Introduction to Application

Application of catalyis
of catalyis for
for material
material synthesis
synthesis

Electrocatalysis is a process dealing

with electrochemical reactions in the
interconversion of chemical energy and
electrical energy. Precise synthesis of
catalytically active nanostructures is
one of the key challenges that hinder
the practical application of many
important energy-related
electrocatalytic reactions. Compared
with conventional wet-chemical, solid-
state and vapor deposition synthesis,
electrochemical synthesis is a simple,
fast, cost-effective and precisely
controllable method for the
preparation of highly efficient catalytic
materials. In this review, we summarize
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recent progress in the electrochemical
synthesis of catalytic materials such as
single atoms, spherical and
shaped nanoparticles, nanosheets,
nanowires, core-shell nanostructures,
layered nanomaterials, dendritic
nanostructures, hierarchically
porous nanostructures as well as
composite nanostructures.
Fundamental aspects of
electrochemical synthesis and several
main electrochemical synthesis
methods are discussed. Structure-
performance correlations between
electrochemically synthesized catalysts
and their unique electrocatalytic
properties are exemplified using
selected examples. We offer the reader
with a basic guide to the synthesis of
highly efficient catalysts using
2
electrochemical methods, and we
propose some research challenges and
future opportunities in this field
Breif Study
To a large extent, economic growth
and social development in the current
world rely on the energy supply
originally derived from conventional
fossil fuels such as coal, petroleum and
natural gas, as well as from emerging
renewable energy sources such as
solar and wind. Over the past two
centuries, the utilization of fossil fuels
has been increasing the concentration
of atmospheric carbon dioxide (CO 2),
thus leading to severe environmental
issues and climate change. There is an
urgent need to reduce
CO2 emission via developing new
3
strategies and technologies in energy
supply processes. The long-term goal
of the Paris Agreement is to limit
global warming to well below 2,
preferably to 1.5 °C, compared to pre-
industrial levels. China aims to peak its
total CO2 emissions by 2030 and
achieve carbon neutrality by 2060.
While recently renewable energy has
grown rapidly, it is still too early to
completely replace the use of fossil
fuels. In this context, the optimized
utilization of fossil energy aiming to
emit less CO2 as well as the
implementation of renewable energy
free of CO2 emission can serve as two
parallel routes in the near future. Both
routes involve the conversion of
substances and energy in different
forms, highlighting the key role of
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chemistry in addressing the energy
challenge
Catalysis, a process that alters the rate
of a chemical reaction, stands at the
heart of energy production and
utilization, as it can improve the
conversion efficiency of substances
and energy [3]. Electrocatalysis is a
process dealing with electrochemical
reactions in the interconversion of
chemical energy and electrical energy
[4]. Fuel cells are the most classical
scenarios in which a wide range of
electrocatalytic reactions are involved,
such as oxygen reduction reaction
(ORR), hydrogen oxidation reaction
(HOR), the electrooxidation of alcohols
and hydrocarbons. In general, the fuels
fed to fuel cells undergo complete
oxidation/combustion to water and
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CO2 to produce power, while it is also
likely to acquire high-value products
such as hydrogen peroxide via two-
electron reduction of oxygen [ 5] and
methanol via partial oxidation of
methane [6] through using appropriate
catalysts and controlling suitable
potentials/currents. Under electrolysis
conditions, electrocatalytic reactions
are designed to be driven by
renewable electricity, simultaneously
generating useful products and storing
intermittent renewable energy. This
unique feature has attracted enormous
research interest from researchers in
the context of CO2 emission reduction
as well as carbon capture, utilization
and storage (CCUS). Typical examples
of such electrocatalytic reactions
include water electrolysis including
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cathodic hydrogen evolution reaction
(HER) and anodic oxygen evolution
reaction (OER), CO 2/CO reduction
reaction (CO2/CORR), electrochemical
ammonia synthesis from nitrogen,
nitrogen oxides and nitrite, as well as
upgrading of biomass-derived platform
molecules. Recently researchers have
also explored a group of new
electrocatalytic reactions such as
hydrogen peroxide synthesis via water
oxidation, methane oxidation to
oxygenates, and alkyne reduction to
alkene. Compared with traditional
thermal catalysis, the hydrogen (or
oxygen) species needed in
electrocatalytic reduction (or
oxidation) reactions are in
situ generated from water under
specific polarization conditions, rather
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than using any external reductants (or
oxidants). This is particularly important
for hydrogenation reactions in which
H2 used in thermal catalysis usually
comes from syngas via water gas shift
reaction that produces substantial
CO2 [12]. Moreover, electrocatalytic
reactions are possible to proceed at
low, even room temperature
While the overall performance of a
given electrocatalytic reaction is
determined by multiple factors such as
potential, current, temperature,
pressure, catalyst, electrolyte,
electrode structure and reactor
configuration, the core aspect of
electrocatalysis is to develop efficient
catalysts with high activity, selectivity
and stability. Heterogeneous catalytic
reactions occur at the interface of
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different phases, for instance solid-gas,
solid-liquid and solid-liquid-gas
interfaces [3]. The size, shape,
composition, oxidation state,
coordination structure, surface
chemistry and near surface
microenvironment of catalysts often
play decisive roles in improving
electrocatalytic performances,
therefore, the rational design and
synthesis of catalytically active
nanostructures is of great importance.
Over the past few decades, the
remarkable advances in nanoscience
and nanotechnology have enabled a
variety of methods for the synthesis of
catalytic materials with tunable
compositions and morphologies. The
most widely used one is wet-chemical
synthesis, a bottom-up approach using
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liquid-phase precursors in aqueous or
organic solutions to produce a broad
range of nanomaterials. The wet-
chemical synthesis techniques include
impregnation, precipitation,
deposition, hydrothermal synthesis,
solvothermal synthesis, sol-gel
synthesis, as well as colloidal synthesis
that provides unique opportunities to
control the size, shape and
composition of nanoparticles and
nanocrystals [23]. Solid-state synthesis
shows unique ability in preparing
metal- and nitrogen-doped carbon
materials, porous metal catalysts as
well as perovskite oxide catalysts.
Physical vapor deposition (PVD),
chemical vapor deposition (CVD) and
atomic layer deposition (ALD)
techniques provide alternative
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methods to produce ultrathin films,
carbon-supported NPs and finely
dispersed metal particles as model or
real catalysts in electrocatalytic
reactions. While these synthesis
methods have produced a large
number of nanostructures with
excellent electrocatalytic
performances, they suffer either from
the difficulty in precisely controlling
size, shape and composition, or from
the complexity during synthesis.
Catalyst reconstruction under reaction
conditions has been observed during
many electrocatalytic reactions, and
the structural differences between pre-
catalysts (as-prepared) and true
catalysts (reconstructed) are governed
by applied potentials, electrolyte
compositions, solvent, reactants,
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intermediates and products. This
phenomenon suggests electrochemical
synthesis as an alternative approach
for the production of highly efficient
catalysts. Electrochemical synthesis is
featured with simple operation, low
cost, easy manipulation of synthesis
variables (e.g., pH, additive,
electrolyte, temperature, potential,
current) as well as high degrees of
freedom in tuning morphologies and
compositions of catalytic materials.
Furthermore, the electrochemically
synthesized materials are usually
electrically conductive or grown on
conductive substrates, so that they can
directly serve as candidate catalysts or
integrated electrodes for
electrocatalytic applications. A
comparison in Table 1 indicates that
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electrochemical synthesis method
shows many advantages compared
with other physical and chemical
synthesis methods. The method of
electrochemical synthesis can be
traced back to over one century ago
when Fritz Haber observed the
formation of metal nanoparticles when
applying a negative potential to metal
wires [48]. This electrochemical
phenomenon was further recognized
and confirmed as cathodic corrosion
with the aid of modern
characterization techniques for
nanoscience and nanotechnology in
2011 by Koper and co-workers [49].
Later on, cathodic corrosion has
evolved into an important method for
nanoparticle synthesis and catalyst
modification [50]. Apart from the
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historical method, many other
electrochemical methods have been
reported and used for the rational
design and synthesis of nanostructured
catalysts.
The present review article will
summarize main electrochemical
synthesis methods, classify
electrochemically synthesized catalysts
in terms of morphology, and highlight
their applications in the above-
mentioned energy-related
electrocatalytic reactions (Fig. 1). We
will exemplify the unique
electrocatalytic properties of
representative catalysts synthesized by
specific electrochemical methods.
Since this study mainly focuses on
electrochemical synthesis methods for
the preparation of catalytic materials,
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Results :
the fundamental principles and
mechanistic understanding of
electrocatalytic reactions of interest
will not be discussed in details.
Interested readers are suggested to
refer to previous excellent
reviews Experimental methods for
electrochemical synthesis of catalytic
materials

Catalytic materials can be

electrochemically prepared under
potential/current control, initially
starting from either metal
salts via bottom-up synthesis or bulk
metals via top-down synthesis. For
given metals, the structure,
composition and morphology of target
catalysts depend on many parameters
such as electrolyte, pH and additive, as
well as the way how potential/current
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is applied. In this section, we briefly
introduce the fundamentals of
electrochemical synthesis and several
important

Electrochemically synthesized
catalysts and their applications in
energy catalysis

As of now, the above-introduced

electrochemical methods as well as
others have been vastly applied in the
synthesis of catalysts for energy
catalysis, especially electrocatalysis.
These catalysts differ from each other
in terms of size, shape, morphology,
composition and so on. In this section,
we classify them into different groups
and demonstrate the unique role of
electrochemical methods in shaping
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their specific structures and properties.
Representative examples of
electrochemically

ConcludingConclusions
remarks and
perspectives

In this we have discussed different

electrochemical strategies for the
synthesis of high-performance
catalytic materials and exemplified the
unique catalytic properties of
representative electrochemically
synthesized catalysts for energy
electrocatalysis applications.
Electrochemical synthesis is a simple,
fast, cost-effective and precisely
controlled approach for the preparation
of a wide range of catalytically active

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nanostructures such as single atoms,
spherical and shaped

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