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Nanophotocatalysis
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Energy Conversion and Chemical
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Environmental Chemistry for a Sustainable
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Inamuddin • Mohd Imran Ahamed
Abdullah M. Asiri • Eric Lichtfouse
Editors
Nanophotocatalysis and
Environmental Applications
Energy Conversion and Chemical
Transformations
Editors
Inamuddin Mohd Imran Ahamed
Chemistry Department, Faculty Department of Chemistry
of Science Aligarh Muslim University
King Abdulaziz University Aligarh, India
Jeddah, Saudi Arabia
Abdullah M. Asiri Eric Lichtfouse

Chemistry Department, Faculty CEREGE, CNRS, IRD, INRA, Coll France
of Science Aix-Marseille University
King Abdulaziz University Aix-en-Provence, France
Jeddah, Saudi Arabia
ISSN 2213-7114 ISSN 2213-7122 (electronic)

ISBN 978-3-030-04948-5 ISBN 978-3-030-04949-2 (eBook)
https://doi.org/10.1007/978-3-030-04949-2
Library of Congress Control Number: 2019932801
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Preface
v
vi Preface
The global energy crisis and climate change have been labelled as the most critical
environmental challenges in terms of both research and remediation. Non-renewable
energy resources fulfil nearly 85% of world energy demands leading to global
warming and depletion of resources. The exhaustion of finite fuels should be
addressed for a sustainable energy future. Therefore, research is ongoing to harness
the renewable energy during the processes such as photocatalytic and bioproduction
of hydrogen and other fuels. The use of renewable sources of energy and the
mitigation of climate change or global warming are interrelated, and, if both are
worked upon simultaneously, it certainly will make a difference.
The increasing global demand for energy is a result of a population explosion,
which is demanding the intention towards the development of effective strategies for
energy conversion and the reduction of greenhouse gas emissions. This can obvi-
ously be achieved by focussing on non-fossil sources of energy such as solar,
thermal, hydrogen and nuclear energy as well as CO2 capture and photoconversion
of CO2 into fuels. Advanced oxidation processes have evolved during the years, and
scientists are using photocatalysis for energy conversion especially harnessing of
solar energy.
Photocatalytic water splitting for H2 and O2 production using semiconductors is
the most promising fields as a green technology that is accounted for economic
importance. The direct semiconductors mediated water splitting for hydrogen gen-
eration as clean fuel can be performed on a large scale for practical applications. In
general, there are many efficient catalysts reported for the same, but these are active
in ultraviolet light only. The challenge still lies in designing low-cost catalysts that
show high quantum efficiency, ability to work under visible and sunlight as well as
the ability to work without noble metals as co-catalysts. Many works with high
quantum efficiencies have reported on solar- and visible-powered hydrogen emis-
sion by designing novel catalysts by surface modifications, sensitizations, immobi-
lization, formation of Z-scheme junctions, dye-sensitized solar cells, etc. Recently,
significant progress is made to develop and engineer various photocatalysts for this
purpose. The prime solution is bandgap engineering that involves bandgap broad-
ening or narrowing, interparticle electron coupling, reducing recombination of
charge carriers, plasmon-exciton coupling and high surface energy of the catalysts.
Additionally, combustion of fuels and industrial effluents has been threatening as
they release alarming amounts of greenhouse gas as CO2. According to the various
studies, the CO2 level may reach 750 ppm and raise the global temperature further.
Photocatalytic reduction of CO2 into syngas, methane, carbon monoxide, methanol,
formic acid and formaldehyde has its own advantages as lowering of greenhouse gas
levels and energy production simultaneously. Photocatalytic reduction of CO2 into
fuels is, however, more complicated process as compared to water splitting. This is
because of its dependence on thermodynamics and kinetics of light absorption, band
potentials, charge separation and largely the activation of catalyst, i.e. adsorption of
CO2. Various organic materials as part of catalysts or supports such as carbon
nanotubes, graphene, graphene oxide, carbon nitride, etc. for CO2 activation as
adsorption and interaction with the catalyst is an important requirement of the
reaction. In addition, very few solar active catalysts are available which are capable
Preface vii
of reducing carbon dioxide. The photocatalytic conversion of CO2 into fuels is in its
embryonic stage, and a substantial development and progress are still required. It is
therefore important to study and analyse various catalysts and technologies devel-
oped so far for better modification and upgradation. Among various energy conver-
sion applications, photocatalysis has also been promising for removal of NOx gases,
volatile organic carbon removal, air clean-up filters and catalytic converters for
vehicle exhausts.
Nanophotocatalysis and Environmental Applications: Energy Conversion and
Chemical Transformations is focussed on fuel production as a source of renewable
energy using photocatalysis. The application of photocatalysis is discussed in areas
such as fuel production including carbon monoxide, formic acid, methanol, methane
and hydrogen and CO2 reduction and water splitting, water purification and purifi-
cation of food industry wastewater and organic synthesis using various types of
photocatalytic materials such as quantum dots, graphitic carbon nitride, metal
oxides, Z-scheme photocatalysts, metal organic frameworks, composites and poly-
meric semiconductors. This is beneficial for analysing the current progress under-
way, which certainly paves ways for new directions for breakthrough technologies to
be developed. Based on thematic topics, the book edition contains the following nine
chapters:
Chapter 1 gives an overview of the main methods to obtain quantum dots and
some examples of their use as a photocatalyst for fuel production.
Chapter 2 summarizes the works on the photocatalytic hydrogen production using
highly stable TiO2-based heterostructured photocatalysts. The emphasis is given on
three important characteristics, namely, UV-active TiO2-based photocatalysts,
visible-active TiO2-based photocatalysts and the effects of various carbon
nanostructures on the photocatalytic hydrogen production efficacy of TiO2-based
heterostructured photocatalysts.
Chapter 3 highlights the method of synthesis of photocatalysts and their possible
modification for performance enhancement in water splitting and CO2 reduction.
Chapter 4 provides the basic principles, terminologies, concepts, state-of-the-art
achievements and the charge transfer mechanism of the photocatalytic reduction of
CO2 using artificial Z-scheme photocatalysts. In spite of these, the development on
semiconductor photocatalytic materials from the perspective of light harvesting as
well as the co-catalyst strategy for potentially boosting the activity and/or product
selectivity for the photocatalytic reduction of CO2 along with the future direction of
research using Z-scheme systems are also discussed and highlighted.
Chapter 5 deals with the importance of photocatalysts and their applications for
artificial photosynthesis. The primary photosynthetic applications of photocatalysts
such as supramolecular artificial photosynthetic systems, covalently linked molecu-
lar systems and general mechanism of photosynthesis are also discussed in detail.
Chapter 6 discusses various chemical methodologies, properties and
photocatalytic applications of polymeric semiconductors (carbon nitride, C3N4),
graphene, and metal-organic framework (MOF)-based hybrid nanostructured
photocatalysts for the water purification and the solar hydrogen production.
viii Preface
Chapter 7 summarizes the innovative aspects of the applicability of

photocatalysis and technological advances with particular attention to the
photocatalytic energy recovery, organic synthesis and new reactor configurations.
In particular, the chapter discusses the possibility to produce an energy source such
as hydrogen and/or methane from the degradation of organic substance present in
wastewater by heterogeneous photocatalysis. The chapter also reports simultaneous
valorization and purification of food industry wastewater using structured
photocatalysts.
Chapter 8 focusses on some important nano-semiconductor photocatalysts like
TiO2, ZnO and graphitic carbon nitride and various strategies adopted for improving
their photocatalytic activity under sunlight. Different methods for improving visible
light active photocatalysts including metal/nonmetal doping, the addition of photo-
sensitive materials, the incorporation of other nanoparticles, the composite formation
with other semiconductors and the formation of heterojunctions and nanohybrids are
discussed.
Chapter 9 reviews the state-of-the-art progresses in the use of common
photocatalytic materials for the purpose of four important classes of organic synthe-
sis, namely, oxidation of alcohols, oxidative cleavage of olefins, reduction of nitro
compounds and cyclisation; carbon-hetero bond formation and alkylation will be
reviewed.
Jeddah, Saudi Arabia Inamuddin

Aligarh, India Mohd Imran Ahamed
Jeddah, Saudi Arabia Abdullah M. Asiri
Aix-en-Provence, France Eric Lichtfouse
Contents
1 Nanophotocatalysts for Fuel Production . . . . . . . . . . . . . . . . . . . . . 1

Annelise Kopp Alves
2 Highly Stable Metal Oxide-Based Heterostructured
Photocatalysts for an Efficient Photocatalytic Hydrogen
Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Murikinati Mamatha Kumari, Raghava Reddy Kakarla,
N. Ramesh Reddy, U. Bhargava, M. V. Shankar, and S. K. Soni
3 Novelty in Designing of Photocatalysts for Water Splitting
and CO2 Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Santanu Sarkar, Shubhrajit Sarkar, Chiranjib Bhattacharjee,
and Supriya Sarkar
4 Z-Scheme Photocatalysts for the Reduction of Carbon Dioxide:
Recent Advances and Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . 67
Xiaodi Zhu and Song Sun
5 Photocatalysts for Artificial Photosynthesis . . . . . . . . . . . . . . . . . . . 103
Busra Balli, Buse Demirkan, Betul Sen, and Fatih Sen
6 Polymeric Semiconductors as Efficient Photocatalysts for
Water Purification and Solar Hydrogen Production . . . . . . . . . . . . 125
Sudesh Kumar, Raghava Reddy Kakarla, Ch. Venkata Reddy,
Enamul Haque, Veera Sadhu, and S. Naveen
7 Advances and Innovations in Photocatalysis . . . . . . . . . . . . . . . . . . 155
Giuseppina Iervolino, Vincenzo Vaiano, and Paolo Ciambelli
8 Solar Light Active Nano-photocatalysts . . . . . . . . . . . . . . . . . . . . . . 185
Jesty Thomas and K. S. Ambili
ix
x Contents
9 High-Performance Photocatalysts for Organic Reactions . . . . . . . . 219

R. Goutham, K. P. Gopinath, A. Ramprasath, B. Srikanth,
and R. Badri Narayan
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
Contributors
Annelise Kopp Alves Universidade Federal do Rio Grande do Sul, Porto Alegre,
RS, Brazil
K. S. Ambili Research Department of Chemistry, Kuriakose Elias College,
Kottayam, Kerala, India
R. Badri Narayan Department of Chemical Engineering, Sri Sivasubramaniya
Nadar College of Engineering, Chennai, Tamil Nadu, India
Busra Balli Sen Research Group, Biochemistry Department, Faculty of Arts and
Science, Dumlupınar University, Kütahya, Turkey
U. Bhargava Nano Catalysis and Solar Fuels Research Laboratory, Department of
Materials Science & Nanotechnology, Yogi Vemana University, Kadapa, Andhra
Pradesh, India
Chiranjib Bhattacharjee Chemical Engineering Department, Jadavpur Univer-
sity, Kolkata, West Bengal, India
Paolo Ciambelli Department of Industrial Engineering, University of Salerno,
Fisciano, SA, Italy
Buse Demirkan Sen Research Group, Biochemistry Department, Faculty of Arts
and Science, Dumlupınar University, Kütahya, Turkey
K. P. Gopinath Department of Chemical Engineering, Sri Sivasubramaniya Nadar
College of Engineering, Chennai, Tamil Nadu, India
R. Goutham Department of Chemical Engineering, Sri Sivasubramaniya Nadar
Enamul Haque School of Medicine and Centre for Molecular and Medical
Research, Deakin University, Waurn Ponds, VIC, Australia
xi
xii Contributors
Giuseppina Iervolino Department of Industrial Engineering, University of

Salerno, Fisciano, SA, Italy
Raghava Reddy Kakarla The School of Chemical and Biomolecular Engineering,
The University of Sydney, Sydney, NSW, Australia
Sudesh Kumar Department of Chemistry, Banasthali University, Banasthali
Vidyapith, Vanasthali, Rajasthan, India
Murikinati Mamatha Kumari Nano Catalysis and Solar Fuels Research Labora-
tory, Department of Materials Science & Nanotechnology, Yogi Vemana Univer-
sity, Kadapa, Andhra Pradesh, India
S. Naveen School of Basic Sciences, Jain University, Bangalore, India
A. Ramprasath Department of Chemical Engineering, Sri Sivasubramaniya Nadar
N. Ramesh Reddy Nano Catalysis and Solar Fuels Research Laboratory, Depart-
ment of Materials Science & Nanotechnology, Yogi Vemana University, Kadapa,
Andhra Pradesh, India
Ch. Venkata Reddy School of Mechanical Engineering, Yeungnam University,
Gyeongsan, South Korea
Veera Sadhu School of Physical Sciences, Banasthali University, Banasthali
Vidyapith, Vanasthali, Rajasthan, India
Santanu Sarkar Environment Research Group, R&D, Tata Steel Ltd.,
Jamshedpur, Jharkhand, India
Shubhrajit Sarkar Chemical Engineering Department, Jadavpur University,
Kolkata, West Bengal, India
Supriya Sarkar Environment Research Group, R&D, Tata Steel Ltd., Jamshedpur,
Jharkhand, India
Betul Sen Sen Research Group, Biochemistry Department, Faculty of Arts and
Fatih Sen Sen Research Group, Biochemistry Department, Faculty of Arts and
M. V. Shankar Nano Catalysis and Solar Fuels Research Laboratory, Department
of Materials Science & Nanotechnology, Yogi Vemana University, Kadapa, Andhra
Pradesh, India
S. K. Soni Sustainable Living Lab, School of Science, RMIT University,
Melbourne, VIC, Australia
B. Srikanth Department of Chemical Engineering, Sri Sivasubramaniya Nadar
Contributors xiii
Song Sun National Synchrotron Radiation Laboratory, Collaborative Innovation

Center of Chemistry for Energy Materials, University of Science & Technology of
China, Hefei, China
Jesty Thomas Research Department of Chemistry, Kuriakose Elias College,
Kottayam, Kerala, India
Vincenzo Vaiano Department of Industrial Engineering, University of Salerno,
Fisciano, SA, Italy
Xiaodi Zhu National Synchrotron Radiation Laboratory, Collaborative Innovation
Center of Chemistry for Energy Materials, University of Science & Technology of
China, Hefei, China
Chapter 1
Nanophotocatalysts for Fuel Production
Annelise Kopp Alves
Contents
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Quantum Dot Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Synthesis of Quantum Dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4 Application of Quantum Dots for Fuel Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Abstract Quantum dots, particles with diameters from 2 up to 20 nm, are one of the
sweethearts of nanotechnology because their properties are intermediate between
bulk and discrete molecules and can be tuned according to their size and shape.
Nowadays, quantum dots are one of the most common nanophotocatalysts used to
produce fuel using ultraviolet, visible, or solar light. Traditional methods such as
sol-gel, hydrothermal synthesis, e-beam lithography, microwave synthesis, and
chemical vapor deposition, among others, are suitable for produced quantum dot
photocatalysts. In this context, the most common fuels obtained using photocatalysts
are carbon monoxide, formic acid, methanol, methane, and hydrogen. In this chap-
ter, it will be given an overview of the main methods to obtain quantum dots and
some examples of their use as a photocatalyst for fuel production.
Keywords Quantum dots · Photocatalysis · Fuel · Hydrogen · Semiconductors ·

Solar light
A. K. Alves (*)
Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Brazil
e-mail: [email protected]
© Springer Nature Switzerland AG 2019 1

Inamuddin et al. (eds.), Nanophotocatalysis and Environmental Applications,
Environmental Chemistry for a Sustainable World 31,
https://doi.org/10.1007/978-3-030-04949-2_1
2 A. K. Alves
1.1 Introduction
The search for an alternative to fossil fuels as an energy source is more in evidence
than ever. The number of gases in the atmosphere that may cause climate changes is
ever growing due to industrialization, the need to transport goods and people, and the
increasing consumption of energy in general. There are already different approaches
to harvest energy in a not-so-environmentally damaging way. Energy is available
from the wind, the tides, and the sun at practically no cost. All that is needed is a
mechanism that collects, stores, and transfers efficiently the energy nature already
offers to the human been use.
In this regard, researches have tried to find similar results to what happens in
plants, the photosynthesis. It is a complex group of chemical reactions that basically
transforms CO2 and water into carbohydrates (fuels) using the sun’s light. In the last
10 years (up to April 2018), there are approximately 3921 scientific papers published
regarding the synthesis and application of photocatalysts for fuel production
(Fig. 1.1).
The most common fuel photocatalytic produced is, by far, hydrogen, followed by
methanol and methane. In these processes, UV, visible light, or solar simulators as
light sources and different types of photocatalysts were used. This chapter will
describe a review of the most recent publications relating to the synthesis of
nanophotocatalysts for fuel production.
Fig. 1.1 A number of publications by year, consulting the term “photocatalyst fuel production” in
the Web of Science database
1 Nanophotocatalysts for Fuel Production 3
1.2 Quantum Dot Semiconductors
Quantum dots are semiconductors particles with diameters from 2 up to 20 nm. They
are one of the sweethearts of nanotechnology because their properties are interme-
diate between bulk and discrete molecules and can be tuned according to their size
and shape.
Different routes have been used to synthesize quantum dots using both top-down
and bottom-up techniques. Top-down methods include molecular beam epitaxy
(Biswas et al. 2018), ion implantation (Kwak et al. 2018), e-beam lithography
(Kaganskiy et al. 2018), and X-ray lithography (Bertino et al. 2007). In bottom-up
methods, wet chemical and vapor phase methods are used. Wet chemical methods
are generally microemulsion (Liu et al. 2014), sol-gel (Adhikari et al. 2017),
competitive reaction chemistry (Liu et al. 2018a), and microwave synthesis (Lia
et al. 2018). Vapor phase methods include sputtering (Hong et al. 2017), vapor phase
epitaxy (Tile et al. 2018), and chemical vapor deposition (Yang et al. 2016). The
process mechanism of quantum dot-based photocatalysis is not yet fully understood.
In homogeneous photocatalysis, the light can be absorbed by both the quantum dot
and the pollutant molecule. According to a proposed pathway for the photocatalytic
activity of the quantum dots, electrons in the valence band of quantum dots could be
excited to the conduction band and electron-hole pairs could be generated. The
photogenerated electrons can produce superoxide and hydrogen peroxide radicals.
The valence band holes can directly oxidize the pollutants adsorbed on the surface of
quantum dots or mineralize them indirectly through hydroxyl radicals generated by
the reaction of holes and water molecules (Rajabi 2016). Table 1.1 summarizes some
of the most recent application of quantum dot used in the photocatalytic process.
1.3 Synthesis of Quantum Dots
The most traditional approach for the synthesis of quantum dots is called
hot-injection organometallic synthesis. It is based on the heating of organic solvents
and the rapid injection of the semiconductor precursor, under an inert atmosphere in
a batch reactor. This technique was introduced by Murray et al. in 1993 (1993). In
this foundational work, a series of quantum dots (CdE; E¼S, Se, Te) with sizes from
1.5 to 11.5 nm was obtained by controlling the growth temperature.
In 2016, Mir et al. (2016) compared the structural, optical, and sensing properties
of CdSe synthesized using the hot-injection method and a room temperature syn-
thesis protocol. In the first method, the quantum dot had sizes from 2.5 up to 6.3 nm,
compared to the practically monomodal 3.3 nm obtained using the room temperature
method. It was observed by the authors that despite the versatility of the hot-injection
synthesis that may be considered to be supreme as room temperature methods
regarding the production of particles of different size, it yields products that have
limited sensing capability compared to those synthesized at room temperature.
4 A. K. Alves
Table 1.1 Application of quantum dots in the photocatalytic process

Type of quantum
dot Synthesis method Parameter evaluated Reference
Carbon quantum Hydrothermal Photoreduction of Cr Wang et al.
dots/graphene (VI) (2018a)
aerogel
N-rich carbon Microwave assisted CO2 photoreduction Li et al.
quantum dots (2018)
decorated
two-phase TiO2
ZnO1x/carbon Aerosol CO2 photoreduction Lin et al.
dots composite (2018)
Carbon dots mod- Hydrothermal Tetracycline Xie et al.
ified MoO3/g- photocatalysis (2018)
C3N4
TiO2 quantum Sol-gel Photocatalytic H2 Panb et al.
dots embedded in evolution (2018)
SiO2 foams
CdS quantum Conventional wet-chemistry Methyl orange and phe- Pan et al.
dots/BiOCl precipitation nol photodegradation (2018)
nanocomposites
CdS quantum Hydrothermal-chemical bath Methylene blue visible Zhao et al.
dots/Ti3+-TiO2 deposition light photocatalysis and (2018)
nanobelts hydrogen production
Carbon dots and Sol-gel and microwave assisted Rhodamine B, methy- Asadzadeh-
AgCl over g-C3N4 lene blue, methyl Khaneghah
nanosheets orange, and phenol et al. (2018)
photocatalysis
Carbon dots and Carbo dots: hydrothermal treat- Visible light Wang et al.
CdS quantum dot ment; CdS quantum dots: con- photocatalysis of ben- (2018b)
– TiO2 composite ventional wet-chemistry zene and toluene
precipitation
Vanadate quan- Ultrasound Salmonella under visible Wang et al.,
tum dots/g-C3N4 light disinfection (2018c)
Reactive direct current magnetron sputtering method is one of the methods used
to obtain quantum dots for large-scale production. In the work of Patel et al. (2018),
NiO quantum dots were produced by this method using Ni target of 99.999% purity,
with flowing Ar and O2. They have used a sputtering power of 50 W and working
pressure of 3 mTorr. The NiO quantum dot was deposited over glass or fluorine-
doped tin oxide (FTO) glass substrates and presents an average diameter from
5 to7 nm (Fig. 1.2).
Alternatively, the group of Hong et al. (2018) produced NiO quantum dot
embedded into TiO2 particles using the temperature-programmed method. This
method consists of mixing TiO2 powder, urea, and nickel nitrate and heating this
mixture under an N2 atmosphere at 500 C, followed by annealing at 800 C,
obtaining N-doped carbon coating. To remove the carbon the temperature was
Fig. 1.2 NiO quantum dot obtained by magnetron sputtering method: (a) X-ray diffraction
analysis; (b) transmission electron microscopy image of the NiO quantum dot; (c) thickness of
the samples obtained over glass and fluorine-doped tin oxide glass (Reprinted with permission from
Patel et al. 2018)
maintained at 800 C in air. NiO quantum dot of 2 nm covered TiO2 nanoparticles of

50–200 nm (Fig. 1.3) were synthesized by this method.
Colloidal quantum dots can be obtained using water as a solvent. In the work of
Li et al. (2017), AgInSe2 quantum dot for sensitized solar cell was produced using a
direct aqueous synthesis using glutathione as a stabilizer. The method was based on
the dissolution of SeO2 and NaBH4 in deionized water at room temperature and the
mixture of this solution to an AgNO3 and I(NO3)3 solution. The final mixture was
microwaved in the presence of a stabilizer (thioglycolic acid, 3-mercaptopropionic
acid, or glutathione) at 160 C for 10 min. Agglomerated particles of average
diameter of 50 nm were obtained (Fig. 1.4a) and the incident photon to current
efficiency (IPCE) of the samples synthesized using different stabilizers was mea-
sured. The glutathione was the best stabilizer using the proposed synthesis protocol,
due to the functional moieties that promote a strong coordination with the quantum
dots, facilitating electron injection between the quantum dots and TiO2 in solar cells.
Typically, quantum dots synthesized via colloidal methods have an insulating
layer of a long-chain organic ligand. This prevents their direct use in electronic
devices due to the weak interparticle coupling (Choi et al. 2017). To overcome this
issue, considering a large-scale method for the production of quantum dot films, the
spray synthesis is an interesting alternative. Among these methods, supersonic (Choi
et al. 2017), ultrasonic (Ji et al. 2017), and thermal spray coating (Yadav et al. 2016)
are the most suitable for the production of quantum dot.
Choi et al. (2017) produced quantum dot films over fluorine-doped tin oxide glass
substrates by supersonic spraying technique using PbS quantum dot inks, prepared
by solution-phase ligand exchange using methylammonium lead iodide (MAPbI3)
(Fig. 1.5). This method promotes the rapid evaporation of the solvent and the
deposition of the PbS quantum dot without further annealing treatments. Varying
the number of sweeps during the deposition process, it was possible to obtain
different film thickness, with an average roughness of 3.4 nm.
The ultrasonic spray coating method was used by Ji et al. (2017) to deposit
ZnCdSSE/ZnS core/shell-structured quantum dot (Fig. 1.6b), over indium tin
oxide (ITO)-coated glass substrate and multilayers of NiO, Al2O3, and NiO
(Fig. 1.6a). In the deposition process, the solution precursor (using toluene for the
6 A. K. Alves
Fig. 1.3 NiO quantum dot/TiO2 obtained by temperature-programmed method: (a) X-ray diffrac-
tion pattern, (b) transmission electron microscopy image of NiO quantum dots/TiO2, (c, d) high-
resolution transmission electron microscopy image of NiO quantum dots/TiO2, (e, f) high-angle
annular dark-field images of NiO quantum dots/TiO2 and elemental mapping results of (g) Ti, (h) O,
and (i) Ni (Reprinted with permission from Hong et al. 2018. Copyright 2018 American Chemical
Society)
quantum dot and ethanol for the other precursors) flowed into an atomizer, using N2
as a carrier gas and subsequently atomized at a spray rate of 0.3 mL/min. The
thicknesses of the layers were around 40 nm.
Fig. 1.4 (a) Transmission electron microscopy image of AgInSe2 quantum dot for sensitized solar
cell produced using a direct aqueous synthesis using glutathione as a stabilizer. (b) AgInSe2
quantum dot incident photon to current efficiency results comparing different stabilizers (Adapted
and reprinted with permission from Li et al. 2017)
Fig. 1.5 (a) Schematic of ultrasonic spray deposition of PbS quantum dot ink. (b) Atomic force
microscopy image (scale bar 1 μm), (c) photographic image, and (d–g) cross-sectional scanning
electron microscopy images (scale bars 500 nm) of PbS quantum dot films deposited by ultrasonic
spray coating for (d) 8 sweeps, (e) 10 sweeps, (f) 12 sweeps, and (g) 14 sweeps (Reprinted with
permission from Choi et al. 2017)
1.4 Application of Quantum Dots for Fuel Production
The use of photocatalytic processes to obtain fuels using nanoparticles (quantum

dots) is a focus of research around the world. The most common fuels produced
using these methods are methane, methanol, and formic acid (via CO2 fixation) and
hydrogen (via water splitting into electrochemical cells).
8 A. K. Alves
Fig. 1.6 (a) Schematic diagram of an ultrasonic spray nozzle and deposited layers. (b) Transmis-
sion electron microscopy image of the ZnCdSSe/ZnS quantum dots (Reprinted with permission
from Ji et al. 2017. Copyright 2018 American Chemical Society)
The group of Yadav et al. (2016) synthesized graphene quantum dot

photocatalysts to produce formic acid from CO2 using visible light. The graphene
quantum dot was functionalized with a chromophore organic molecule. To promote
the selective production of formic acid, an enzyme (formate dehydrogenase) was
added to the photocatalysis reaction flask. A Rh complex was used as proton transfer
molecule. The reaction occurs at room temperature using a 450 W xenon lamp
(100 mWcm2), under a CO2 flow (0.5 ml/min). The authors achieved a selective
production of formic acid in these conditions at a rate of 1.658 μmol/min, when
using functionalized graphene quantum dot as a photocatalyst, in comparison with a
rate of 0.0475 μmol/min when pristine graphene quantum dot where used.
Another way to transform CO2 in useful compounds using photocatalysis is
exemplified in the work of Xu et al. (2018). In their work, TiO2 nanofibers obtained
using the electrospinning technique were doped with CuInS2 quantum dot (1, 2.5,
5 and 10 wt%) via hydrothermal synthesis (Fig. 1.7).
These doped fibers had their capacity to reduce CO2 to methane and methanol
evaluated via photocatalysis under the illumination of a solar simulator (350 W, Xe
arc lamp). The photocatalytic reaction occurs in a CO2/water vapor atmosphere. The
suspension of the catalyst and water was previously purged with nitrogen to assure
an anaerobic environment. The author found out that the presence of CO2 and light is
fundamental to the production of the hydrocarbons. The maximum efficiency of the
system was achieved using a TiO2 composite fiber doped with 2.5 wt% of CuInS2
quantum dot, which yield 2.5 μmol h1 g1 for CH4 and 0.86 μmol h–1 g–1 for
CH3OH.
Another common product (fuel) obtained from the photocatalytic reduction of
CO2 is CO. The work of Lin et al. (2018) studied this photoreduction phenomenon
using a ZnO1x/carbon dots composite as a photocatalyst (Fig. 1.8). Carbon dots are
a class of carbon particles with sizes below 10 nm that have unique photoinduced
electron transfer properties. The composite particles were obtained using the furnace
aerosol reactor (FuAR) method, where hollow particles were obtained. The ZnO
Fig. 1.7 Scanning electron microscopy images of pristine TiO2 fibers before (a) and after (b)
NaOH etching. (c, d) TiO2 composite fibers with 2.5 wt% CuInS2 quantum dot. Transmission
electron microscopy image (e) and high-resolution transmission electron microscopy image (f) of
fibers with 2.5 wt% CuInS2 quantum dot. (g) Energy-dispersive X-ray spectroscopy element
mappings of the elements Ti, O, Cu, In, and S in the fibers with 2.5 wt% CuInS2 quantum dot
(Reprinted with permission from Xu et al. 2018)
10 A. K. Alves
Fig. 1.8 (a, b) High-resolution transmission electron microscopy images, (c) Selected area (elec-
tron) diffraction pattern. (d–g) Energy-dispersive X-ray spectroscopy elemental mapping images of
the ZnO1x/C composite particles. (h, i) High-resolution transmission electron microscopy images
of Zn-free C (Reprinted with permission from Lin et al. 2018)
particles have around 2 nm in diameter and the carbon quantum dot have around
0,21 nm in diameter. The photocatalytic reaction was carried out using a 400 W Xe
arc lamp, in a previously CO2 purged reactor, under CO2 and water vapor atmo-
sphere. The authors observed that in the conditions that the reaction occurs using this
catalyst, only CO was produced, preferably over methane or methanol, at a rate of
34.1 μmol h1 g1. This is probably because CO needs a minimum number of
electrons and protons to be reduced than CH4.
One of the most researched fuels synthesized using photocatalysis is hydrogen,
especially when derived from the water-splitting reaction in a photoelectrochemical
cell. Although the storage of hydrogen is difficult nowadays, the idea of using a fuel
that generates only water as emission and that the water is the main source of the fuel
is very appealing.
One of the most recent works regarding hydrogen production using
nanophotocatalysts was published by Liu et al. (2018b). In their work,
two-dimensional (2D) SnS2/g-C3N4 catalysts were produced using microwave-
assisted hydrothermal technique. Graphitic carbon nitride (g-C3N4) is a layered 2D
nonmetal photocatalyst that has a conduction band (1.22 eV) interesting for H2
generation and also a valence band (1.56 eV) interesting for the photodecomposition
of pollutants. Usually, to promote a better photocatalysis activity, this material is
exfoliated using ultrasound. In the work of Liu et al., after synthesis and exfoliation
of SnS2/g-C3N4, hydrogen production performance was evaluated using a 300 W Xe
lamp. The authors produced samples doping the g-C3N4 with 1, 3, 5 and 10% of
SnS2 (named 1-SCNNs, 3-SCNNs, 5-SCNNs, and 10-SCNNs, respectively). The
results in Fig. 1.9, reprinted with authorization from the authors, show that the best
H2 generation rate reached 972 μmolh1g1 when doping the nitride with 5% of
SnS2. This sample was evaluated considering its reusability and stability in recycling
experiments (Fig. 1.9b). After five cycles, the hydrogen rate was stable, suggesting
great stability of this catalyst.
Usually, the photocatalysts have a specific selectivity toward CO2 reduction or H2
production; rarely there is a catalyst that is effective to both reactions. However, as
observed in the work of Roy et al. (2018), metal-nitrogen-carbon (m-n-c)
electrocatalysts, synthesized using the sacrificial support method, are active to
produce CO from CO2 and hydrogen from water splitting at the same time. They
have used as metals Cu, Mo, Pr, and Ce and aminoantipyrine as a source of nitrogen
and carbon. After the synthesis, the catalysts particles have a diameter from 20 up to
50 nm. Although H2 and CO are produced during electrolysis in a CO2 environment
for all the m-n-c tested catalysts, the results showed that in controlling the amount of
nitrogen present in the catalyst, it is possible to guide the reaction to the formation of
one of the products. A 50/50 CO/H2 ratio (the highest ratio observed) was achieved
for the metal-free catalyst. Adjusting this system to more negative potentials, the
ratio, in this case, shifts toward H2 production (30% CO2–70% H2). In a nitrogen-
rich catalyst, the reaction products shift to the production of hydrogen, preferably.
When using Cu or Mo, the main product was H2. Just trace amounts of CO (less than
1%) were formed when using these metals in the metal-nitrogen-carbon catalysts.
12 A. K. Alves
Fig. 1.9 (a) H2 production rate for the different catalysis synthesized. (b) The H2 production rate of
five-layer SnS2/g-C3N4 catalyst in a circulation experiment (Reprinted with permission from Liu
et al. 2018b)
Thus, in controlling the composition of the catalyst and the medium where the
photoelectrolysis works, it is possible to control the composition of the product.
1.5 Conclusion
In summary, quantum dots are a trend in the photocatalysis for fuel production
scientific community due their superior and tunable catalytic properties. Different
methods are used to produce quantum dots, each one adapted to achieve the desired
characteristic for a specific fuel production. The most common fuels obtained using
photocatalysts are methane, methanol, formic acid, and hydrogen. Among the
catalysts applied for this purpose, it is possible to highlight the transformation of
CO2 using enzymes to produce formic acid, TiO2-CuInS2 quantum dots to produce
methane and methanol, and ZnO-carbon dots to produce CO and the synthesis of H2
using SnS2-g-C3N4 as catalyst. Despite the increased number of publication over the
recent years, there is no standard solution to attend the energetic conundrum, mainly
because scalable, reliable, and reproductive results in large scale are practically
nonexistent. More investment is necessary from companies and governments to
promote the effective use of photocatalyst for fuel production.
References
Adhikari T, Pathak D, Wagner T, Jambor R, Jabeen U, Aamir M, Nunzi J-M (2017) Structural,
optical, electrochemical and photovoltaic studies of spider web like silver indium diselenide
quantum dots synthesized by ligand mediated colloidal sol-gel approach. Opt Mater 73:70–76.
https://doi.org/10.1016/j.optmat.2017.08.005
Asadzadeh-Khaneghah S, Habibi-Yangjeh A, Abedi M (2018) Decoration of carbon dots and AgCl
over g-C3N4 nanosheets: novel photocatalysts with substantially improved activity under visible
light. Sep Purif Technol 199:64–77. https://doi.org/10.1016/j.seppur.2018.01.023
Bertino MF, Gadipalli RR, Martin LA, Rich LE, Yamilov A, Heckman BR, Leventis N, Guha S,
Katsoudas J, Divan R, Mancini DC (2007) Quantum dots by ultraviolet and x-ray lithography.
Nanotechnology 18:315603. https://doi.org/10.1088/0957-4484/18/31/315603
Biswas M, Singh S, Balgarkashi A, Makkar R, Bhatnagar A, Sreedhara S, Chakrabarti S (2018)
Vertical strain-induced dot size uniformity and thermal stability of InAs/GaAsN/GaAs coupled
quantum dots. J Alloys Compd 748:601–607. https://doi.org/10.1016/j.jallcom.2018.03.163
Choi H, Lee J-G, Mai XD, Beard MC, Yoon SS, Jeong S (2017) Supersonically spray-coated
colloidal quantum dot ink solar cells. Sci Rep 7(622):1–8. https://doi.org/10.1038/s41598-017-
00669-9
Hong X, Xu Z, Zhang F, He C, Gao X, Liu Q, Guo W, Liu X, Ye M (2017) Sputtered seed-assisted
growth of CuS nanosheet arrays as effective counter electrodes for quantum dot-sensitized solar
cells. Mater Lett 203:73–76. https://doi.org/10.1016/j.matlet.2017.05.078
Hong W, Zhou Y, Lv C, Han Z, Chen G (2018) NiO quantum dot modified TiO2 toward robust
hydrogen production performance. ACS Sustain Chem Eng 6:889–896. https://doi.org/10.1021/
acssuschemeng.7b03250
Ji W, Liu S, Zhang H, Wang R, Xie W, Zhang H (2017) Ultrasonic spray processed, highly efficient
all-inorganic quantum-dot light-emitting diodes. ACS Photon 4:1271–1278. https://doi.org/10.
1021/acsphotonics.7b00216
Kaganskiy A, Fischbach S, Strittmatter A, Rodt S, Heindel T, Reitzenstein S (2018) Enhancing the
photon-extraction efficiency of site-controlled quantum dots by deterministically fabricated
microlenses. Opt Commun 413:162–166. https://doi.org/10.1016/j.optcom.2017.12.032
Kwak GY, Kim TG, Hong S, Kim A, Ha MH, Kim KJ (2018) Efficiency improvement of Si
quantum dot solar cells by activation with boron implantation. Sol Energy 164:89–93. https://
doi.org/10.1016/j.solener.2018.02.029
Li P-N, Ghule AV, Chang J-Y (2017) Direct aqueous synthesis of quantum dots for high-
performance AgInSe2 quantum-dot-sensitized solar cell. J Power Sources 354:100–107.
https://doi.org/10.1016/j.jpowsour.2017.04.040
Li M, Wang M, Zhu L, Li Y, Yan Z, Shen Z, Cao X (2018) Facile microwave assisted synthesis of
N-rich carbon quantum dots/dualphase TiO2 heterostructured nanocomposites with high activity
14 A. K. Alves
in CO2 photoreduction. Appl Catal B Environ 231:269–276. https://doi.org/10.1016/j.apcatb.

2018.03.027
Lia M, Wang M, Zhu L, Li Y, Yan Z, Shen Z, Cao X (2018) Facile microwave assisted synthesis of
N-rich carbon quantum dots/dual-phase TiO2 heterostructured nanocomposites with high activ-
ity in CO2 photoreduction. Appl Catal B Environ 231:269–276. https://doi.org/10.1016/j.
apcatb.2018.03.027
Lin L-Y, Kavadiya S, Karakocak BB, Nie Y, Raliya R, Wang ST, Berezin MY, Biswas P (2018)
ZnO1x/carbon dots composite hollow spheres: facile aerosol synthesis and superior CO2
photoreduction under UV, visible and near-infrared irradiation. Appl Catal B Environ
230:36–48. https://doi.org/10.1016/j.apcatb.2018.02.018
Liu L, Wang Y, An W, Hu J, Cui W, Liang Y (2014) Photocatalytic activity of PbS quantum dots
sensitized flower-like Bi2WO6 for degradation of rhodamine B under visible light irradiation.
J Mol Catal A Chem 394:309–315. https://doi.org/10.1016/j.molcata.2014.07.029
Liu Q, Jiang M, Ju Z, Qiao X, Xu Z (2018a) Development of direct competitive biomimetic
immunosorbent assay based on quantum dot label for determination of trichlorfon residues in
vegetables. Food Chem 250:134–139. https://doi.org/10.1016/j.foodchem.2017.12.079
Liu E, Chen J, Ma Y, Feng J, Jia J, Fan J, Hu X (2018b) Fabrication of 2D SnS2/g-C3N4
heterojunction with enhanced H2 evolution during photocatalytic water splitting. J Colloid
Interface Sci 524:313–324. https://doi.org/10.1016/j.jcis.2018.04.038
Mir IA, Das K, Rawat K, Bohidar HB (2016) Hot injection versus room temperature synthesis of
CdSe quantum dots: a differential spectroscopic and bioanalyte sensing efficacy evaluation.
Colloids Surf A Physicochem Eng Asp 494:162–169. https://doi.org/10.1016/j.colsurfa.2016.
01.002
Murray CB, Norris DJ, Bawendi MG (1993) Synthesis and characterization of nearly monodisperse
CdE (E ¼ sulfur, selenium, tellurium) semiconductor nanocrystallites. J Am Chem Soc
115:8706–8715. https://doi.org/10.1021/ja00072a025
Pan J, Liu J, Zuo S, Khan UA, Yu Y, Li B (2018) Synthesis of cuboid BiOCl nanosheets coupled
with CdS quantum dots by region-selective deposition process with enhanced photocatalytic
activity. Mater Res Bull 103:216–224. https://doi.org/10.1016/j.materresbull.2018.03.043
Panb D, Hanb Z, Miao Y, Zhang D, Li G (2018) Thermally stable TiO2 quantum dots embedded in
SiO2 foams: characterization and photocatalytic H2 evolution activity. Appl Catal B Environ
Patel M, Kim JS, Kim BS, Kim Y-H, Kim J (2018) Optical and photoelectrochemical properties of
transparent NiO quantum dots. Mater Lett 218:123–126. https://doi.org/10.1016/j.matlet.2018.
01.162
Rajabi HR (2016) Photocatalytic activity of quantum dots, semiconductor photocatalysis – mate-
rials, mechanisms and applications, Prof. Wenbin Cao (Ed.), InTech. https://doi.org/10.5772/
63435
Roy A, Hursán D, Artyushkova K, Atanassov P, Janáky C, Serov A (2018) Nanostructured metal-
N-C electrocatalysts for CO2 reduction and hydrogen evolution reactions. Appl Catal B Environ
Tile N, Ahia CC, Olivier J, Botha JR (2018) Atmospheric pressure-MOVPE growth of GaSb/GaAs
quantum dots. Phys B Condens Matter 535:20–23. https://doi.org/10.1016/j.physb.2017.06.014
Wang R, K-Q. L, Zhang F, Tang Z-R, Xu Y-J (2018a) 3D carbon quantum dots/graphene aerogel as
a metal-free catalyst for enhanced photosensitization efficiency. Appl Catal B Environ
Wang M, Hu J, Yang Y (2018b) Fabrication of CDs/CdS-TiO2 ternary nano-composites for
photocatalytic degradation of benzene and toluene under visible light irradiation. Spectrochim
Acta A Mol Biomol Spectrosc 199:102–109. https://doi.org/10.1016/j.saa.2018.03.041
Wang R, Kong X, Zhang W, Zhu W, Huang L, Wang J, Zhang X, Liu X, Hu N, Suo Y, Wang J
(2018c) Mechanism insight into rapid photocatalytic disinfection of Salmonella based on
vanadate QDs-interspersed g-C3N4 heterostructures. Appl Catal B Environ 225:228–237.
https://doi.org/10.1016/j.apcatb.2017.11.060
Xie Z, Feng Y, Wang F, Chen D, Zhang Q, Zeng Y, Lv W, Liu G (2018) Construction of carbon
dots modified MoO3/g-C3N4 Z-scheme photocatalyst with enhanced visible-light photocatalytic
activity for the degradation of tetracycline. Appl Catal B Environ 229:96–104. https://doi.org/
10.1016/j.apcatb.2018.02.011
Xu F, Zhang J, Zhu B, Yu J, Xu J (2018) CuInS2 sensitized TiO2 hybrid nanofibers for improved
photocatalytic CO2 reduction. Appl Catal B Environ 230:194–202. https://doi.org/10.1016/j.
apcatb.2018.02.042
Yadav D, Yadav RK, Kumar A, Park N-J, Baeg J-O (2016) Functionalized graphene quantum dots
as efficient visible-light photocatalysts for selective solar fuel production from CO2.
ChemCatChem 8:3389–3393. https://doi.org/10.1002/cctc.201600905
Yang D, Wang L, Hao Z-B, Luo Y, Sun C, Han Y, Xiong B, Wang J, Li H (2016) Dislocation
analysis of InGaN/GaN quantum dots grown by metal organic chemical vapor deposition.
Superlattice Microst 99:221–225. https://doi.org/10.1016/j.spmi.2016.02.016
Zhao T, Xing Z, Xiu Z, Li Z, Shen L, Cao Y, Hu M, Yang S, Zhou W (2018) CdS quantum
dots/Ti3+-TiO2 nanobelts heterojunctions as efficient visible light-driven photocatalysts.
Mater Res Bull 103:114–121. https://doi.org/10.1016/j.materresbull.2018.03.029
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greatly embarrassed to deal with it.[293] Any reply that should
repudiate either the treaty obligation or the principles of American
liberty and self-government was out of the question; any reply that
should affirm either the one or the other was fatal to the system
established by Congress in Louisiana. John Randolph, on whose
shoulders the duty fell, made a report on the subject. “It is only under
the torture,” said he, “that this article of the treaty of Paris can be
made to speak the language ascribed to it by the memorialists;” but
after explaining in his own way what the article did not mean, he
surprised his audience by admitting in effect that the law of the last
session was repugnant to the Constitution, and that the people of
Louisiana had a right to self-government.[294] Senator Giles said in
private that Randolph’s report was “a perfect transcript of Randolph’s
own character; it began by setting the claims of the Louisianians at
defiance, and concluded with a proposal to give them more than they
asked.”[295]
Under these influences the three delegates from the creole
society succeeded in getting, not what they asked, but a general
admission that the people of Louisiana had political rights, which
Congress recognized by an Act, approved March 2, 1805, to the
extent of allowing them to elect a General Assembly of twenty-five
representatives, and of promising them admission into the Union
whenever their free inhabitants should reach the number of sixty
thousand. Considering that the people of Louisiana were supposed
to be entitled to “all the rights, advantages, and immunities of
citizens,” Messieurs Sauvé, Derbigny, and Destréhan thought the
concession too small, and expressed themselves strongly on the
subject. Naturally the British minister, as well as other ill-affected
persons at Washington, listened eagerly to the discontent which
promised to breed hostility to the Union.
“The deputies above mentioned,” wrote Merry to his Government,
[296] “who while they had any hopes of obtaining the redress of their
grievances had carefully avoided giving any umbrage or jealousy to
the Government by visiting or holding any intercourse with the agents
of foreign Powers at this place, when they found that their fate was
decided, although the law had not as yet passed, no longer abstained
from communicating with those agents, nor from expressing very
publicly the great dissatisfaction which the law would occasion among
their constituents,—going even so far as to say that it would not be
tolerated, and that they would be obliged to seek redress from some
other quarter; while they observed that the opportunity they had had of
obtaining a correct knowledge of the state of things in this country,
and of witnessing the proceedings of Congress, afforded them no
confidence in the stability of the Union, and furnished them with such
strong motives to be dissatisfied with the form and mode of
government as to make them regret extremely the connection which
they had been forced into with it. These sentiments they continued to
express till the moment of their departure from hence, which took
place the day after the close of the session.”
Another man watched the attitude of the three delegates with
extreme interest. Aaron Burr, March 4, 1805, ceased to hold the
office of Vice-president. Since the previous August he had awaited
the report of his friend Colonel Williamson, who entered into
conferences with members of the British ministry, hoping to gain their
support for Burr’s plan of creating a Western Confederacy in the
Valley of the Ohio. No sooner was Burr out of office than he went to
Merry with new communications, which Merry hastened to send to
his Government in a despatch marked “Most secret” in triplicate.[297]
“Mr. Burr (with whom I know that the deputies became very
intimate during their residence here) has mentioned to me that the
inhabitants of Louisiana seem determined to render themselves
independent of the United States, and that the execution of their
design is only delayed by the difficulty of obtaining previously an
assurance of protection and assistance from some foreign Power, and
of concerting and connecting their independence with that of the
inhabitants of the western parts of the United States, who must always
have a command over them by the rivers which communicate with the
Mississippi. It is clear that Mr. Burr (although he has not as yet
confided to me the exact nature and extent of his plan) means to
endeavor to be the instrument of effecting such a connection.”
For this purpose Burr asked the aid of the British government,
and defined the nature of the assistance he should need,—a British
squadron at the mouth of the Mississippi, and a loan of half a million
dollars.
“I have only to add that if a strict confidence could be placed in
him, he certainly possesses, perhaps in a much greater degree than
any other individual in this country, all the talents, energy, intrepidity,
and firmness which are required for such an enterprise.”
Pending an answer to this proposal, Burr was to visit New
Orleans and make himself the head of creole disaffection.
Merry was launched into the full tide of conspiracy. At the close of
Jefferson’s first term he saw reason to hope that he might soon
repay with interest the debt of personal and political annoyance
which he owed. While Yrujo was actively engaged in bringing upon
Madison the anger of Spain and France, Merry endeavored to draw
his Government into a system of open and secret reprisals upon the
President.
That the new French minister was little better disposed than
Merry and Yrujo has been already shown; but his causes for ill-will
were of a different and less personal nature. Before Turreau’s arrival
at Washington in November, 1804, Pichon in one of his last
despatches declared that Jefferson had already alienated every
foreign Power whose enmity could be dangerous to the United
States.
“The state of foreign relations offers a perspective which must put
Mr. Jefferson’s character to proof,” Pichon wrote to Talleyrand in
September, 1804.[298] “The United States find themselves
compromised and at odds with France, England, and Spain at the
same time. This state of things is in great part due to the indecision of
the President, and to the policy which leads him to sacrifice everything
for the sake of his popularity.”
The complaint was common to all French ministers in the United

States, and meant little more than that all Presidents and policies
displeased them by stopping short of war on England, which was the
object of French diplomacy; but this letter also showed that in
Pichon’s eyes the President had no friends. When Turreau arrived, a
few weeks afterward, he quickly intimated that the President need
expect from him not even such sentimental sympathy as had been
so kindly given by Pichon.
At the same moment it was noticed that Jefferson changed his
style of dress. “He has improved much in the article of dress,” wrote
Senator Plumer in December, 1804;[299] “he has laid aside the old
slippers, red waistcoat, and soiled corduroy small-clothes, and was
dressed all in black, with clean linen and powdered hair.” Apparently
the President had profited by the criticisms of the British minister,
and was willing to avoid similar comments from the new French
envoy; but he supposed that the Frenchman would show equal
civility, and assume an equally republican style. He was mistaken.
November 23, undisturbed by Merry’s experience, Turreau
presented himself at his first audience in full regimentals, and with so
much gold lace that Jefferson was half inclined to resent it as an
impertinence.[300] Turreau next refused to meet Merry at dinner. He
followed up these demonstrations by embracing the cause of Yrujo,
and ridiculing Madison to his face. He began by warning his
Government that “these people have been thoroughly spoiled; it is
time to put them back into their place.”[301]
Turreau became intimate with the deputies from Louisiana, and
notified Talleyrand that a separation of the western country from the
Union was universally expected. Already, within three months of his
arrival, he put his finger on the men who were to accomplish it.[302]
Destréhan, he said, was a man of high merit; “but being only
moderately ambitious, and head of a numerous family,—having
acquired, too, a great personal esteem,—he is not likely to become
the principal mover in innovations which are always dangerous
without a combination of evidently favorable chances. It is still less
likely that he will ever be the instrument of strangers who should
seek to excite troubles for their personal advantage.” As for Sauvé,
much inferior to his colleague in abilities, he would be guided by
Destréhan’s influence. Derbigny was different. “Young still, with wit,
ready expression, and French manners, I believe him to be greedy of
fortune and fame; I suspect that every rôle will suit him, in order to
acquire the one or the other; but there are men of more importance
whom circumstances are taking to Louisiana.”
Then Turreau, for the information of Talleyrand, drew a portrait of
the military commander of Upper Louisiana, who had his
headquarters at St. Louis, and whose influence on future events was
to be watched.
“General Wilkinson is forty-eight years of age. He has an amiable
exterior. Though said to be well-informed in civil and political matters,
his military capacity is small. Ambitious and easily dazzled, fond of
show and appearances, he complains rather indiscreetly, and
especially after dinner, of the form of his government, which leaves
officers few chances of fortune, advancement, and glory, and which
does not pay its military chiefs enough to support a proper style. He
listened with pleasure, or rather with enthusiasm, to the details which I
gave him in regard to the organization, the dress, and the force of the
French army. My uniform, the order with which I am decorated, are
objects of envy to him; and he seems to hold to the American service
only because he can do no better. General Wilkinson is the most
intimate friend, or rather the most devoted creature, of Colonel Burr.”
Talleyrand had become acquainted with Burr in the United States,
and needed no warnings against him; but Turreau showed himself
well-informed:
“Mr. Burr’s career is generally looked upon as finished; but he is far
from sharing that opinion, and I believe he would rather sacrifice the
interests of his country than renounce celebrity and fortune. Although
Louisiana is still only a Territory, it has obtained the right of sending a
delegate to Congress. Louisiana is therefore to become the theatre of
Mr. Burr’s new intrigues; he is going there under the ægis of General
Wilkinson.”
Perhaps Turreau received this information from Derbigny, which
might account for his estimate of the young man. Certainly Derbigny
knew all that Turreau reported, for in an affidavit[303] two years
afterward he admitted his knowledge.
“In the winter of 1804–1805,” Derbigny made oath, “being then at
Washington City in the capacity of a deputy from the inhabitants of
Louisiana to Congress, jointly with Messrs. Destréhan and Sauvé, he
was introduced to Colonel Burr, then Vice-president of the United
States, by General Wilkinson, who strongly recommended to this
deponent, and as he believes to his colleagues, to cultivate the
acquaintance of Colonel Burr,—whom he used to call ‘the first
gentleman in America,’ telling them that he was a man of the most
eminent talents both as a politician and as a military character; and ...
General Wilkinson told him several times that Colonel Burr, so soon
as his Vice-presidency would be at an end, would go to Louisiana,
where he had certain projects, adding that he was such a man as to
succeed in anything he would undertake, and inviting this deponent to
give him all the information in his power respecting that country; which
mysterious hints appeared to this deponent very extraordinary, though
he could not then understand them.”
What Derbigny in 1807 professed not to have understood,
seemed in 1804 clear to Turreau and Merry as well as to others.
Turreau closed his catalogue by the significant remark: “I am not the
only person who thinks that the assemblage of such men in a
country already discontented is enough to give rise to serious
troubles there.” The treasonable plans of Burr and Wilkinson were a
matter of common notoriety, and roused anxious comment even in
the mind of John Randolph, who was nursing at home the
mortification of Judge Chase’s acquittal.[304] Randolph complained
of “the easy credulity of Mr. Jefferson’s temper,” which made the
President a fit material for intriguers to work upon. Certainly at the
close of his first administration Jefferson seemed surrounded by
enemies. The New England Federalists, the Louisiana creoles, Burr
and his crew of adventurers in every part of the Union, joined hands
with the ministers of England and Spain to make a hostile circle
round the President; while the minister of France looked on without a
wish to save the government whose friendship Bonaparte had
sought to obtain at the cost of the most valuable province and the
most splendid traditions of the French people.
CHAPTER XVIII.
After aiding to negotiate the Louisiana treaty at Paris, in April
and May, 1803, Monroe, as the story has already told, being
forbidden by Bonaparte to pursue his journey to Madrid, followed his
alternative instructions, to take the post which Rufus King was
vacating in London. King left England in the middle of May, 1803;
Monroe arrived in London July 18, when the war between England
and France was already two months old.
The mild Addington ministry was still in power, and nothing had
yet happened to excite Monroe’s alarm in regard to British policy in
the United States. On the contrary, the ministry aided the Louisiana
purchase with readiness that might reasonably have surprised an
American minister, while the friendliest spirit was shown by Lord
Hawkesbury in all matters of detail. Except the standing dispute
about impressments, every old point of collision had been
successfully removed by King, whose two conventions,—the one for
discharging British debts recognized by treaty, the other for settling
the boundaries of New England and of the northwest territory,—
seemed to free the countries for the first time from the annoying
inheritance of disputes entailed by the definitive treaty which closed
the Revolutionary War in 1783. The calm which seemed to prevail
throughout England in regard to her relations with America
contrasted sharply with the excitement shown by the English people
in all their allusions to the Corsican demon, as they thought him,
whose regiments, gathering at Boulogne, they might expect to see at
any moment encamped at Hastings, where no hostile camp-fire had
burned since the night, seven hundred years before, when the body
of an English king, hedged about with the dead bodies of a whole
English aristocracy, lay stiff and stark on the bloody hillside, victims
of another French adventurer. England was intent on her own
imminent dangers; and under the strain which the renewal of her
painful efforts brought with it, she was glad to leave America alone.
Yet calm as the atmosphere appeared to be, signs of future storm
were not wholly wanting. Had Monroe been naturally anxious, he
might, without seeking far, have found cause for anxiety serious
enough to take away all appetite for Spanish travel, and to hold him
close to his post until some one should consent to relieve him from
an ungrateful and unpromising duty. The American minister at
London in 1804 could hope to gain nothing either for his country or
for himself, and he stood always on the verge of disaster; but when
he was required to take a “high tone” in the face of a nation almost
insane with anxiety, he challenged more chances of mortification
than any but a desperate politician would have cared to risk.
Monroe had at first nothing to do but to watch the course of public
opinion in England. During the autumn of 1803, while President
Jefferson and Secretary Madison at Washington received Merry with
a changed policy, and all through the winter, while Washington was
torn by “canons of etiquette” and by contests of strength between
Jefferson, Madison, Casa Yrujo, and Merry, the United States
minister in London was left at peace to study the political problems
which bore on his own fortunes and on those of his friends at home,
as well as on the interests of the Union.
Beneath the calm of general society mutterings of discontent
from powerful interests could be heard,—occasional outbursts of
jealousy, revivals of old and virulent passions, inveterate prejudices,
which made as yet but little noise in the Press or in Parliament, but
which rankled in the breasts of individuals. One of the earlier
symptoms of trouble came in a familiar shape. For twenty years,
whenever a question had arisen of hostility to American trade or of
prejudice against American character, the first of Englishmen to
stimulate it, and the loudest to proclaim the dangers of Great Britain,
had been John Baker Holroyd, Earl of Sheffield, whose memory
might have been lost under the weight of his pamphlets had it not
been embalmed in the autobiography of Gibbon. Lord Sheffield felt
such devotion to the British navigation laws as could be likened only
to the idolatry which a savage felt toward his fetich; one might almost
have supposed that to him the State, the Church, and the liberties of
England, the privileges of her nobility, and even the person of her
sovereign, were sacred chiefly because they guaranteed the safety
of her maritime system. This fanaticism of an honest mind led to
results so extravagant as to become at times ridiculous. The
existence of the United States was a protest against Lord Sheffield’s
political religion; and therefore in his eyes the United States were no
better than a nation of criminals, capable of betraying their God for
pieces of silver. The independence of America had shattered the
navigation system of England into fragments; but Lord Sheffield
clung the more desperately to his broken idol. Among the portions
which had been saved were the West Indian colonies. If at that day
the navigation laws had one object more important than another, it
was to foster the prosperity of these islands, in order that their sugar
and molasses, coffee and rum, might give freight to British shippers
and employment to British seamen; but to Lord Sheffield the islands
were only a degree less obnoxious than the revolted United States,
for they were American at heart, complaining because they were
forbidden to trade freely with New York and Boston, and even
asserting that when the navigation laws were strictly enforced their
slaves died of starvation and disease. Lord Sheffield seriously
thought them ungrateful to murmur, and held it their duty to perish in
silence rather than ask a relaxation of the law.
The rupture of the Peace of Amiens, in May, 1803, set Lord
Sheffield again at work; and unfortunately the material lay ready to
his hand. The whole subject of his discourse related to a single fact;
but this fact was full of alarm to the English people. The
extraordinary decrease of British tonnage in the American trade, the
corresponding increase of American shipping, and the loud
exultation of the Yankees over the British shipmasters were proofs of
the danger which menaced England, whose existence depended on
maritime strength. In the month of February, 1804, Lord Sheffield
published a pamphlet,[305] which dwelt on these calamities as due to
the wanton relaxation of the navigation laws and the senseless
clamor of the colonies. He was answered in a pamphlet[306] written
by one of the colonial agents; and the answer was convincing, so far
as Lord Sheffield’s argument was concerned, but his array of
statistics remained to disturb the British mind.
Monroe might therefore count on having, some day, to meet
whatever mischief the shipping interest of Great Britain could cause.
No argument was needed to prove that the navy would support with
zeal whatever demands should be made by the mercantile marine.
There remained the immense influence of the West Indian colonies
to consider; and if this should be brought into active sympathy with
the shipowners and the royal marine against American trade, no
minister in England—not even Pitt himself at the height of his power
—would be strong enough to resist the combination.
The staple product of the West Indian islands was sugar, and
owing to several causes the profits of the planters had until 1798
been large. The insurrection of the Haytian negroes in 1792
annihilated for the time the supply of sugar from St. Domingo; prices
rose in consequence, and a great increase in the number of sugar
plantations naturally followed. Several of the Dutch and French
islands fell into the hands of England, and adventurers flocked to
them, eager to invest British capital in new sugar-fields. Under this
impulse the supply again increased. Cuba, Porto Rico, Guadeloupe,
and at last St. Domingo itself under Toussaint’s rule poured sugar
into the market. American ships carried French and Spanish sugar to
Europe until it became a drug. The high price lasted till 1798; in that
year Pitt even imposed a heavy additional duty upon it as a sure
source of revenue. In 1799 the effect of over-production first became
apparent. During the next few years the price of sugar fell, until great
suffering began to prevail in the islands, and the planters wrote
piteous letters of distress to England. Their agents wrote back that
the English market was flooded with colonial produce: “Send no
more sugar home; give it away rather!” was their advice,—and the
colonists, without the means of purchasing even the necessaries of
life, supplicated government to let them send their sugar to the
United States, to be exchanged for American produce.[307]
This the government dared not do, for the shipping interest must
in such a case be sacrificed. Debarred from this outlet for their
produce, the colonists looked about them for some other resource;
and since they were not allowed to act independently of the
shipmasters, they saw no other course than to join hands with the
shipping interest, and to invoke the aid of the navigation laws. The
glut of the European market was caused by American neutrals, who
were allowed to carry French and Spanish sugars from the West
Indies to Europe. If this neutral trade could be stopped, the supply of
French and Spanish sugar would be left to rot in Cuba and
Guadeloupe, while British colonial produce would enjoy a monopoly
throughout Europe.
Even before the Peace of Amiens this policy gained many
adherents, and the Peace tended to strengthen their influence. The
Addington ministry was not only weak in character, but timid in
policy; and by a natural reaction it threw restless and ambitious
younger statesmen into an attitude of protest. A new departure was
felt to be necessary; and the nervous energy of England, strained
almost to insanity by the anxieties of ten years’ desperate danger,
exhausted itself in the cry for one great commanding spirit, who
should meet Bonaparte with his own weapons on his own field.
This cry produced George Canning. Of him and his qualities
much will be said hereafter, when his rise to power shall have made
him a more prominent figure; here need be noticed only the forces
which sought assertion through him, and the nature of the passions
which he was peculiarly qualified to express. At all times nations
have been most imperilled by the violence of disappointed or terrified
interests; but the danger was never so great as when these interests
joined to a greed for selfish gain the cry for an unscrupulous chief.
Every American schoolboy once knew by heart the famous outburst
of Canning, which began, “Away with the cant of ‘measures, not
men’!” but of the millions of persons who read or heard this favorite
extract few understood its meaning to American interests and
feelings. This celebrated speech, made Dec. 8, 1802, at a time when
Addington’s cautious ministry still held office, was intended to dwarf
Addington and elevate Pitt,—to ridicule caution and extol violence.
“Sir,” cried Canning, “to meet, to check, to resist, to stand up against
Bonaparte, we want arms of the same kind. I vote for the large
military establishments with all my heart; but for the purpose of
coping with Bonaparte, one great, commanding spirit is worth them
all.”
“Arms of the same kind” were, speaking generally, irresponsible
violence and disregard of morality. The great, commanding spirit of
the moment was Mr. Pitt; but between the lines of this speech, by the
light of its author’s whole career, the secret was easily read that in
his opinion the man of the future who could best meet Bonaparte on
his own ground with his own weapons was not William Pitt, but
George Canning.
After many months of warfare against Addington, Canning was
gratified. In May, 1804, Addington retired from office, carrying into
the House of Lords the new title of Lord Sidmouth, while Pitt returned
to power. No one of note returned with him. His old colleague, Lord
Grenville, refused to join his Administration, and Charles James Fox
was personally excluded by King George. To fill the Foreign Office
Pitt could find no better man than Lord Harrowby,—a personage of
very second-rate importance in politics. With a Cabinet so weak as
to command little respect, and reactionary as was required to suit the
King’s growing prejudices, Pitt was obliged to disguise his
feebleness by the vigor of his measures. While creating, by
expenditure of money, a new coalition against Napoleon, he was
unable to disregard the great moneyed and social interests which
were clamoring for a spirited policy against neutrals and especially
against America. In private he avowed his determination to re-
establish the old system, and his regret that he should ever have
been, most reluctantly, induced to relax the maritime rights of Britain.
[308]
That Monroe should have been the last person in London to

know the secret thoughts of Pitt was not surprising. The Board of
Trade commonly exerted more influence than the Foreign Office over
the relations of England with the United States; and George Rose,
Vice-President of the Board of Trade, Pitt’s devoted friend and a Tory
after Lord Sheffield’s heart, would never have chosen Monroe as a
confidant of schemes under discussion in his department. Lord
Harrowby was but the mouthpiece of other men. From him Monroe
could expect to hear only what had already been decided.
Nevertheless a little study of the mercantile interests of the city, and
a careful inquiry into the private opinions of men like Rose and
Canning, might have thrown some light on the future, and would
naturally have roused anxiety in the mind of Monroe.
Pitt’s return to power, with the intention of changing the American
policy which had been pursued since the negotiation of Jay’s treaty,
happened very nearly to coincide with the arrival at the Foreign
Office of Merry’s most alarming despatches, announcing that
Madison required the total abandonment of impressments, the
restriction of blockades and the right of search, and complete
freedom in the colonial trade, as the conditions on which the
friendship of the United States could be preserved. The
announcement of President Jefferson’s high tone was accompanied
by the British minister’s account of his own social mortifications by
the President and the Secretary of State; of the Senate’s refusal to
approve the fifth article of Rufus King’s boundary convention, in
order to attack the British right of navigating the Mississippi; and by
drafts of bills pending in Congress, under which any British admiral,
even though it were Nelson himself, who should ever have taken a
seaman out of an American vessel, was to be arrested in the streets
of the first American port where he might go ashore, and to suffer
indefinite imprisonment among thieves and felons in the calaboose.
May 30, 1804, Monroe had his first interview with Lord Harrowby.
In such cases the new secretary, about to receive a foreign minister,
commonly sent for the late correspondence, in order to learn
something about the subjects on which he was to have an opinion.
Beyond a doubt Lord Harrowby had on his table the despatches of
Merry, written between November and April, which he probably
finished reading at about the moment when Monroe was announced
at the door.
Under such circumstances, Monroe reported to his Government
that Lord Harrowby’s manners were designedly unfriendly; his
reception was rough, his comments on the Senate’s habit of
mutilating treaties were harsh, his conduct throughout the interview
was calculated to wound and to irritate.[309] After this unpromising
experience, two months were allowed to pass without further
demonstration on either side. Then Lord Harrowby called Monroe’s
attention to the twelfth article of Jay’s treaty, which regulated the
commercial relations between the British West Indies and the United
States, and which had expired by limitation. He suggested its
renewal, according to its old terms, until two years after the next
general peace. To this offer Monroe replied, with the utmost
frankness, “that the President wished to postpone this matter until he
could include impressment and neutral rights in the treaty; that we
must begin de novo; that America was a young and thriving country;
that in 1794 she had had little experience, since then she understood
her interests better; and that a new treaty should omit certain things
from that of 1794, and include others. The most urgent part was that
which respected our seamen.”[310]
An approaching contact of opposite forces always interests men’s
imagination. On one side, Pitt and Lord Harrowby stood meditating
the details of measures, which they had decided in principle, for
taking from the United States most of the commercial advantages
hitherto enjoyed by them; on the other side stood Monroe and
Jefferson, equally confident, telling the Englishmen that very much
greater advantages must be conceded. That one or the other of
these forces must very soon give way was evident; and if ever an
American minister in London needed to be on the alert, with every
faculty strained to its utmost, the autumn of 1804 was such a
moment. Monroe, aware of his danger, gave full warning to the
President. Even as early as June 3, after his first interview with Lord
Harrowby, he wrote that a change of policy was imminent. “My most
earnest advice is to look to the possibility of such a change.”[311]
Lord Harrowby also gave every reasonable warning. His reply to
Monroe’s demands for further negotiation was simple,—nothing
need be expected from him. He refused to do any business at all, on
the plea of other occupations incident to the formation of a new
ministry.[312] Monroe sent him the draft of the comprehensive treaty
which Madison had forwarded, but Lord Harrowby declined for the
present to discuss it. Then Monroe came to the conclusion that his
presence in London was no longer necessary; and accordingly, Oct.
8, 1804, he started for Paris and Madrid. Until July 23, 1805, the
legation at London was left in charge of a secretary.
A month after his departure, Lord Harrowby wrote a letter of
instructions[313] to Merry in reply to the series of despatches
received from Washington.
“His Majesty’s government,” he said, “have perceived with
considerable concern, from some of your most recent despatches, the
increasing acrimony which appears to pervade the representations
that have been made to you by the American Secretary of State on
the subject of the impressment of seamen from on board of American
ships. The pretension advanced by Mr. Madison that the American
flag should protect every individual sailing under it on board of a
merchant-ship is too extravagant to require any serious refutation. In
the exercise of the right, which has been asserted by his Majesty and
his predecessors for ages, of reclaiming from a foreign service the
subjects of Great Britain, whether they are found on the high seas or
in the ports of his own dominions, irregularities must undoubtedly
frequently occur; but the utmost solicitude has been uniformly
manifested by his Majesty’s government to prevent them as far as
may be possible, and to repress them whenever they have actually
taken place.”
Intending to pursue the same course in the future, the
Government would without delay give the strictest orders to its naval
officers “to observe the utmost lenity in visiting ships on the high
seas, and to abstain from impressments in the ports of the United
States.”
In regard to commercial questions, Lord Harrowby offered to
consider the treaty of 1794 as in force until some new arrangement
could be formed. Until the decision of the President should be
known, it was “intended to propose to Parliament to lodge the power
of regulating the commerce with America in the King in Council, in
the same manner as before the treaty of 1794.” The offer of
considering the treaty as in force “must be regarded as a boon to
America; and it was made merely under the persuasion that if
accepted it would be accepted with a view to maintain a friendly
relation between the two countries, and to avoid in the interval
everything which could lead to interrupt it. If this system is followed in
America, it will be followed here in every respect with an anxious
desire for the continuance of harmony and cordiality.”
The same conditional and semi-threatening disposition toward
good-will ran through the rest of these instructions. In regard to the
boundary convention, his Majesty’s government would at all times be
ready to reopen the whole subject; “but they can never acquiesce in
the precedent which in this as well as in a former instance the
American government has endeavored to establish, of agreeing to
ratify such parts of a convention as they may select, and of rejecting
other stipulations of it, formally agreed upon by a minister invested
with full powers for the purpose.”
Finally, Merry was to “avoid, as far as possible, any language
which might be conceived to be of a menacing or hostile tendency,
or which might be construed into an indication of a desire on the part
of his Majesty’s government to decline any discussion of the several
points now pending between the two countries.” Lord Harrowby
clearly wished to encourage discussion to the utmost. He left the
“canons of etiquette” unnoticed, and offered not even a hint at any
change of policy meditated by his Government.
So matters remained in England during the last months of
President Jefferson’s first term. On both sides new movements were
intended; but while those of the United States government were
foreseen and announced in advance by Merry, those of the British
ministry were hidden under a veil of secrecy, which might perhaps
have been no more penetrable to Monroe had he remained in
London to watch them than they were to him in his retreat at
Aranjuez.
To the world at large nothing in the relations of the United States
with England, France, or Spain seemed alarming. The world knew
little of what was taking place. Only men who stood between these
forces could understand their movements and predict the moment of
collision; but if these men, like Merry, Turreau, and Yrujo, had been
asked March 3, 1805, to point out the brightest part of Jefferson’s
political horizon, they would probably have agreed with one voice
that everything in Europe threatened disaster, and that the only
glimpse of blue sky was to be seen on the shores of Africa. The
greatest triumph to be then hoped from Jefferson’s peace policy was
the brilliant close of his only war.
During the year 1804 the little American fleet in the
Mediterranean made famous some names which within ten years
were to become more famous still. With the “Constitution,” the only
heavy frigate on the station after the loss of the “Philadelphia,” and
with half-a-dozen small brigs and schooners, Preble worked manfully
at his task of annoying the Pacha of Tripoli. Three years’ experience
showed that a mere blockade answered no other purpose than to
protect in part American commerce. It had not shaken the Pacha in
the demand of black-mail as his condition of peace. Bainbridge, still
held a prisoner in the town, believed that Jefferson must choose
between paying what the Pacha asked, or sending eight or ten
thousand men to attack him in his castle. Black-mail was the life of
the small pirate rulers, and they could not abandon it without making
a precedent fatal to themselves, and inviting insurrection from their
subjects. Preble could only strike the coast with fear; and during the
summer of 1804 he began a series of dashing assaults with the
“Constitution,” helped by four new craft,—the “Argus” and “Syren,”
fine sixteen-gun brigs; the “Nautilus” and “Vixen,” fourteen-gun
schooners; the “Enterprise,” of twelve guns, and a captured
Tripolitan brig of sixteen guns, re-named the “Scourge,”—all
supported by eight small gunboats borrowed from the King of Naples
who was also at war with Tripoli. Thus commanding a force of about
one hundred and fifty guns, and more than a thousand men, August
3, carrying his flag-ship into the harbor, Preble engaged the
Tripolitan batteries at very short range for two hours. Fortunately, the
Mussulmans could not or did not depress their guns enough to injure
the frigate, and after throwing many broadsides into the batteries and
town, Preble retired without losing a man. His gunboat flotilla was
equally daring, but not so lucky. One division was commanded by
Lieutenant Somers, the other by Stephen Decatur. They attacked the
Tripolitan gunboats and captured three, besides sinking more; but
James Decatur was killed. A few days afterward, August 7, the
attack was repeated, and some five hundred 24-lb. shot were thrown
into the batteries and town. August 24 a third bombardment took
place within the month; and although Preble knew that Barron was
near at hand with a strong reinforcement, August 29 he carried his
flotilla a fourth time into the harbor, and again threw several hundred
solid shot into the town. A fifth bombardment, the heaviest of all, took
place early in September. In these affairs, so poor was the Tripolitan
gunnery or courage that the Americans suffered almost no loss
beyond that of a few spars. The only serious disaster, besides the
death of James Decatur, was never explained. Preble, wishing to try
the effect of a fireship, on the night of September 4 sent one of his
best officers, Lieutenant Somers, into the harbor with the ketch
“Intrepid” filled with powder, bombs, and shell. The “Argus,” “Vixen,”
and “Nautilus” escorted Somers to shoal water, and waited for him to
rejoin them in his boats. They saw the batteries fire upon him; then
they heard a sudden and premature explosion. All night the three
cruisers waited anxiously outside, but Somers never returned. He
and his men vanished; no vestige or tidings of them could ever be
found.
Considering Preble’s narrow means, the economy of the
Department, and the condition of his small vessels, nothing in
American naval history was more creditable than the vigor of his
blockade in the summer of 1804; but he could not confidently assert
that any number of such attacks would force the Pacha to make
peace. A week after the loss of Somers in the “Intrepid” Commodore
Samuel Barron arrived, bringing with him nearly the whole available
navy of the United States, and relieved Preble from the command.
Preble returned home, and was rewarded for his services by a gold
medal from Congress. Two years afterward he died of consumption.
Barron had with him such a force as the United States never
before or since sent in hostile array across the ocean,—two forty-
fours, the “Constitution” and the “President;” two thirty-eight gun
frigates, the “Constellation” and the “Congress;” the “Essex,” of
thirty-two guns; the new brigs, “Hornet” of eighteen, and the “Syren”
and “Argus” of sixteen; the twelve-gun schooners “Vixen,” “Nautilus,”
and “Enterprise;” ten new, well-built American gunboats; and two
bomb-vessels. With the exception of the frigates “Chesapeake” and
“United States,” hardly a sea-going vessel was left at home.
Commanded by young officers like John Rodgers and Stephen
Decatur, Chauncey, Stewart, and Isaac Hull, such a squadron
reflected credit on Robert Smith’s administration of the navy.
Nevertheless the Pacha did not yield, and Barron was obliged by
the season to abandon hope of making his strength immediately felt.
Six months later the commodore, owing to ill-health, yielded the
command to John Rodgers, while the Pacha was still uninjured by
the squadron. As the summer of 1805 approached, fear of Rodgers’s
impending attack possibly helped to turn the Pacha’s mind toward
concession; but his pacific temper was also much affected by events
on land, in which appeared so striking a combination of qualities,—
enterprise and daring so romantic and even Quixotic that for at least
half a century every boy in America listened to the story with the
same delight with which he read the Arabian Nights.
A Connecticut Yankee, William Eaton, was the hero of the
adventure. Born in 1764, Eaton had led a checkered career. At
nineteen he was a sergeant in the Revolutionary army. After the
peace he persisted, against harassing difficulties, in obtaining what
was then thought a classical education; in his twenty-seventh year
he took a degree at Dartmouth. He next opened a school in Windsor,
Vermont, and was chosen clerk to the Vermont legislature. Senator
Bradley, in 1792, procured for him a captain’s commission in the
United States army. His career in the service was varied by
insubordination, disobedience to orders, charges, counter-charges, a
court-martial, and a sentence of suspension not confirmed by the
Secretary of War. In 1797 he was sent as consul to Tunis, where he
remained until the outbreak of the war with Tripoli in 1801. Tunis was
the nearest neighbor to Tripoli, about four hundred miles away; and
the consul held a position of much delicacy and importance. In the
year 1801 an elder brother of the reigning Pacha of Tripoli resided in
Tunis, and to him Eaton turned in the hope of using his services.
This man, Hamet Caramelli, the rightful Pacha of Tripoli, had been
driven into exile some eight or nine years before by a rebellion which
placed his younger brother Yusuf on the throne. Eaton conceived the
idea of restoring Hamet, and by this act of strength impressing all the
Mahometan Powers with terror of the United States. In pursuit of this
plan he spent more than twenty thousand dollars, embroiled himself
with the Bey of Tunis, quarrelled with the naval commanders, and in
1803 returned to America to lay his case before the President and
Congress.

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Nanophotocatalysis and Environmental Applications

Nanophotocatalysis and Environmental Applications:

Energy Sources. Fundamentals of Chemical Conversion

Photovoltaic Solar Energy Conversion: Technologies,

High-Temperature Electrochemical Energy Conversion and

Nanosensor Technologies for Environmental Monitoring

Nanomaterials in energy and environmental applications

Polymers Coatings: Technology and Applications 1st

Organic Contaminants in Riverine and Groundwater Systems

Sustainable Agriculture Reviews

More information about this series at http://www.springer.com/series/11480

Abdullah M. Asiri Eric Lichtfouse

ISSN 2213-7114 ISSN 2213-7122 (electronic)

Library of Congress Control Number: 2019932801

© Springer Nature Switzerland AG 2019

Chapter 7 summarizes the innovative aspects of the applicability of

Jeddah, Saudi Arabia Inamuddin

1 Nanophotocatalysts for Fuel Production . . . . . . . . . . . . . . . . . . . . . 1

9 High-Performance Photocatalysts for Organic Reactions . . . . . . . . 219

Giuseppina Iervolino Department of Industrial Engineering, University of

Song Sun National Synchrotron Radiation Laboratory, Collaborative Innovation

Annelise Kopp Alves

Keywords Quantum dots · Photocatalysis · Fuel · Hydrogen · Semiconductors ·

© Springer Nature Switzerland AG 2019 1

1.2 Quantum Dot Semiconductors

1.3 Synthesis of Quantum Dots

Table 1.1 Application of quantum dots in the photocatalytic process

maintained at 800 C in air. NiO quantum dot of 2 nm covered TiO2 nanoparticles of

1.4 Application of Quantum Dots for Fuel Production

The use of photocatalytic processes to obtain fuels using nanoparticles (quantum

The group of Yadav et al. (2016) synthesized graphene quantum dot

in CO2 photoreduction. Appl Catal B Environ 231:269–276. https://doi.org/10.1016/j.apcatb.

The complaint was common to all French ministers in the United

That Monroe should have been the last person in London to

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