
at acid or neutral pH. Al–Al electrodes performed better in COD and color removal, whereas Fe–Fe
electrodes achieved higher efficiency in oil and grease removal (Kobya et al. 2006; Yetilmezsoy
et al. 2009). Asselin et al. reported 82%, 100%, and 90% removal of COD, turbidity, and metals,
respectively, after treating slaughterhouse wastewater with Fe–Fe electrodes at pH 6.1. In several
other studies, the EC process allowed COD removal percentages ranging from 86% to 98% with
both Al–Al and Fe–Fe electrodes (Bayramoglu et al. 2006; Chen et al. 2000; Kobya et al. 2006).
Wastewater from dairy production has been treated by EC with Fe–Fe, Al–Al, and Fe–Al elec
trodes. Treatment at pH 7.0 yielded COD removal efficiencies within 61% and 98%, and turbidity
removal of 100% employing Al–Al electrodes (Şengil and Ozacar 2006; Tchamango et al. 2010;
Yavuz et al. 2011). In effluents from the egg processing sector, the use of Al–Al, Fe–Fe, and SS–SS
electrodes allowed removal above 92% of COD and 96% of turbidity at pH 7.0 (Xu et al. 2002).
Treatment of gelatin production wastewater with Al–Al electrodes removed 54.7% COD at pH 5.9
(Lakshmi Kruthika et al. 2013).
Regarding the olive oil industry, wastewater from the milling process was treated with the
EC process with Al–Al and Fe–Fe electrodes. Here, the wastewater treatment at a pH range
from 4.2 and 6.0 removed the color up to 93%–100%, while the COD removal ranged from 42%
to 70% (Coskun et al. 2012; Hanafi et al. 2010; Inan et al. 2004). As alternate materials, Zn–SS
electrodes were tested to treat olive oil milling wastewater showing low removal efficiencies at
pH 3.2 (<21% COD removal) (Fajardo et al. 2015). The EC treatment of wastewater from palm
oil production with Al–Al electrodes showed a reduction of 30.4% in COD, 70% in turbidity, and
100% of metals (Agustin et al. 2008). While in the almond industry, Al–Fe electrodes at pH 6.1
allowed the reduction of 81% of COD, 99.6% of color, and 99.7% of turbidity removal (Valero
et al. 2011).
Distilleries correspond to a sector of the food industry in which EC has been studied utiliz
ing electrodes made of materials other than Al and Fe. At values of neutral pH, Al–SS electrodes
proved to remove 80.1% of COD, 100% of color, and 99% of turbidity (Kannan et al. 2006). EC per
formed with SS–SS electrodes, yielded 61.6% COD removal, as well as reduced the color in 98.4%
(Thakur et al. 2009). COD removal within 41.9% and 81.3% were achieved using Al–Al and Fe–Fe
electrodes, respectively, at a pH ranging from 3.0 to 6.0 (Davila et al. 2011; Khandegar and Saroha.
2012; Kirzhner et al. 2008; Krishna et al. 2010).
12.4.3 oil industry

EC has been conducted for removing oil from petroleum refineries and petrochemical industries,
being aluminum and iron the most commonly used electrodes for this purpose (An et al. 2017;
Emamjomeh and Sivakumar 2009; Safari et al. 2016).
Studies about removing diesel from oil petroleum refinery wastewater were carried out by Safari
et al. (2016), who employed Al and Fe as electrode materials. They reported that a higher capacity
for removing diesel was achieved using Al anodes and cathodes, compared to that obtained with
Fe electrodes. This is attributed to Al electrodes generating better stability during the EC process.
However, Martínez–Delgadillo et al. (2010) investigated oil removal from similar oily wastewater
also using Al and Fe electrodes. They reported that the use of Fe electrodes improves the removal
efficiency compared to Al electrodes.
Chavalparit and Ongwandee (2009) showed that Al anodes and graphite cathodes can be an
effective electrode combination to remove residual oil and grease from biodiesel wastewater. In
addition, they developed a model for the prediction of oil and grease removal efficiency, which was
verified with experimental results.
Due to the growing interest in improving oil removal efficiency from oil petroleum refinery
wastewater, some modifications have been studied in the electrochemical processes. For example,
dimensionally stable anodes (DSA) of nominal composition Ti/Ru0.34Ti0.66O2 were employed in
electrochemical remediation of oily wastewaters from the petroleum industry (Santos et al. 2006).
The results showed changes on the catalytic surface of the DSA due to the possible adsorption of
organic material at the electrode surface by the oil concentration, however, a high removal effi
ciency was reported.
On the other hand, the combination of carbon steel and aluminum as electrodes is efficient for
removing oil and grease from bilge water using EC treatment (Rincón and La Motta 2014). The
removal efficiency of oil and grease from bilge water was studied by Körbahti and Artut (2010),
who proposed the use of platinum/iridium (Pt/Ir) anodes in electrochemical processes in order
to enhance the resistance to possible chemical attacks and improve electrical conductivity and
mechanical stability.
Oil removal from bio-oils and synthetic oils was evaluated using SS and Al anodes. The SS
employed in the study was austenitic steel with molybdenum and 67% of iron. The results did not
reveal a significant difference using an SS or Al anode. However, the SS anode showed a slightly
higher efficiency for synthetic oil removal, while the Al anodes presented slightly better perfor
mance at reducing bio-oils (Karhu et al. 2015). The results presented in this section have demon
strated that the EC process is a feasible technique for the treatment of oily wastewaters.
12.4.4 pulp and papEr industry

In the pulp and paper industry, pollutants are released into water during wood bleaching, digestion,
pulp washing, pulp bleaching, and papermaking processes (Vepsäläinen et al. 2011). For this rea
son, effluents are commonly blackish in color and contain high concentrations of lignin, cellulose,
COD, BOD, organics, suspended solids, and arsenic (Moussa et al. 2017). In this sense, Al, Fe, and
combinations of both electrodes have been employed in the treatment of this type of wastewater by
EC. Al proved to be more effective, although the combination of electrodes has also shown high
removal efficiencies (Vepsäläinen 2012).
Al–Al electrodes have been used in the treatment of black wastewater by the EC process. This
black effluent is usually loaded with about 50% of lignin. Zaied and Bellkhal (2009) reported that
COD reduction was about 98% with a color removal of 99% at pH 7.0. An effluent generated during
the bleaching process has also been treated by EC, using Al–Al electrodes. Lignin and inorganic
chloride are common constituents of this wastewater. After the EC treatment, COD was reduced by
90%, with a color reduction percentage of 94% (Sridhar et al. 2011); the EC process was performed
at pH 7.0.
Another highly contaminated effluent coming from the pulp and paper industry is wastewater
from the paper milling process. It commonly has high concentrations of lignin and phenol (Uğurlu
et al. 2008). EC treatment with Al–Al electrodes at neutral pH ranges proved to be effective in the
reduction of DOC with removal as high as 80%; however, the process yielded low removal effi
ciencies for COD (4.8%) (Uğurlu 2004). Further studies were performed in order to enhance the
efficiency of the EC process in COD removal specifically. EC performed with Fe–Fe electrodes
allowed COD reduction by about 55% at pH 7.5. Under the same conditions but with the use of
Al–Al electrodes, COD removal reached 75% (Uğurlu et al. 2008).
12.4.5 pharMacEutical industry

Electrocoagulation has been successfully performed on the treatment of wastewaters from the phar
maceutical industry. Some reports can be found in this area of interest. One of them reported EC
as a way to remove oxytetracycline hydrochloride by using Fe and Al as anodes, and SS as the
cathode at 20 mA/cm2. Iron was found better than aluminum on removal efficiency (Nariyan et al.
2017). Another report mentioned EC to effectively remove diclofenac, ibuprofen, and ketoprofen
from water. Herein, Al electrodes were used along with cationic surfactants in the EC cell (Liu et al.
2015). Likewise, iron and aluminum plates were used as electrodes in the removal of salicylic acid
from aqueous solutions. Some electrode combinations were tested, and the best removal efficiency
was achieved by the Al–Al electrode pair, reaching 90% removal (Chou et al. 2011).
In terms of materials involved in EC, the goal must be focused on the electrode materials. As
expected, most of the electrodes are made of iron and aluminum because both Fe2+ and Al3+ ions
generated from these electrodes can work as coagulants. However, some authors have researched
other materials since conventional materials have shown some drawbacks, such as electrode dis
solution or low removal efficiencies (Sirés and Brillas 2012). In addition, it has been found that
the aqueous system has turned turbid because of the Fe2+ ions, which can oxidize to Fe3+ and then
Fe(OH)3 is produced after a redox reaction with OH− ions. This turns water to yellow and turbidity
is increased. In this case, Al is chosen as electrode material (Linares-Hernández et al. 2009). Novel
materials other than Fe and Al that are being used in EC are stainless steel (Olmez-Hanci et al.
2012) and titanium (Shon et al. 2010).
In Chou et al.’s (2011) report regarding salicylic acid removal, a comparison between Fe–Fe and
Al–Al electrode pairs was made. Under the same operating conditions, both electrode pairs were
tested and very different results were obtained. On the one hand, the EC involving the Al–Al pair
achieved 92% removal by reaching steady-state conditions in about 20 minutes. On the other hand,
the Fe–Fe pair allowed only a 68% removal, including a longer reaction time as 80 min were neces
sary to finally reach the steady state in the process.
A colorless effluent is obtained when EC was operated using the Al electrodes, whereas a highly
turbid residue resulted from the usage of the Fe electrodes. A better performance of Al electrodes
is related to the pH variation. A pH increase is observed for both electrode combinations, but in
the case of Al, that increment is higher because of the different behavior between Al and Fe domi
nant species during the process. In other words, some dominant aluminum species like Al3+ and
Al(OH)2+ generated at the 2–3 pH range, and Al3+ and OH− generated by electrodes at a pH range of
4–9 can form some intermediate species, which in turn form Al(OH)3 that could lead to very effi
cient pollutant removal. Fe(OH)3 was dominant in the pH range of 6–10, but this is not good enough
since pH operating conditions for salicylic acid were in a pH range of 3.4–5.8. Consequently, no
Fe-based coagulant agent is completely produced under these conditions, whereas these are optimal
for Al(OH)3 production (Chou et al. 2011).
In a report regarding removal of the antibiotic oxytetracycline hydrochloride, biological treat
ments were found to be not useful at all, as microorganism activity is inhibited by antibiotics
(Nariyan et al. 2017). Therefore, EC is considered to be a more effective technique for antibiotic
removal from wastewater. The electrode materials tested were Fe and Al as anodes, and SS as the
cathode. Thus, the electrode pairs Fe–SS and Al–SS were assessed. Under optimum conditions,
removal efficiencies of 93.2% and 87.8% were achieved by Fe–SS and Al–SS, respectively. In the
two cases, pH was found to increase up to 12, where iron and aluminum were in the forms of
hematite and gibbsite, according their Eh-pH diagrams, respectively. These species are capable of
absorbing oxytetracycline through some mechanisms like hydrogen bonding or electrostatic attrac
tion (Nariyan et al. 2017).
Other parameters such as current density and oxygen produced by the anodes are supposed to
affect removal efficiency. Moreover, dissolved oxygen was also analyzed due to its relevance in terms
of showing the self-cleaning capability of water. For instance, it has been demonstrated that removal
of organic matter is feasible when oxygen in water is exhausted (Kabdaşlı et al. 2009). Dissolved
oxygen as well as redox potential decreased in all experiments performed. Production of hematite
and gibbsite is also related to this trend in both cases, except for lower current density values when
using an aluminum anode, where no pH increase occurred because of repulsion between oxytetra
cycline (in its positive form) and aluminum-dominant species (Al3+ ions). The initial concentration
of oxytetracycline was found to have a nonsignificant effect over removal efficiency, no matter the
electrode material. Regarding the power consumption, the Al–SS had a higher level of consumption;
therefore, Al electrodes demand more energy than Fe. This is an issue for the operation, considering
that removal was even lower using the Al–SS electrode pair as well (Nariyan et al. 2017).
A rarely used material is titanium. For example, laboratory-scale research was performed with
synthetic pharmaceutical wastewater. In this study, titanium was used as the anode in order to
generate Ti4+ ions. Since most of the colloids to be treated by EC are negatively charged, Ti4+ ions
are more likely to work better than Fe3+ or Al3+ ions as coagulants. Like Fe and Al, Ti4+ ions are
hydrolyzed to form hydroxides and polyhydroxides capable of producing the precipitation/flota
tion of the destabilized colloids as aggregated flocs (Moreno-Casillas et al. 2007). In this research,
the optimum current density was found to be higher than the iron or aluminum values, due to
less dissolution of ions from the titanium-based anode. In terms of pH, an optimum condition for
titanium-based EC (Ti-EC) is supposed to be a pH value of 4, but when OH− ions are generated, pH
is expected to increase, and removal efficiency might decrease during the first stages of the process.
Regarding chemical oxygen demand, under optimum parameters, Ti-EC reached 70% removal. It
is also suggested that using Ti-EC could be more effective than chemical coagulation when remov
ing compounds when a much smaller molecular weight is required. Finally, this research includes a
preparation route of titanium dioxide nanoparticles from the Ti-EC sludge, so that the environmen
tal impact of the sludge can be mitigated (Shon et al. 2010).
When comparing the last detailed reports, it can be concluded that there is no optimal electrode
material for all types of pharmaceutical wastewaters, i.e., every pollutant may react in a different
way according to the electrode materials used and the operating conditions performed. Therefore,
several preliminary tests must be done to find out the optimum electrode materials as well as the
operating conditions.
Table 12.1 shows a comparative overview of different reports regarding EC for pharmaceutical
wastewater treatment.
12.4.6 WastEWatEr containing hEavy MEtals

EC has been successfully applied to remove heavy metals and metalloids from wastewaters.
Generally, high pollutant removal can be achieved by choosing the appropriate electrode material.
In literature, Al, Fe, and combination of the two have been reported as electrode material for heavy
metals removal via EC (Balasubramanian et al. 2009; Hansen et al. 2019; Ratna Kumar et al. 2004;
Song et al. 2017).
Studies regarding arsenic (As) removal from industrial effluent by EC have reported strong As
adsorption on hydrous metal oxides such as Al and Fe hydroxides/oxyhydroxides. These species are
formed in electrochemical reactions during EC (Song et al. 2017). Several authors have reported Fe
electrodes in As removal by the EC process (Balasubramanian et al. 2009; Ratna Kumar et al. 2004;
Wan et al. 2010). Balasubramanian et al. (2009) employed mild steel as the sacrificial anode, thus
EC yielded 94% of arsenic removal. Ratna Kumar et al. (2004) evaluated three types of electrodes:
Fe, Al, and Ti. The highest efficiency achieved (99%) was obtained with Fe electrodes. Studies on
EC performed with Fe electrode, have reported As(III) oxidation to As(V), with As(V) adsorbing
into hydrous ferric oxides (Ratna Kumar et al. 2004; Wan et al. 2010). Alternative materials to Fe
and Al have been proposed to improve removal efficiency with EC technology. For example, high
removal efficiencies were reported for EC performed with zinc (Zn), copper (Cu), and Cu–Zn elec
trodes (Ali et al. 2012; Maldonado-Reyes et al. 2007). Cu electrodes were more efficient than Al and
Fe for this type of industrial effluent (Gomes et al. 2010).
Fe electrodes have been used in Se removal from oil refinery wastewater, as well as Cu pro
duction wastewater. For both, above 90% of selenium was removed. Researchers suggested that
Fe hydroxides were the chemical species capable of adsorbing Se (Hansen et al. 2019; Mavrov
et al. 2006).
Fe and Fe–Cu electrodes have shown high Cu, Cr, Ag, Zn, and Ni removal when EC was applied
to metal plating and automotive industry wastewater (Beyazit 2014; Gatsios et al. 2015; Golder et
al. 2007b; Hanay and Hasar 2011; Heidmann and Calmano 2008; Mercado-Martínez et al. 2013).
Beyazit (Beyazit 2014) reported a set of possible electrode pair combinations using Al, Fe, and SS
electrodes. The author concluded that Fe–SS electrode pairs were optimal for removing the afore
mentioned metals. Al electrodes have been used in heavy metal ion (e.g. Zn2+, Cu2+, Ni2+, Ag+, and
TABLE 12.1
Overview of Pharmaceutical Wastewater Pollutants Treated by EC Process
Distance Effective Reactor
between Area Volume Initial Pollutant EC Time
Pollutant Electrodes Electrodes (cm) (cm2) (L) Concentration Current Density % Removal pH (min) Reference
Dexamethasone Al — 61 1.0 100 µg/L — DEX (38) — 45 Arsand et al. 2013
(DEX)
Hydrolyzed peptone Fe 2.0 31 0.5 COD: 1753 mg/L 763.0 A/m2 Turb (91) 6.0 90 Boroski et al. 2009
COD (86)
Salicylic acid (SA) Fe, Al 2.0 33 0.5 100 mg/L — Al/Al: SA (92) 7.0 20–80 Chou et al. 2011
Fe/Fe: SA (68)
Ciprofloxacin (CIP) Al 2.3 450 1.0 25 mg/L 18.0 A/m2 TOC (87) 9.0 40 Espinoza-Quiñones
CIP (98) et al. 2016
Oxytetracycline Fe, Al, SS 5.0 35 0.2 50 mg/L 20.0 mA/cm2 Fe: SS (93.17) Al: — 60, 40 Nariyan et al. 2017
hydrochloride SS (87.68)
Naphthalene 316 SS 0.3 286 3.0 — — COD (98) 11.0 150 Olmez-Hanci et al.
Materials Involved in Electrocoagulation Process
sulfonates COD (91) 2012

TOC (88)
Salicylic acid (SA) Hybrid 0.2 35 1.0 100 mg/L 50.0 A/m2 COD (85) 6.0 10 Ozyonar and
Al–Fe Aksoy 2016
Hospital wastewater Fe, Al, SS — 176 2.0 TOC: 276 mg/L 4.9, 4.5, 2.7 mA/cm2 TOC: 5.5–7.8 — Veli et al. 2016
Fe (99), Al (100),
SS (100)
Synthetic wastewater Ti — 207 5.0 10 mg/L 8.3 mA/cm2 COD (60–70) 4.0 4 Shon et al. 2010
Flurbiprofen Fe 0.5 81 0.6 — 2.5 mA/cm2 TOC (66.3) 6.5 20 Barısçı et al. 2015
Ayurveda SS, Al — 82 1 — Al: 99.9 A/m2, Al: COD (58), Al: 6.0, 120 Singh et al. 2016
pharmaceutical SS: 125.8 A/m2 SS: COD (79) SS: 7.5
wastewater
Azithromycin Fe 0.2 48 1 190 mg/L 20.0 mA/cm2 COD (96) 3.0 60 Yazdanbakhsh
et al. 2015
205
Cr2O72−) removal. In this application, Zn, Cu, Ni, and Ag ions were first hydrolyzed and then copre
cipitated as hydroxides. Cr(VI) is reduced at the cathode to Cr(III) to then precipitate as hydroxide
(Golder et al. 2007b; Heidmann and Calmano 2008). Al alloy anodes (including Zn, In, Fe, and Si
in the alloy) have been also utilized to remove Cr from water (Vasudevan et al. 2011).
Complete removal of indium from water was achieved in studies considering Fe–Al electrode
pair (Chou et al. 2009). Al and Fe electrodes have been reported to effectively remove mercury from
wastewater (Nanseu-Njiki et al. 2009). Al electrodes showed to improve the removal of manganese
(Gatsios et al. 2015; Hanay and Hasar 2011; Shafaei et al. 2010).
12.5 FUTURE PERSPECTIVES

Even though new materials in EC are being investigated, there are still some problems in the process.
Namely, it should not be focused only on electrode materials and their dependence on the operating
conditions such as pH range, current density, or the type of the pollutant to be removed, but also
other drawbacks regardless of the materials used as electrodes. Few weaknesses have been detected
in EC like the inexorable production of sludge, electrode dissolution and subsequent replacement, or
power consumption (Sirés and Brillas 2012).
One of the possibilities to reach a process enhancement might be combining EC with other
wastewater treatment techniques or modifying the electrode materials by coating them or adding
some compounds to remediate some of the mentioned problems.
For example, in a study about urban wastewater treatment, a process called electrodisinfection/
electrocoagulation (ED-EC) was performed employing boron-doped diamond as the anode and
stainless steel as the cathode. Additionally, a perforated iron plate was settled between the elec
trodes to work as a bipolar electrode. The aim of this work was to achieve simultaneously the
removal of turbidity and microbiological content. In this context, total disinfection and more than
90% of turbidity removal were obtained. Compounds formed during the ED-EC process such as
hypochlorite and chloramines were found responsible for disinfection, and its efficiency mostly
depends on the anode material. Meanwhile, turbidity removal is attributed to the electrochemical
cell arrangement, reaching a better performance when using iron as a bipolar electrode, mainly,
at low current densities when the bipolar electrode dissolution is inhibited (Llanos et al. 2014). In
addition, novel anodic materials like boron-doped conductive diamond electrodes appear to be more
stable and efficient (Linares-Hernández et al. 2010).
Given that electro-Fenton (EF) treatment is not good enough for the treatment of cyanotoxins
removal due to its high energy consumption and some issues about the use of chemicals, EC has
been coupled to the Fenton processes (An et al. 2019). Hence, EC-Fenton appears to be an improved
EF where no chemicals need to be added, and the energy consumption is reduced. The EF process
is an advanced oxidation process (AOP), which consists in producing highly oxidizing species, e.g.,
hydroxyl radicals (·OH). These radicals can completely oxidize some organic compounds into CO2
and H2O. In EF, Fe2+ ions are added to the continuous generation of H2O2 (which is formed through
oxygen reduction on the cathode). This interaction between Fe2+ and H2O2 can produce hydroxyl
radicals. In this case, EC could enhance the EF process by providing coagulating agents to the
hydroxyl radicals, improving the pollutant removal efficiency. Iron is the key element in this process
because both EC and EF use Fe ions in their wastewater treatment mechanisms.
The experimental stage consisted of a three-electrode setup, where iron was used as the anode.
A graphite cathode and a Ti/IrO2 counter electrode were also employed. The aim is to alternate
EC and EF in a single reactor by only switching the electrode connection, where Fe ions and ·OH
were produced in situ, so that the addition of chemicals was not required. A final comparison was
made in terms of the single EF process and the new EC-Fenton. Results have shown an improve
ment of the 30% for TOC removal efficiency by using this new technique, and energy consumption
decreased by up to 92%. More research efforts need to be done in this field of interest as new elec
trode materials can be discovered (An et al. 2019).
Among the applications of EC, wastewater treatment from the textile, food, oil, pulp and paper,
and pharmaceutical industries were discussed so far. However, there are other uncommon types of
wastewater, for instance, cooling tower blowdown water could also possibly be treated by EC, due
the presence of scale-forming species. Specifically, hardness ions (Ca2+ and Mg2+) and dissolved
silica are considered as the scale-forming species mentioned in this report. These pollutants are
generated when water evaporates from the cooling tower, when solids concentrate in water, caus
ing scale deposits over heat transfer surfaces. Therefore, hardness and silica ions must be removed
in order to avoid decreasing efficiencies in terms of heat transfer. Sampling was made from a urea
fertilizer industry in Egypt (Hafez et al. 2018). In this case, three different electrode materials were
tested (Al, Fe, and Zn) and aluminum appeared to be more efficient than the other two materials,
as removal efficiencies of 55.4% and 99.5% for both hardness and silica ions were obtained, respec
tively. Additionally, at optimum conditions, power consumption is also lower for the Al electrodes
(Hafez et al. 2018).
Future perspectives for electrode materials in EC processes should be focused to treat other types
of wastewater, so that more industries can employ EC as a cost-effective water treatment technique.
In consequence, new materials could be developed as electrodes.
Considering a recent report including wastewater from the olive mill industry, EC was combined
with a novel technique called the catalytic sonoperoxone process (Khani et al. 2019). Here, EC
was performed to improve the biological degradability of the mentioned wastewater. In this case,
traditional EC was performed using Fe and Al electrodes followed by several processes involving
advanced oxidation processes. In other words, EC was carried out as a pretreatment, whereas the
other processes were assessed to determine which one was better for removal efficiency. These
techniques are the following: single ozonation process (SOP), catalytic ozonation process (COP),
ultrasonic process (US), H2O2, COP/US, a peroxone process (H2O2/O3), and a catalytic sonoperox
one process (H2O2/COP/US). This last one is a combination of the others. In terms of total organic
carbon removal, Figure 12.3 shows the efficiency of each AOP.
A previous EC pretreatment was performed in order to evaluate the removal performance of both
iron and aluminum electrodes. Here, the optimal conditions were reached using the Fe electrodes.
Then, the AOPs were performed over the pretreated water from EC at optimal conditions. As can
be seen in Figure 12.3, the catalytic sonoperoxone process showed better performance since a 75%
TOC removal was obtained with this technique (Khani et al. 2019).
FIGURE 12.3 Wastewater degradability for different AOPs. (From Khani et al. 2019.)
FIGURE 12.4 Comparison of the textile wastewater sample before and after the treatments. (From Tavangar
et al. 2019.)
On the other hand, the combination of EC with a nanofiltration (NF) process was performed to
treat wastewater from the textile industry (Tavangar et al. 2019). Here, an individual comparison
between EC and NF was made, and then their hybrid (EC-NF) was assessed. Figure 12.4 shows a
comparison of the samples after the treatment.
For the EC process, Al, Fe, and Ti electrodes were used. Al has appeared as the best of these
three materials, reaching 64% and 94% of COD and color removal, respectively. On the other
hand, NF was made using an NF membrane, which achieved more than 87% color removal.
In the end, EC-NF is expected to improve certain drawbacks of the individual processes. For
instance, NF can remove the color of the solutions remaining from EC, thus improving the
whole process performance. Once again, EC is intended to be a pretreatment that works at
decreasing the membrane contamination, so that permeate flux can increase. Overall results
led to a 95% color removal and 99% turbidity removal for the EC-NF hybridization (Tavangar
et al. 2019).
Table 12.2 provides an overview of some recent studies about EC-based processes.
12.6 CONCLUSIONS
In this work, we have outlined the approach of using the EC process to treat wastewaters from dif
ferent industries that contain toxic and nonreadily biodegradable pollutants (e.g., textile, pulp and
paper mill, food, oil, and pharmaceutical industries). As detailed in Section 12.3, many operational
factors play an important role in the removal efficiency of the EC process, including the electrode
material, pH, electrode arrangement, current density, temperature, and conductivity. The choice of
an appropriate electrode material is a crucial issue to ensure the success of EC through the in situ
formation of coagulating agents that can remove several pollutants from effluents.
According to the results of this chapter, it has been detailed that both aluminum and iron work
better as electrode materials for the EC process. However, in the last years, many studies have
focused on developing new electrode materials for EC, such as the use of stainless steel, zinc, cop
per, and titanium-based anodes, as indicated in Section 12.4. On the other hand, different combina
tions among the EC process and other wastewater treatment technologies have been employed to
remove some pollutants from industrial effluents that are not easily removed by conventional meth
ods. Particularly, it has been detailed in Section 12.5 that the use of EC with other electrochemical
processes and advanced oxidation processes allow removal of refractory compounds from many
types of effluents, reaching removal efficiencies close to 100%, and therefore improving the water
quality of the mentioned wastewaters.
TABLE 12.2
Overview of Recent Reports about Future Perspectives for EC-Based Wastewater Treatment Processes
Process Pollutant/Wastewater Electrodes Removal Efficiency (%) Reference
EC-Fenton Cyanobacteria/cyanotoxins Fe, graphite and a Ti/ Cyanobacterial cells (98), An et al. 2019
IrO2 counter electrode Microcystins (100),
TOC (96)
EC Hardness (H) and dissolved silica (DS) from Al, Fe, Zn Al: H (55), DS (100); Hafez et al. 2018
cooler tower blowdown water Fe: H (37), DS (99);
Zn: H (39), DS (96)
EC-H2O2/COP/US Olive mill wastewater Fe, Al TOC (75) Khani et al. 2019
Materials Involved in Electrocoagulation Process
EC-Nanofiltration Textile wastewater Al, Fe, Ti Color (95), Tavangar et al. 2019
Turbidity (99)
EC-AOP (photoelectro–Fenton and Raw cheese whey wastewater Fe, Al, SS (AISI 304 TOC (49) Tirado et al. 2018
electrochemical oxidation) and AISI 316 L)
EC-Fenton Oil mill effluent Fe COD (100) Chairunnisak et al. 2018
EC-AOP (peroxi–coagulation, anodic Mixture of reactive dyes (mainly methylene blue) Fe, Boron doped Optimal EC-Fenton: TOC (97), Zazou et al. 2019
oxidation, and electro–Fenton) diamond (BDD) Turbidity (100),
Color (100)
EC-Electrooxidation (EC–EF), Canola oil refinery wastewater Al, BDD, SS EC-EF: Sharma and Simsek 2019
Electrochemical peroxidation (ECP) Soluble COD (99)
209
ACKNOWLEDGMENTS
This work was financially supported by a grant from CONICYT (Scholarship Programs No.
21150520 and 21151390). The authors acknowledge the support of Escuela Politécnica Nacional,
Ecuador, through the Internal Project PII-DCN-2012.
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13 Role of Organic Materials in
S. Ganesan
CONTENTS
13.1 Introduction .......................................................................................................................... 217
13.2 Photoelectrochemical Measurements ................................................................................... 219
13.2.1 Preparation of Solar Cells......................................................................................... 220
13.3 Organic Materials as Photosensitizers in Dye-Sensitized Solar Cells ................................. 220
13.3.1 Organic Molecules as Additives in Redox Electrolyte in DSSCs ............................ 220
13.3.2 Conductivity Studies of Organic Compounds as Additives in

Polymer Electrolytes................................................................................................. 221
13.3.3 Differential Scanning Calorimetry (DSC) with Organic Molecules
as Additives in Polymer Electrolytes........................................................................ 223
13.3.4 X-Ray Diffraction (XRD) Studies ............................................................................224
13.3.5 Scanning Electron Microscope (SEM) Analysis of Organic-Compound-Doped

Polymer Electrolytes................................................................................................. 225
13.3.6 Photoelectrochemical Analysis................................................................................. 225
13.4 Conclusions........................................................................................................................... 228
References...................................................................................................................................... 229
13.1 INTRODUCTION
In the context of environmental concerns, solar energy systems offer more advantages in that they
are clean and emit no pollutants into the atmosphere. Solar energy is renewable, whereas fossil
fuels are not. In recent years, an ever-increasing interest has been directed toward photoelectro
chemical processes as applied for solar energy to electric energy conversion (Harris and Wilson
1978; Memming 1980; Fujishima and Honda 1972; Maruthamuthu and Ashokkumar 1988; Chapin
et al. 1954). In dye-sensitized solar cells, a di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,2′
bipyridyl-4,4′-dicarboxylato)ruthenium(II) (N719 dye)-coated TiO2 on fluorinated tin oxide (FTO)
was employed as the working electrode, the KI and I2 in acetonitrile solvent as redox electrolyte, and
platinum-coated FTO as the counter electrode (O’Regan and Gratzel 1991). Dye-sensitized solar
cells (DSSCs) are assured as next-generation solar cells due to their potentially high conversion effi
ciency (Nazeeruddin et al. 1993). However, the liquid electrolyte in DSSCs creates low stability, due
to easy evaporation of solvent and sublimation of iodine. For the past two decades, most research
groups focused on replacing of liquid electrolyte by polymer electrolyte, gel polymer electrolyte,
incorporation of inorganic fillers such as Al2O3 and ZnO, and organic compounds as plasticizers
(Kubo et al. 2001; Tennakone et al. 1998; Kruger et al. 2002; Wang et al. 2003; Nogueira et al. 2002;
McFarland and Tang 2003; O’Regan and Schwartz 1996) with polymer electrolytes.
To make a dye-sensitized solar cell, a solution containing nanoparticles of TiO2 is pasted on
an FTO-coated conducting glass plate, then dried and heated to form a porous, high surface area
TiO2 structure that when magnified would look like a thin membrane. The prepared TiO2 film
on FTO plate is dipped into a solution of a cis-dithiocyanato-bis(2,2′bipyridyl-4,4′-dicarboxy)
217
ruthenium (II) (N3 dye). To complete the device, a drop of liquid electrolyte containing potassium
iodide and iodine as electrolyte placed on the TiO2 film and the platinum-coated FTO plate as a
counter electrode forms sandwich-type solar cells that are illuminated through the TiO2 film. The
possibility for charge transfer within the dye layer is low, and hence it is reasonable to assume that
only a very thin layer is interconnected in the case of nanocrystalline DSSCs. The electrons lost by
the N3 dye through light absorption are replaced by the mediator, which is the iodide ion within the
redox electrolyte. The oxidized mediator forms I− and I3−, which in turn obtains an electron at the
counter electrode after it has moved through the circuit.
The energy producing reactions in the dye-sensitized solar cells are
Dye + light ® Dye* (13.1)
Dye* + TiO2 ® e ( TiO2 ) + oxidized dye (13.2)
Oxidized dye + 3/2 I ® Dye + ½ I3 (13.3)
1 2 I3 + e ( counter electrode ) ®3 2 I (13.4)
The voltage produced by the DSSC is the difference in energy levels between the TiO2 and the
electrolyte, and depends on the electrolyte and solvent used as well as the conduction of TiO2 apart
from the intensity of illumination (Gratzel 2003; O’Regan and Gratzel 1991; Smestad et al. 1994;
Nazerruddin et al. 1993). The DSSC is a photoelectrochemical cell that resembles natural photosyn
thesis in two respects: (1) the organic dye molecule acts like chlorophyll to absorb light and produce
a flow of electrons, and it uses multiple layers to enhance both the light absorption and electron
collection efficiency (Equation 13.2). The choice of the charge mediator, the electrolyte material,
and its composition are also crucial in making efforts to obtain optimized overall efficiencies of
DSSC. For more than a decade most research groups focused on modifying dye-sensitized solar
cells. The presence of redox couple in the electrolyte is of crucial importance for the stable opera
tion of a DSSC, and in transporting the charge between the photoanode and the counter electrode
during regeneration of the dye. The ionic liquid electrolyte has been actively pursued as a nonvola
tile electrolyte for DSSCs (Oskam et al. 2001; Papageorgiou et al. 1996). Molten salts based on
imidazolium iodides have revealed very attractive stability features (Murai et al. 2003; Matsumoto
et al. 2001; Wand et al. 2002). Owing to their high viscosity, linear photocurrent response up to full
light intensities have been observed. The redox electrolyte (I−/I3−) system in DSSCs provides contact
between the solar cell electrodes (working and counter), and it exists in different forms such as solid
or liquid. The redox electrolytes typically working in photoelectrochemical solar cells are dissolved
in organic solvents, as the dye degenerates in the presence of solvent. For long-term operation, liquid
electrolytes cause stability problems due to leakage of solvent, sensitivity to air and water, as well
as elevated temperatures (Wang et al. 2003; Kuciauskas et al. 2001; Alebbi et al. 1998). The organic
molecules are like dendrimers with regular and highly branched three-dimensional structure with
variety of applications in light harvesting systems.
In recent years organic dyes such as BODIPY and carbazole-based dendrimers with or without
metal complexes were analyzed. Organic sensitizers/dyes (Yen et al. 2012; Mishra et al. 2009)
gained popularity in recent decades and are replacing metal-based dyes due to their easy structural
design, high absorbance value, and low cost when compared to the expensive Ru metal. Organic
sensitizers consist of a D-π-A type molecular structure (Liang and Chen 2013; Wu and Zhu 2013).
When the sensitizer absorbs the incident light, a push–pull mechanism operates between the donor
(D) molecules and acceptor (A) molecules through π conjugation, which results in the intramolecu
lar charge transfer. The synthesized dendrimer macromolecules with highly disperse structure and
excellent material are made more attractive by adding organic molecules of some functionality at the
Role of Organic Materials in Electrochemical Applications 219
margin to create versatile macromolecules for solar to electric energy conversion. The carbazole
based dendrimer is an excellent hole transporting material with high ability for donating electrons
and is broadly used in DSSCs (Degbia et al. 2014). Some research groups focused on modifying
and replacing N3 dye with organic molecules particularly BODIPY. Hattori and coworkers (2005)
first introduced the synthesized BODIPY as a photosensitizer for dye-sensitized solar cells. Zhang
et al. (2016) reported 4.42% efficiency with 9H-carbazol-9-yl group-based BODIPY core molecules.
Other than dye molecules, the electrolyte in DSSCs plays a vital role in determining efficiency (Wu
and Zhu 2013). The redox couple is more responsible for electron transfer and regeneration of the
Ru metal complex dye molecules. Leakage and evaporation of electrolyte are the major problems
faced when we use the liquid electrolyte and thus reduced the durability of the cells, which results
in very low performance in harvesting solar energy. When I−/I3− redox mediator in the electrolyte
is used, the results in the sublimation of iodine from the cell also drastically affect the performance
of the DSSCs. Satoh et al. (2005) reported the use of a fifth generation hole transporting phenylazo
methine-based dendrimer and triphenylamine core as an additive to improve the efficiency of solar
energy harvesting systems with Ru (II)-based dye molecules. Similarly, nitrogen- and sulfur-based
heterocycles are employed as additives in redox couple electrolyte solutions to improve the solar to
electric energy conversion efficiency of DSSCs (Kusama et al. 2008).
In the polymer electrolyte field, polymer blending techniques are used to increase the conductiv
ity of the polymer and enhance the efficiency of DSSCs (Nogueira et al. 2001; Stathatos et al. 2001;
Wang et al. 2004; Katsaros et al. 2002; Masamoto et al. 1996). The presence of polar moiety such as
ether linkage (-C-O-C-) in PEO, ester linkage (-COO-) in PMMA, and high electronegative atoms
(-CF2-) in PVdF exhibit reasonable ionic conductivities and eliminate the problems of sealing and
solvent leakage (Liu et al. 2004; Kim et al. 2005; Scully et al. 2001; Lee et al. 2008; Ganesan et
al. 2013). The incorporation of organic compounds, namely 2,6-bis (N-pyrazolyl)isonicotinic acid
(BNIN) (Ganesan et al. 2013), 2,6-bis(2-thiopyridyl) pyridine (BTPP) (Ganesan et al. 2016), and
2,6-bis (N-pyrazolyl) pyridine (BNPP) (Donald and Kenneth 1990) in polymer electrolyte reduce
the sublimation of iodine in the redox couple and tend to shift the negative band of TiO2 and improve
open-circuit voltage (Voc) (Kusama et al. 2008; Ganesan et al. 2013; Ganesan et al. 2016).
13.2 PHOTOELECTROCHEMICAL MEASUREMENTS

When the circuit system containing DSSC is switched on by light, a voltage is developed, which
under infinite load resistance is called the open-circuit voltage, Voc, and then by connecting the ter
minals directly, thus closing the circuit, the so-called short-circuit current, Jsc, can be obtained. To
compare the current–voltage (J-V) characteristics for each dye-sensitized solar cell, the illuminated
areas were measured separately, and the Jsc is introduced and most often chosen. The efficiency of
the solar energy to electric energy conversion is generally distinct by the ratio between the maxi
mum power output and the power of the incident sunlight. The performance of the solar cell also
depends on the fill factor, representing the ratio of the maximum power output to the product of the
short-circuit current and the open-circuit voltage. The photocurrent–photovoltage diagrams were
monitored and recorded using a BAS 100A electrochemical analyzer unit.
The short-circuit current density (Jsc) and the open-circuit voltage (Voc) were calculated from the
J-V curve. The fill factor (FF) and the solar to electric energy conversion efficiency (η) were deter
mined using the following equations, where Ps means the power of the incident (solar) light (W m−2).
(JV )MAX
FF = (13.5)
J scVoc
J SC ×VOC × FF
h= (13.6)
Ps
Dye-sensitized solar cells
Working electrode Counter electrode (Platinum or

(transparent, dye-sensitized, nanocrystalline carbon coated on FTO electrode)
and porous TiO2 film coated on a conducting
fluorine-doped tin dioxide (FTO) glass)
Electrolyte
sandwiched
SCHEME 13.1 The schematic diagram for the preparation of dye-sensitized solar cells.
The value of the maximum power point, (JV)MAX, was received from the largest area of a rectangle
possible under the J-V curve. The product of Jsc and Voc, being the point of connection with their
axes, is the area of a rectangle formed outside the J-V curve. The solar cells were irradiated by a
tungsten halogen lamp (OSRAM, Germany) providing AM 1.5.
13.2.1 prEparation of solar cElls

Solar cells containing two electrodes merged into a sandwich-type construction have been prepared.
The active area of the cell was 1 cm2 (Scheme 13.1).
13.3 ORGANIC MATERIALS AS PHOTOSENSITIZERS

IN DYE-SENSITIZED SOLAR CELLS
The organic compound carbazole dendrimer (Figure 13.1) based BODIPY (Janakiramanbabu et al.
2018) (Figure 13.2) was used as a photosensitizer in dye-sensitized solar cells with a good efficiency
of 2.7%. The photosensitizing ability of the dendrimer with carbazole moiety acts as the electron
donating unit, the BODIPY core acts as the electron acceptor, and the BODIPY is anchored to TiO2
material and the transporting role is played by the triazole units in between them.
13.3.1 organic MolEculEs as additivEs in rEdox ElEctrolytE in dsscs

The performance of DSSCs mainly depends on (1) concise charge recombination fatalities at the
interface of N3 dye coated TiO2 and redox electrolyte and (2) the dye restoration efficiency. The
charge recombination at the interface of the TiO2 and redox electrolyte leads to loss in the short-
circuit current (Jsc) and the open-circuit voltage (Voc), resulting in a decrease in solar to electric
energy conversion efficiency. In general, the addition of organic nitrogenous compounds in potas
sium iodide and iodine significantly improves the open-circuit voltage, which is commonly recog
nized by the shift of the conduction band edge of TiO2 toward more negative potentials, and this is
FIGURE 13.1 The structure of carbazole-dendrimer-based BODIPY as photosensitizer for DSSCs.
FIGURE 13.2 The schematic diagram of an organic molecule as a photosensitizer for dye-sensitized solar cells.
probably attributed to electron recombination between TiO2 and redox electrolyte in dye-sensitized
cells. The synthesized cyclohexadienone cored 3,6-ditertiary butyl carbazole decorated triazolyl
bridged dendrimers (Figure 13.3) with I−/I3− (Babu et al. 2019) increased the current and Voc and
reported high efficiency and more stability up to 85% in one week (Figure 13.4).
13.3.2 conductivity studiEs of organic coMpounds

as additivEs in polyMEr ElEctrolytEs
Figure 13.5 shows the conductivity of polymer electrolyte based on PEO-PVdF/KI/I2 with organic
compounds such as 2,6, bis (N-pyrazolyl) methyl isonicotinate (BNMI), 2,2′-((4-methyl pyri
dine-2,6-diyl) bis (sulfanediyl)) dipyridine (MBSD), and 2,6-bis (N-pyrazolyl) 4-methyl pyridine
(BNMP), and the conductivity values are listed in Table 13.1. The organic compounds (Figure 13.6)
nitrogen, oxygen, and sulfur have a lone pair of electrons that can interact with iodine in redox elec
trolytes, which decreases the sublimation and enhances the conductivity of polymer (Kang et al.
2005; Wu et al. 2006; Jacob et al. 1997). The BNMI-doped polymer electrolyte reports high con
ductivity of 5.7 × 10 −4 Scm−1. The BNMI organic molecule has nitrogen and oxygen with resonance
activity; they easily interact with iodine in polymer electrolytes, which increases the segmental
motion and enhances the conductivity.
FIGURE 13.3 Structure of cyclohexadienone cored carbazole dendrimer.
FIGURE 13.4 A schematic diagram of carbazole-dendrimer-doped additive for DSSC performance.
COOCH3
N
N N N
N
2,6, bis (N-pyrazolyl) methyl isonicotinate (BNMI)
S N S
N N
2 2’-((4-methyl pyridine-2,6-diyl) bis (sulfanediyl)) dipyridine (MBSD)
N
N N N
2,6-bis (N-pyrazolyl) 4-methyl pyridine (BNMP)
FIGURE 13.5 The structure of synthesized organic compounds as plasticizer for PEO-PVdF/potassium
iodide/iodine.
TABLE 13.1
DSC and Conductivity Data of Polymer Electrolyte Systems
System Melting Melting Degree of Conductivity
Temperature Enthalpy Crystallinity (σ) Scm−1
(Tm) °C (ΔHm) J/g (χc)
PEO-PVdF/potassium × iodide/iodine 36 53 29 4.5 × 10−5
PEO-PVdF/potassium × iodide/iodine/BNMI −23 −24 13 5.7 × 10−4
PEO-PVdF/potassium × iodide/iodine/MBSD −19 −33 18 3.1 × 10−4
PEO-PVdF/potassium × iodide/iodine/BNMP −18 −38 21 2.6 × 10−4
9000
(a)
8000 (d)
(b)
7000 (c)
6000
5000
Z’’ (Ohm)
4000
3000
2000
1000
0
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Z’ (Ohm)
FIGURE 13.6 Complex impedance graph of (a) PEO-PVdF/potassium iodide/iodine, (b) PEO-PVdF/potas
sium iodide/iodine/BNMI, (c) PEO-PVdF/potassium iodide/iodine/MBSD, and (d) PEO-PVdF/potassium
iodide/iodine/BNMP.
13.3.3 diffErEntial scanning caloriMEtry (dsc) With organic

MolEculEs as additivEs in polyMEr ElEctrolytEs
As seen in Figure 13.7a the melting temperature of 36°C and high enthalpy of 54 J/g resulted in the
appearance of more crystallinity for the PEO-PVdF/potassium iodide/iodine system. However, the
melting enthalpy and melting temperature were shifted by the incorporation of synthesized organic
compounds, namely BNMI, MBSD, and BNMP to poly (ethylene oxide)/poly (vinylidene fluoride/
potassium iodide/iodine, and these values are listed in Table 13.1. As seen in the Figure 13.7b–d,
the melting temperatures observed for the synthesized organic compounds of BNMI-, MBSD-, and
BNMP-doped polymer blends are −23°C, −19°C, and −18°C, respectively. The changes in melting
temperature confirm the free segmental motion of polymers, which decreases the crystallinity of
polymers and enhances the conductivity.
The degree of crystallinity (χc) in the polymer electrolyte was calculated by using the following relation:
cc = ΔH m /ΔH m ° × 100
where ∆Hm° represents the pure melting enthalpy of PEO (~181.3).

Exo
(d)
Heat flow (a.u)
(c)
(b)
(a)
–50 0 50 100
Temperature (°c)
FIGURE 13.7 The differential scanning calorimetry curves of (a) PEO-PVdF/potassium iodide/iodine, (b)
PEO-PVdF/potassium iodide/iodine/BNMI, (c) PEO-PVdF/potassium iodide/iodine/MBSD, and (d) PEO
PVdF/potassium iodide/iodine/BNMP.
13.3.4 x-ray diffraction (xrd) studiEs

Figure 13.8 confirms the morphological studies of changes of the polymer electrolyte samples poly
(ethylene oxide)/poly (vinylidene fluoride)/potassium iodide/iodine and incorporation of organic
compounds (BNMI, MBSD, and BNMP). The figure shows the x-ray diffraction (XRD) peak is
broader and less intense due to the incorporation of organic compounds with polymer electrolytes.
The broadening of the XRD peak confirms the low crystallinity of the polymer, which increases the
conductivity as well as the efficiency of DSSCs (Ganesan et al. 2011; Yang et al. 2008). This XRD
again proves the important role of organic compounds with polymer electrolytes.
(c)
Intensity (a.u)
(d)
(b)
(a)
10 20 30 40 50 60 70
2 q (degree)
FIGURE 13.8 XRD patterns obtained for (a) PEO-PVdF/potassium iodide/iodine, (b) PEO-PVdF/potassium
iodide/iodine/BNMI, (c) PEO-PVdF/potassium iodide/iodine/MBSD, and (d) PEO-PVdF/potassium iodide/
iodine/BNMP.
13.3.5 scanning ElEctron MicroscopE (sEM) analysis of organic

coMpound-dopEd polyMEr ElEctrolytEs
Figure 13.9 shows the scanning electron microscope (SEM) images at 30 μm of PEO-PVdF/potas
sium iodide/iodine, PEO-PVdF/potassium iodide/iodine/BNMI, PEO-PVdF/potassium iodide/
iodine/MBSD, and PEO-PVdF/potassium iodide/iodine/BNMP. As seen in Figure 13.9a, there is
very little space between the spherical grains, confirming that PEO-PVdF/potassium iodide/iodine
possesses considerable crystallinity. The organic-compound-doped PEO-PVdF/potassium iodide/
iodine system (Figure 13.9b–d) shows free space between the spherical grains and confirming more
randomness in the polymer. It is well known that an increase in randomness decreases the degree
of crystallinity. As seen in Figure 13.9b, the BNMI-doped polymer electrolyte shows more space
between the spherical grains and it confirms that BNMI has more interaction with the redox couple
due to its higher number of lone pairs of electrons from nitrogen and oxygen. This result also holds
good with conductivity, DSC, and XRD results.
13.3.6 photoElEctrochEMical analysis

Figure 13.10 shows the current–voltage curve of the doped and undoped organic compound polymer
electrolytes of PEO-PVdF/potassium iodide/iodine, PEO-PVdF/potassium iodide/iodine/BNMI,
PEO-PVdF/potassium iodide/iodine/MBSD, and PEO-PVdF/potassium iodide/iodine/BNMP. The
short-circuit current (Jsc), the open-circuit voltage (Voc), fill factor, and conversion efficiency values
for DSSCs employing the undoped and BNMI-, MBSD-, and BNMP-doped polymer electrolytes
are listed in Table 13.2. The Voc and Jsc values and efficiency were high with synthesized organic
compound-doped polymer blend electrolytes compared to undoped organic compound (PEO-PVdF/
potassium iodide/iodine). The conversion efficiency of 9.5% and 8.9% under the illumination of 60
mW cm−2 was observed with the MBSD- and BNMP-doped polymer electrolyte, and the BNMI-
added polymer electrolyte reported high efficiency of 9.9% in PEO-based DSSC field. Usually,
organic nitrogenous compounds influence the redox couple to make it more stable and enhance the
conversion efficiency of DSSC (Ganesan et al. 2008; Kusama et al. 2005; Kawano et al. 2004). The
organic compounds MBSD, BNMP, and BNMI possess conjugated aromatic ring and a lone pair
of electron from nitrogen, oxygen and sulfur, which interact with iodine in the redox electrolyte.
The schematic electron transfer mechanism of organic nitrogenous compound-doped PEO-PV dF/
potassium iodide/iodine polymer blend electrolyte is shown in Figure 13.11. Table 13.3 represents
the results of research on particularly organic compounds as additives in redox electrolyte-based
performance of dye-sensitized solar cells, and this result reveals that the synthesized organic com
pound-doped electrolyte is best in DSSCs. Table 13.4 reports the research on organic molecules as
photosensitizer dye instead of Ru complex dye in dye-sensitized solar cells. These results confirm
that the organic molecules work best in dye-sensitized solar cells.
TABLE 13.2
Current and Voltage Data of DSSCs Fabricated Using Synthesized Organic-Compound
Doped PEO-PVdF/Potassium Iodide/Iodine under Illumination of 60 mW cm−2
Voltage Current Fill Efficiency
System (mV) (mA) Factor (η) %
TiO2/N719dye/PEO-PVdF/potassium iodide/iodine/Pt 690 5.7 0.47 3
TiO2/N719dye/PEO-PVdF/potassium iodide/iodine/BNMI/Pt 890 13.4 0.5 9.9
TiO2/N719dye/PEO-PVdF/potassium iodide/iodine/MBSD/Pt 881 12.7 0.51 9.5
TiO2/N719dye/PEO-PVdF/potassium iodide/iodine/BNMP/Pt 874 12 0.51 8.9
FIGURE 13.9 Scanning electron microscope (SEM) images of organic-compound-doped polymer elec
trolyte for (a) PEO-PVdF/potassium iodide/iodine, (b) PEO-PVdF/potassium iodide/iodine/BNMI, (c) PEO
PVdF/potassium iodide/iodine/MBSD, and (d) PEO-PVdF/potassium iodide/iodine/BNMP.
14
(a)
13
(d)
12
(c)
11 (b)
10
9
Current (mA) 8
7
6
5
4
3
2
1
0
0 100 200 300 400 500 600 700 800 900 1000
Voltage (mV)
FIGURE 13.10 The photovoltaic (I-V) curves under 60 mWcm−2 illumination of DSSCs fabricated of
(a) PEO-PVdF/potassium iodide/iodine, (b) PEO-PVdF/potassium iodide/iodine/BNMI, (c) PEO-PVdF/potas-
sium iodide/iodine/MBSD, and (d) PEO-PVdF/potassium iodide/iodine/BNMP.
FIGURE 13.11 The electron transfer mechanism taking place in the DSSCs fabricated using organic com-
pound doped as additive in PEO-PVdF/potassium iodide/iodine.
TABLE 13.3
Comparison of Efficiency of Organic Compound as Additive in Redox-Electrolyte-Based
Dye-Sensitized Solar Cells
Organic Compound Redox Dye Used Photo Photo Efficiency
Used As Additive Couple in DSSC Anode Cathode Attained Reference
(4,4′-((((oxybis(ethane-2,1 I−/I3− N719 TiO2 Platinum 9.2% Karthika et al. 2018
diyl))bis(oxy))bis(ethane
2,1diyl))bis(sulfanediyl))
dipyridine))
1,1′-(3,3′,5,5′-tetramethyl Co2+/Co3+ N719 TiO2 Platinum 9.10% Karthika et al. 2019
[1,1′-biphenyl]-4,4′-diyl)
bis(3-(3,4,5-trimethoxy
phenyl)thiourea)
Cyclohexadienone cored I−/I3− N3 TiO2 Platinum 9% Babu et al. 2018
3,6-ditertiary butyl carbazole
decorated triazolyl dendrimer
Triazole-based phenothiazine I−/I3− N3 TiO2 Platinum 8.6% Rajakumar et al. 2013
dendrimer
Phenothiazine I−/I3− N3 TiO2 Platinum 8.5% Ganesan et al. 2013
TABLE 13.4
Comparison of Efficiency of Organic Compound as Photosensitizer Dye in Dye-Sensitized
Solar Cells
Organic Compound Used As Redox Photo Photo Efficiency
Photosensitizer Couple Anode Cathode Attained Reference
BODIPY dendrimer I /I3
− − TiO2 Platinum 2.7% Janakiraman Babu et al. 2018
9H-carbazol-9-yl group based BODIPY I−/I3− TiO2 Platinum 4.4% Zhang et al. 2016
3,6-ditert-butyl-9H-carbazole I−/I3− TiO2 Platinum 2.66% Barea et al. 2010
BODIPY with N-carbazole I−/I3− TiO2 Platinum 0.67% Cheema et al. 2016
Benzothiadiazole- hexylthiophene I−/I3− TiO2 Platinum 1.96% Yang et al. 2010
13.4 CONCLUSIONS
In the photoelectrochemical field, particularly dye-sensitized solar cells, the organic molecule plays a
vital role. In dye-sensitized solar cells, the dendrimer-based BODIPY molecule reports good solar to elec
tric energy conversion efficiency. The organic compounds were reported as the best additives, with high
conversion efficiency with polymer electrolyte-based dye-sensitized solar cells. The influence of organic
compounds, such as BNMI, MBSD, and BNMP as additives, with PEO-PVdF/potassium iodide/iodine–
based polymer electrolyte systems were successfully analyzed. The organic compounds BNMI, MBSD,
and BNMP have an aromatic ring and special atoms like N, S, and O, and have more lone pairs of elec
trons. These electrons interact well with iodine in the redox electrolyte to minimize the sublimation of
iodine leading to enhanced stability and efficiency of DSSCs. XRD, SEM, DSC, and conductivity stud
ies also proved the organic-doped polymer electrolytes decrease the degree of crystallinity of polymer
sand improves the conductivity. High efficiencies for solar energy to electric energy conversion—9.9% for
BNMI-, 9.5% for MBSD-, and 8.9% for BNMP-doped polymer electrolytes—were also reported.
ACKNOWLEDGMENTS
The authors are sincerely thankful to the Department of Science and Technology (DST) Fast Track,
New Delhi, for financial support (SB/FT/CS-063/2013).
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14 Advanced Conducting
Polymers for Electrochemical
Applications
R. Suresh, R. V. Mangalaraja, Paola Santander,
and Jorge Yáñez
CONTENTS
14.1 Introduction .......................................................................................................................... 233
14.2 Examples of Conducting Polymers....................................................................................... 234
14.2.1 Polyaniline and Its Derivatives................................................................................. 234
14.2.2 Polythiophene and Its Derivatives ........................................................................... 235
14.2.3 Polypyrrole ............................................................................................................... 235
14.3 Electrochemical Applications of Conducting Polymers....................................................... 235
14.3.1 Solar Cells................................................................................................................. 235
14.3.2 Batteries .................................................................................................................... 238
14.3.3 Fuel Cells .................................................................................................................. 238
14.3.4 Supercapacitors.........................................................................................................240
14.3.5 Electrochemical Sensors...........................................................................................240
14.4 Conclusions........................................................................................................................... 245
References...................................................................................................................................... 245
14.1 INTRODUCTION
The polymer is a long-chain organic molecule that is made up of a number n of repeating units, usually
known as “monomers.” For example, polyethylene is composed of n ethylene monomers. Moreover,
polymers such as polyvinyl chloride (PVC), polyethylene terephthalate (PET), polytetrafluroethyl
ene (PTFE), and polymethylmethacrylate (PMMA) are widely used in our daily lives. Based on the
electrical conductivity, polymers are classified as (a) nonconducting or insulating polymers, and (b)
metallic or semiconducting or conducting polymers. As the name implies, nonconducting polymers
don’t conduct electricity. Polyethylene and polyvinyl chloride are examples of insulating polymers.
On the other hand, conducting polymers (CPs) conduct electricity due to the presence of conjugated
double bonds in their structure. Poly(ethylenedioxythiphene), polypyrrole, polyfuran, polyaniline,
polyindole, polyacetylene, poly(thieno[3,2-b]thiophene), and poly(phenylene-vinylene) are some of
the typical examples of widely used CPs (Figure 14.1). CPs have high electrical conductivity due
to delocalization of π electrons through the polymer chain. They also exhibit magnetic, optical,
mechanical, and redox properties. They have high chemical sensitivity, easy processability, are
lightweight, and microwave shielding properties when compared to insulating polymers (Das and
Prusty 2012).
CPs in nanoscale with different morphologies are of particular interest. Like inorganic nanopar
ticles, the nanostructures of CPs significantly differ from their bulk form (Ghosh et al. 2016). CP
233
FIGURE 14.1 Structure (undoped form) of (a) poly(ethylenedioxythiphene), (b) poly(pyrrole),

(c) poly(furan), (d) poly(aniline), (e) poly(indole), (f) poly(acetylene), (g) poly(thieno[3,2-b]thiophene) and
(h) poly(phenylene-vinylene).
nanomaterials have served in catalysts; photocatalysts; drug delivery agents; electroheological flu
ids; EMI shielding; light emitting diodes; lithium sulfur batteries; electrodes in solar cells; chemical,
gas, and biosensors; field-effect transistors; field emission devices; electrochromic display devices;
tissue engineering; and supercapacitors (Das and Prusty 2012; Ghosh et al. 2016; Malinauskas et al.
2005). Among many applications, the vital role of CPs in electrochemical devices such as solar
cells, batteries, fuel cells, supercapacitors, and electrochemical sensors are discussed in this book
chapter.
14.2 EXAMPLES OF CONDUCTING POLYMERS

14.2.1 polyanilinE and its dErivativEs
In the 19th century, Henry Lethe discovered polyaniline (PANI) during his experiments on “oxi
dation of aniline” (Bhandari 2018) (Figure 14.2). Later, it gained much attention from researchers
worldwide due to its low weight, easy synthesis, flexibility, low cost, and good stability. The opti
cal absorption coefficient of PANI is also very high. Therefore, it can trap vast amounts of light
from solar radiation. It can be easily doped with inorganic or organic acids, thereby tuning its
electrical conductivity. However, it suffers in practical applications due to its poor processability.
Advanced Conducting Polymers for Electrochemical Applications 235
H H
N N N N
y 1-y
Polyaniline
S D S D S *
S S
n
Polythiophene
N D N D N *
N N
n
Polypyrrole
FIGURE 14.2 Structure of conducting polymers in doped form. D – represents anionic dopant.
To solve this issue, researchers introduced polar functional groups (-COOH, -OH, -OCH3) in
PANI, i.e., substituted PANI such poly(2-methoxyaniline) and poly(anthranilic acid) have been
prepared.
14.2.2 polythiophEnE and its dErivativEs

In the early 1980s, polythiophene (PT) (Jaymand et al. 2015) was first synthesized via oxida
tive polymerization of thiophene monomer. Nowadays, PT (Figure 14.2) and its derivatives are
the most attractive conducting polymer nanomaterials in electrochemical devices. Like PANI,
unsubstituted PT is also insoluble in many solvents, which made it poor in processability. This
restriction can be invoked by functionalization in the side chain of PT. The numerous derivatives
of thiophene have been synthesized by chemical and electrochemical methods, resulting in good
processability.
14.2.3 polypyrrolE
In 1968, polypyrrole (PPY) was shown to be a conducting polymer (Vernitskaya and Efimov 1997).
It is a p-type organic semiconductor (Figure 14.2) that has broad absorption from ultraviolet (UV) to
the visible light region, easy preparation, superior electrochemical properties, electrical conductiv
ity, water solubility, and flexibility. Hence, PPY is also widely studied for its various electrochemical
applications.
14.3 ELECTROCHEMICAL APPLICATIONS OF CONDUCTING POLYMERS

14.3.1 solar cElls
A human population explosion leads to increasing demand for energy. At the same time, the inten
sive use of fossil fuels for production of energy has seriously affected our biosphere. Hence, produc
tion of energy by sustainable green technologies is of current interest. In this regard, solar cells are
promising to produce clean and sustainable energy. Moreover, solar cells can be used in portable
electronic devices, home, garden, electric vehicles, etc.
A solar cell is a device that converts incident solar radiation into electricity by the photoelectric
principle. A schematic diagram of a simple solar cell is shown in Figure 14.3 (Husain et al. 2018).
FIGURE 14.3 Schematic representation of a solar cell.
The main components of a solar cell are conductive glass substrate, an active layer, and a metal
electrode. It is generally constructed in the following way:
(a) A polymer film is made in between the photo anode and cathode.
(b) A double-layer junction is developed between the donor and acceptor material. CPs and
methano fullerene are used as donor and acceptor material, respectively.
The conversion of solar radiation into electricity occurs in the following steps: (a) The photoanode
absorbs incident solar radiation, which excites the active layer from the ground state to the excited
state, (b) excited electrons diffuse toward the interface between donor and acceptor material, (c)
charge separation occurs through the interface, and (d) charge transport and charge collection take
place at opposite electrodes.
Generally, the light harvesting capacity of a solar cell is highly dependent on the type of material
used. Therefore, the choice of appropriate materials could significantly improve the efficiency of
solar cells. In this regard, CPs are considered suitable light-absorbing materials owing to the fol
lowing reasons.
(a) High light harvesting capacity—The CP has stable photoexcitation with UV-visible light,
and thereby achieves high photon harvesting efficiency.
(b) They are lightweight materials (Awuzie 2017).
(c) They can be easily coated on flexible substrates. For example, polymer-based solar cells
are constructed by simple screen/inkjet printing, coating, and doctor blading techniques
(Krebs 2009).
(d) Relatively, monomers of CP are cheaper. Hence, they significantly reduce the cost of
devices, especially in dye-sensitized solar cells (DSSCs). Usually in DSSCs, platinum (Pt)
is used as a counter electrode, which is an extremely rare and costly metal. Therefore,
replacement of Pt counter electrode with cheaper materials is highly desirable. Herein, CP

nanostructures are also considered as one of the best alternatives for Pt counter electrodes
(Wang et al. 2018).
(e) Improved photoconversion efficiency—The CP based solar cells exhibit greater photocon
version efficiencies than Pt electrode tailored DSSCs (Liu et al. 2014).
Though pure CP-based solar cells have several merits over the inorganic solar cells, there are
some disadvantages such as low conversion efficiency and short lifetime. It was found that sunlight
induces the photochemical reaction within a polymer chain, which causes chain scission (Mehmood
et al. 2016). This reduces the charge transport property of conducting polymers, which results in a
decrease of photoconversion efficiency. To eliminate these drawbacks, the following measures have
been adopted.
(a) Structural modification/functionalization (Siddiqui et al. 2017)—The property of polymers

can be altered through the functionalization of suitable functional groups. For instance,
poly(1,5napthyridine-[3-hexylthiophene]), a functionalized thiophene polymer, has been
synthesized and its application in DSSCs studied.
(b) Conducting-polymer-based nanocomposites—To achieve better performances, a number
of binary nanocomposites such as CP-metal, CP-alloys, CP-metal oxide, CP-metal chalco
genide, CP-carbon materials, CP-C3N4, and CP-CP were prepared and their photoconver
sion efficiency determined. These composites showed improved light harvesting capacity
and hole transporting properties than their pure polymers. Also, these nanocomposites
exhibited greater or comparable photoconversion efficiency than Pt counter electrode tai
lored DSSCs (Figure 14.4). For example, PtM@PANI (M = Ni, FeNi) as counter electrodes
were fabricated for DSSCs and their photoconversion efficiencies evaluated. It was found
that PtNi@PANI and PtFeNi@PANI counter electrodes (Duan et al. 2018a) exhibited
8.52% and 8.39% photoconversion efficiency, which is greater than Pt electrodes. Recently,
PPY/carbon black nanocomposites coated counter electrode was used in DSSCs. The PPY/
carbon-coated electrode showed efficiency of 7.2%. The observed better efficiency of
FIGURE 14.4 Comparison of photoconversion efficiency of conducting-polymer-based counter electrodes.

C, carbon; HNS, hierarchical nanospheres; NS, nanospheres; IS, irregular sheets; MWCNT, multiwalled car
bon nanotubes. (Data from Duan et al. 2018a,b, Peng et al. 2012, Chang et al. 2015, Wang et al. 2013a, Zhang
et al. 2015a, Bora et al. 2015.)
PPY/carbon black composite is attributed to its good catalytic property and greater active
surface area (Peng et al. 2012).
(c) Morphology—If the morphology of amorphous polymers changes, then their photocurrent
efficiency will also be changed. For example, PPY irregular sheets, PPY hierarchical nano
spheres, and PPY nanospheres were prepared by the chemical polymerization method and
constructed as counter electrodes in DSSCs. The photoconversion efficiency was found to
be of the following order (Chang et al. 2015): PPY hierarchical nanospheres > PPY nano
spheres > PPY irregular sheets. From this result, it could be inferred that morphology has
a key role in the performance of DSSCs.
(d) Processing in oxygen-free atmosphere—The photodegradation of polymer active layers
can also be decreased by processing them in an oxygen-free atmosphere and at relatively
low temperatures.
14.3.2 BattEriEs
Batteries are the most common power source for handheld devices to large-scale industrial applica
tions. A battery consists of a cathode, anode, and electrolyte. They can be classified as two types.
They are (a) primary battery or nonrechargeable battery, and (b) secondary or rechargeable battery
(Landi et al. 2009). Among them, rechargeable batteries are used in many devices. However, con
ventional rechargeable batteries have some limitations like low capacity and short durability.
On the other hand, lithium-sulfur (Li-S) batteries are superior due to their relatively greater
energy density, low weight, longer cycle life, and low environmental impact. However, to further lift
their energy densities, further research is being performed worldwide. In addition, they have issues
like the insulating nature of sulfur and safety concerns that need to be solved (Zhu et al. 2019). In
this view, conductive polymers could eliminate the observed drawbacks in Li-S batteries. Because
sulfur molecules interact with polymer chains through hydrogen bonding that can stabilize poly-
sulfides, enhanced electrochemical performance of Li-S batteries is achieved. For example, PPY/S
composite (Wang et al. 2006) provides a discharge capacity of 1280 mAh g−1 at a current density
of 50 mA g−1. These values were higher than that of the cell with the pure sulfur (1100 mAh g−1).
The observed improvement is attributed to (a) improved electrical conductivity of the PPY layer and
(b) porous surface morphology of PPY that enhances the absorption of polysulfides.
Conductive polymers are also used as interlayers in Li-S batteries, since they possess rich het
eroatoms that can provide effective binding energies for polysulfide trapping. For instance, PANI
(Zhang et al. 2013a), PPY (Ma et al. 2015), and PT have been incorporated in sulfur cathodes to
trap polysulfides. The main advantages of conductive polymers as interlayers are (a) they decrease
internal resistance by providing additional electron pathways and (b) abundant heteroatoms act as
strong binding sites for polysulfides. In order to improve performance of CP-tailored Li-S batteries,
various binary and ternary nanocomposites were developed (Table 14.1).
14.3.3 fuEl cElls

A fuel cell is a device that directly converts chemical energy into electric energy without emission
of greenhouse gases. They are classified (Wang et al. 2016) as direct methanol, proton exchange
membrane, polymer electrolyte membrane, microbial, and alkaline fuel cells. A fuel cell contains a
cathode, anode, electrolyte, and fuel, such as oxygen, hydrogen, or methanol. At the cathode, oxygen
reduction occurs, whereas at the anode fuel oxidation takes place.
Generally, both the anode and cathode are made up of Pt/carbon material. As we know, Pt is
expensive and carbon suffers from corrosive degradation. Moreover, the high cost and short life
cycle also hinder the commercialization of Pt-based catalysts. Therefore it is necessary to find
an alternative catalyst for electrode material with improved performance. Hence, chalcogenides,
metals, metal oxides, polymer nanocomposites, carbon-based catalysts, and CP-based catalysts are
used in fuel cells due to their good conductivity, high flexibility, and variable morphologies. For
TABLE 14.1
Comparison of CP-Based Binary and Ternary Composites
Tailored Li-S Batteries
Performances Capacity (Number
Materiala of Cycles, Current Density) Reference
PT/S 830.2 mA h g (80 cycles)
−1 Wu et al. 2011
PPY/V2O5 271.8 mAh g−1 (1st cycle, 0.1 C) Ren et al. 2012
S/PPY/graphene 641.5 mAh g−1 (40th cycle, 0.1 C) Zhang et al. 2013b
PPY/TiO2@S 1,150 mAh g−1 (100th cycle, 0.1 C) Zhao et al. 2016
PEDOT:PSS 638 mA h g−1 (100 cycles, 0.2 C) Li et al. 2015
C-PANI-S@PANI 835 mAh g−1 (100 cycles, 0.2 C) Wang et al. 2013b
PANI nanowires/S 725 mAh g−1 (100 cycles) Zhang et al. 2013a
PPY/S 823 mAh g−1 (10 cycles, 0.1 C) Nakamura et al. 2015
a S, sulfur; PSS, poly(styrenesulfonate); PEDOT, poly(3,4-ethylenedioxythio

phene); C, carbon.
example, PANI as support for metal catalysts has been reported for its several advantages, like high
flexibility, high conductivity, controllable morphologies, and enhanced dispersibility, low cost, and
high electrochemical activity. A PANI/MoS2 hybrid also exhibited high hydrogen evolution reaction
activity (Zhang et al. 2015b). In addition, iron phthalocyanine/polyaniline/carbon black as an effi
cient electrocatalyst supports the oxygen–reduction reaction (Yuan et al. 2011). Similarly, CoFe2O4/
PANI-MWCT catalyst for oxygen–reduction reaction has also reported. PANI/MWNCT provides
more active sites. Due to the synergistic effect of PANI, MWCNT, and CoFe2O4 nanoparticles, elec
trical conductivity and stability of the catalyst was significantly increased (Liu et al. 2016).
PANI-supported Pt catalysts were also reported in fuel cells. For instance, PANI/carbon black
(CB)/Pt composites (Wu et al. 2005) have been reported as the best catalyst in fuel cells. This is
because CB significantly improves the degree of polymerization, lowers the defect in PANI, pro
vides more active sites, and quickens the charge transfer at the electrode/electrolyte interface. The
performances of various CP-based materials in fuel cells are compared in Table 14.2.
TABLE 14.2
Comparison of CP-Based Material Tailored Fuel Cells
Materiala Power Density Current Density Reference
PANI/MoS2 — 50 mAcm −2 Zhang et al. 2015b
Phthalocyanine/PANI/CB 630.5 mW m−2 0.60 mA cm−2 Yuan et al. 2011
CoFe2O4/PANI/MWCNT — 10 mA cm−2 Liu et al. 2016
PANI/CB/Pt — 16.2 mA cm2 Wu et al. 2005
PPY/GF and PT/GF 1.22 and 0.8 W/m2 4.1 and 1.9 A/m2 Sumisha and Haribabu 2018
SS/PANI-W 0.288 and 0.187 mW cm−2 1.108 and Sonawane et al. 2018
and SS/PPy-W 0.713 mA cm−2
Ni-Co/SPAni 659.79 mWm−2 1441.35 mA/m2 Papiya et al. 2018
Ti4O7/PANI/Graphene 2073 mW/m2 — Li et al. 2019
PPY/N-CNT — 400 mA/cm2 Ozturk et al. 2018
PPY/Pt/CP — 7.19 mA cm–2 Carrillo et al. 2018
a CB, carbon black; MWCNT, multiwalled carbon nanotube; GF, graphitic felt; SS-W, stainless steel wool;
SPAni, sulfonated polyaniline; N-CNT, nitrogen-doped carbon nanotubes; CP, carbon paste.
TABLE 14.3
Comparison of CP-Based Material Performance in Supercapacitors
Cycling/Capacity
Specific Retention
Materiala Discharge Rate Capacitance (F g−1) (Number of Cycles) Reference
PANI 10 mV s −1 503 85% (10000) Hu and Chu 2001
PANI/Ni(OH)2 — 55.5 79.5 (25000) Zhang et al. 2015c
PANI/CNT 5 mV s−1 440 93% (1000) Otrokhov et al. 2014
PANI-MnO2 5 A g−1 715 96.5% (5000) Prasad and Miura 2004
MoS2/PANI/G 1 A g−1 618 78% (2000) Sha et al. 2016
PPY/CuO 1 A g−1 553.7 90% (500) Ma et al. 2013
PPY/MoS2 2.5 A/cm3 1275.5 F/cm3 100% (3000) Qian et al. 2015
PPY/cellulose 300 mA/cm2 127 93% (5000) Wang et al. 2015
Ni/PPY/MnO2 2 A/g 350 91.3% (5000) Chen et al. 2015
Fe3+/PT — 108.1 21.2% (1000) Wu et al. 2018
PT and PFPT 2.5 mA cm−2 260 and 110 — Laforgue et al. 1999
PEDOT/WO3 1.4 A g−1 689 96% (260) Zhuzhelskii et al. 2019
a CNT, carbon nanotube; G, graphene; PFPT, polyparafluorophenylthiophene; PEDOT,

poly-3,4-ethylenedioxythiophene.
14.3.4 supErcapacitors
A supercapacitor (ultracapacitor) is used to store electrical energy. It contains electrodes and dielectric
material to achieve high specific capacitances. This device has applications in electric vehicles, uninter
ruptible power supplies, etc. In order to achieve high capacitance, a high surface area electrode material
is essential. In this regard, carbon, metal oxides and conducting polymers are used as electrode material
(Meng et al. 2017). Among them, CPs showed high specific capacitance due to their redox behavior. For
example, PANI stores charges via redox reaction by changing its various oxidations states.
However, due to swelling, shrinkage, and cracking of the polymer, PANI showed poor cycle sta
bility. Furthermore, the degradation of PANI may also occur at high potentials due to overoxidation.
These issues make it necessary to develop conducting-polymer-based composites. This strategy also
allows composite materials with synergistic activity, enhanced structural stability, optimized porosity,
and improved electric conductivity, which lead to extra charge storage via improved charge transporta
tion and kinetic behavior. The performances of some CPs and their composites are given in Table 14.3.
14.3.5 ElEctrochEMical sEnsors

In medical diagnosis and pollution monitoring, several types of electrochemical sensors are used.
Electrochemical sensors are devices that transform chemical information into electrical signals.
Electrochemical sensors contain two components (Figure 14.5). They are the (a) receptor that trans
forms the chemical information into a form of energy and (b) transducer that transforms the energy,
bearing chemical information, into an electrical signal (Lima et al. 2018).
Generally, a working electrode acts as a receptor in electrochemical sensing devices. Glassy car
bon, carbon paste, nickel foam, and platinum electrodes are used as working electrodes. It has been
found that these electrodes suffer in real sample detection due to their poor sensitivity, selectivity,
interference, and stability. Hence, various kinds of nanomaterials are used to construct the best
electrode for practical applications (Ahmad et al. 2017). Among them, conducting polymers such as
PANI, PPY, and PEDOT have been widely utilized as electrochemical sensors for the detection of
various molecules (Table 14.4) due to the following reasons.
FIGURE 14.5 Pictorial representation of an electrochemical sensor.
TABLE 14.4
Analytes That Need to Be Determined
Molecular
Analyte Formula Reason for Detection Determination in
Ascorbic acid C6H8O6 Deficiency leads to scurvy Fruit juices
Uric acid C5H4N4O3 High level causes gout and kidney stones Human urine, serum
Dopamine C8H11NO2 Parkinson’s disease, nervous system problems Blood
Cysteine C3H7NO2S Deficiency causes disease Human plasma
Nitrophenol C6H5NO3 Irritates eyes, skin, and respiratory tract Soil and water
Hydrogen peroxide H2O2 Extremely toxic to cellular life In vivo and in vitro
Hydroquinone C6H6O2 Skin disorder Tap water
Gallic acid C7H6O5 Has biological and pharmaceutical applications Tea and plant extracts
Xanthine C5H4N4O2 Xanthinuria, hyperuricemia, renal failure, etc. Serum
Glucose C6H12O6 Low or high concentrations lead to health effects Serum
Diclofenac C14H11Cl2NO2 Pharmacological activity Pharmaceutical preparations
Picric acid C6H3N3O7 Causes anemia, cancer, cyanosis, and affects Soil and water
respiratory systems, liver malfunction
Hydroxylamine H3NO Toxic to human, animals and plants. Water
Folic acid C19H19N7O6 Causes deficiency disease Biological fluids
Formaldehyde CH2O Carcinogenic Air
Paraquat C12H14Cl2N2 Toxic to human beings and animals Ground and lake water
Aminobenzimidale C7H6N2 Pharmacological activity Plant samples
Chlorpyrifos C9H11Cl3NO3PS Pharmacological activity Tap water and Soil
Zinc ion Zn2+ Health effects Water
Copper ion Cu2+ Health effects Water
Ferrous ion Fe2+ Health effects Tap water
Mercuric ion Hg2+ Acrodynia, Hunter-Russell syndrome, and Tap water
Minamata disease
Cadmium ion Cd2+ Chronic health effects Tap water
Lead ion Pd2+ Chronic health effects Tap water
Nitrate NO3– Health effects Tap water
(a) Compatible with biological molecules—The conducting polymers modified themselves to

bind biomolecules that need to be detected (Mulchandani and Wang 1996).
(b) Electrical conductivity and redox behavior—Conducting polymers are having greater elec
trical conductivity. For example, the conductivity of PANI, PT, a PPY are 1–100, 40–100,
and 10–100 S cm−1, respectively. Therefore, they are suitable to modify bare electrodes to
attain high sensitivity. Also, they are redox active polymers that facilitate electron transfer
from the analyte molecule into the electrode or vice versa. For example, PANI (Figure 14.6)
can effectively mediate the reduction and oxidation of analytes (Ambrosi et al. 2008).
(c) Direct deposition of conducting polymer on the surface of the electrode—The success of
a modified electrode depends on the uniform thickness of the modifying layer. Among
different methods, electrochemical deposition is the best method. Due to their electroac
tive nature, conducting polymers can be easily deposited on bare electrodes by applying
potential. It is also possible to control film thickness by this method (Gerard et al. 2002).
(d) The charge and nature of polymer chain—The doped conducting polymer chain has a posi
tive charge and the dopant has a negative charge. Therefore, the polymer chain can attract
and detect anionic molecules or ions more selectively, while the dopant attracts and detects
cationic molecules. Also, aromatic groups interact with the aromatic moiety of analyte
through π–π interactions. For example, PANI-doped with 5-sulfosalicylic acid–modified
electrode (Chatterjee et al. 2013) was used to detect ammonia gas through coordination
with sulfosalicylate molecule. Ammonia vapors absorb protons from emeraldine salt of
PANI and form an emeraldine base as well as ammonium cations. Then, ammonium cat
ions form coordination bonding with anionic dopant. The deprotonation of PANI nitrogen
atoms results in a drop in electrical conductivity. This drop in conductivity is directly
related to the concentration of ammonia vapors and thereby efficient ammonia detection
was achieved.
(e) Nature of doping agent—The dopant in conducting polymers such as PANI has also played
a significant role in their sensing behavior. PANI doped with ferrocene sulfonic acid (Fc
Fe3+) as a sensor for H2O2 is the best example (Yang and Mu 2005). The Fe3+ ion in ferro
cenesulfonic acid undergoes a redox reaction in a reversible manner. When H2O2 interacts
with Fe3+, a chemical reaction takes place first, which leads to the formation of an interme
diate followed by the electrode reaction. The Fc-Fe2+ formed during the reaction process
is immediately oxidized to Fc-Fe3+ at the electrode. It suggests that the Fc-Fe2+/Fc-Fe3+ is
involved in charge transfer, which enhances the rate of oxidation of H2O2 (Equations 14.1
to 14.3):
Leucoemeraldine
H H H
N N N
n
B(ox) A
B A(red)
H
N N N
n
Emeraldine
FIGURE 14.6 Electron transfer from analyte to PANI-modified electrode. A and B are analytes, A(red) is a
reduced form of analyte A, and B(ox) is an oxidized form of analyte B.
SO3H SO3H
H 2 O2 + Fe3+ Fe 2+
+ HO2 + H+ (14.1)
HO2 O 2 + H+ + e (14.2)
SO3H SO3H
(14.3)
Fe2+ Fe3+ +e
Even though pure conducting polymers are widely used as the modifying layer for bare elec-
trodes, they lack in sensitive and selective detection of many analytes. To improve upon this, the
following methods were reported.
(a) Uses of derivatives of conducting polymer—Derivatives of PANI and PT have been used
as sensor materials. For example, a PEDOT-modified glassy carbon electrode exhibits sen-
sitive and selective detection of uric acid and ascorbic acid in milk with minimum interfer-
ence (Motshakeri et al. 2018). The linear response range of this sensor is 6 to 100 μM for
uric acid and 30 to 500 μM for ascorbic acid (Suresh et al. 2012).
(b) Fabrication of composites—It was found that a sensor composed of conducting polymers
containing carbon, metal, semiconductors, or polymer (Figure 14.7) has enhanced sen-
sitivity, high selectivity, low inference, and long-term stability. The synergistic effect,
improved conductivity, and selective absorptivity are the major reasons for the observed
improvement in nanocomposite-based sensors. For example, the electrochemical depo-
sition of PEDOT/CNT film on a glassy carbon electrode showed high sensing ability
toward dopamine, with a detection limit of 20 nM (Xu et al. 2013). This sensor is easy to
FIGURE 14.7 Conducting-polymer-based nanocomposites as electrochemical sensors. CP, conducting poly-

mer; CNT, carbon nanotube; MWCNT, multiwalled carbon nanotube; RGO, reduced graphene oxide; PAA,
poly(acrylic acid); PS, polysulfone; PSX, polysiloxane; DNA, deoxyribonucleic acid; PVA, polyvinyl alcohol;
PSSA, poly(styrene sulfonic acid).
fabricate, very stable, and free of interference. The PANI/reduced graphene oxide nano
composite modified glassy carbon electrode was also reported for selective detection of
diclofenac (Ghanbari and Moludi 2016). The sensing performance of CP-based nanocom
posite is given in Table 14.5.
(c) Immobilization of biomolecules—To construct sensitive biosensor, the enzyme is immo
bilized on conducting polymer modified working electrode. The reasons for choosing
conducting polymers are (a) they are good electron transfer medium (Figure 14.8) and
(b) they provide stable support for the enzyme through covalent linkages. For example,
the PANI/PAA film has a carboxyl group that reacts with the amino group of glucose
oxidase and forms amide linkages (Homma et al. 2014). Therefore PANI/PAA film acts
as a stable support for glucose oxide through amide linkages resulting in good sensing
behavior.
TABLE 14.5
Comparison of CP-Based Nanocomposites as Sensors
Sensora Analyte Linear Range Limit of Detection Reference
PEDOT/CNT Dopamine 0.1 to 20 µM 20 nM Xu et al. 2013
ZnO/PANI/RGO Dopamine 0.001−1 μM and 0.8 nM Ghanbari et al. 2016
1−1000
AgCl@PANI Dopamine — 0.2 μM Yan et al. 2008
Au@PANI Dopamine 10–1700 μM 5 μM Yang et al. 2012
Au/rGO/PANI Serotonin 0.2–10.0 μmol L−1 11.7 nmol L−1 Xue et al. 2014
Au/SiO2@PANI Ascorbic acid 0.15 to 8 mM 3.775 μM Weng et al. 2013
Cu/PANI Ascorbic acid 0.005 to 3.5 mM 0.002 mM Xi et al. 2010
P3PT/Pd, Pt Dopamine 0.05–1 µM 9 nM Atta and El-Kady 2010
PANI-PPY Uric acid 2.5 × 10–6 to 1.0 × 0.10−6 M Arslan 2008
8.5 × 10−5 M
NiHCF/PANI H2O2 1 × 10–6 to 1.24 × 10−7 M Wang et al. 2012
3 × 10−3 M
α-Fe2O3/PANI Uric acid 0.01 to 5 μM 0.038 μM Mahmoudian et al. 2019
a RGO, reduced graphene oxide; P3MT, poly(3-methylthiophene); NIHCF, nickel hexacynaoferrate.
FIGURE 14.8 Electrochemical behavior of analyte at enzyme immobilized conducting polymer modified
electrode.
14.4 CONCLUSIONS
In this book chapter, the significant role of conducting polymers in solar cells, batteries, fuel cells,
supercapacitors, and electrochemical sensors was described. The following points were explored
through an adequate literature survey.
(a) In solar cells, CP is used as electrode material. Photodegradation and low photoconversion
efficiency were observed for pure CPs. Hence, strategies like functionalization, making
nanocomposites, and controlled morphologies were reported. Especially CP-based nano
composite exhibits superior performance in solar cells, even more than platinum-based
counter electrodes.
(b) In Li-S batteries, CP was used as cathode material and as interlayer active material. Owing
to the existence of heteroatoms, they effectively bind with polysulfides and enhance their
efficiency of Li-S batteries. The battery performance was further improved by utilizing
CP-based nanocomposites as electrode.
(c) In fuel cells, CP-based nanocomposites were effectively used as both cathode and anode mate
rials. Because of their synergistic effect and fast charge transfer ability, nanocomposite-based
electrodes act as effective catalysts for hydrogen evolution and oxygen reduction reactions.
(d) The role of CP-based nanocomposites is significant in supercapacitor devices. The fabrica
tion of nanocomposites with suitable combinations gave high specific capacitance.
(e) Pure CP and their composites were vastly utilized as electrochemical sensors for clinically
important biomolecules and pollutants. The major reasons for the application of CPs and
improvements have been described.
ACKNOWLEDGMENTS
R. Suresh acknowledges the National Commission for Scientific and Technological Research
(CONICYT), Santiago, Chile, for financial assistance in the form of a Post-Doctoral Fellowship
(Fondecyt Project No: 3160499). The authors thank the support of the projects FONDECYT 1151296;
and Center Optics and Photonics, Grant CONICYT-PFB-0824, CONICYT/FONDAP/15110019.
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15 Electrochemical Studies for
Biomedical Applications
Rajesh Parsanathan
CONTENTS
15.1 Introduction......................................................................................................................... 251
15.2 General Working Principles of Electrochemical Sensors ................................................... 252
15.3 Electrochemical Methods.................................................................................................... 252
15.3.1 Types of Voltammetry ............................................................................................ 252
15.4 Electrochemical Sensor and Circuit.................................................................................... 254
15.4.1 Microelectrode ....................................................................................................... 254
15.5 Biological Analytes and Electrochemical Methods ............................................................ 254
15.6 Gasotransmitter Electrochemical Sensors........................................................................... 255
15.6.1 Electrochemical Sensors for Carbon Monoxide (CO) Detection ........................... 255
15.6.2 Determination of Nitric Oxide (NO) Electrochemical Sensors.............................. 257
15.6.3 Hydrogen Sulfide (H2S) Electrochemical Sensors.................................................. 258
15.6.3.1 Ion-Sensitive Electrodes (ISEs) for Hydrogen Sulfide (H2S) .................. 258
15.6.3.2 Amperometric–Polarographic H2S Sensors ............................................. 259
15.7 Electrochemical Sensors for Nucleic Acids........................................................................ 259
15.7.1 Biomedical Applications of Electrochemical Sensors for Nucleic Acids...............260
15.8 Redox Electrochemical Sensors.......................................................................................... 261
15.9 Electrochemical Immunoassays and Immunosensors......................................................... 261
15.10 Paper-Based Electrochemical Sensors and Inkjet-Printed ................................................. 261
15.11 Conclusions......................................................................................................................... 262
Acknowledgments ......................................................................................................................... 262
References...................................................................................................................................... 262
15.1 INTRODUCTION
Analytical chemistry is the field where analytical techniques determine an analyte’s concentration
or characterize the chemical reactivity by measuring its potential, charge, or current (Siddiqui,
AlOthman, and Rahman 2013). Electrochemistry is a branch of analytical chemistry that deals with
the interaction of electrical and chemical effects; where the chemical changes are due to the pas
sage of electrical current and the production of electrical energy by chemical reaction. Movement of
electrons is an oxidation–reduction reaction, hence this field is named electrochemistry (Prabhulkar
et al. 2012). Though there is much diversity in instrumentation, the majority of the electrochem
ical techniques and methods share numerous similar features (Kim et al. 2011). Because of its
high sensitivity and precision, as well as a broad linear dynamic range with relatively economical
instrumentation, these electrochemical methods (Figure 15.1) have become dominant and versatile
analytical techniques in the field of biomedical applications (Nemiroski et al. 2014; Turner 2013).
In traditional laboratories, this can be time-consuming and expensive. It is attractive to provide low-
cost fabrication methods and point-of-care diagnostic tools with the capacity to detect and check
various biological and chemical compounds. By combining well-established materials and fabrica
tion methods, it is possible to produce electrochemical devices that meet the needs of many patients,
251
Potentiometry
Electroanalytical
Coulometry
methods
Polarography
Voltammetry
Amperometry
FIGURE 15.1 Schematic of classification of electroanalytical methods.
healthcare and medical professionals, and environmental specialists. Furthermore, continuing to

innovate, by merging each of these favorable electrochemical sensing techniques and materials,
is incredibly selective and provides accurate and repeatable quantitative results without expensive
measurement equipment.
15.2 GENERAL WORKING PRINCIPLES OF ELECTROCHEMICAL SENSORS

The five critical interrelated and essential concepts of electrochemistry are as follows
(Faulkner 1983):
(1) Analytes form at the electrode’s surface determined by the electrode’s potential.
(2) At a given time point, the concentration of analyte on the surface of the electrodes may not
be equivalent to its concentration in bulk solution/biological matrix.
(3) An analyte may participate in any reaction apart from the oxidation–reduction reaction.
(4) The rate of current is a measure of the analyte’s oxidation or reduction reaction at a given
time point.
(5) Simultaneous control over both current and potential is not possible.
Hence, the analysis is based on electrochemical methods either within a medium or at the phase
boundary and related to changes in the structure, chemical composition, or concentration of the
compound being analyzed in any biological matrix qualitatively and quantitatively (Tripathi, Su,
and Hwang 2018). Further, these methods are classified into five main groups: potentiometry,
voltammetry, coulometry, conductometry, and dielectrometry.
15.3 ELECTROCHEMICAL METHODS

Working electrode types vary due to their variety of combinations, and hence, it is possible to
change the parameters in the electrochemical experiments according to applications in the biomedi
cal field. Electroanalytical techniques using different types of voltammetry and their parameters
(advantages and limitations) are mentioned in Table 15.1.
15.3.1 typEs of voltaMMEtry

(1) Sweep methods
• Cyclic voltammetry
• Linear sweep voltammetry
• Rotating disk electrode
Electrochemical Studies for Biomedical Applications 253
(2) Step and pulse methods

• Step voltammetry
(a) Chronoamperometry
(b) Chronocoulometry
(c) Chronopotentiometry
• Pulse voltammetry
(a) Normal pulse voltammetry
(b) Differential pulse voltammetry
(c) Square wave voltammetry
TABLE 15.1
Electroanalytical Techniques, Types of Voltammetry, and Parameters (Advantages
and Limitations)
Electroanalytical Techniques Parameters and Advantages Limitations
Cyclic voltammetry (CV) CV determines the nature of nernstian or Not suitable for quantitative analysis.
non-nernstian behavior, and the rate/
formation constants, formal potential,
and diffusion coefficients.
Linear sweep voltammetry Quantitative electrochemical analysis; the The bandpass limitations of the
(LSV) potential of the electrode varied at a potentiostat and current measurer may
constant rate during the reaction, and the affect the shape and characteristics of the
resulting current is measured. LSV polarization curves.
Square wave voltammetry SqWV has the advantages of a faster scan Like the alternative current-voltammetry
(SqWV) rate and increased sensitivity relative to with sinusoidal alternating potential, it
differential pulse. Three current- suffers from the fact that irreversible
potential plots are generated, namely systems give low currents, especially at
reverse, forward, and difference current higher frequencies.
versus potential, thus resulting in higher
sensitivity compared to CV technique.
Chronoamperometry Determination of diffusion coefficients Limited information about the identity of
and reaction kinetics investigation and the electrolyzed species can be obtained
its mechanisms. from the ratio of the peak oxidation
current versus the peak reduction current.
Chronopotentiometry This technique determines higher The measurement of the transition times
concentration where a constant current is negatively affected by the presence of
applied to the electrode, and the adsorbed electroactive material or
resulting potential change is plotted oxidation of the electrode surface.
against time. Hence, it is not commonly used for
accurate measurements of diffusion
coefficients.
Chronocoulometry It is a modified version of The signal increases over time instead of
chronoamperometry, which advances decreasing. There are better ways to do
relatively more accurate measurement of both of these with more modern
the kinetic rate constant with detection techniques.
of reactant adsorption on the surface of
an electrode.
15.4 ELECTROCHEMICAL SENSOR AND CIRCUIT

The circuit that controls the potential of the working electrode and converts the signal current to a
voltage is called a potentiostat (Fitzpatrick 2015). A simplified diagram of the sensor and potentiostat
is illustrated in (Figure 15.2). The signal (current) from the working electrode (WE) is converted to a
voltage by the operational amplifier U2 (Dobbelaere, Vereecken, and Detavernier 2017). This circuit
also maintains the voltage of the working electrode at the bias potential, Vbias. The reference elec
trode (RE) potential is compared to the stable input voltage, Vbias (Sarkar et al. 2014). The op-amp
U1 generates a voltage at the counter electrode (CE), which is sufficient to produce a current that is
precisely equal and opposite to the working electrode current (Dryden and Wheeler 2015). At the same
time, a constant voltage is maintained between the reference electrode and the working electrode.
15.4.1 MicroElEctrodE
The aforementioned technology can be modified to give sensors that will respond to the different
gases of interest. This can be accomplished by using different working electrodes, bias potentials,
and chemically selective filters. Table 15.2 shows which catalysts are used for each gas (Cretescu,
Lutic, and Manea 2017).
15.5 BIOLOGICAL ANALYTES AND ELECTROCHEMICAL METHODS

The foremost important application of electrochemical detection in the biomedical field was for
quantitative detection at a deficient concentration in real time in biological media (serum, plasma,
blood, tissues, cell culture media, which includes all biological materials) without loss of sensitivity.
FIGURE 15.2 Schematic of electrochemical sensor and circuit.
TABLE 15.2
Biologically Important Gases and
Frequently Used Electrocatalyst Metals
Gas Analyzed Electrocatalyst Metals
CO Platinum (Pt)
H2S Gold (Au)
H2 Au
NO Au
NO2 Au
O2 Au, Pt, Silver (Ag)
SO2 Au
FIGURE 15.3 Electrochemical methods for determining biological analytes.
Electrochemical biosensing is one of the compelling methods to quantify concentrations of biologi

cal molecules (glucose, gasotransmitters [carbon monoxide, nitric oxide, hydrogen sulfide, carbon
dioxide, and sulfur dioxide], ascorbic acid, uric acid, dopamine, hydrogen peroxides, nucleic acid,
and proteins) in different matrices (biocompatibility) with the superior advantages of sensitivity,
selectivity, low-detection limit, stability, long lifetime, wide linear range, fast response time, real-
time, and reproducibility with simple operation (Krishnan et al. 2019). With these advantages,
several types of research developed new electrochemical methods for determining biological mol
ecules (Figure 15.3). Henceforth, it can provide vital information in a variety of applications related
to chemistry, biology, and medicine. A few of these applications will be described in the following
sections.
15.6 GASOTRANSMITTER ELECTROCHEMICAL SENSORS

Gases such as CO2, NO2, SO2, O2, CO, and H2S are biologically important since those gases have a
role in the pathophysiology (Chen et al. 2007; Mathew, Schlipalius, and Ebert 2011). Electrochemical
gas sensors are a kind of gas detector that measure the levels of a target gas by either oxidizing or
reducing the gas at an electrode and measuring the resulting current (Liu et al. 2012).
15.6.1 ElEctrochEMical sEnsors for carBon MonoxidE (co) dEtEction

Carbon monoxide (CO) has high affinity to hemoglobin, which impedes oxygen delivery leading
to intoxication and death (Blumenthal 2001). CO has many effects in biology due to its complex
biochemical activities (Blumenthal 2001; Queiroga, Almeida, and Vieira 2012). Whether CO is
derived from exogenous or endogenous sources, its cellular activity is related to its concentration
and the concentration of molecular O2, as well as to the availability of reduced transition metals
such as Fe(II) (Queiroga, Almeida, and Vieira 2012). Finally, CO is involved in several cellular
processes, acting as an anti-inflammatory, cytoprotective, maintenance of tissue homeostasis, and,
in some particular cases, antiproliferative and vasodilator (Boczkowski, Poderoso, and Motterlini
2006; Motterlini and Otterbein 2010; Queiroga et al. 2011; Queiroga, Vercelli, and Vieira 2015;
Queiroga, Almeida, and Vieira 2012).
Compared to other gasotransmitters, such as nitric oxide (NO) and hydrogen sulfide (H2S), CO
is a quite inert molecule. CO needs to be activated by coordination with low-valent metals or ions
to react chemically. In biological systems, Fe2+ of reduced heme proteins are the main CO tar
gets (Boczkowski, Poderoso, and Motterlini 2006). The best-described candidates are hemoglo
bin (erythrocytes), myoglobin (myocytes), and cytochrome c oxidase (mitochondrial complex IV)
(Almeida, Figueiredo-Pereira, and Vieira 2015).
Cytochrome c oxygenase (COX), the final electron acceptor of the mitochondrial respiratory
chain, was found to be the main mitochondrial target for CO at cytochrome a and a3 (Brown and
Piantadosi 1990; Chance, Erecinska, and Wagner 1970). COX is involved in CO-induced cyto
toxicity due to the CO capacity of inhibiting its activity and cell respiration (Chance, Erecinska,
and Wagner 1970). The binding of CO to COX is highly dependent on oxygen levels because,
under hyperbaric oxygen conditions, there is the dissociation of a cytochrome and a3–CO complex
(Brown and Piantadosi 1990).
The carbon monoxide sensor consists of three electrodes immersed in a liquid electrolyte (a
nonmetallic liquid that conducts electricity, usually through acids or dissolved salts) (Bai and Shi
2007). The three electrodes are the working electrode, the reference electrode, and the counter
electrode (Guy and Walker 2016). The most important of these is the working electrode (WE) (Guy
and Walker 2016). The working electrode is made of platinum, which is a catalytic metal to CO (it
catalyzes the oxidation of CO to CO2), backed by a gas-permeable but hydrophobic (waterproof)
membrane (Cheng, Liu, and Logan 2006). The CO gas diffuses through the porous membrane and
is electrochemically oxidized (see Equation 15.1) (Scott 1995).
Figaro electrochemical-type gas sensors are amperometric fuel cells with two electrodes. The
essential components of two electrode gas sensors are a working (sensing) electrode, a counter elec
trode, and an ion conductor in between them. When toxic gas such as carbon monoxide (CO) comes
in contact with the working electrode, oxidation of CO gas will occur on the working electrode
through a chemical reaction with water molecules in the air:
CO + H 2O ® CO2 + 2H + + 2e (15.1)
Connecting the working electrode and the counter electrode through a short circuit will allow pro
tons (H+) generated on the working electrode to flow toward the counter electrode through the ion
conductor. Also, generated electrons move to the counter electrode through the external wiring. A
reaction with oxygen in the air will occur on the counter electrode:
(1/2) O2 + 2H + + 2e ® H 2O (15.2)
The overall reaction is shown in Equation 15.3. Figaro electrochemical-type gas sensors operate like
a battery with gas being the active material for this overall battery reaction.
CO + (1/2) O2 ® CO2 (15.3)
By measuring the current between the working electrode and the counter electrode, this electro
chemical cell can be utilized as a gas sensor.
The electrons involved in the electrochemical reaction flows from the working electrode through
the external circuit, producing the output signal of the sensor (Grieshaber et al. 2008). In order
for the reaction to take place, the thermodynamic potential of the working electrode is of critical
importance (Duret-Thual 2014). The reference electrode provides a stable electrochemical potential
in the electrolyte (Frank and James 1994). The reference electrode is protected from exposure to the
CO gas so that its thermodynamic potential is always the same and remains constant (Frank and
James 1994). Also, no current is allowed to flow through the reference electrode (this would change
the thermodynamic potential) (Elgrishi et al. 2018). A counter electrode is provided to complete the
circuit of the electrochemical cell (Elgrishi et al. 2018). The counter electrode functions solely as the
second half-cell and allows electrons to enter or leave the electrolyte (Elgrishi et al. 2018).
The CO sensor is also equipped with a chemically selective filter. This filter removes potentially
interfering gases before they reach the working electrode. With the filter operating correctly, the
sensor will have minimal response to interfering gases (Helm, Jalukse, and Leito 2010).
15.6.2 dEtErMination of nitric oxidE (no) ElEctrochEMical sEnsors

In 1987, nitric oxide (NO) was identified as being responsible for the physiological action of endo
thelium-derived relaxing factor (Ignarro et al. 1987). NO is now known to play a critical functional
role in a variety of physiological systems. Within the vasculature, NO induces vasodilation, inhib
its platelet aggregation, prevents neutrophil/platelet adhesion to endothelial cells, inhibits smooth
muscle cell proliferation and migration, regulates programmed cell death (apoptosis), and maintains
endothelial cell barrier function (Rosselli, Keller, and Dubey 1998; Majed and Khalil 2012).
Since NO plays a significant role in a variety of biological processes, where its physiological
and pathological spatial and temporal concentrations are of extreme importance, measurement of
NO is difficult due to its shorter half-life; further, the complexity arises by its high reactivity with
superoxide, oxygen, thiols, and other biological components (Zielonka and Kalyanaraman 2010;
Griendling et al. 2016). From the classical Griess methods, several techniques (chemiluminescence,
paramagnetic resonance spectrometry, paramagnetic resonance imaging, spectrophotometry, and
bioassay) have been developed for the measurement of NO from different sources including bio
logical samples (Csonka et al. 2015; Samouilov et al. 2007). The sensitivity of the electrochemi
cal (amperometric) detection of NO is the real-time sensitive method up to date. With the recent
development of micro- and nanoelectrodes, the measurement of NO becomes more effortless in
the biological systems with detection limits ranging from below 1 nM up to 100 µM (Zhang 2004).
The principles of determination of NO by electrochemical sensors (ISO-NOP) are almost the
same: the sensor is immersed in a solution containing NO and positive potential of –800mV vs.
Ag/AgCl reference electrode (Serpe and Zhang 2007). This first electrochemical NO sensor was
based on a classical Clark electrode design (Zhang 2008). NO diffuses across the gas permeable
(NO – selective membrane) and oxidizes at the surface of the working electrode producing a redox
current (Zhang 2008). The NO cation formed due to the transfer of one electron to the electrode is
as follows:
NO + e ® NO+ (15.4)
Further, NO cation is a relatively strong Lewis acid and in the presence of OH– irreversibly converts
into nitrite:
NO+ + OH ® HNO2 ® H + + NO2 (15.5)
Nitrite can then be further oxidized into nitrate. The amount of NO oxidized is thus proportional
to the current flow between the working and the reference electrodes, which is measured by a NO
meter (Sarkar, Lai, and Lemay 2016). A typical redox current is relatively low for NO oxidation
(1–10 pA) (Zhang 2008). Hence, a sensitive amperometric-based electrode for NO and ultra-low
noise amplification circuitry is needed; it was overcome by electronic devices ISO-NO and ISO-NO
Mark II NO meters (Zhang 2008). These meters can measure as low as 0.1 pA.
Various other types of carbon fiber NO sensors, which utilize a variety of different coatings,
have been described (Huffman and Venton 2009; Ozel, Wallace, and Andreescu 2011), including
recently a coating of a 10 µM Pt disc electrode with a cross-linked sol–gel Langmuir-Blodgett film
of siloxane polymer to render the electrode permselective for NO. Another report shows the addition
of sol–gel films to a Pt electrode for NO detection (Matharu et al. 2007).
15.6.3 hydrogEn sulfidE (h2s) ElEctrochEMical sEnsors

H2S, which has evolved from a noxious gas to a physiological gasotransmitter, is deemed as the third
endogenous gaseous mediator exhibiting properties similar to nitric oxide and carbon monoxide
(Farrugia and Szurszewski 2014). However, much like CO and NO, the initial negative perception
of H2S has developed with the discovery that H2S is generated enzymatically in animals under
normal conditions (Xiao et al. 2018). A multitude of evidence supports that H2S is widely involved
in the roles of the physiological and pathological process, including hypertension, atherosclerosis,
angiogenesis, myocardial infarction, Alzheimer’s disease, Parkinson’s disease, inflammation, and
metabolic abnormalities (Wen, Wang, and Zhu 2018). In recent years, its cytoprotective properties
have been recognized in multiple organs and tissues (Xiao et al. 2018). In particular, H2S plays
essential roles in combating oxidative species such as reactive oxygen species (ROS) and reactive
nitrogen species (RNS), and protecting the body from oxidative stress (Di Meo et al. 2016; Shefa et
al. 2018; Birben et al. 2012).
Due to the extensive attention in its biological function, in vitro and in vivo H2S detection meth
ods have evolved from simple colorimetric assays to the more recently used techniques, including
fluorescence spectroscopy electrochemiluminescence (ECL), high-performance liquid chroma
tography, gas chromatography, electrochemistry gas sensors such as ion sensitive electrodes, and
polarographic H2S sensors (Richter 2004). Investigation of these processes requires a reliable and
effective analytical system of low detection limit, fast response, and the possibility for in situ mea
surements (Everton et al. 2016; Shrivastava and Gupta 2011).
Similar to NO, under physiological conditions, the stability of H2S and HS– is influenced by
inorganic and organic components that catalyze oxidation reactions, and this reactivity limits the
practicality of most standard available analytical methods for real-time detection of H2S (Olson
2012; Hartle and Pluth 2016). Though several analytical procedures are highly sensitive to detect
micromolar to submicromolar levels, due to multiple steps and procedures, it is unclear if these
methods also measure H2S that existed as a persulfide or other labile species (Ono et al. 2014).
In the chemical industry, commonly employed H2S quantitation methods are solid-electrolyte
sensors (metal oxide-based sensor and solid polymer electrolyte (SPE)-Pt) (Chiou and Chou 2002).
There were two well-established methods/devices used for the detection and quantification of H2S
in case of biological samples: ion-sensitive electrodes and amperometric (polarographic) H2S sen
sors (Kraus, Doeller, and Zhang 2008).
15.6.3.1 Ion-Sensitive Electrodes (ISEs) for Hydrogen Sulfide (H2S)

The ISE-based method is most easily obtained and commonly used to measure plasma H2S with a
detection range of 1–100 µM (Giep et al. 1996). ISE has a good sensitivity toward sulfide anions with
a dynamic range of sulfide concentrations within a minute (Xu et al. 2016). The Ag/Ag2S prepared
by dipping a silver wire into a saturated solution of sodium sulfide. The slow reaction of silver wire
with the S2– ions, forming a thin dark layer of Ag2S on the surface of the wire, acts as protection
membrane preventing the interference of the sample (Allen and Larry 2001). Earlier, this method
had been reported without detailed procedure, but Khan et al. later described the detailed procedure
to the measurement of plasma H2S (Khan and Malik 1971). Recent commercially available micro
ISE for H2S detection requires a lesser volume of sample (10 µl) with a detection limit as low as 100
nM (Khan et al. 2015).
Careful inspection of the electrode surface is necessary; often, without a Ag2S layer, it loses
its selectivity due to Ag response to redox changes in the solution. Also, daily reconditioning and
calibration of electrode surface is more laborious (Cheng and Da-Ming 2005). Further, it requires
an alkaline environment that favors the equilibrium of S2–, operating in a low concentration range,
and maintaining the connection between the electrolyte bridge and the reference electrode (Brewer,
Stoica, and Brown 2011).
15.6.3.2 Amperometric–Polarographic H2S Sensors

A polarographic H2S sensor (PHSS) has three essential features like other polarographic sensors
(Doeller et al. 2005): the anode, cathode, and electrolyte (alkaline K3Fe(CN)6), which are protected
from solution constituents by H2S-permeable polymer membrane that permits diffusion of only
free H2S across the membrane and facilitates the interaction electrochemically with the polarized
anode (Anani et al. 1990). H2S was dissociated into HS– after crossing the permeable membrane
and then chemically oxidized S0, which simultaneously reduces ferricyanide to ferrocyanide, which
donates electrons to the anode. The ferrocyanide electrochemically oxidized back to ferricyanide
(100–200 mV) on the surface of the platinum electrode, producing a current proportional to sample
H2S concentration (Huang et al. 2007). The background current, which is subtracted from the signal
current, dictates the PHSS lower limit of detection (Kraus, Doeller, and Zhang 2008). Compared to
the ISE-based method, this method detects H2S without an external electrical potential, with simple
structure and good reproducibility, quick response time, and less containment of noble metals. The
disadvantage of the liquid electrolyte sensors are that they leak easily, are prone to dry up, and have
sizeable residual current due to impurities in the solution (Xu et al. 2016).
The applications of PHSS in biological samples have been studied on tissue homogenates, cultured
and isolated cells, intact tissues and organs, and isolated mussel gill mitochondria (Wen, Wang, and
Zhu 2018). The dynamic changes in H2S concentration reported by the PHSS were not firmly seen
with other techniques of H2S measurement in biological samples (Vitvitsky and Banerjee 2015).
The PHSS design is continually evolving to change based on measurement needs; the miniaturiza
tion allows in situ measurement of H2S in blood, tissues, cells, and organelles (Doeller et al. 2005).
15.7 ELECTROCHEMICAL SENSORS FOR NUCLEIC ACIDS

Current sensing methods, such as lateral flow immunoassay, fluorescent microarray, polymerase
chain reaction (PCR)-based methods, DNA microarrays, DNA sequencing technology, enzyme-
linked immunosorbent assay (ELISA), require expensive reagents, high-precision instruments, and
quantification methods to achieve highly sensitive detection (Gui and Patel 2011; Song et al. 2014).
Additionally, most of the reactions cannot be monitored quantitatively in real-time. Thus, in the
biomedical field, sensitive, specific, and fast analysis of nucleic acid is strongly needed (Vidic et
al. 2019). Electrochemical sensor properties such as robust, simple, sensitivity, selectivity, and low
cost for nucleic acid detection makes them more attractive than other available standard methods
(Zhu et al. 2015). These methods are employed to detect selected DNA sequences or mutated genes
associated with human disease (Drummond, Hill, and Barton 2003).
Currently, PCR-based and other target amplification strategies are most extensively used in
practice. At the same time, such assays have limitations that can be overcome by alternative
approaches (Gerasimova and Kolpashchikov 2014). There has been a recent explosion in the design
of methods that amplify the signal produced by a nucleic acid target, without changing its copy
number (Wang et al. 2015; Gerasimova and Kolpashchikov 2014). DNA-based electrochemical
sensors exploit a range of different chemistries, but all take advantage of nanoscale interactions
between the target in solution, the recognition layer, and a solid electrode surface (Drummond,
Hill, and Barton 2003). Numerous approaches to electrochemical detection have been developed,
including direct electrochemistry of DNA, electrochemistry at polymer-modified electrodes, elec

trochemistry of DNA-specific redox reporters, electrochemical amplifications with nanoparticles,
and electrochemical devices based on DNA-mediated charge transport chemistry (Drummond,
Hill, and Barton 2003).
15.7.1 BioMEdical applications of ElEctrochEMical sEnsors for nuclEic acids

The testing of nucleic acids for various diseases is practiced mostly in clinical settings, mainly PCR-
based, complex, and expensive. Alternative user-friendly options remain challenging in a clinical
setup (Niemz, Ferguson, and Boyle 2011). Due to the promising nature of detection and diagno
sis of various diseases such as metabolic disorders (cancer, diabetes, cardiovascular diseases) and
infectious diseases (tuberculosis, hepatitis, dengue, and foodborne diseases like diarrhea, cholera,
salmonellosis, etc.), electrochemical-based sensors for nucleic acids and aptamer in various com
municable and noncommunicable diseases/disorders are listed in Table 15.3.
Ongoing efforts with DNA chips and other smart nanomaterials, however, are directed toward
developing PCR-free DNA detection systems, which are yet to be fully commercialized (Du and
Dong 2017). Tremendous progress has been noted in electrochemical DNA-based biosensors and
arrays (Mok and Li 2008). Various types of electrodes immobilized with specific probes are at
various stages of development, fabrication, and testing for the diagnosis of fatal diseases (Huang
et al. 2017). Carbon nanotubes based on the electrochemical biosensor, surface plasmon resonance
(SPR), quantum dot, and piezoelectric biosensors are promising candidates in molecular diagnosis
(Tilmaciu and Morris 2015). The use of DNA biochip technology would eliminate the role of PCR
in the future. New fabrication methods are emerging to develop fiber-optic DNA biosensors (Wei,
Lillehoj, and Ho 2010).
The high stability and specificity of nucleic-acid-based biosensors can be promising candidates
in the future for the clinical diagnostic market (Inan et al. 2017). However, the major bottleneck is
TABLE 15.3
Electrochemical-Based Sensors for Nucleic Acids and Aptamer Detection in the Diagnosis
of Various Diseases
Low Detection
Target Disease Detection Type Limit or Range Reference
IS6110 gene Tuberculosis Labeled probe 0.01 ng/μl Torres-Chavolla and
Alocilja 2011
Mycobacterium Tuberculosis Labeled probe 0.065 ng/μL Das et al. 2010
tuberculosis
31-mer oligonucleotide Dengue Label-free 2.7 × 10–12 M Deng and Toh 2013
sequence
miRNA-21 Cancer Direct detection 100 aM Hong et al. 2013
miRNA-21 Carcinoma Indirect detection 0.006 pM Meng et al. 2013
MCF-7 cells Breast cancer Sandwich type ~38 cells/mL Yan et al. 2013
Thrombin Inflammatory Labeled probe 2.3 × 10–11 mol/L Cui, Fan, and Lin 2013
disorder
Vasopressin Traumatic injuries Label-free 43 pM He et al. 2013)
C-reactive protein Cardiovascular Label-free 100–500 pg/ml Qureshi et al. 2010
disease
IFN- γ Tuberculosis Direct 100 fM (RNA), 1–10 pM Min et al. 2008
(DNA) buffer dependent
Mucin 1 Breast cancer Sandwich assay <100 cells Zhu et al. 2013
the requirement of strategic investments for commercialization of biosensor technology in the clini
cal field. These biosensors can be particularly useful in life sciences and medicine since in clinical
practice, biosensors with high sensitivity and specificity can significantly enhance patient care,
early diagnosis of diseases, and pathogen detection (Peña-Bahamonde et al. 2018). In this review,
we will present the research conducted with antibodies, DNA molecules, and enzymes to develop
biosensors that use graphene and its derivatives as scaffolds to produce capable biosensors able to
detect and identify a variety of diseases, pathogens, and biomolecules linked to diseases (Peña-
Bahamonde et al. 2018).
15.8 REDOX ELECTROCHEMICAL SENSORS

In the electrochemistry field, great attention was paid for the development of methods able to detect
superoxide, hydrogen peroxide (H2O2), reactive oxygen species (ROS), and reactive nitrogen spe
cies (RNS) in biomedical research. ROS are involved in normal cellular homeostasis; during dif
ferent pathological conditions as a consequence of imbalance, redox homeostasis leads to disease
manifestation or progression. To detect the extracellular production of ROS, the choice of methods
are high-performance liquid chromatography (HPLC), liquid chromatography–mass spectrometry
(LC-MS), and mass spectrometry (Dikalov and Harrison 2014). Methods such as electron paramag
netic resonance, fluorescence microscopy, and genetic probes are a few bioanalytical approaches
not based on electrochemistry that are routinely employed (Armbrecht and Dittrich 2017). Since
available methods have their caveats, the electrochemical monitoring of these reactive species in the
biological system will grow in importance and diffusion. Superoxide and H2O2 are present in defi
cient concentrations due to relatively shorter half-lives in reducing cellular environments. Hence,
monitoring superoxide and H2O2 produced by living cells in real-time are thus rather challenging.
Although plenty of electrochemical sensors for superoxide and hydrogen peroxide were reported
in the scientific literature, few articles describe their use in biological systems (Prasad et al. 2015;
Lvovich and Scheeline 1997; Flamm et al. 2015; Sadeghian et al. 2015; Cai et al. 2019; Ganesana,
Erlichman, and Andreescu 2012; Balamurugan et al. 2018; Gao et al. 2018)
15.9 ELECTROCHEMICAL IMMUNOASSAYS AND IMMUNOSENSORS

Electrochemical immunosensors merge the inherent selectivity of the biological component and the
sensitivity of electroanalytical methods. The electrochemical immunosensor, a type of biosensor,
employs an antibody as a capture agent and quantitatively measures the electrical signal resulting
from the binding event between the antibody and target molecule (i.e., the analyte) “sandwich immu
noassay.” It is a miniaturized favorable device for the detection of point-of-care testing (POCT). A
few of these sensor devices are in the commercial stage and are consistently used in clinical, envi
ronmental, industrial, and agricultural applications (Piro and Reisberg 2017; Cho et al. 2018; Pollap
and Kochana 2019; Tang et al. 2019; Contreras-Naranjo and Aguilar 2019). The principle behind
them is that catalytic or binding of the biological analyte with sensor selectivity ultimately produces
an electrical signal monitored by a transducer that is proportional to the analyte concentration.
15.10 PAPER-BASED ELECTROCHEMICAL SENSORS AND INKJET-PRINTED

A low-cost paper-based/inkjet-printed platform for electrochemical analyses can be produced that
meets the needs of patients and the medical community, and it is also very likely that these devices
will be considered disposable (Das et al. 2016). Previous studies demonstrated that inkjet-printed/
paper-based electrochemical sensors are suitable for this application due to their enormous advan
tages including carefully selected materials and fabrication methods with incredible control over
the material deposition process; in case of paper substrates, pump-free microfluidic devices can be
set up due to their wicking property (Das et al. 2016; Cinti 2019; Gebretsadik et al. 2019; Loo et
al. 2019; Felix, Baccaro, and Angnes 2018; Evans et al. 2018; Nyein et al. 2018). By merging fac
tors of innovation with low-cost, sensitivity at the point-of-care sensors make the electrochemical
technique more favorable.
15.11 CONCLUSIONS
Finally, it may be concluded that the development and research of electrochemical (bio)sensors or
any analytical method is becoming a trendy scientific area at the intersection of the biological and
engineering sciences and possibly will be extensively used shortly. The future possibility of devel
opment of simple, disposable, biocompatible, multiplexing, and low-cost implantable electrochemi
cal sensors for biomedical and clinical applications are of great interest for their ability to monitor
clinically relevant analytes such as blood gases (CO, NO, H2S, CO2, and SO2), bodily electrolytes,
macromolecules (protein, DNA, RNA and others), and metabolites in real-time. Furthermore, con
tinuing to innovate, by merging each of these favorable electrochemical-sensing techniques and
materials is incredibly selective and provides accurate and repeatable quantitative results without
expensive measurement equipment. As an alternative to conventional methods, advance, electro
chemical analytic methods might be promising for future needs of the biomedical field for many
patients, healthcare and medical professionals, and environmental specialists.
ACKNOWLEDGMENTS
The author acknowledges Mr. William McLean for critical proofreading and excellent editing of
this book chapter.
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Index
ABPE, see Applied bias photon to current efficiency

BP-S configuration, 197–198
Accuracy parameter, 130

Butler-Volmer equation, oxygen reduction reaction of, 92
Acid blue 113 dye, 189
A-CNTs, see Amine functionalized carbon nanotubes

Carbazole-dendrimer, 221, 222
Advance oxidation processes (AOPs), 184, 207

Carbon monoxide detection, electrochemical sensors for,
Ag–Ni alloys, 38
255–257
Al–Al electrodes, 202

Cathode, significance of, 4
ALD, see Atomic layer deposition

Cathodic coatings, 10
Amine functionalized carbon nanotubes (A-CNTs), 172

Cathodic polarization, 29
Amperometric–polarographic H2S sensors, see

CE, see Counter electrode
Polarographic H2S sensor

Central Electrochemical Research Institute (CECRI), 42
Amperometry, 4
Chemical oxygen demand (COD), 88, 98
experiments, 5
removal, 199, 201, 202
Analytes, significance of, 124

Chemiresistive gas sensing materials, 121–122
Anode, significance of, 4

analytes and, 124
Anodic coatings, 10
chemiresistive sensors and, 122
Anodic oxidation, see Direct oxidation

complexes, 127
Anodic polarization, 29
composites, 126–127
AOPs, see Advance oxidation processes

device design and mechanism, 122–124
Applied bias photon to current efficiency (ABPE), 108

future directions, 130–131
Aqueous medium electrolytes, 73–74

metal organic frameworks (MOFs), 128
Artificial photosynthesis, see Photoelectrochemical

metal oxide sensors, 126
process
nanoparticles, 127–128
As-synthesized nanotubes, 55
parameters, 129–130
Asymmetric supercapacitors, 64–65

polymers, 126
Atomic layer deposition (ALD), 55

sensing platform, 129
types of, 125
Batteries, 238
Chronoamperometry, 253
BDD, see Boron-doped diamond

Chronocoulometry, 253
BDM, see Bockris-Devanathan-Müller model

Chronopotentiometry, 253
Binary metal sulfides, 141

Clay cup modified MFC, 95
Biocatalyst metabolic losses, 93

Cobalt electrodeposition, 36
Biocatalysts, 92
COD, see Chemical oxygen demand
Biomedical applications, 251–252

Complexes, 127
biological analytes and electrochemical methods, Composite coatings, 43
254–255 Composites, 126–127
electrochemical immunoassays and fabrication of, 243–244
immunosensors, 261
Conducting polymers (CPs), 69, 140, 233–234
electrochemical methods, 252–253

electrochemical applications of
electrochemical sensor and circuit, 254

batteries, 238
electrochemical sensors and working principles, 252

electrochemical sensors, 240–244
gasotransmitter electrochemical sensors, 255

fuel cells, 238–239
carbon monoxide detection and electrochemical solar cells, 235–238
sensors, 255–257 supercapacitors, 240
hydrogen sulfide electrochemical sensors, 258–259 examples of
nitric oxide electrochemical sensors determination, polyaniline (PANI) and derivatives, 234–235, 239
257–258 polypyrrole (PPY), 235
nucleic acids and electrochemical sensors, 259–261 polythiophene and derivatives, 235
paper-based electrochemical sensors and Conductivity studies of organic compounds, as additives in

inkjet-printed, 261–262 polymer electrolytes, 221–223
redox electrochemical sensors, 261

Congo red, 188
Biomolecules, immobilization of, 244

CoNiFe ternary alloy, 39
Biosensor
Convection, 30
glucose, 15–16 Conway model, 32
hydrogen peroxide (H2O2), 16

Copper–indium alloy, 38
Bockris-Devanathan-Müller (BDM) model, 32

Copper oxide, 139
BODIPY, 218–221
Copper-oxide-based electrodes, 110
Boron-doped diamond (BDD), 158, 160, 185

Coulombic efficiency, 88
267
268 Index
Counter electrode (CE), 254, 256, 257

direct method, 184–185
COX, see Cytochrome c oxygenase
by indirect method, 185–186
CPs, see Conducting polymers
Electrochemical immunoassays and
CuI nanoplates, 141–142
immunosensors, 261
CuNi dentric nanostructures, 143

Electrochemical sensors, 240–244
Cyclic voltammetry, 253

Electrochemical supercapacitors, 63–65
Cyclic voltammetry oriented electrochemical reduction

electric double-layer capacitors, 65–66
procedure, 56
material advances for, 68–69
Cytochrome c oxygenase (COX), 256

pseudocapacitors, 66–68
advances in materials for, 69–72
Dead time, 129

and reactions, advancements in
Decolorization, of textile dye, 186–188

electrolytes for, 72–73
Deposit thickness, 28
aqueous medium, 73–74
D-Glucose, 135
ionic liquids, 74–75
Differential scanning calorimetry (DSC), 224

organic solvent medium, 74
with organic molecules as additives in polymer Electrocoagulation, 193–194

electrolytes, 223–224
fundamentals of, 194
Diffusion, 30
colloidal stability, 194–195
Dimensionally stable anodes (DSA), 201

principle, 195–196
Direct deposition (DP), 27

future perspectives, 206–209
Direct electrolysis, 17
of industrial wastewater, materials for, 200
Direct electrolytic decontamination, 157

food industry, 200–201
Direct oxidation, 158–159

oil industry, 201–202
Dissolvable anodes, see Sacrificial anodes

pharmaceutical industry, 202–204
DLVO theory, 194–195

pulp and paper industry, 202
DP, see Direct deposition

textile and tannery industry, 200
Drift, 129
wastewater containing heavy metals, 204, 206
DSA, see Dimensionally stable anodes

operating parameter effects on performance of, 196
DSC, see Differential scanning calorimetry

current density, 198
DSSCs, see Dye-sensitized solar cells

electrode configuration, 197–198
Dye elimination, 187

electrode material, 196
Dye-sensitized solar cells (DSSCs), 54–56, 217–219

initial pH, 196–197
organic materials as photosensitizers in, 220–228

solution conductivity, 199–200
preparation of, 220

temperature, 198–199
Dynamic range, 129

Electrode–electrolyte interface, 29
Electrode fouling, 136
EAOPs, see Electrochemical advanced oxidation processes Electrodeposition, 26
EAPs, see Electroactive polymers fundamentals of, 27–32

EDL, see Electrical double layer material tunable properties by parameters of, 34–35
EDLC, see Electric double-layer capacitor composition, 35–36
Electrical double layer (EDL), 31–32, 194–195 morphology, 40–41
Electric double-layer capacitor (EDLC), 64–66 structure, 37–40
material advances for, 68–69
mechanism of, 29–31
Electroactive polymers (EAPs), 186

of metals and alloys, 5–10
Electrocatalysts, for wastewater treatment, 153–154

of metals, as sacrificial coatings, 10
decontamination advances, 161–163 of organic materials, 10
fundamentals of, 154

parameters affecting, 32
electrocatalytic anode material categorization, 160

agent addition, 33
electrocatalytic oxidation mechanism, 156–160

agitation effect, 34
electrocatalytic reactor configuration, 155–156

bath concentration effect, 33
superiorities and inferiorities, 163–164

bath temperature effect, 33
Electrocatalytic advance oxidation processes, 154

complexing agent, 33
Electrochemical advanced oxidation processes (EAOPs)

current density effect and distribution, 32
anodes, advantages of, 183–184

hydrogen embrittlement, 34
general setup of, 183

pH effect, 33
of textile dyes from wastewater, 186

plating time effect, 33–34
acid blue 113 dye, 189

Electrodes, 4, 28, 86, 136; see also individual entries
Congo red, 188

Electrolysis, 17
indigo carmine dye, 188–189

Electrolyte, significance of, 86
methylene blue dye, 186–188

Electrolyzer mode, 4
rhodamine B dye, 188

Electrophoretic deposition (EPD), 10–11
triphenylmethane dye, 189–190

Electrospinning, 75
yellow 3 (DY3) dye, 189

Enzymatic glucose sensor, 136–137
types of, 182, 184

EPD, see Electrophoretic deposition
Index 269
Faradaic current, 28
Innovative material, in electrochemical glucose sensors,
Faradaic reaction, 66
135–136
Faraday’s laws of electrolysis, 27–28, 33

enzymatic glucose sensor and, 136–137
FESEM, see Field emission scanning electron microscopy

nonenzymatic glucose sensors, 137–142
FF, see Fill factor

alloying, 142–144
Field emission scanning electron microscopy (FESEM), 170

doping, 145
Figaro electrochemical-type gas sensors, 256

functionalization, 142
Fill factor (FF), 219

morphology, 144
Flexible supercapacitors, 68
nanocomposites, 145–146
Fluorinated tin oxide (FTO), 217–218

Inorganic heterojunction and organic solar cells
Food industry, 200–201
applications, 50–52
Fossil fuels, 105

Intensiostatic/galvanostatic method, 4
FTO, see Fluorinated tin oxide

Ionic liquids, 74–75
Fuel cells, 238–239

Ion-sensitive electrodes (ISEs), 258–259
IPCE, see Incident photon to current conversion efficiency
Gallium nitride (GaN), 110

ISEs, see Ion-sensitive electrodes
Galvanostatic potential difference, 29
GaN, see Gallium nitride

Lewis basicity, 127
Gasotransmitter electrochemical sensors, 255

Limit of detection (LOD), 129
carbon monoxide detection and electrochemical Linear response, 130
sensors, 255–257 Linear sweep voltammetry, 253
hydrogen sulfide electrochemical sensors, 258–259 LOD, see Limit of detection
nitric oxide electrochemical sensors determination,

257–258
Marcus model, 32
Giant magneto resistance (GMR), 42

Mass transfer, 30
Gibbs free energy, 88–89

Materials synthesis, controlled electrochemical deposition
Glucose biosensors, 15–16

for, 26–27; see also Electrodeposition
Glucose dehydrogenase, 137
Material synthesis, by electrode position method
Glucose oxidase, 136, 137

electrophoretic deposition, 10–11
GMR, see Giant magneto resistance

metals and alloys electrodeposition, 5–10
Gouy-Chapman double layer, 31, 65

metals electrodeposition, as sacrificial coatings, 10
Grahame layer, 32
organic materials electrodeposition, 10
Graphitic carbon nitride, 111

Maxwell-Boltzmann statistic, 31
MDC, see Microbial desalination cell
Health, energy, and environment, electrochemistry MEC, see Microbial electrolysis cell
application for
Metal azolate framework, 142
biosensor, 15–16
Metal ion doping, 145
chemiresistive gas sensor, 12–14

Metal nanoparticles, 137–138
hydrogen generation, 11–12

Metal organic frameworks (MOFs), 128
wastewater treatment, 17
Metal oxides, significance of, 138–139
Helmotz double layer, 31

Metal oxide sensors, 126
History, of electrochemistry, 1–4

Metals and alloys electrodeposition, 5–10
HRT, see Hydraulic retention time

Metals electrodeposition, as sacrificial coatings, 10
Hybrid solar cells, 52–54

Metal tellurides, 141
Hybrid supercapacitors, 67–68

Methylene blue dye, 186–188
Hydraulic retention time (HRT), 87

MFCs, see Microbial fuel cells
Hydrogen
Microbial desalination cell (MDC), 97
production, from biomass and water, 113–116 Microbial electrolysis cell (MEC), 97
and solar energy, 106

Microbial fuel cells (MFCs), 84–85
Hydrogen embrittlement, 34
activation losses, 92–93
Hydrogen peroxide (H2O2) biosensors, 16

biocatalyst metabolic losses, 93
Hydrogen sulfide electrochemical sensors, 258–259

components of, 86–87
Hydroxyl radicals, 156, 157, 182, 184

concentration losses, 93
future directions, 100
IHP, see Inner Helmholtz plane limitations, 97–98
Incident photon to current conversion efficiency biochemical constraints, 98–99
(IPCE), 108
economic constraints, 99–100
Indigo carmine dye, 188–189

functional materials constraints, 99
Indirect electrolysis, 17
microbial conversion of organic material into
Indirect electrolytic decontamination, 158
electricity production prototypes, 94–97
Indirect oxidation, 159–160

microbial conversion of organic matters into fuel, 97
Indium phosphide, 11
ohmic losses, 93
InGAN, 111
parameters in treatment of, 87–88
Inner Helmholtz plane (IHP), 65

potential losses, 91–92
270 Index
thermodynamics of, 89–91

Organic molecules, as additives in redox electrolyte in
Microelectrode, 254
DSSCs, 220–221
Microorganisms, 87
Outer Helmholtz plane (OHP), 65
Migration, 30
Oxidant generation mechanism, 183
Mild steel corrosion and prevention, A-MWCNTs/tetra

Oxidation, significance of, 4, 26
functional epoxy coatings for, 169–172 Oxide electrodeposition, 36
experimental details, 172

Oxygen evaluation reaction (OER), 156, 160
mild steel specimen surface preparation, 172–173

Oxynitride, in PEC, 113
sample preparation, 173
results and discussion, 174–175

Palladium alloys, 38
electrochemical impedance study, 176

PANI, see Polyaniline and derivatives
morphology studies, 176–177

Paper-based electrochemical sensors and
thermal properties, 175–176

inkjet-printed, 261–262
Mixed transition metal oxides (MTMOs), 69

Paper-cup-based integrated microbial fuel cell (PC-MFC), 95
MOFs, see Metal organic frameworks

PEC, see Photoelectrochemical process
Molybdenum disulfide, 113

PED, see Pulsed electrodeposition
MP-P configuration, 197, 198

PEDOT, see Poly ethylenedioxythiophene
MP-S configuration, 197, 198

Perovskite solar cells, 57–58
MTMOs, see Mixed transition metal oxides

Pharmaceutical industry, 202–204
Multilayer coatings, 41–43

Phosphide, in PEC, 112
Multiwalled carbon nanotubes (MWCNTs), 170

Photoelectrochemical (PEC) process, 106–107
analysis, 225
N,N,N′N″-Tetrakis(2,3-epoxypropyl)-4,4 calculations in, 108–109
(1,4-phenylenedioxy)
experimental setup, 107
dianiline synthesis, 172

hydrogen production from biomass and water and,
Nafion, 99
113–116
Nanobiosensors, electrochemical-based, 14
mechanism of, 107–108
Nanocomposites, 145–146
quantum-dot-based photoelectrode and, 113
Nanofiltration, 208
water splitting
Nanoparticles, 127–128
metal oxide as photoelectrode in, 109–110
NER, see Normalized energy recovery
nonmetal oxide as photoelectrode in, 110–113
Nernst equation, 90
Photovoltaic energy generation system, 49–50
Nernst-Monod model, 92–93
electrochemical synthesis
NHE, see Normal hydrogen electrode
for dye-sensitized solar cells, 54–56
Nickel–zinc alloy deposits, 35–36
for hybrid solar cells, 52–54
Ni-Mn alloys, 37–38
inorganic heterojunction and organic solar cells
Nitric oxide electrochemical sensors
applications, 50–52
determination, 257–258
in perovskite solar cells construction, 57–58
Nitride, in PEC, 110–112
for quantum dot-sensitized solar cells, 56–57
Ni–Zn–Fe system, 36
PHSS, see Polarographic H2S sensor
Nondissolvable anodes, 26
Plant-intermitted MFC prototypes, 96
Nonenzymatic biosensors, 16
Point-of-care testing (POCT), 261
Nonenzymatic glucose sensors, 137–142

Polarizable electrodes, 28
alloying, 142–144
Polarographic H2S sensor (PHSS), 259
doping, 145
Polyaniline (PANI) and derivatives, 234–235, 239
functionalization, 142
Poly ethylenedioxythiophene (PEDOT), 56
morphology, 144
Polymer electrolytes, 26
nanocomposites, 145–146
Polymers, significance of, 126
Non-faradaic current, 28
Polypyrrole (PPY), 126, 235
Nonpolarizable electrodes, 28
Polythiophene and derivatives, 235
Normal hydrogen electrode (NHE), 90

Polyvinyl alcohol (PVA), 69
Normalized energy recovery (NER), 88

removal of, 199
Nucleic acids, electrochemical sensors for, 259–261

Positive electrode, 4
Potentiometry, 4
OER, see Oxygen evaluation reaction

Potentiostatic setup, 4
Ohmic losses, 93
Power, 87
OHP, see Outer Helmholtz plane

Power output comparison, 98
Oil industry, 201–202

PPY, see Polypyrrole
Organic electrolytes, 74
Pseudocapacitor, 64, 66–68
Organic materials, 217–219

advances in materials for, 69–72
electrodeposition, 10
Pt alloys, 142–143
photoelectrochemical measurements, 219–220

Pulp and paper industry, 202
solar cells preparation, 220

Pulsed electrodeposition (PED), 27
as photosensitizers in DSSC, 220–228

PVA, see Polyvinyl alcohol
Index 271
QDSSCs, see Quantum dot-sensitized solar cells

Sulfide, in PEC, 113
Quantum-dot-based photoelectrode, 113

Supercapacitor, 32, 64–65, 240
Quantum dot-sensitized solar cells (QDSSCs), 56–57

Symmetric supercapacitors, 64
RE, see Reference electrode

Tantalum oxynitride (TaON), 113
Reactive oxygen species (ROS), 261

TEM, see Transmission electron microscope
Receptor function, 13–14

Ternary alloys, electrodeposition of, 36
Recovery time, 129

Textile and tannery industry, 200
Redox electrochemical sensors, 261

Textile dyes, 181–182; see also Electrochemical advanced
Redox-type electrolytes, 73
oxidation processes
Reduced graphene oxide (rGO), 110

Titanium-dioxide-based electrodes, 109
Reduction, significance of, 4, 26

TMOs, see Transition metal oxides
Reference electrode (RE), 4, 26, 254, 257

Transducer function, 13, 14
Response time, 129

Transient current, see Non-faradaic current
Reversability parameter, 129

Transition-metal-based alloys, 143
rGO, see Reduced graphene oxide

Transition metal oxides (TMOs), 69
Rhodamine B dye, 188

Transition metal phosphides, 141
ROS, see Reactive oxygen species

Transmission electron microscope (TEM), 37
Trasatti-Buzzanca model, 32
Sacrificial anodes, 26
Trimethylamine, 128
SAED, see Selected area electron diffraction

Triphenylmethane dye, 189–190
Scanning electron microscope (SEM), 226

Two-photon system, 12
analysis, of organic-compound-doped
polymer electrolytes, 225, 227–228
Utility factor, 13, 14
Selected area electron diffraction (SAED), 37
Selectivity
Van der Waals (vdW) force, 194, 195
parameter, 129–130
Vertical integrated MFC, 94–95
poor, 136
Voltammetry methods, 252–253
Sensitivity
parameter, 129
Wastewater treatment, 17; see also
poor, 136
Electrocatalysts, for wastewater
Sensor response, 124
treatment
Sensors, definition of, 121
Water splitting over semiconductor photocatalysts, 12
Separators, 86–87
WE, see Working electrode
Sodic–saline inoculum, electrical stress directed, 94

Wire wool, 200
Solar cells, 235–238

Working electrode (WE), 254, 256
Solar energy, 106, 217
Solar to electric energy conversion efficiency, 219

X-ray diffraction (XRD) studies, 224
Solar to hydrogen (STH) efficiency, 107, 108
Specific energy consumption, 88

Yellow 3 (DY3) dye, 189
Spin trapping, 157
Square wave voltammetry, 253

Zeta potential, 40
Stability parameter, 129

Zinc oxide, 139
Standard electrode potential, 29

Zinc-oxide-based electrodes, 109
Stern layer, 32, 65–66

Zn–Fe–Mo system, 36
STH, see Solar to hydrogen efficiency

Z-scheme photocatalysis, 12

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New Technologies for

New Technologies for

Mu. Naushad, Saravanan Rajendran, and

© 2020 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

International Standard Book Number-13: 978-0-367-19067-5 (Hardback)

Visit the Taylor & Francis Web site at

and the CRC Press Web site at

Contributors ................................................................................................................................... xiii

Chapter 1 Electrochemistry: Different Materials and Applications: An Overview .....................1

D. Durgalakshmi, Saravanan Rajendran, and Abdullah M. Al-Enizi

Chapter 2 Controlled Electrochemical Deposition for Materials Synthesis...............................25

T. Sivaranjani, T. A. Revathy, and A. Stephen

Chapter 3 Photovoltaic Energy Generation System: Material, Device, and Fabrication............ 49

Ananthakumar Soosaimanickam and Moorthy Babu Sridharan

Chapter 4 Role of Advanced Materials in Electrochemical Supercapacitors............................. 63

Joyita Banerjee, Kingshuk Dutta, and M. Abdul Kader

Chapter 5 Microbial Electrochemical Technologies for Fuel Cell Devices................................ 83

S. V. Sheen Mers, K. Sathish-Kumar, L. A. Sánchez-Olmos,

Chapter 6 Photoelectrochemical Process for Hydrogen Production......................................... 105

S. Devi and V. Tharmaraj

Chapter 7 Recent Trends in Chemiresistive Gas Sensing Materials......................................... 121

Baskaran Ganesh Kumar, J. Nimita Jebaranjitham, and Saravanan Rajendran

Chapter 8 Role of Innovative Material in Electrochemical Glucose Sensors........................... 135

R. Suresh, Claudio Sandoval, Eimmy Ramirez, R. V. Mangalaraja, and Jorge Yáñez

Chapter 9 Electrocatalysts for Wastewater Treatment .............................................................. 153

Prasenjit Bhunia, Kingshuk Dutta, and M. Abdul Kader

Chapter 10 Development and Characterization of A-MWCNTs/Tetra Functional Epoxy

Coatings for Corrosion and Prevention of Mild Steel .............................................. 169

D. Duraibabu, A. Gnanaprakasam, and S. Ananda Kumar

Eswaran Prabakaran and Kriveshini Pillay

Carlos Navas-Cárdenas, Herman Murillo, Maibelin Rosales, Cesar Ron, and

Chapter 13 Role of Organic Materials in Electrochemical Applications ................................... 217

Chapter 14 Advanced Conducting Polymers for Electrochemical Applications ........................ 233

R. Suresh, R. V. Mangalaraja, Paola Santander, and Jorge Yáñez

Chapter 15 Electrochemical Studies for Biomedical Applications............................................. 251

D. Duraibabu Florinella Muñoz

Carlos Navas‑Cárdenas Maibelin Rosales

Cesar Ron T. Sivaranjani

Moorthy Babu Sridharan A. Stephen

Ananthakumar Soosaimanickam V. Tharmaraj

and Abdullah M. Al-Enizi

1.2 Oxidation and Reduction ..........................................................................................................4

1.3 Material Synthesis by Electrode Position Method ...................................................................5

1.3.1 Electrodeposition of Metals and Alloys ....................................................................... 5

1.3.2 Electrodeposition of Organic Materials...................................................................... 10

1.3.3 Electrodeposition of Metals as Sacrificial Coatings................................................... 10

1.3.4 Electrophoretic Deposition ......................................................................................... 10

1.4.1 Hydrogen Generation.................................................................................................. 11

1.4.2 Chemiresistive Gas Sensor ......................................................................................... 12

1.4.3.2 H2O2 Sensor ................................................................................................. 16

1.4.4 Wastewater Treatment ................................................................................................ 17

1.5 Summary and Future Directions ............................................................................................ 17

1.1 INTRODUCTION TO ELECTROCHEMISTRY: HISTORY

1.2 OXIDATION AND REDUCTION