Available online at www.sciencedirect.

com Current Opinion in

ScienceDirect Electrochemistry

Review Article

The principles of bipolar electrochemistry and its

electroanalysis applications
Nashmil Karimian1, Pegah Hashemi1, Abbas Afkhami2 and
Hasan Bagheri3

Abstract spherical particles fluidized by electrolyte flow where

The present study reports the wireless technique that gener- voltage applied between two driving electrodes enables
ates asymmetric reactivity on the surface of the conducting electrochemical reactions at separate conductive parti-
substrate without any direct electrical connection in the elec- cles [1e6]. Therefore, this phenomenon that creates
trolyte solution by inducing external power. In recent years, asymmetric reactivity on an isolated conducting sub-
bipolar electrochemical systems have received special strate without any direct connection and under an
attention that they are used for new kinds of electrochemical external power supply is called BPE. Also, it can be
applications ranging from electrodeposition to electroanalytical known as a “wireless technique.” BPE is very similar to
chemistry. Bipolar electrochemistry is a unique technique conventional electrochemistry except that the
because of the lack of direct electrical connection to the bipolar cathode and anode are physically separated, and the
electrode. In this perspective article, we first illustrate the potential difference at the electrodeesolution interface
concept and history of the bipolar electrochemistry as well as is directly controlled with a power supply.
their application based on the open and closed bipolar
configuration in different fields. BPE has been used since the 1970s in the field of
electrosyntheses [7e9], in photoelectrochemical cells
Addresses [10,11], electrochemical reactors, and batteries [12]. In
1
Research and Development Department, Farin Behbood Tashkhis
the recent years, BPE gained considerable attention for
LTD, Tehran, Iran
2
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran analytical purposes such as preconcentration [13,14],
3
Chemical Injuries Research Center, Systems Biology and Poisonings separation [15,16], electrochemical sensing [17,18], and
Institute, Baqiyatallah University of Medical Sciences, Tehran, Iran optical detection [19,20]. So far, there have been many
reviews on the concept and various applications of BPE
Corresponding author: Bagheri, Hasan ([email protected]), (h.
[email protected])
[21e25]. Here, we summarize the basic initial concept
of BPE and their applications, especially since 2010, in
microfluidic systems, electrochemical sensing, optical
Current Opinion in Electrochemistry 2019, 17:30–37 detections, and bipolar membranes for environmental
This review comes from a themed issue on Environmental pollution control.
Electrochemistry
Edited by Xing-Jiu Huang Fundamentals of bipolar electrochemistry
For a complete overview see the Issue and the Editorial
The principle of BPE is based on potential applied be-
tween the feeder (driving) electrodes across an elec-
Available online 19 April 2019
trolyte solution and electrochemical reactions generated
https://doi.org/10.1016/j.coelec.2019.04.015
at the anodic and cathodic poles of the BPE [4,6,26]. In
2451-9103/© 2019 Elsevier B.V. All rights reserved. BPE, similar to three-electrode electrochemical sys-
tems, any substance with sufficient conductivity is used
Keywords as driving electrodes without the need for physical
Bipolar electrochemistry, Electroanalysis, Electrochemiluminescence, connection in the presence of a power supply [27]. The
Electrochemical sensors, Microfluidic systems. experimental setup of a BPE consists of an electrolyte
solution, driving electrodes, and uniform electric field
across the electrolyte solution. The electrochemical
Introduction setup includes a platinum BPE, an aqueous solution
This study aims to introduce basic concepts underlying containing a dilute, inert electrolyte, and an external
bipolar electrochemistry (BPE) and investigate their power supply (Figure 1) [24,25]. Once the power supply
applications in electrochemical and optical detection is turned on to apply a 1-V potential, Faradaic reactions
based on electrodissolution and electro- are not seen at bipolar electrodes. Critical voltage de-
chemiluminescence (ECL). In the late 1960s, Fleisch- pends on a number of experimental factors. Bubbles are
mann et al. defined a bed of electrically conducting observed at the poles of the BPE. In other words, even

Current Opinion in Electrochemistry 2019, 17:30–37 www.sciencedirect.com

 The principles of bipolar electrochemistry Karimian et al. 31

Figure 1 reactions in a classic electrochemical cell with a three-

electrode setup, which consists of working, auxiliary,
and reference electrodes. The potential of the working
electrode is controlled against a reference electrode
using a potentiostat, which means controlling the energy
of the electrons within the working electrode.[8] The
potential of the solution is at a floating value that de-
pends on the composition of the solution in the absence
of externally applied electric field [28]. By driving the
working electrode to more negative potentials (raising
the energy of the electrons) than those of electroactive
molecules in the solution, electrons may move from the
electrode to reduce species in the solution inducing a
cathodic current [29]. Similarly, oxidation reactions
occur when electrons move from the solutes in the so-
lution to the electrode when the latter has a significantly
lower potential than the solution [29]. Thus, in con-
ventional electrochemistry, the driving force of the
redox reaction is directly controlled by tuning the po-
tential of the working electrode that is connected to a
power supply.

Scheme of a conductive substrate positioned between two feeder elec- Once the potential drops at the driving electrode-
trodes in an electrolytic solution in the bipolar open configuration
("Reprinted with permission from Ref. [25]. Copyright (2016) WILEY-VCH
electrolyte interface, the distorted electric field at the
Verlag GmbH & Co. KGaA, Weinheim."). surface of driving electrodes by Faradaic current is very
small and neglected. Hence, it can be concluded that
applied potential Eappl drops linearly through the elec-
trolytic solution. The value of overpotentials depends
though the BPE has an equipotential surface (or nearly on the magnitude of total potential and the length of the
so), electrolysis of water occurs at its two poles. BPE. The location of BP electrodes is in the boundary
Importantly, charge must be conserved at the BPE, and between its two poles, so the solution has zero over-
therefore, the rates of formation of 12O2 and H2 are the potential. Therefore, the value of overpotentials
same. Faradaic reactions might also occur at the driving changed along the length of the BPEs where the
electrodes, but although this is usually a nuisance, it maximum overpotential occurred at the end of elec-
does not directly affect the BPE. To maintain electro- trodes [30]. The nonequality of the interfacial potential
neutrality at the bipolar electrode, the electron pro- along the length of a BPE is useful for synthesizing thin
duction and consumption must be equal at both sides films with different rates.
[24e27].
The material used as driving electrodes in BPE can be
The bipolar cells can be made with various materials and metallic (e.g., Au, Ag, Pt, or stainless steel) [31,32],
different dimensions depending on their application in carbonaceous (e.g., glassy carbon or graphite) [33], or
various fields. Transparent materials such as polymethyl nonpolarizable (e.g., Ag/AgCl reference electrode)
methacrylate, glass, and polyethylene were mainly used [34,35]. The formed electric field between the two
for cell preparation so as to observe the bubble forma- electrodes is variable according to the geometry of the
tion at the driving electrodes. The voltage applied be- cell and the electrolyte conductivity.
tween the two driving electrodes (Etot) results in an
electric field in solution that causes the BPE to float an Duval et al. [36e40] reported the relationship between
equilibrium potential (Eelec) that depends on its posi- the parameters that control bipolar electrochemical
tion in the field and the composition of the electrolyte processes including Etot, the distance between the
solution. Because the electrode is a conductor, its po- driving electrodes (lchannel), and the length of the BPE
tential (Eelec) is the same (or nearly so) everywhere on (lelectrode), and finally, DEelec was estimated using the
its surface. However, the interfacial potential difference following equation [30, 36e40]:
between the BPE and the solution varies along its length
due to the presence of an electric field in solution. DEelec ¼ Etotal ðlelectrode =lchannel Þ

For better understanding of the electrochemistry in bi- The magnitude of DEelec is the main parameter
polar configurations, let us first look at the redox considered for analyzing electrochemical processes at
BPEs. DEelec is the fraction of Etot that is dropped across
www.sciencedirect.com Current Opinion in Electrochemistry 2019, 17:30–37
32 Environmental electrochemistry

the BPE, and it represents the total driving force avail- Figure 2
able to couple the two Faradaic reactions at the poles of
the BPE.

In addition, BPE can be divided based on whether the

conductor is immersed into a solution (open BPE) or
two separate solutions (closed BPE), which will be
illustrated in the two following sections.

The open configuration of bipolar electrochemistry

In the open bipolar system, an electronic substrate is
immersed into the electrolyte between two driving
electrodes without any electrical connection between it
and the external power supply (wireless manner), as
shown in Figure 1 [25]. Open BPE systems have been
especially useful in electroanalytical studies and
microfluidic environment [28]. BPE can be coupled
with electrochemistry and ECL reaction at each pole of Scheme of a closed bipolar electrochemical cell ("Reprinted with
the BPE while a voltage is applied to a pair (or more) of permission from Ref. [44]. Copyright (2010) American Chemical
driving electrodes. In open BPE, the potential differ- Society.").
ence between the conductor and the electrolyte is
proportional to the magnitude of the electric field (£) in
the solution whose relationship is as follows: [46]. Also, the voltage across the substrate in closed
BPEs is equal to the voltage applied to the pair of
£ ¼ Ea  Ec =l driving electrodes, and consequently, the voltage is
dropped approximately at the solution interface near
Ea and Ec represent the potential of the anode and both the ends of the BP electrodes. These features of
cathode, respectively, and l represents the distance closed BPEs and their geometry lead to increase in
separating the driving electrodes. Cheng et al. [41] have their application in various fields such as sensing,
reported a theoretical model for the investigation of the catalysis, screening, and so on [35,44,47e57].
potential gradient at the BP electrodes and the reac-
tivity at the end of the polarized interface. In 2012, Guerrette et al. [45] reported the first coupled
electrochemical reactions at the bipolar microelectrodes
In another work performed by Ulrich et al. [42], the and nanoelectrodes in closed bipolar systems that they
magnitude of potential and current density distribution were authenticated the type of voltammetric responses
was studied in the interface of bipolar electrodes and of BPE from the conventional system. Also, they opened
electrolyte, and they provided information to optimize up possibilities of novel application of these systems in
and design specific gradient geometries. transient electrochemical imaging and high-throughput
screening for new electrocatalysts.
In recent years, BPE-ECL has attracted special attention
because of simplicity, ease of operation, and suitability A cloth-based closed bipolar ECL glucose sensor was
for performing simultaneous screening. For instance, Liu designed in 2019 by Wang et al. [58], which detected
et al. [43] developed a novel paper-based open BPE- glucose in human serum samples based on the integra-
ECL sensing platform for visual detection. This open tion of chitosan and poly (diallyldimethylammonium
BPE-ECL imaging sensing platform was successfully chloride)-functioned multiwalled carbon nanotubes. In
designed for the detection of tri-n-propylamine with an this work, combined advantages of ECL and closed BPE
inexpensive couple-charged device (CCD) camera that systems (C-BP-ECL) with high current efficiency were
was used for simple visual detection. demonstrated. Therefore, the C-BP-ECL system pro-
cess features high sensitivity and good selectivity and is
The closed configuration of bipolar electrochemistry simple and inexpensive, and hence, it is often preferred
In a closed BPE system, the electrolyte connected to over expensive and complex microfluidic systems.
the anodic and cathodic poles of the BPE are physi- Table 1 provides several reports of applications of BPE in
cally isolated from one another, thus forming two half- different fields.
cells containing a driving electrode each (Figure 2)
[44,45]. The current that passes through the BPE Applications of bipolar electrochemistry
between the two half-cells is only one current without Electrochemical detection
the presence of the ionic current path, and as a result, BPE is used as a suitable platform in micro-devices for
the rates of the Faradaic processes can be investigated identification of electroactive analytes when a strong

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 The principles of bipolar electrochemistry Karimian et al. 33

Table 1

Literature overview of the type of bipolar electrochemistry categorized by their application.

Method Bipolar electrode System Sensing Reference

material configuration

Enrichment and separation Au Close BODIPY2- [14]

Concentration enrichment Au Open BODIPY2- [66]
Enrichment Au – [Ru (bpy)3]2+ [67]
Separation and enrichment PDMS Close BODIPY2− and [68]
of both anions and cations Ru (bpy)2+
3
High-performance enrichment PDMS – Fluorescein [69]
of anions
ECL-BPE PDMS – c-Myc mRNA [70]
Electrodissolution Cr Close Au, Co, W [71]
Paper-based bipolar Pure – Cancer marker PSA [72]
electrode-ECL cellulose paper
ECL-BPE PDMS-ITO Close H2O2 [48]
ECL—Au-ITO hybrid ITO/Au – Cell surface protein [73]
bipolar electrode
ECL—bipolar electrode PET Close Alpha-fetoprotein [74]
array carcinoembryonic antigen
Microfluidic-BPE-ECL Carbon Close Glucose [58]
BPE-ECL Pt-graphite Close H2O2 and biomarker [75]
paper hybrid
BPE-ECL Au – Single-nucleotide [76]
polymorphisms genotyping
BPE-ECL Au Close MB-conjugated DNA [77]
Dual-BPE-ECL ITO-coated glass slice – HL-60 cancer cells [78]
BPE-ECL Gold-CD-R Close Aflatoxin M1 [65]

BODIPY2−, 4,4-Difluoro-1,3,5,7,8-pentamethyl-4-bora-3a,4a-diaza-s-indacene-2,6-disulfonic acid; PDMS, polydimethylsiloxane; PET, poly(ethylene

terephthalate); ECL, electrochemiluminescence; PSA, prostate specific antigen; ITO, indium tin oxide; MB, methylene blue.

electric field is applied. Hadjixenis et al. [59] reported bipolar membrane electrodialysis as the method for
on a BPE analytical device for measuring reducing reclamation of NaOH from glyphosate neutralization
compounds that oxidized at the anode pole of a “closed” liquor and its subsequent use as an absorbent for CO2
bipolar electrode cell by recording the onset driving capture. The proposed method produces NaOH solu-
voltage as a measure of the target concentration. This tion for further reaction with CO2 while recovering the
study represents a novel method for the detection of glyphosate from the wastewater. NaOH solution with a
observed signals such as intensity of emitted light, concentration of z1.45 mol L1 and purity of 96.5% was
fluorescence, or electrode’s length at the submillimeter obtained. Accordingly, a current efficiency of 80.8%,
level without the need for extra instruments or devices. 76.2%, 68.7%, and 69.0% at current densities of 30, 40,
The determination of ascorbic acid and hydrogen 50, and 60 mA cm2 was observed, respectively. In addi-
peroxide in an acidic solution of copper (II) chloride at tion, the lowest energy utilization recorded as
the anode pole by recording the onset driving voltage at 2.15 kW h kg1 was obtained by the bipolar membrane
which the electrodeposition of copper occurs at the electrodialysis process at a low current density of
cathode pole (indicating event) at a “closed” BPE 30 mA cm2, resulting in a better performance in terms of
system is commenced. The onset potential of electro- energy saving. A glyphosate recovery of approximately
deposition of metal at the cathode pole is dependent on 98.2% was also achieved. In this work, the system’s
oxidizable species, and its electrodeposition is visible to performance was studied in a pilot-scale plant to
the naked eye. demonstrate the industrial application. Furthermore,
the concept can also be extended to other applications
The proposed analytical intention holds promise for a of alkali recovery and wastewater management (e.g.,
wide scope of application in the measurement of reverse osmosis concentrate, spent caustic, and other
reducing compounds and evaluation of the total anti- types of wastewater with high salinity) through this
oxidant activity in real samples as well as to the devel- comprehensive research.
opment of biosensors based on oxidase enzymes.
Concentration and separation of analytes in microfluidic
Postcombustion CO2 capture by reaction with a strong systems
alkali such as NaOH appears a promising strategy to BPE is widely applied in analytical techniques for
mitigate CO2 emission. Wenyuan et al. [60] proposes measuring the concentration and/or separation of
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34 Environmental electrochemistry

analytes. The methods of microfluidic-based sensing Optical detection based on ECL

and separation are usually required to both separate and ECL is a phenomenon that involves luminescence pro-
enrich the analytes before detection. Concentration duced during electrochemical reactions in solutions.
enrichment or preconcentration is dependent on the ECL is created by applying a potential at a surface
electrophoretic mobility of the analyte. Capillary elec- electrode in the presence of both the luminophore and
trophoresis (CE) is one of separation techniques that coreactant. Arora et al. repoted [64], for the first time,
can be directly coupled with BPE. Nyholm and Klett the coupling of ECL with BPE (BP-ECL) as a new
[17] reported for the first time the use of integration of technique, which has recently been used in many fields
CE and bipolar electrode arrays for on-chip electro- particularly in bioanalysis. BP-ECL has advantages that
chemical detection. In this report, amperometric overcome limitations of fluorescence and chem-
detection in CE is introduced based on the use of gold iluminescence methods [24, 62e64].
microband array electrodes located in the CE electric
field that was applied for measuring the potential dif- Bagheri et al. introduced a sensitive ECL aptasensor for
ference in the CE separation high-voltage field. The aflatoxin M1 (AFM1) detection by a closed bipolar
overall CE electric field has a direct effect on the electrodes array [65]. Aflatoxins are poisonous carcino-
maximum polarization between both terminals of the gens that are produced by certain molds that grow in
bipolar electrode, and the current is adjusted by the soil, decaying vegetation, hay, and grains. They, in this
type and concentration of the involved redox species, as work, used luminol-functionalized, silver nanoparticlee
represented with the Fe(CN)6 4-/3- couple. decorated, graphene oxide (GO-L-AgNPs) as the
signaling probe and gold-coated, magnetic nanoparticles
Optical detection based on electrodissolution of a bipolar (GMNPs) as both the separation/enrichment tool and
electrode the immobilization support for the aptamer. Briefly, the
The method relies on electrodissolution of the metallic aptamer-conjugated GMNPs (Apt-GMNPs) were
bipolar electrode that has been reported as the new mixed with the GO-L-AgNPs, resulting in pp in-
sensing platform by Crooks’ group [34]. In this report, teractions between the unhybridized parts of the
hybridization of DNA labeled with horseradish peroxi- aptamer and GO (Apt-GMNPs-GO-L-AgNPs). Then,
dase activates the oxidation of tetramethylbenzidine. the anodic poles of the BPE array were exposed to Apt-
Once a sufficiently high electric field is applied across GMNP-GO-L-AgNPs under a magnetic field below the
the BPE, oxidized tetramethylbenzidine is reduced at BPE array. After the introduction of AFM1 at each in-
the cathodic pole, and simultaneous oxidation and dividual anodic pole, the GO-L-AgNPs’ nanocomposite
dissolution of Ag metal occur at the anodic pole because releases from the Apt-GMNPs’ surface as a result of the
of the charge neutrality. The dissolution of metals can strong interaction between the aptamer and AFM1.
be seen with the naked eye, which is proportional to the Under a sufficient electric field across the electrolyte
number of electrons passing through the BPE. There- solution, the ECL reaction occurs on the accumulated
fore, the decrease in the length of the BPE can be GO-L-AgNPs at the anodic poles, and the emission of
directly proportional to the number of electrons passing luminol in the presence of H2O2 is monitored using a
through the BPE and hence to the DNA-binding process photomultiplier tube or smartphone.
at the cathode.
Concluding remarks
In another work, Zhenlian et al. studied a wireless BPE is a very versatile technique with inherent features
electrocoagulation system based on BPE in which iron such as inexpensiveness, simple operation, and wireless
sheets were used as sacrificial bipolar electrodes and nature. The principle of wireless contact also makes it
two graphite plates were used as driving electrodes possible to carry out electrochemical experiments on
[61]. In wireless electrocoagulation, the electric field mobile electrodes. The concept of BPE is known to
was produced by the driving electrodes in a solution, researchers for many years, but its initial application was
which leads to floating of sacrificial BPE in equilib- limited to electrolysis and corrosion. In the last decade,
rium interfacial potential. Once the equilibrium scientists rediscovered the actual potential of BPE in
interfacial potential is sufficiently high, iron dissolu- detection, concentration enrichment, and separation of
tion starts at the anodic pole, and iron coagulant is analytes in a microfluidic environment and also in the
produced, which eliminates the contaminants. development of analytical bio sensors for the detection
Because the whole iron concentration generated is of biomolecules.
more dependent on the geometrical configuration of
BPE rather than electrochemical parameters, param-
eters such as the length, angle, and shape of sacrificial Conflict of interest statement
BPEs were optimized. The authors declare that they have no conflict of interest.

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 The principles of bipolar electrochemistry Karimian et al. 35

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 The principles of bipolar electrochemistry Karimian et al. 37

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chemiluminescence biosensor based on Au-ITO hybrid

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