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org/EF Review

Advanced Two-Dimensional Materials for Green Hydrogen

Generation: Strategies toward Corrosion Resistance Seawater
Electrolysis�Review and Future Perspectives
Sankhula Lokesh and Rohit Srivastava*

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ABSTRACT: Excessive usage of nonrenewable resources to meet

global energy requirements has become a serious concern from the
energy and environmental perspective. The continuous emission of
CO2 in the environment from fossil fuels has become a major cause
of global warming. Green hydrogen generation through seawater
electrolysis has been an emergent technology that can play a
prominent role in replacing conventional energy sources.
Electrolysis of seawater using renewable sources such as solar,
wind, and geothermal generates green hydrogen which has almost
negligible harmful byproducts. Different ions present in seawater
such as chlorides and sulfates impose serious corrosion problems
during the electrolysis process as chloride ions penetrate the metal
electrode surface and oxidize it and also liberate chlorine gas at the
anode. For the electrolysis processes, catalysis plays a challenging task to reduce the kinetic barrier for the conversion of water
molecules to hydrogen and oxygen products. Photoelectrocatalysts are another kind of semiconductor-based catalyst in which band
gap, exchange charge carrier, and surface area play key roles in the water-splitting process. Two-dimensional nanomaterials offer
many advantages like high specific surface area for electron transfer, high tunable functionalities, and flexible structural properties
that make them suitable for different applications. Layered double hydroxide (LDH) as a highly efficient catalyst has the potential to
perform the hydrogen production process as per the industrial application. LDH has many advantages in an effective water-splitting
mechanism that includes easy synthesis methods, flexible morphology, long-term stability, and adaptability to different applications.
Another major advantage is the corrosion inhibition property of LDH by different mechanisms like adsorption of corrosion-
responsible ions, self-healing technique, and protective film formation which are discussed briefly in this review. This review provides
a state-of-the-art analysis about the various important strategies to be adopted for effective seawater electrolysis. Finally, we examine
the new challenges and the novel approaches to suppress corrosion processes during seawater electrolysis.

1. INTRODUCTION nonrenewable resources.6−10 Thus, the development of clean,

Most of the energy needs are fulfilled by nonrenewable resources reliable, and sustainable energy resources is of critical
like coal, oil, and natural gas, which impose a huge negative importance for substitution of conventional fossil fuels.
Besides the highest gravimetric energy density of hydrogen
impact on energy and the environment.1 Excess consumption of
(H2), it has the advantage of zero-carbon emission, so it is widely
fossil fuels leads to depletion of energy resources and has adverse
considered a fuel to replace other energy sources and fulfill our
effects on the environment.2 Global warming, acid rains, and
needs sustainably in the future.11 There are many ways to
water pollution are some of the serious issues resulting from the
produce pure hydrogen, but water electrolysis technology is
extraction and refining of crude oil.3 Different unit operations
regarded as an efficient and convenient process to generate
involving the conversion of low-grade fuel to high-grade fuel
hydrogen with nearly zero-carbon emission. Another way to
emits greenhouse gases like NOx and SOx into the atmosphere.4
According to the “new policies” scenario, the increase in global
fertility rate and the industrial revolution were expected to Received: June 17, 2022
accelerate the growth of the global energy requirement from 18 Revised: October 17, 2022
TW to 25 TW during the period from 2013 to 2040.5 Published: October 28, 2022
Researchers across the globe have focused on energy crisis
issues, especially the long-term shifts in temperature and
weather patterns observed due to the consumption of

© 2022 American Chemical Society https://doi.org/10.1021/acs.energyfuels.2c02013

13417 Energy Fuels 2022, 36, 13417−13450
Energy & Fuels
evolve hydrogen is by an inorganic reaction between aluminum
and a base (NaOH/KOH), which yields sodium aluminate or
potassium tetrahydroxyaluminate and hydrogen gas. Sodium
hydroxide or potassium hydroxide base acts as a catalyst to
initiate the reaction, but reaction products have adverse effects
on human health when inhaled and are also corrosive. The
overall efficiency of electrochemical splitting of water is based on
two important half-cell reactions, namely, oxygen evolution and
hydrogen evolution reactions.12,13 The slow kinetics and large
overpotential value for half-cell reactions delay the practical
applications for hydrogen production.14−17 The water-splitting
process does not require high temperature and pressure reactor
vessels compared to conventional steam reforming processes,
which is also an added advantage for the implementation of
industrial scale-up.18
Recently, LDH has become a promising material to captivate
research attention for its adaptability in various domains like
electrochemistry, adsorption, photocatalysis, and biomedical
science.19 The remarkable parameters of LDH materials include
a high adsorption capability for different wavelength ranges via
compositional manipulation, corrosion-resistant mechanism,
ease of synthesis, layered morphology, and homogeneous
distribution of different cations in the interlayer gallery making
them suitable materials for photocatalysis applications.20−22
LDH materials have been widely investigated due to their
additional advantages which include availability, low cost,
durability, and being resource-rich compared to conventional
noble metals.22
1.1. Types of Electrolysis Process. Water electrolysis
technology can be classified into four categories based on the
electrolyte used in an electrochemical cell: alkaline, proton-
exchange membrane, steam electrolysis, and anion exchange
membrane, as shown in Figure 1.
Figure 1. Classification of electrolysis process for hydrogen production.
1.1.1. Alkaline Electrolysis. Alkaline electrolysisis the oldest
technology used for hydrogen production, and this is one of the
simplest and environmentally friendly methods (when a
renewable energy source is used). The electrolyte is an aqueous
solution of NaOH or KOH with a typical concentration of 20−
40 wt %, operating temperature range of 343−363 K, and
operating pressure up to 3 MPa. Long-term durability and
running efficiency of 70% are the advantages of alkaline
electrolysis. The hydrogen production process from water in
an alkaline electrolyzer is represented in Figure 2, where water
molecules introduced into the electrolytic cell from the bottom
side are dissociated into H2 and OH− ions at the cathode, and
these ions are transferred toward the anode through the alkaline
pubs.acs.org/EF Review
electrolyte medium. The reaction mechanism of water
electrolysis that occurs in an alkaline electrolytic cell is described
by eqs 1, 2, and 3.
Cathode: 2H 2O + 2e H 2 + 2OH (1)
1
Anode: 2OH O2 + H 2O + 2e
2 (2)
1
Overall: H 2O H2 + O2
2 (3)
1.1.2. Proton-Exchange Membrane. The proton-exchange
membrane electrolysis process is performed with a polymeric
membrane as a solid electrolyte, which is characterized by simple
construction and compactness. A PEM electrolyzer mainly
utilizes the polymeric membrane for transport of H+ ions across
the electrodes and produces hydrogen gas at the cathode as
illustrated in Figure 3. High purity of H2, low power
consumption, ecological cleanness, high safety, and easy
handling and maintenance are the benefits of the PEM
electrolyzer. The reaction mechanism in PEM electrolysis cells
is described by eqs 4, 5, and 6.
Cathode: 2H+ + 2e H2 (4)
1
Anode: H 2O 2H+ + O2 + 2e
2 (5)
1
Overall: H 2O H2 + O2
2 (6)
1.1.3. Steam Electrolysis (Solid Oxide Electrolysis). Steam
electrolysis (solid oxide electrolysis) technology has the
advantage of higher efficiency compared with alkaline and
PEM electrolysis technologies. This process utilizes thermal
energy for the conversion of water to steam and is then
introduced into the electrolyzer. This technology operates at
higher temperatures (700−1000 °C approximately) for
electrolysis; however, it can reduce the energy consumption
significantly and also increase the power to hydrogen efficiency
(more than 95%HHV H2). The significant increase in the
efficiency of hydrogen production can lead to a reduction in
cost as power utilization is the key factor for the cost of the
electrolysis process. This process is considered a reverse reaction
for a solid oxide fuel cell (SOFC) represented in Figure 4(b),
which is an electrochemical conversion device that generates
electricity by redox reactions between H2 and O2, characterized
by a solid oxide electrolytic medium for transferring oxygen ions.
The high-temperature steam electrolysis (HTSE) involves the
conversion of water into steam, dissociation of hydromolecules
into O2− ions and hydrogen gas at the cathode surface, and
migration of ions through the solid oxide electrolyte to produce
oxygen gas at the anode surface as shown in Figure 4(a). The
ionic conductivity of the electrolyte and the rate of electro-
chemical reactions at electrode surfaces increase at higher
temperatures. Equations 7, 8, and 9 show the half-cell reaction
mechanism taking place in high-temperature steam electrolysis
cells.
Cathode: H 2O + 2e H 2 + O2 (7)
1
Anode: O2 O2 + 2e
2 (8)
1
Overall: H 2O H2 + O2 + 2e
2 (9)
13418 https://doi.org/10.1021/acs.energyfuels.2c02013
Energy Fuels 2022, 36, 13417−13450
Energy & Fuels
Figure 2. Schematic of alkaline electrolyzer system for hydrogen production.
Figure 3. Simplified scheme of a proton exchange membrane
electrolyzer.
1.1.4. Anion Exchange Membrane (AEM). Anion exchange
membrane (AEM) electrolysis is one of the advanced
technologies, where the membrane introduced for the
electrolysis process allows only anions to migrate through the
membrane. This is a promising technology for seawater
electrolysis; however, it is a developing technology. Many
researchers are working on AEM-based electrolyzer develop-
ment to resolve challenges such as membrane stability, ease of
handling, power efficiency, robustness, and cost reduction. This
electrolysis process involves the dissociation of a water molecule
into hydrogen gas and OH− ions at the cathode, migration of
OH− ions toward the anode, and evolution of oxygen gas at the
anode. The reaction mechanism taking place in the AEM
electrolyzer is given in eqs 10, 11, and 12
Cathode: 2H 2O + 2e 2OH + H 2 (10)
pubs.acs.org/EF Review
1
Anode: 2OH H 2O + O2 + 2e
2 (11)
1
Overall: H 2O H2 + O2
2 (12)
This AEM technology has many advantages compared to
other conventional electrolysis processes such as the following:
(1) A transition metal catalyst is used rather than expensive
noble metal catalysts (Pt). (2) A cost-effective quaternary
ammonium-based ion exchange group membrane can be used.
(3) It is low-cost and highly stable for hydrogen production from
alkaline seawater and has a high operating pressure. There are
also some challenges to the AEM electrolysis process, which
include membrane durability, excessive catalyst loading, and
lower current densities, so further investigations are to be done
for industrial adaptability. The AEM electrolysis mechanism is
shown in Figure 5.
This review predominantly emphasizes the types of
electrolysis technologies for water splitting and seawater
splitting and their major challenges. The review provides a
deep discussion about 2D materials as electrocatalysts and
photoelectrocatalysts for enhancing hydrogen production at
optimum energy consumption. The corrosion resistance
mechanism of 2D electrocatalysts during seawater splitting is
also discussed. Many researchers have discussed efficient
electrocatalysts for improving HER/OER activity and seawater
electrolysis. However, the performances of the electrocatalysts
in salinemediums and corrosion resistance mechanisms, techno-
economic discussions for seawater splitting, and challenges for
direct seawater splitting are lacking in many articles. Therefore,
this review helps to focus on the key aspects of industrialization
of hydrogen production from seawater and techniques to
withstand corrosion during electrolysis in harsh environments.
13419 https://doi.org/10.1021/acs.energyfuels.2c02013
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Figure 4. Schematic representation of (a) high-temperature steam electrolysis and (b) solid oxide fuel cell mechanism.

of seawater varies from one region to another with an average

Figure 5. Schematic of AEM electrolysis cell for water splitting.
2. SEAWATER ELECTROLYSIS
Seawater contains many salts relative to fresh water, which leads
to the complexity of electrochemical reactions. The composition
salt concentration of different ions ranging from about 3.5 wt %
(pH 8). The ions present in seawater mainly include sodium
(Na+), potassium (K+), calcium (Ca2+), magnesium (Mg2+),
chlorides (Cl−), and sulfate ions (SO42−). The presence of
different ions in seawater helps for good ionic conductivity but
causes complex reaction mechanisms at the electrode surface.
The OH− ions formed during the dissociation of water
molecules may form insoluble precipitates by reacting with
Ca2+ and Mg2+ ions and deposit on the electrode surface. The
precipitate may hinder the reactions at the surfaces of electrodes,
and the rate of the reaction can be slow due to additional
resistance. The concentrations of different species in seawater
along with redox reactions at extreme pH values are given in
Table 1, which illustrate that oxidation of bromine and chlorine
ions might compete with OER. The competing oxidation of
bromine ions was neglected due to lower concentration
compared to chlorine ions. The dominant ions present in

Table 1. Chemical Composition of Seawater Species and Corresponding Redox Reactions at Different pH Values

Sr. No. Species Conc (g/kg H2O) Redox reaction at pH 0 E0 Redox reaction at pH 14 E0
− − − − −
1 Cl 20.057 2Cl ⇋ Cl2 + 2e 1.358 2Cl ⇋ Cl2 + 2e 1.358
Cl− + H2O ⇋ HClO + H+ + 2e− 1.482 Cl− + 2OH− ⇋ ClO− + H2O + 2e− 0.89
Cl− + 2H2O ⇋ HClO2 + 3H+ + 4e− 1.570 Cl− + 4OH− ⇋ ClO2− + 2H2O + 4e− 0.76
Cl− + 3H2O ⇋ ClO3− + 6H+ + 6e− 1.451
Cl− + 4H2O ⇋ ClO4− + 8H+ + 8e− 1.389

2 Br− 0.0695 2Br− ⇋ Br2 + 2e− 1.087 2Br− ⇋ Br2 + 2e− 1.087
Br− + H2O ⇋ HBrO + H+ + 2e− 1.331 Br− + 2OH− ⇋ BrO− + H2O + 2e− 0.761
Br− + 3H2O ⇋ BrO3− + 6H+ + 6e− 1.423 Br− + 6OH− ⇋ BrO3− + 3H2O + 6e− 0.61

3 SO42− 2.8117 2SO42− ⇋ S2O82−+ 2e− 2.010 2SO42− ⇋ S2O82− + 2e− 2.010
S2O62− + 2H2O ⇋2SO42 + 4H+ + 2e− −0.220 SO32− + 2OH− ⇋ SO42− + H2O + 2e− −0.93
H2SO3 + H2O ⇋ SO42− + 4H+ + 2e− 0.172

4 Na+ 11.1768 Na ⇋ Na+ + e− −2.710 Na ⇋ Na+ + e− −2.710

5 K+ 0.4137 K ⇋ K+ + e− −2.931 K ⇋ K+ + e− −2.931
6 Mg2+ 1.3307 Mg ⇋ Mg2+ + 2e− −2.372 Mg ⇋ Mg2+ + 2e− −2.372
7 Ca2+ 0.4268 Ca ⇋ Ca2+ + 2e− −2.868 Ca ⇋ Ca2+ + 2e− −2.868
8 F− 0.0013 2F− ⇋ F2 + 2e− 2.866 2F− ⇋ F2 + 2e− 2.866
9 Sr2+ 0.0079 Sr ⇋ Sr2+ + 2e− −2.899 Sr ⇋ Sr2+ + 2e− −2.899

13420 https://doi.org/10.1021/acs.energyfuels.2c02013
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seawater are Na+ and Cl−, so the NaCl solution is used as an Dissolution by further coordination:
alternative electrolyte for research purposes. MCl ads + xCl MCl x (16)
The chloride ions present in seawater affect the cathode and
anode surfaces by blocking the active sites of catalysts. These
ions may offer additional resistance at the cathodic surface and Conversion from chloride to hydroxide:
accelerates the degradation of the cathodic catalyst, whereas, at
the anodic surface, chlorine gas and hypochlorites were MCl x +OH M(OH)x + xCl (17)
generated due to the competitive oxidation reaction mechanism The development of electrodes that are corrosion resistant for
of chloride to OER. The chloride oxidation reaction rate is fast splitting water into hydrogen and oxygen fuels is important for
compared to OER because of two-electron transfer mechanisms. seawater electrolysis advancement to avoid relying on the costly
The anodic reactions for seawater electrolysis can be desalination process. The chloride oxidation electrochemistry is
manipulated by adjusting the pH value of the electrolyte so complicated, and it depends mainly on the value of pH,
solution. According to the Pourbaix plot, OER reactions are applied potentials, and temperature. Fixing the temperature at
more favorable in electrolytemediums having pH > 7.5, with an 25 °C and the concentration of seawater to 0.5M, a Pourbaix
overpotential of 480 mV. diagram for aqueous chlorine chemistry is shown in Figure 6(a).
2.1. Challenges for Seawater Electrolysis. The main
challenges for direct electrolysis of seawater include local pH
fluctuations, presence of bacteria/microbes and small partic-
ulates, chloride ion oxidation, and deposition of impurities on
the membrane utilized for separating the cathodic and anodic
compartments. The presence of carbonates in saline water acts
as buffers, but the concentration of carbonates cannot restrict
local pH changes at the electrode surface. The pH value changes
near the electrode surface could be in the order of 5−9 units
from that of bulk seawater, even at less current densities (<10
mA/cm2).23−25 The fluctuations in pH value lead to catalyst
degradation and precipitation of Mg(OH)2 and cathode surface
blocking, which occurs at pH > 9.5. The addition of supporting
electrolytes can help in the stabilization of pH fluctuations. The
most serious problem is caused due to the presence of chloride
ions present in seawater (0.5−0.6 M NaCl). The equilibrium
potential for OER vs a normal hydrogen electrode (NHE) is
higher than the chlorine evolution reaction (CLER) by 130
mV,26 but OER is a four-electron oxidation process that requires
a higher overpotential than the two-electron chloride oxidation
reaction with a kinetic advantage. The equilibrium potential of
chlorine evolution does not depend on pH, but OER depends on
the pH of the electrolyte. The OER and hypochlorite formation
reactions are illustrated by eqs 13 and 14. Selective OER over
chlorine generation can be achieved in alkaline electrolytes to
lower the onset potential of OER. However, the formation of
hypochlorite is still competitive with OER with an onset
potential of 490 mV more than that of OER, so highly active
OER electrocatalysts are necessary for higher H2/O2 production
at overpotentials well below hypochlorite formation. The
aggressive chloride ions may still corrode catalysts and substrates
through a metal chloride hydroxide formation reaction
mechanism shown by eqs 15, 16, and 17, even with a highly
Figure 6. (a) Pourbaix diagram of an aqueous saline electrolyte and (b)
active OER catalyst in alkaline electrolytes.27 representation of E vs pH for competing for OER and chloride (Cl−)
oxidation reactions.29 Reproduced with permission from ref 29.
Cl + 2OH OCl + 2e Copyright 2019 Elsevier.
0
E = 1.72 V 0.059*pH vs NHE (13)
When the pH value is below 3.0, the free chlorine evolution
4OH O2 + 2H 2O + 4e occurs predominantly in the chloride oxidation reactions.
0
Hypochlorous acid formation takes place at pH values greater
E = 1.23 V 0.059*pH vs NHE (14) than 7.5. The chloride oxidation reactions at two extreme pH
values are shown in eqs 18 and 19.

Adsorption of Cl− by the surface polarization: CLER:

M + Cl MCl ads + e (15) 2Cl Cl 2 + 2e E0 = 1.36V vs SHE, pH 0 (18)

13421 https://doi.org/10.1021/acs.energyfuels.2c02013
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Table 2. Electrochemical Performances of Various Electrocatalysts for Seawater Electrolysis

Sr. No. Electrocatalyst Electrolyte Overpotential (mV) Tafel slope (mV/Dec) Ref
1 NiFe-LDH 1 M KOH + 0.5 M NaCl 227 (100 mA/cm2) − 33
2 FTO/NiO 1 M KOH + 0.5 M NaCl 401 (10 mA/cm2) − 34
3 Pb2Ru2O7‑x 0.6 M NaCl 500 (10 mA/cm2) 48 35
4 Co(OH)2 0.25 M Mg(ClO4)2 − 125 36
5 Ni2P-Fe2P 1 M KOH + seawater 460 (100 mA/cm2) − 37
6 Fe−Ni (OH)2/Ni3S2 1 M KOH + 0.5 M NaCl 269 (10 mA/cm2) 46 38
7 Mg/Co-MnO2/Co(OH)2 0.25 M MgCl2 − 144 36
8 VS2@V2C Seawater 148 (20 mA/cm2) 37 39
9 NiRuIr_G Seawater 80 (10 mA/cm2) 48 40
10 0.5Rh-GS100 Seawater 320 (10 mA/cm2) − 41
11 Ru-CoOx 1 M KOH + seawater 630 (100 mA/cm2) − 42
12 C-Co2P 0.0412 M MgCl2 and 0.0125 M CaCl2 192 (1000 mA/cm2) − 43
13 Pt-Ru-Ni Seawater 206 (10 mA/cm2) 44.5 44
14 Pt@mh-3D Mxene Seawater 280 (10 mA/cm2) − 45

Hypochlorite formation: such as activity, stability, and efficiency.1,47,48 The selection of

Cl + 2OH ClO + H 2O + 2e
0 as the number of excess electrons, electronegativity, metal−
E = 0.89 V vs SHE, pH 14 (19)
The competing chloride oxidations are thermodynamically
unfavorable compared to OER, and the difference between the
standard electrode potentials increases with an increase in pH
value until hypochlorite formation, where it remains at the
maximum value of 480 mV.28
Several researchers have focused on undesirable chloride
oxidation reactions during seawater electrolysis and suggested
that experiments performed at pH greater than 7.5 can restrict
the reaction. The severe challenge for seawater electrolysis is the
presence of ions that can deactivate the membrane or
diaphragms present in electrolyzer assembly.30 Some of the
direct seawater electrolyzers show a short lifetime (a few
hundred hours), whereas ultrapure water with NaCl as an
additive did not meet industrial standards with a life span of
more than 60,000 h.
3. ELECTROCATALYSTS FOR SEAWATER
ELECTROLYSIS
The chloride ions in seawater reduce the efficiency of OER
catalysts and also produce chlorine damaging the electrodes.
Many OER catalysts have been explored including transition
metal oxides and hydroxides, metal phosphides, metal nitrides,
and metal borides.31 The main problem for cathodic HER
reactions due to the presence of chloride ions in electrolytes is
the blockage and corrosion of active sites, which results in a
reduction in the efficiency and stability of the electrocatalyst.
The efficient electrocatalysts for better HER activity in seawater
include noble metal alloys,32 carbon-supported noble metals,
Mxene-based complexes, metal phosphides, metal oxides and
hydroxides, and metal nitrides. The electrochemical perform-
ances of various electrocatalysts for seawater electrolysis are
represented in Table 2.
3.1. Performance Evaluation of Electrocatalysts.
Electrochemical water splitting has to overcome the energy
barrier resulting from high activation energy to form reaction
intermediates and drives the electron transfer process at an
optimum rate. Electrocatalysts play prominent roles in lowering
the kinetic barrier but do not lead to any change in
thermodynamic equilibrium.46 The performances of electro-
catalysts can be determined on the basis of important properties
13422
metals for catalyst synthesis is mainly attributed to the
adsorption parameter, which is related to key parameters such
oxygen covalent bond structure, p-band center of oxygen atoms,
and more that define the HER and OER activities.49
3.1.1. Activity. According to the Nernst equation, the
thermodynamic potential required for electrolyzing water at a
temperature of 25 °C, pH 0, and 1 atm pressure can be
calculated as 1.229 V, but due to the energy barrier, the actual
potential is greater than the thermodynamic equilibrium
potential. The excess potential required to initiate the electron
transfer process is overpotential, which defines the catalyst
activity.50 The large overpotential is mainly due to the slow
oxidation and reduction reaction kinetics at respective electro-
des.51,52Equation 20 gives the equilibrium potential for the
electrochemical water-splitting process, where Eeq is the
potential under equilibrium conditions, T the temperature in
Kelvin, F the Faraday constant, and n the number of moles of
electrons, and [Ox] and [Red] are the concentrations of
oxidation and reduction species, respectively.
Eeq(NHE) = RT/nFlog[Ox]/[Red] (20)
As the electrode potential changes with pH, reversible
hydrogen electrodes have been widely used as reference
electrodes at 25 °C as given by eq 21:
Eeq(RHE) = [Eeq(NHE) + (0.059 × pH) = 1.23 V (21)
The cell potential can be obtained by following eq 22, with ERHE
(cell potential), Etest as applied potential, and E0 as standard cell
potential
E RHE = [Etest + E0 + (0.059 × pH)] (22)
The overpotential value at a current density of 10 mA/cm2
should be small to be considered an effective electrocatalyst.
Tafel slope and exchange current density are other two key
properties to assess the activity of the electrocatalyst from
overpotential vs current kinetics represented by equation η = a
+b log j, where η refers to overpotential, and j is the current
density. The linear correlation in the Tafel plot determines two
important kinetic parameters which are Tafel slope b and
exchange current density (jo) at zero overpotential. The Tafel
slope defines the electrochemical behavior between the catalyst
and the reactants, where a lower slope implies good electro-
catalytic kinetics that corresponds to the fact that a small
https://doi.org/10.1021/acs.energyfuels.2c02013
Energy Fuels 2022, 36, 13417−13450
Energy & Fuels
increase in overpotential leads to a large increase in the current
density.
3.1.2. Stability. In industrial applications, the stability of an
electrocatalyst is always a key parameter to evaluate the potential
for usage in long-term water electrolysis experiments. There are
two different characterization techniques available for analyzing
the stabilities of electrocatalysts, namely, chronoamperometry
and chronopotentiometry. Both these experiments analyze the
charge transfer process with time at a constant potential or vice
versa. The longer period for which the potential or current is
consistent, the better is the stability of the catalyst. Another
characterization technique is cyclic voltammetry, which
calculates the amount of charge mobility by introducing several
potential cycles and usually requires more than 5000 cycles at a
particular scan rate. Linear sweep voltammetry is also used to
determine the overpotential deviation after performing cyclic
voltammetry analysis; a smaller overpotential shift implies better
electrocatalyst stability.53
3.1.3. Efficiency. The quantitative parameter that defines the
efficiency of electron mobility for the electrochemical reaction is
Faradaic efficiency. This is the ratio of experimental hydrogen
(oxygen) production to theoretical hydrogen (oxygen)
production. The theoretical production rate can be obtained
by the integral of chronoamperometric or chronopotentiometry
analysis, whereas the experimental rate is obtained by downward
displacement of the water technique or gas chromatography
method. Another useful parameter for describing the rate of
reaction in terms of reaction active sites is the turnover
frequency (TOF). The general number of reactant molecules
that can be converted to desired products per active site of the
catalyst per unit of time is determined to find the efficiency of the
catalyst.
4. ADVANCED 2D NANOMATERIALS FOR WATER
ELECTROLYSIS
The semiconductor-based nanomaterial is a promising
candidate for water electrolysis processes, because of the
required band gap and large surface-to-volume ratio. They
have acquired major attention from researchers and scientists
since the discovery of graphene.54,55 They have been working on
new combinations of materials to develop several types of 2D
nanoparticles based on the DFT (density function theory)
formulation. The tools present in the DFT code can manipulate
several properties of nanomaterials to verify the performance of
any application. DFT utilizes electron density values to find the
total energy, and lowering the energy of a system implies more
stability and vice versa. Recent advancements include the
development of 2D metal dichalcogenides (TMDCs) that are
structurally represented as MX2 (where M is a transition metal,
and X = S, Se, and Te), which have grasped outstanding
recognition due to their distinctive structural property and huge
chemical diversity.56,57 The relatively high charge carrier
mobility in TMDCs has led to new avenues for employing
these materials in various applications. The design of electro-
catalysts with low cost, high catalytic activity, good stability, high
specific surface area, corrosive resistance, and inertness in
different electrolytemediums are mainly responsible for
industrial-scale hydrogen production at optimum energy
consumption as shown in Figure 7. There are many transition
metal-based electrocatalysts (Co, Fe, Ni, Cu, Mn, and Al) that
have been synthesized for water splitting, and their derivatives
such as chalogenides, carbides, nitrides, phosphides, and layered
double hydroxides have been intensively studied for better
pubs.acs.org/EF Review
Figure 7. Key properties of an efficient electrocatalyst for water
electrolysis
catalyst activity.58 However, the catalyst durability and perform-
ance are not ideal compared to noble metal-based electro-
catalysts.59
2D nanomaterials have gained considerable interest due to
their novel properties like mechanical strength, chemical
stability, high surface-to-mass ratio, and wide range of
bandgaps.60,61 In addition, these have a great potential to
restrict the passage of ions through the metal interface, which
extends their application in seawater electrolysis. These
materials can be used as surface coatings on metal substrates
because of their highly impermeable nature even for the smallest
atoms like helium. Layered double hydroxides are typical 2D
materials with enormous advantages like highly tunable
composition, structure, and morphology and good corrosion
inhibition capability. During seawater electrolysis, chlorine and
oxygen gases are released at the anode and hydrogen at the
cathode, and LDH materials help in resisting the oxidation of
metal surfaces by trapping the ions in the interlayer so that
harmful gases like chlorine are not evolved during the hydrogen
production process.
4.1. Graphene and Its Derivatives. Graphene is typically a
monatomic layered structure composed of carbon atoms aligned
in a hexagonal lattice arrangement.62 The hexagonal structure of
carbon atoms is sp2 hybridized, which comprises three in-plane
strong sigma bonds (σ) and one pi bond (π) normal to the
planar geometry. The π-bond allows structural rearrangement of
graphene to graphite, which has multiple layers of graphene
connected by van der Walls forces of attraction.63 Graphene is a
semiconductor-based nanomaterial with a narrow band gap,
mobile charge carrier, and ionic conductivity.56 Graphene is
almost 100 times harder compared to steel in thickness.64
Transparent graphene has a visible light absorption capacity of
2.3%, and the transmission rate is 97.7% out of the entire
incident irradiation.56 This unique optical parameter suits the
adaptability of a catalyst in photoelectrochemical (PEC)
systems as most of the incident light on the photocatalyst and
electrode is hugely unimpaired. In addition to that, the 2D
structural assembly is mainly responsible for the entire surface
area of carbon atoms to participate in chemical reactions.65
Graphene has a high exposed area of 2630 m2·g−164,45 and
electronic mobility of 200,000 cm2·V−1s−1,64 and coupled with
its structural morphology performs better in photoelectrochem-
ical processes, specifically for HER. Table 3 briefly describes
different graphene-based electrocatalysts used for hydrogen
production and their performances in different electrolytic
mediums. The graphene-based nanomaterials are found
beneficial for seawater splitting due to their higher mechanical
strength, better physical and chemical properties, and good
corrosion resistance property; thus, many research activities
were being performed on water desalination techniques such as
capacitive deionization, solar steam generation, and nano-
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Table 3. Different Graphene Derivatives Based on Electrocatalysts for Hydrogen Production

Sr. No. Electrocatalyst Electrolyte Overpotential (mV) Tafel slope (mV/Dec) Ref
1 rGO/CoP-Rh-2.5 0.5 M H2SO4 72 43 68
1 M KOH 155 101
2 GO@Ni-Cu@ NF 1 M KOH 70 57 69
3 Pt@GO@Ni-Cu@ NF 1 M KOH 31 51 70
4 Ni-GCS-2 1 M KOH 205 111 71
5 CG-3 1 M KOH 360 107.5 72
6 G-INSCP 0.5 M H2SO4 95 67 73
7 CoRu@NG-3 1 M KOH 62 90 74
0.5 M H2SO4 52 65
8 MoS2 NFs/rGO 0.5 M H2SO4 190 95 75
9 MoS2-CNF 0.5 M H2SO4 207 60 76
10 N-GCSs/CC 0.5 M H2SO4 320 198 77
11 RuO2 NRs/C 0.5 M H2SO4 99 99.4 78
12 MoNiS@NiS/CC 0.5 M H2SO4 33 80 79
1 M KOH 68 136
13 S/N-CLs 0.5 M H2SO4 75 73 80
14 PS/MoS2 NS 0.5 M H2SO4 154 71 81
15 Mo2C/CNT-Graphene 0.5 M H2SO4 62 58 82

Table 4. Phosphorene-Based Electrocatalysts for Water Splitting

Sr. No. Electrocatalyst Electrolyte Overpotential (mV)at 10 mA/cm2 Tafel slope (mV/Dec) Ref
1 Co-BP 0.5 M H2SO4 294 107 91
2 Mo-BP 0.5 M H2SO4 522 112 91
3 Ni-BP 0.5 M H2SO4 691 116 91
4 PtRu NCs/BP 1 M KOH 22 19 92
5 NH2-BP NSs 1 M KOH 290 63 93
6 EBP@NG(1:4) 1 M KOH 125 76 94
7 BP/PB-PN 0.5 M H2SO4 148 79 95
8 MoS2-BP 0.5 M H2SO4 85 68 96
9 Ni2P/BP 0.5 M H2SO4 185 81 97
10 MoSe2-BP 0.5 M H2SO4 380 97 98
11 BP/Co2P 0.5 M H2SO4 340 at 100 mA/cm2 62 99
12 BP/Co2P 1 M KOH 336 at 100 mA/cm2 72 99
13 BPQDs/MXene 1 M KOH 190 83 100
14 CoP-EEBP (CBP-3 composite) 1 M KOH 118 79 101
15 CoP-EEBP (CBP-3 composite) 0.5 M H2SO4 105 92 101

filtration. These nanoparticles are potential materials in
hydrogen production from seawater splitting as the demand
for clean water is increasing progressively.67
4.2. Phosphorene and Its Derivatives. Phosphorene is a
monolayered structure of black phosphorus, which has a close
resemblance to graphene.83,84 The tunable band gap, large
exchange capability of the carrier, and in-plane anisotropy are
some of the immense properties of phosphorene, which made
these nanoparticles an emerging material in electronic and
optoelectronic applications. Major disadvantages of phosphor-
ene catalysts are the probability of oxidation and moisture
absorption capacity during irradiation which limit the operation
in ambient conditions.85,86 Major research has been performed
on the antioxidation of phosphorene, but still, enhancing the
stability of phosphorene-based materials is yet to be a challenge.
Functionalization is done to phosphorene nanomaterials for
embedding additional properties alongside stability enhance-
ment.85,87 Another disadvantage is the synthesis of monolayer
phosphorene, which implies that decreasing the number of
phosphorene layers leads to a change in physical properties. An
experimental result determines that the band gap has been
increased to 2 eV for monolayer phosphorene when compared
13424
to 0.33 eV bulk black phosphorus.88 To synthesize nanomateri-
als with excellent photoelectrochemical activity, we should
prefer the preparation of phosphorene nanoparticles with a
minimum number of layered sheets, which is ideal to obtain
suspensions compared to black phosphorus.85,89 Currently, the
liquid exfoliation synthesis technique has been extensively used
to achieve minimum phosphorene nanosheets, which involves
successive sonication and centrifugation processes. Optimum
quality phosphorene nanosheets with the preferred size can be
synthesized by electrochemical exfoliation techniques. Different
phosphorene-derived electrocatalysts have been synthesized for
improving hydrogen production, and catalyst activity has also
been analyzed in various conditions as illustrated in Table 4. The
phosphorene-based derivatives are one of the potential
candidates in photocatalytic water electrolysis and energy
storage applications due to their unique performance character-
istics similar to carbon derivatives. Transition metal phosphides
are considered bifunctional catalysts for water electrolysis;
however, these materials are quite susceptible to corrosive
environments and used in electrochemical or photoelectro-
chemical (PEC) cells for hydrogen production. The phosphor-
ene-based derivatives are investigated thoroughly for electro-
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chemical, photocatalytic, fuel cell development, and super-
capacitor applications.90
Table 5 gives the comparative study related to the key
properties of graphene, phosphorene, and MoS2 electrocatalysts,
Table 5. Properties of Graphene, Phosphorene, MoS2104
Sr. No. Parameter Graphene Phosphorene
1 Band gap (eV) 0 0.3−2
2 Carrier mobility 2,00,000103 1000
(cm2·V−1·s−1)
3 On/off ratio 5.5−47 103−105
4 Effective mass 0 0.146 (1.246)
(me)
5 ZT 0 1−2.5
6 Thermal 2000−5000 36(110)
conductance
(W/m·K)
7 Critical strain (%) 19.4−34 27(30)
8 Poisons ratio 0.186 0.4 (0.93)
9 Young’s modulus 1 44(166)
(GPa)
which helps to analyze the performance characteristics for
different applications and also to modify the parameters as per
the industrial application. The carrier mobility is one of the key
parameters for determining the rate at which an electron/hole
can move through a solid/liquid electrolyte medium in the
presence of applied electric field,102 which helps to analyze the
rate of the electrochemical reaction and activity of catalyst.103
The photocatalytic performance of a photocatalyst mainly
depends on the electronic band gap energy of the semi-
conductor;66 however, an efficient photocatalyst should have
band gap energy lower than 3 eV for efficient utilization of
incident solar energy. There are some mechanical and thermal
properties indicated in Table 5 that help to analyze the
performances of catalysts in the presence of higher pressure and
temperature conditions at the industrial scale.
4.3. Mxenes and Their Derivatives. MXenes are 2D
transition metal carbides and nitrides denoted by Mn+1XnTx (n =
1, 2, 3), where M stands for early transition metals (3d−5d block
metals), X for carbon/nitrogen, and Tx for the surface functional
group.105 The design of MXene resembles its MAX phase
precursor; M atoms are embedded in closely packed arrays,
whereas X atoms are situated at the octahedral interstitial sites.
The monolayer of MXene consists of one X layer sandwiched
between two M layers. The overall structure of MXene is a
packed hexagonal structure; the ordering of M might change to
attain stability.106 MXenes have a wide range of applications due
to their remarkable properties like high specific surface area,
transition metal oxide availability, and tunable surface chemistry.
These nanomaterials can be used for energy-storing devices
(batteries, pseudocapacitors), desalination operations, tribo-
electric nanogenerators, sensors and chemical noses, and
conductive coatings. The Ti3C2 MXene-based nanostructure
can purify water through evaporation techniques with an energy
efficiency of 84% by trapping solar irradiation. The intercalation
of dimethyl sulfoxide (DMSO) into MXene structures allows
them to exfoliate stacked layers to sheet-like structures to have
MoS2
special characteristics such as flexibility and electrical con-
1.2−1.8 ductivity for their energy storage applications. The exceptional
200 property of MXenes for the conversion of muscular movements
106−108 to electrical power is due to their ability to accept electrons by
0.47−0.6 the incorporation of polymeric composites. MXene layered
structures also are used as highly electrically conductive coatings
0.4 on polymeric materials to withstand mechanical stretching or
52 bending. These MXene structures have additional exceptional
characteristics of sensing a low concentration of gases while gas
19.5−36
molecules are moving across the surface. The chemical
0.21−0.27
composition and porous structure of MXene help in tracing
270 ± 100
different gas molecules, which cannot be detected by the usage
of other materials.107 The electrochemical performances of
different Mxene-based electrocatalysts are shown in Table 6. Li
et al. synthesized heterostructured Ni(OH)2/Ni3S2/NF for an
electrode for efficient water splitting and exhibits lower HER and
OER overpotentials of 185 and 319 mV to achieve a current
density of 100 mA/cm2.108 Qian et al. developed nickel
decorated and nitrogen-doped carbon nanotubes (Ni-
NCNTs) using the hydrothermal synthesis method; however,
Ni-NCNT exhibits a lower HER overpotential of 378 mV at a
current density of 10 mA/cm2 and Tafel slope of 139 mV/
dec.109 Wang et al. designed Cu@CoP/Cu bifunctional
electrodes for water splitting in acid and alkaline mediums,
which exhibit superior performance to noble-based electrolysis
and achieve a cell voltage of 1.65 V to obtain 10 mA/cm2.110
Sapountzi et al. studied the activity and durability of a FeP
catalyst by using the facile impregnation synthesis technique of
an iron complex on a carbon support followed by phosphoriza-
tion for higher electrochemical activity.111
The exceptional physical and chemical properties of MXenes
(transition metal carbides) such as higher electrical con-
ductivity, large specific surface area, high functionalization,
hydroxide sites, and good mechanical stability reveal the
importance of these materials in seawater purification
techniques, and they also act as corrosion resistant materials
during electrolysis of wastewater/seawater to improve the
utilization of brackish water for hydrogen production
applications.112
4.4. Layered Double Hydroxides. LDHs are ion lamellar
crystals composed of three different structural parameters: (a)
cationic 0 layers, (b) anions at the interlayer gallery to maintain
charge neutrality, and (c) solvent used during synthesis.119−121

Table 6. Different MXene-Based Electrocatalysts for Hydrogen Production

Sr. No. Electrocatalyst Electrolyte Overpotential (mV) at 10 mA/cm2 Tafel slope (mV/Dec) Ref
1 Ti3C2Ox 0.5 M H2SO4 190 60.7 113
2 Ti3C2(OH)x 0.5 M H2SO4 217 88.5 113
3 Ti3C2Tx-450 0.5 M H2SO4 266 109.8 113
4 Mo2TiC2Tx-PtSA 0.5 M H2SO4 30 30 114
5 Pt/Ti3C2Tx 0.1 M HClO4 32.7 32.3 115
6 NiCo@Nb-Ti3C2Tx 1 M KOH 43.4 116 116
7 MoSe2/Ti3C2Tx 1 M KOH 95 91 117
8 Vs2/V2CTx 1 M KOH 164 47.6 118

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The LDH crystal structure is represented by a general formula of
[AcBZAcB], where c denotes metal cationic layers, and A, B, and
Z are anionic molecules. Figure 8 is the representation of a
layered double hydroxide structure in which carbonate and
nitrate anions are present in the interlayer space available.
Figure 8. Structure of layered double hydroxide.
The distance between the central parts of two immediate
layers is considered the base space portion available for the
accommodation of anions.9,122−125 The most remarkable
features of LDH nanomaterials are the homogeneous distribu-
tion of divalent and trivalent cations across the hydroxide
layered structure. The atoms with large ionic radii like Ca2+,
Cd2+, and Sc2+ seem to be inappropriate to form stable brucite-
like layers.126−129 The broad modification capability of LDH
includes different types of cations, molar ratios of M(II)/M(III),
and the nature of interlayer anion compensation, which helps to
develop different LDH particles of varying composition that
leads to synthesizing LDH nanostructured materials with
flexible key parameters.124,130−132 Besides, certain component
changes of M2+ and M3+ also yield LDH with attractive
properties. For example, transition metal-based LDH nanoma-
terials (Ni, Fe, and Zn) have exhibited better catalytic
properties.133−137 In addition to that, several layered triple
hydroxides with three cations were also investigated, where the
cation choice and the ratio introduced have major effects on
catalytic activity and specific surface area for specific
applications.138−141 The following table shows different catalysts
in the water electrolysis process. Table 7 gives electrochemical
analysis like cyclic voltammetry and a Tafel slope of different
electrocatalysts under alkaline medium, which help for better
understanding of the HER and OER performances of the
catalyst.
The LDH materials have numerous advantages such as
chloride binding activity, excellent OER activity, flexible
structural morphology, and high surface area, which are mainly
essential for overcoming the challenges during seawater
electrolysis. The incorporation of various organic compounds
in the interlayer gallery enhances the usage of LDH materials in
various research areas such as seawater splitting, hydrogen
storage, and fuel cell applications. The LDH nanoparticles are
also used as precursors for the development of several
bifunctional electrocatalysts such as transition metal nitrides,
sulfides, phosphides, borides, carbides, and mixed metal
alloys.130
The performances of various electrocatalysts for the HER and
OER activities were analyzed by using cyclic voltammetry and
linear sweep voltammetry under alkaline and acidic mediums
and are compared in terms of overpotential and Tafel slope
(obtained by plotting current density concerning overpotential)
as mentioned in Tables 8 and 9.
4.5. Advantages of 2D Materials. Several 2D nanoma-
terials have been synthesized after the discovery of graphene in
2004 to investigate the alluring electrochemical, mechanical, and
optoelectronic mechanisms, which are mainly responsible for
photocatalytic applications.60,173 Additional advantages of 2D

Table 7. Different Electrocatalysts for Water Electrolysis

Sr. No. Catalysts Electrolyte ηHER at j (mA/cm2) ηOER at j (mA/cm2) Tafel slope (mV/dec) Tafel slope (mV/dec) Ref
1 CoO3@C@NF 1.0 M KOH 42 (10) 96 (10) 56 89 142
2 NF/H-CoMoO4 1.0 M KOH 295 (10) − 91 − 143
3 NF/T (Ni3S2/MnS-O) 1.0 M KOH 116 (10) 228 (10) 41 46 144
4 N-CoS2/NF 1.0 M KOH 28 (10) 200 (20) 42.6 55 145
5 MoS2/NiS 1.0 M KOH 244 (10) 370 (10) 97 108 138
6 MoS2-Ni3S2HNRs/NF 1.0 M KOH 98 (10) 314 (10) 61 57 146
7 Ni3S2/NF 1.0 M KOH 189 (10) 296 (10) 89.3 65.1 94
8 MoS2/NiS2 1.0 M KOH 62 (10) 278 (10) 50.1 91.7 147
9 Ni3Se4@NiFeLDH/CFC 1.0 M KOH 85 (10) 223 (10) 98.6 55.5 148
10 CoSe@NiFeLDH/NF 1.0 M KOH 98 (10) 201 (10) 89 39 149
11 Co-Ni-Se/C/NF 1.0 M KOH 90 (10) 275 (30) 81 63 150
12 MoSe2/MXene 1.0 M KOH 95 (10) 340 (10) 91 90 151
13 CoP2/RGO 1.0 M KOH 88 (10) 300 (10) 50 96 152
14 (Ni0.33Fe0.67)2P 1.0 M KOH 214 (50) 230 (50) − 55.9 153
15 NF@Fe2-Ni2P/C 1.0 M KOH 39 (10) 205 (10) 30 52 154
16 NiCoP@NCNA/NF 1.0 M KOH 37 (10) 305 (50) 53.9 70.5 155
17 CoFeP TPAs/Ni 1.0 M KOH 43 (10) 198 (10) 65.3 42 156
18 Mo-NiCoP 1.0 M KOH 76 (10) 269 (10) 60 76.7 157
19 Ni3FeN 1.0 M KOH 45 (10) 223 (10) 75 40 158
20 Ni3N-NiMoN 1.0 M KOH 31 (10) 277 (10) 64 118 159
21 CoAl-Fe2N/Fe3N 1.0 M KOH 145 (10) 307 (10) 54 69 160
22 NiCo-nitrides/NiCo2O4 1.0 M KOH 71 (10) 183 (10) 41 54 161
23 EBP@NG 1.0 M KOH 125 (10) 265 (10) 76 89 162

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Table 8. Different Carbon-Based Nanomaterials for HER in Electrochemical Water Splitting

Sr. No. Catalysts Electrolyte Overpotential (mV) Tafel slope (mV/Dec) Ref
1 N-Gr 0.5 M H2SO4 490 116 163
2 Co-NGR 0.5 M H2SO4 49 79.3 164
3 C3N4@NG 0.5 M H2SO4 240 51.5 163
4 MoS2/Mesographene 0.5 M H2SO4 100 42 165
5 Co-Nx|P-GC/FEG 1 M KOH 260 115 166
6 MoSx/GO 0.5 M H2SO4 180 60.5 166
7 MoS2/GO 0.5 M H2SO4 107 86.3 167
8 Co-NGR 0.5 M H2SO4 49 79.3 168
9 GQD/Au 0.5 M H2SO4 140 78 169

Table 9. Different Electrocatalysts for OER in an Electrochemical Cell

Sr. No. Catalyst Electrolyte Overpotential (mV) Tafel slope (mV/Dec) Ref
1 Co-Nx|P-GC/FEG 1 M KOH 320 54 170
2 Ni-NGR 1 M KOH 380 60 171
3 S-g-C3N4 1 M (KOH + NaClO4) 290 120 164
4 g-C3N4/CNT 0.1 M KOH 370 83 172

Figure 9. Schematic of synthesis techniques of graphene.

materials involve different applications like energy storage
devices such as batteries, capacitors, sensors, and electro-
des.174,175 The following are several advantages of 2D
semiconductors concerning bulk counterparts in the context
of photocatalytic applications:
(a) Low-dimensional nanoparticles are preferred due to their
homogeneous distribution mechanism.
(b) More sphericity and high specific surface area are
necessary for electrolytic and hybridized components.
(c) Creating additional active reaction sites on the nano-
structure surface due to a large number of atoms is a key to
improved catalyst performance.
(d) Tuning of key functionalities is very easy in low-
dimensional nanoparticles.
(e) An ultrathin layer facilitates the charge carrier mobility to
reaction active sites at the surface, thus manipulating the
reshuffling of photogenerated charge and their segrega-
tion.
(f) Surface defects also modulate the absorption of specific
components to improve the activation mechanism.
13427
(g) Heterostructures, which are a combination of catalysts
and cocatalysts with high porosity, enhance the
absorption range of solar illumination and activity.
(h) Two-dimensional nanoparticles are appropriate for the
formation of heterostructures with 0D, 1D, and 3D
materials having different electronic states and also
develop novel materials with remarkable synergetic
mechanisms and excellent photoelectrocatalytic proper-
ties.
5. SYNTHESIS METHODS
5.1. Graphene and Its Derivatives. There are certain great
challenges to synthesizing graphene for industrial scale, which
are low capital cost, high stability, easy scale-up, and more yield
with better quality.176 Different synthesis techniques of
graphene involve top-down (destruction) and bottom-up
(construction) approaches. The top-down method includes
mechanical exfoliation,177 arc discharge,178 oxidative exfoliation-
reduction,179,180 liquid exfoliation,181,182 and CNT unzip-
ping178,183 which are used for isolation and delamination of
bulk graphite into few-layered arrangements. Usually, these
techniques yield good quality nanoparticles and have high scale-
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Table 10. Advantages and Limitations of Graphene Synthesis Methods.176

Sr. No. Synthesis methods
1 Mechanical Exfoliation
2 Arc discharge method
3 Oxidative exfoliation-
reduction
4 Liquid phase exfoliation
5 Unzipping of CNTs
6 Chemical vapor deposition
7 Epitaxial growth
8 Substrate-free gas phase
9 Template route
10 Total organic synthesis
Advantages Limitations
Uniform and nanosize graphene thickness fragmentation More reaction time consumption, high energy consumption
for residue elimination
Low-cost graphene, fine graphene layers (2−10) synthesis Energy-intensive nature and high precision in process control
Low synthesis temperature, high yield of GO Release of toxic gases (NO2), usage of expensive and toxic
chemicals like hydrazine during reduction, less surface area,
and poor electronic conductibility
High concentration of graphene products, single-layer Produces defects on its edges and basal planes during
nanosheets can be synthesized sonication process, optimization of parameters to reduce
defects is still lacking in the literature
Controlled thickness of graphene based on nanotubes Low yield, usage of expensive precursors and chemicals
High-quality graphene with low defects, large surface area, and High production cost, low throughput, high-temperature
highly interconnected structure operation, purification of residue catalyst, and transfer of
graphene consume more energy
Simple operation and production of high-quality graphene Lacks homogeneity, release of toxic gases like
(<1 wt % of O) polytetrafluoroethylene(C2F4), expensive process
Clean and high-quality graphene, high potential for industrial Removal of amorphous materials lacks comprehensive study
scale-up, cheaper precursors usage and still, more research to be done
High throughput, good quality, and well-defined structure, Tedious washing step and potential in destroying produced
highly controllable under mild conditions, produces stable graphene during template removal
single-layer graphene of 0.6 nm thick
High yield and quality graphene, layer thickness of 12 nm can Occurrence of side reactions and precise parametric control
be synthesized, stable dispensability

up, but there are certain drawbacks in obtaining a product with
compatible parameters and less yield and relying only on coarse-
sized graphitic precursors. The bottom-up techniques are a
combination of chemical vapor deposition (CVD),184,185
epitaxial growth,186,187 substrate-free gas-phase synthesis
(SFGP),188 template route,189 and total organic synthesis.190
These methods derive graphene from other sources of carbon
except graphite through atomic-sized precursors. The main
disadvantages of bottom-up methods are high production
capital cost and sophisticated operational setup. Figure 9 gives
a brief classification of different synthesis techniques available
for graphene-derived electrocatalysts for industrial applications.
As discussed earlier, there are various techniques for the
synthesis of graphene derivatives, but there are certain benefits
and limitations to their industrial adaptability. Table 10 gives a
comparison of several techniques and would be helpful to pick
the appropriate method for distinct applications.
5.2. Phosphorene and Its Derivatives. The main
challenge for the development of nanomaterials is the
fabrication of environmentally stable and large area phosphor-
ene.104 There are several exceptional techniques for obtaining
better quality phosphorene derivatives such as mechanical,
liquid exfoliation, and pulsed laser deposition, but certain
demerits in every method restrict its usage on a commercial
scale.191,192 Mechanical exfoliation is an effective synthesis
technique for cleaving bulk material into an ultrathin layered
structure.193,194 The black phosphorene layered structure is
interlinked by weak van der Walls attraction forces, which
explains that few-layered phosphorene can be obtained
mechanically by exfoliation.195 A thick flake of phosphorene
was formed through an exfoliation process using blue Nitto tape
to a 275 nm substrate of SiO2/Si and treated under O2 plasma
etching by an ICP-RIE system at optimized parameters.196,197
Pei et al.196 utilized 400 W ICP generator power and 30 W RF
bias power, with 30 sccm O2 flow at 10 mTorr pressure to obtain
a few single-layered phosphorene plasma etchings. Besides, lone
pairs of phosphorus atoms are responsible for phosphorene
structural and chemical stability, which implies that degradation
occurs under ambient atmospheric conditions.198,199 Another
alternative improved method of a fabricating technique involves
13428
faster and controlled synthesis of monolayered phosphorene by
a plasma-assisted method.198,200−202 In this technique, initially
few layers are mechanically exfoliated and then treated with a
plasma layer-by-layer etching process to obtain a better quality
of phosphorene. Lu et al.200 investigated using Ar + plasma
(commercial 13.56 MHz RF of power capacity 30 W and
pressure 30 Pa) to yield single-layered phosphorene by
modifying flakes of phosphorene. Jia et al.202 performed the
inductively coupled plasma technique (ICP) at 30 mTorr and
350 W power at 13.56 MHz for operating on tape exfoliated BP
flakes on the silica substrate. This combined synthesis procedure
extensively improves the controlling strategy of phosphorene
thickness and also restricts the oxidized phosphorene surface
degradation.202 Liquid phase exfoliation is dedicated to large-
scale ultrathin layered nanosheet production from the
conversion of bulk layered structures through electrostatic
repulsion in liquid solvents and matching surface energy in
organic solvents of the most prominent techniques for
commercial yield.203 Brent et al.204 obtained a high-quality
atomic layer of phosphorene through the liquid sonication
method. They performed sonication of bulk BP crystals with a
N-methyl-2-pyrrolidone (NMP) solvent (5 wt %) at 820 W
across four horns operating at 37 kHz frequency and 30% power
for 24 h and a bath temperature of less than 30 °C for the entire
sonication period by using a water jacket system. The final
dispersions were centrifuged to separate unwanted large flakes
and obtained pale yellow/brown dispersions of phosphorene.
Yasaei et al.205 performed experiments on different organic
solvents having a wide range of polar interaction parameters of
(2.98−9.3 MPa1/2) and surface tensions (21.7−42.78 dyn/cm)
to obtain a better phosphorene structure. Another famous
synthesis method that yields excellent quality phosphorene is the
chemical vapor deposition technique,206−208 but this is not
completely explored due to the complicated chemistry strategies
of phosphorus. Many researchers have been performing several
experiments for development of phosphorene in a large scale, so
that phosphorene can be a new emerging technology for
different applications like graphene and TMDs.209−212 Recently,
Li et al. designed a thin film BP of 4 nm thickness on a polyester
substrate.213 The BP can also be obtained from red phosphorus
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Table 11. Different Synthesis Methods of Phosphorene-Related Derivatives

Thickness
Sr. No. Synthesis method Precursor Operating conditions (nm) Ref
1 Mechanical exfoliation Black phosphorus (BP) Scotch tape on SiO2/Si 0.7−6 215
2 Hydrothermal Red phosphorus (RP), NH4F Teflon lined autoclave, 200 °C 3 216
3 Electrochemical exfoliation BP, platinum (Pt), Na2SO4 +7 V voltage was applied across the electrode for 1.5 h 1.4−10 217
4 Plasma-assisted exfoliation BP Ar + plasma at 30W, pressure of 30 Pa, 20 s 2−10 200
5 Liquid phase exfoliation BP/organic solvent/water/ Bath sonication for 24−48h/tip sonication for 2−4 h, centrifugation at 0.7−6 215
ionic liquids 1000−2000 rpm for 30 min
6 Chemical vapor deposition BP thin film over Si Tube furnace, 950 °C 3.4 218
(substrate) SnI4, Sn
7 Pulsed layer deposition BP KrF (λ, 248 nm; ν, 5 Hz), 150 °C, vacuum chamber Not 214
specified
8 Mechanical exfoliation- BP Scotch tape on SiO2/Si, curved PDMS 1.6−2.8 198
PDMS
9 Chemical vapor deposition RP thin film on a polyester High-pressure multianvil cell at room temperature 4 104
substrate

under high pressure and room temperature in a multianvil cell. fluoride ions for the synthesis of Ti3C2Tx layers. This layered
In addition, the poor crystal form of the BP film can be grown structure is quite unstable under an alkaline environment and
successfully on Si/SiO2 or graphene/Cu substrates via pulsed also initiates a corrosion reaction by etching of aluminum layers;
laser deposition using a BP crystal as the precursor.214 The thus maintaining the stability of synthesized carbide MXene
different key operational parameters for the synthesis of structures by proper etching of Al atoms is the major challenge.
phosphorene-based electrocatalysts to obtain the required 5.3.5. Other Techniques. There are several other methods
particle size based on different synthesis methods are explained available for the synthesis of high quality and high yield of
briefly in Table 11. MXenes such as chemical vapor deposition, pyrolysis, and wet
5.3. Mxenes and Their Derivatives. There are different etching followed by the stripping process. Xu et al.225 developed
synthesis procedures for MXene by forming bonds with M α-Mo2C layered structure by a chemical vapor deposition
atoms in the MAX phase and different end groups for method, which possesses a high specific surface area.220,226−229
minimizing the Gibb’s free energy of surface and building Different studies have been performed for developing efficient
coordination spheres. Modification of surface characteristics can synthesis techniques for MXene based on the structural
be done by using various etching techniques.219 morphology requirement.
5.31. HF Etching Technique. This traditional synthesis 5.4. Layered Double Hydroxides. There are several
method was proposed by Naguib et al.220 in 2011 for developing techniques available for the synthesis of LDH which includes
the Ti3AlC2MAX phase and removing Al layers by a displace- coprecipitation, hydrothermal synthesis, sol−gel method, anion
ment reaction that also generates hydrogen. This synthesis exchange method, urea synthesis, and in situ growth method as
procedure has become the most commonly used for many years, shown in Figure 10.
whereas etching time, temperature, and fluoride ion density are 5.4.1. Coprecipitation Method. This synthesis approach has
the key parameters for obtaining better structural morphology, become the most prominent process for distributing compo-
but usage of stronger acid may lead to surface defects and also nents of a reaction to form the desired material. This facile
reduce the yield of nanoparticles.221 This synthesis method
produces MXenes having surface structures with −F, −OH, and
�O functional groups.
5.3.2. Acid-Modified Etching. The excess usage of strong
acids may pose a corrosive problem, so researchers have decided
to substitute HF with fluoride salts (NH4HF2, LiF, NaF, KF, and
FeF3) and HCl.222,223 The intercalation of different cations
helps to increase in interlayer distance of MXenes, which in turn
leads to the reduction of interlayer forces and is advantageous for
the delamination process by a simple ultrasonic technique. This
synthesis method has an additional advantage of single-step
implementation rather than following multiple steps as in the
HF etching method.222
5.3.3. Molten F-Salt Etching. The Al bonds present in
nitride-based MXenes are stronger than carbide MXenes, hence
the introduction of molten fluoride salts (LiF, NaF, and KF) as
an etchant for the synthesis of Ti4N3Tx MXene. This method has
the drawback of poor crystallinity during the synthesis of carbide
2D materials, compared to the HF etching technique.
5.3.4. Non-F Etching. The fluoride-containing acids are quite
corrosive and toxic, and many researchers have adopted
alternative solutions for the etching process. Yang et al.224
performed experiments by using an electrolyte solution (1 M
NH4Cl and 0.2 M tetra-methylammonium hydroxide) without Figure 10. Types of experimental processes for LDH synthesis.

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Figure 11. Flowchart representing coprecipitation synthesis procedure.
Figure 12. Scheme demonstration of effect of different parameters on LDH synthesis by coprecipitation method.
Figure 13. Schematic of hydrothermal synthesis procedure of nanoparticles.
technique is used for the production of composite nanomaterials
through intermediate (hydrous oxide or oxalates) formation,
precipitation, and calcination yielding a uniform distribution of
chemical components.230,231 This synthesis methodology
includes the development of nanomaterials via nucleate
formation, growth of particles, and agglomeration occurring
concurrently. This coprecipitation process involves the mixing
of aqueous metallic salts in stoichiometric proportions at desired
temperatures with a precipitating agent.232,233 The main
advantage of this method is the smaller crystal size when
compared to other methods, depending on the precipitating
agent used. The crystalline size and morphological structure can
be varied by different capping agents.234 The following flow
sheet gives a brief explanation of the steps to be followed during
the coprecipitation synthesis method shown in Figure 11.
Different parameters can influence the LDH particle size such as
temperature, pressure, pH, stirring time, and concentration of
reactant. Figure 12 briefly illustrates the optimum parameters
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responsible for better yield of LDH by using this synthesis
method.
5.4.2. Hydrothermal Synthesis. This approach is one of the
most widely used techniques for the preparation of nanoma-
terials. The mechanism of the hydrothermal process is a
solution-reaction approach, which depends on the dissolution of
compounds in solution at higher pressure.235−237 The crystalline
structure development can be observed in a high-pressure
autoclave, where required nutrients are provided in solution
form. The stainless-steel chamber is designed to maintain
temperature change across the cross section, where nutrients
solubilize at the hotter end and deposit on seed crystals at the
cooler end until the desired crystal size is obtained. There are
several benefits of this synthesis methodology including the
capability to develop crystal structures that are unstable at the
freezing point and the formation of nanomaterials in a wide
range of temperatures.238,239 Materials of high volatility at a
melting point can be prepared with minimum loss of materials.
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The composition of nanomaterials to be synthesized can be well
controlled through a liquid phase or multiphase chemical
reactions.240 The schematic of the LDH synthesis procedure by
the hydrothermal method is shown in Figure 13.
5.4.3. Sol−Gel Method. This wet chemical technique is used
to produce an integrated crystal network by the use of a chemical
solvent or colloidal materials. Precursors such as transition metal
alkoxides and metal chlorides are preferred for colloidal
formation and distribution of nanomaterials in the liquid
phase through the hydration and polycondensation process.
The solution thus proceeds with building a continuous network
of inorganic phases including an aqueous phase and metal oxide,
which connects the oxo (M-O-M) or hydroxo (M-OH-M)
bridges with metallic centers, thus developing metal oxo or
hydroxo polymers in a solution. The liquid phase is separated
from the gel solution by a constant heat treatment process before
calcination that favors polycondensation and improves mechan-
ical strength. The synthesis procedure of the sol−gel method for
developing LDH nanoparticles is shown in Figure 14.
Figure 14. Flowchart of sol−gel synthesis procedure of LDH
nanoparticles.
5.4.4. Urea Synthesis. This synthesis technique for nanoma-
terials involves solutions of urea and required metal salts, which
are to be mixed uniformly in appropriate proportions and
heated. During this process, hydrolysis of urea takes place, and
carbonate and ammonia ions are released into the solution.240
The structural form of the nanomaterial is mainly due to the
nature of the basic solution which is continuously raised to pH 9,
where precipitation of metal hydroxides occurs or layered
double hydroxides form due to the presence of more than one
metal salt. Layered double hydroxide with an intercalated
carbonate anion can be synthesized by these urea techniques.127
Table 12. Comparison of Different Synthesis Techniques of LDH
Synthesis methods Advantages
Coprecipitation • Easy synthesis methodology
• Adjustable composition
• Usage in powder form for paints and epoxies manufacture
Hydrothermal • Good crystalline structure
• Preferable thickness of coating
• Powder and film formation
In situ growth • Easily synthesized
• Strong interactions
Anion exchange • Simple operation
• Good exchange capability of anions
Urea hydrolysis • Easy and simple operation
Sol−gel • Good uniformity and high purity
• Low-temperature operation
• Coatings and fibers can be prepared
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5.4.5. In Situ Growth Method. This method has been
extensively investigated to design membranes or films of
different inorganic particles like zeolites, ZnO, and TiO2. This
synthesis methodology has the advantage of strong bonding
between the substrate material and film when compared with
other deposition methods due to good chemical bond
interactions between the two phases.241,242 Besides, this method
is not restricted to the substrate shape, which helps to widen
application areas. Several materials have been investigated as
substrates to develop LDH films through in situ growth.
5.4.6. Anion Exchange Method. This technique is mainly
used for exchanging anions in the interlayer structure of LDH
nanomaterials with other representative anions. This method
involves intercalation of preferable ions in already synthesized
LDH by constant stirring in the solution. Furthermore, this
synthesis process is used when the coprecipitation technique
fails for the formation of nanomaterials effectively. The anion
exchange method is the most feasible method when metal ions
tend to be unstable in an alkaline medium or there is an
opportunity for reacting cations with interlayer anions.243,244
Nitrate anions have been included in the layered double
hydroxide structure as they can be easily interchanged due to less
binding energy, with several inorganic and natural anions as per
application.127Table 12 gives the comparative study for LDH
synthesis techniques available which might help choose an
appropriate technique and also describes the limitations for
industrial scale-up.245,246
6. RECENT ADVANCEMENTS IN WATER
ELECTROLYSIS
6.1. Photoelectrocatalysis. Seawater electrolysis poses
many problems due to the presence of different ions, so the
membrane used for the migration of ions can be deactivated.
The membrane-based challenges can be overcome by using
photocatalytic splitting of water. Ji et al. studied photocatalytic
seawater splitting by using a La2Ti2O7 suspension under
ultraviolet light, CdS/TiO2 suspension under visible light, and
Fe2O3 film under photoelectrochemical conditions; however,
there no chlorine evolution has been detected.247 Maeda et al.
and Dresp et al. developed different cocatalysts like (Ga1‑xZnx)-
(N1‑xOx) with either Rh2‑yCryO3 or RuO2 nanoparticles for
natural seawater electrolysis under visible light conditions (λ >
400).248,249 There are many technologies for solar energy-based
Disadvantages
• Weak interactions
• Low crystallinity
• More time consumption
• Adaptability complexion
• High-temperature treatment
• Requires more time
• High energy operation
• Precursor used is substrate material
• Less crystallinity
• Time management is more
• Only used for synthesis of carbonate intercalated LDH
• Long processing time
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water splitting for the production of hydrogen fuel; however,
photoelectrochemical water electrolysis is one of the promising
technologies and utilizes photoelectrodes for absorbing solar
energy and converting it to chemical energy.250
The efficient electrolysis process is defined by the narrow
band gap of the photoelectrocatalyst and high electronic charge
mobility.251,252 The catalysts should possess a band gap of 1.23−
3.0 eV in the visible light spectrum for efficient hydrogen
production. Thus, appropriate band gaps and suitable positings
of the conduction band (CB) and valence band (VB) are
necessary to meet the oxidation and reduction potential energy
requirements for the water electrolysis process.253,254 Therefore,
a photoelectrocatalyst with an appropriate bandgap and band
alignment is necessary for water electrolysis.55,255 A photo-
catalyst with low cost and high efficiency can help in the light
harvesting and facile charge transfer process during the
photocatalytic process.256 Hydrogen production in a photo-
electrochemical (PEC) cell shown in Figure 15 explains the
Figure 15. Schematic representation of photocatalytic water-splitting
mechanism.
phenomena of photocatalytic activity for hydrogen and oxygen
evolutions from water by using solar light illumination. The
principle of PEC hydrogen production is the conversion of solar
irradiation to electricity and then utilization for H2 generation.
This process uses a strongly acidic or basic electrolyte solution
for minimizing voltage losses. Hence, the development of highly
efficient photocatalysis may increase the efficiency of green
hydrogen and decrease the cost by adopting the photo-
electrochemical techniques and will make a great contribution
to the hydrogen economy.
6.2. Mechanism of Photoelectrochemical Water
Electrolysis. The photocatalytic electrolysis of the water
mechanism involves four steps: (1) generation of electron−
hole pairs due to irradiation of light on a photoanode, (2)
oxidation of water by photogenerated holes on the surface of a
photoanode to produce O2 and H+, (3) photogenerated
electrons transferred to the cathode by an external circuit, and
(4) a reduction process of H+ by photogenerated electrons at the
cathode surface to produce H2. The water electrolysis process
occurs only when the practical potential is higher than the
minimum potential value to minimize system loss and overcome
overpotential. The hydrogen production process involves two
half-cell reactions, namely, HER and OER, which require voltage
for semiconductors generated from sunlight via photovoltaics.
The first step in the conversion of sunlight and water to
hydrogen and oxygen fuels is light absorption. The incident light
fraction helps for the generation of charge carriers based on the
optical properties of the absorber material, but this is affected by
device design and other cell components, which cause optical
losses due to absorption or reflection losses. There are also
different techniques used for enhancing light absorption such as
plasmonic nanoparticles and resonance (constructive interfer-
ence) in thin films. The photons are absorbed to excite the
electrons present in the valency band (low energy state) to the
conduction band (high energy state), which creates an
electron−hole pair in the photoanode. The holes present at
the electrolyte interface drive OER at the anode, whereas the
electrons at the electrode surface move toward the external
electrical circuit for driving HER at the cathode surface. The
electron−hole pair recombines either in the bulk of the
semiconductor or at the electrolyte interface. The operating
cycle is completed by the transport of ions in the electrolyte and
by the continuous supply of water and removal of gaseous
products (H2 and O2).257Table 13 gives information regarding
hydrogen production using graphene composites for the
photoelectrochemical water-splitting process.
6.3. Factors Affecting Photoelectrocatalyst Activity.
6.3.1. Layer Thickness Reduction. Ubiquitously, modification
of layer size to the single-layer limit is one of the suitable
approaches toward catalyst parameter tuning, because of the
enhanced active surface and quantum confinement effects. A
decrease in photocatalyst (semiconductor) thickness has shown
conspicuous effects on the activity, broadening the band gap of
the material.268−270 For example, ultrathin layers of C3N4 NSs

Table 13. Photocatalytic Hydrogen Production by Using Graphene-Based Nanocompositesa

Sr. No. Photocatalyst Synthesis Energy source H2 production Ref
1 RGO-Pt-TiO2 Step wise SS (AM-1.5G) 1075.68 μmole·h−1·g−1 258
2 GR-CdS Solvothermal 300W Xe lamp 175 μmole·h−1 259
3 GO reduced TiO2 Laser ablation in liquid SS (AM-1.5G) 16 mmol·h−1·g−1 260
4 GR-Au-TiO2 Hydrothermal and photodeposition 450W Hg lamp 1.34 mmol 261
5 GR-MoS2-ZnS Hydrothermal 350W Xe lamp 2258 μmole·h−1·g−1 262
6 GR-Au-TiO2 Microwave-assisted hydrothermal LED lamp (420 nm) 296 μmole·h−1·g−1 263
7 RGO-TiO2 Sol−gel 500W Xe lamp 8.6 μmole·h−1 264
8 g-C3N4 + graphene Impregnation-chemical reduction 350W Xe lamp (>400 nm) 0.451 mmol·h−1·g−1 265
9 CdS-thiolated graphene Hot injection 300 W Xe lamp (>420 nm) 29.655 mmol·g−1·h−1 266
10 EosinY + NiSx/graphene In situ chemical deposition 300 W Xe lamp(>420 nm) 12.378 mmol·g−1·h−1 267

a
GR, graphene; RGO, reduced graphene oxide; LED, light emitting diode; SS, solar simulator.

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Figure 16. Effect of bandgap on hydrogen generation technique.
exhibit a band gap of about 2.86 eV, which is more than its bulk
material of 2.7 eV.271 Likewise, exfoliated few-layer black
phosphorus (BP) NSs have an increased band gap, compared to
that of bulk material of ∼0.34 eV. Monolayer (ultrathin) BP
(referred to as phosphorene) exhibits a large band gap of ∼2
eV.272 Phosphorene emphasizes improved light absorption
capability as its band gap deviates to the visible spectrum range.
Besides, the ultrathin layers possess high charge separation and
exchange operations along with a long lifespan of photo-
generated carriers, in contrast to their bulk forms.84 As discussed
earlier, the band gap is the key parameter for effective hydrogen
production by light illumination on photoelectrochemical
catalysts. The phenomena of electron transfer in photo-
electrochemical catalysts from one state to another by absorbing
energy from the light source are shown in Figure 16.
6.3.2. Importance of Functional Groups. Photoelectroca-
talysis is generally a surface phenomenon, engineering nano-
particle surface areas improves the performance of catalysts.
Several ultrathin photocatalysts have a high surface area and
terminate with various functional groups that are coordinated.
Hence, simple chemical treatment methods can anchor different
molecular structures on the surface and allow modification of
surface properties through which the structure and charge of a
material can be manipulated as per specifications. Furthermore,
this resilient property allows composition modification at the
surface and provides advantages to developing excellent
properties at the interface geometry. Graphene oxide (GO),
nitrogen-doped GO, and reduced graphene oxide (r-GO) are
typical examples of previously reported experiments. Graphene
derivatives mainly comprise oxygen-based functional groups like
carboxyl, epoxy, and hydroxyl compounds along with edges and
basal planes.273 Furthermore, graphitic carbon nitride (g-C3N4)
is a nonmetallic conjugated polymer system consisting of
different functional groups with H-bonding interactions, and the
electron donor mechanism plays a key role in catalysis.
Functional groups are mainly responsible for the interaction
with target species (H2O and CO2) during photoelectrochem-
ical reactions. The pyrometallic dianhydride functional group
with electron deficiency mainly influences the electronic band
edge positions of g-C3N4.274 Besides, surface charges also affect
directly the efficiency of photocatalysts.273 For instance,
negatively charged species (anionic) between the layers of
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LDH are being supported by the positively charged (cationic)
surface.273,275
6.3.3. Doping of Foreign Atoms. Another effective way for
band gap tuning of 2D semiconductor-based photocatalysts is
doping foreign elements. Generally, the surface portion of the
catalyst is utilized for synthetic foreign element doping, but the
introduction of dopants in the bulk core is very rare compared to
the surface, which implies uncertainty in the distribution of
dopant molecules throughout the nanoparticle structure.
However, an ultrathin photocatalyst layer with a high surface-
to-volume ratio exhibits uniform dispersion of foreign atoms.
Besides, the availability of a few layers of nanomaterial can help
dopants penetrate the nanostructures of layered particles.
Dopants can shift the localized electron sites in the interdicted
band gap regime and also provide shallow electronic sites near
the valence band maximum position (VBM) or conduction band
minimum (CBM).276 In addition, this technique also plays a
crucial role by creating defects in a lattice structure, which
enhance the efficiency of the photocatalyst. During the doping
process, some atoms can elude from the layer creating holes on
the surface that reduces the coordination numbers of atoms
available on the surface. These vacancies generate defective sites
in DOS and deflect the absorption edge spectrum from the UV
range to the visible light region, which has a strong influence on
the electronic structure of two-dimensional semiconductors
interlinked by van der Walls forces. Oxygen concentration may
enhance the population of DOS near the conduction band
minimum and affect the carrier densities and photocatalytic
conductivities of semiconductors.
6.3.4. Heterostructures Formation. Pristine 2D materials
have emerged as the most feasible candidates for conversion of
solar to chemical energy over other-dimensional nanostructures
due to their high exposed surface areas, electron density of state
spectra, unique thickness-dependent properties, and adaption to
different geometries. However, the major disadvantage that
limits potential application is a short life span mainly due to the
presence of many surface atoms and less coordination
responsible for recombination sites of photogenerated car-
riers.172,277 Two-dimensional nanostructures have significantly
large binding energies compared to their bulk counterparts
because of their reduced electronic screening mechanism that is
undesired for photocatalytic activity.172 In many situations, the
oxidation and reduction potentials for water electrolysis and
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CO2 reduction are not appropriate for band edge positions.278
Furthermore, most nonoxide-based semiconductors are prone
to oxidation; thus, stability is another problem during
experimental conditions like illumination and electrolyte
solution. To enhance the photocatalytic efficiency by over-
coming various challenges, a photocatalyst could be coupled
with appropriate other-dimensional materials by designing
several kinds of heterostructures.254 Hybridizations among
different heterostructures such as semiconductor−metallic
arrangement and semiconductor−semiconductor−metallic
composite materials help in the development of interfaces
with exceptional functionalities. In addition, the heterostructure
layers exhibit an increase in solar illumination capturing
capacity, high charge division, and long lifespan of photon-
induced hole−electron pairs.254,277,279 Furthermore, hybrid
structures result in the reduction of agglomeration which
improves durability and corrosion resistance. Exfoliated self-
assembly of hybrid species with a layered structure is modified to
stacked structural species, which results in the formation of a
nanohybrid configuration.275 The hierarchical porosity of this
configuration can enhance the capability of light capture and
photocatalytic activity. Different heterostructure cocatalysts
have been synthesized and investigated for photocatalytic
activity. All these two-dimensional interfacial structures yield
better results due to the high exposed surface area, more reaction
sites, and efficient charge mobility.275 Furthermore, the interface
between different 2D materials possesses a large contact area for
the high separation of charged species. Besides, these structures
also have the advantage of more reaction-active sites that
enhance energy conversion efficiency.
6.3.5. Defective Engineering of Materials. Defects in 2D
materials also play a significant role in photocatalytic water
electrolysis and CO2 reduction processes. The intriguing key
parameters of semiconductors, namely, stable structural arrange-
ment, electronic DOS manipulation, electrical resistivity,
coordination number of metal atoms, and carrier charge density
can be modified significantly as per our application. Different
surface defects in two-dimensional photocatalysts like ionic
vacancies and their benefits are discussed briefly.280 Here, we
discuss several experiments related to defective engineering of
2D semiconductors for green hydrogen production and solar
fuels from CO2 reduction through photochemical experiments.
Huang et al.281 developed a single unit cell of Bi2WO6 that
stabilizes in [BiO]+−[WO4]2−−[BiO]+ units, which has a
sandwich-like structural assembly. The single layer of Bi2WO6
is observed to have a structurally stable arrangement with more
“W” vacancies in the internal portion. This defective structural
array exhibits enhancement in illumination capturing capacity
and improved photogenerated charge carrier transport, which
significantly increases the activity of photocatalysts. Calcination
of bulk graphitic carbon nitride (BGCN) at high temperature
under a NH3 atmosphere produces holey graphitic carbon
nitride (HGCN) nanostructures with carbon vacancies in the
form of abundant planar holes. The porous HGCN NSs exhibit
an enhancement of the hydrogen evolution process282 which
was raised by a margin of 20 compared to BGCN and possesses
much superior activity than 3D-porous g-C3N4. Highly exposed
surface area, high donor concentration, longer lifetime, and
remarkable high separation efficiency of photon-generated holes
and electrons result in enhancement of photocatalytic activity of
HGCN. Besides, protonated porous graphitic carbon nitride
nanosheets (P-PCNNS) have an exceptional quantum yield of
6.1% at 420 nm and long durability. This behavior is mainly
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attributed to mesoporous structural morphology having a large
number of reaction active sites, recombination reduction, and an
increase in charge carrier mobility. Furthermore, the activity of
P-PCNNS was far superior to bulk g-C3N4 and C3N4 NS.283
Similarly, the porous metal sulfide Zn0.5Cd0.5S NSs,284 cyano/
hexagonal boron nitride (h-BN) heterojunction NSs,285 and
TiO2/g-C3N4 (2D/2D) heterostructure286 exhibits efficient
hydrogen production from the photocatalysis process.
Porous 2D NSs of Co3O4 were also been investigated for
photocatalytic CO2 reduction applications. The Co3O4 NSs
exhibit a certain increase in reduction of CO2 to CO and H2
selectively. The photoactivity can be significantly improved due
to the well-developed porosity of high surface area and more
activation sites when compared to bulk material, which has more
affinity toward capturing carbon dioxide. Moreover, enhance-
ment of the charge separation mechanism leads to a reduction of
diffusion length owing to this structural morphology. Density
functional theory calculations show that a higher adsorption
capacity of Co3O4 NSs is observed because the energy of
adsorption is very less compared to bulk Co3O4.287 Another
emergent heterostructure developed between MXene (Ti3C2)
and Bi2WO6 through an in situ growth mechanism was also
studied by Peng et al.288 Hence, the Ti3C2/Bi2WO6 composite
exhibits 4- and 6-fold conversion rate enhancements of CH4 and
CH3OH, respectively, under solar light illumination.
6.3.6. Cocatalyst Modification. Another extensive strategy
for photocatalytic activity enhancement is the combination of a
cocatalyst with photocatalyst. Here, graphene, modified
graphene, tin-based metal chalcogenides, and MXene act as
electron acceptors or mediators (cocatalysts) for the efficient
separation of photoexcited charge carriers for water electrolysis
and CO2 reduction due to their unique structural morphologies
and high electrical conductivities.128,289,290 Besides, ultrathin
sheets of these materials have several advantageous properties
like more coordinated atoms and a highly exposed surface.
Moreover, 2D cocatalyst-based composites help in the improve-
ment of photocatalytic performance and also enhance durability
in solar illumination and electrolytic conditions.291−295 The
development of a cocatalyst helps in the compatibility of
electronic band structures of the catalyst and cocatalyst and
several issues with experimental conditions. The interfacial
charge transfer is mainly dependent on the performances of
interface electronic sites. Here, we summarize a few recent
developments of cocatalyst materials (MXene and graphene-
related materials) alongside 2D photocatalysts for photo-
catalytic hydrogen generation from water electrolysis and CO2
reduction to valuable fuels. For instance, a novel 2D/2D
heterojunction of MXene (0.5 wt % Ti3C2)/MoS2 has been
studied139 for the photocatalytic hydrogen evolution reaction
(HER). The heterojunction (0.5 wt % Ti3C2/MoS2) possesses a
hydrogen generation rate of ∼380.2 μmol·h−1·g−1 and is an
excellent activity as compared to the individual systems. In
another report on the production of solar fuels like CH4 and
CH3OH from the conversion of CO2, a novel heterojunction of
Ti3C2/Bi2WO6 was synthesized and examined.296 The compo-
site has CH4 and CH3OH production rates of 1.78 and 0.44
μmol·h−1·g−1; however, this total production yield was 4.6 times
more than that of pristine Bi2WO6 nanosheets. A few recent
reports of different cocatalyst/catalyst composites or hetero-
junctions are also reported in the literature such as Ti3C2/ZnS or
Ti3C2/ZnxCd1‑xS nanoparticles and BiVO4@ZnIn2S4/Ti3C2
MXene quantum dots (QDs)297 for H2 production.298 In a Z-
schemed-based photocatalyst (BiVO4/metal sulfides/r-GO), r-
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GO functions as an electron mediator for overall water
electrolysis and CO2 reduction.299
6.4. Corrosion Resistance Mechanism. Researchers
across the globe focused on post-treatment of LDH by anion
exchange for intercalation of respective aimed species
responsible for corrosion studies.300 The different factors
responsible for the corrosion resistance mechanism are
discussed in Figure 17.
Figure 17. Factors responsible for corrosion resistance.
The anionic exchange of LDH is based on different key
parameters like electrostatic and hydrogen bonding between
mixed metal hydroxide layers and interspatial anions.301 There
are also certain parameters to be taken into consideration before
performing the anion exchange process; affinity between the
anions and hydroxide layers is one of them.302,303 Scientists have
claimed that the equilibrium constant for an anion exchange
reaction is inversely proportional to the radius of the bare anion,
which means that the smaller the anion radius is, the higher the
Figure 18. Chloride and sulfate ion binding mechanism of LDH.
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charge density is, and the more favorable it is for exchange
reaction.304 Various equilibrium constants for various exchange
reactions are calculated, and the order of affinity of LDH for
different anions is mentioned below.305−307
Monovalent ions < Divalent ions < Trivalent ions < Tetravalent ions
PO4 3 > CO32 > SO4 2 > OH > F > Cl > NO2 > NO3 > I
Monovalent ions: OH > F > Cl > Br > NO3 > I
Bivalent ions: CO32 > C10H4N2O8S2 > SO4 2
6.4.1. Chloride Binding Activity. The essence of corrosion
reaction kinetics in a NaCl solution is the oxidation and
dissolution of metal elements. Chloride ions present in
electrolytic cells penetrate and tend to interact with metal ions
for the occurrence of corrosion.308,309 Hence, trapping Cl− ions
and isolating them from the metallic interface are the most
effective strategies for corrosion inhibition; this principle is
called the chlorine binding effect. This trapping of the chloride
ion mechanism enhances the importance of LDH in
anticorrosion studies.310 The relative binding energy of various
anions and Gibbs energy changes due to anion exchange
reactions can be studied by density function theory and
molecular dynamics. The binding energy is a function of the
carried charge of anions in the interlayer gallery; if the anions are
of the same charge, it is linearly correlated to the interlayer
spacing of LDH.311 In other words, if interlayer space is more
than the anionic radius, the exchange rate is high; thus, due to
the large anionic radius, organic ions cannot be encapsulated in
the LDH structure. The chloride ion exchange capability of
LDH can be found by the batch experiment process under
vacuum.308 The chloride ion binding mechanism of LDH is
described in Figure 18.
6.4.2. Protective Film. We are all aware that the composition
of seawater is majorly composed of 3.5 wt % NaCl, which is
responsible for corroding the metallic layer because of chloride
ion interaction with the metal substrate. Inhibition of chloride
ions from the metal layer is the only feasible technique to avoid
metal oxidation reactions.312 Layered double hydroxide is an
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Figure 19. Schematic of aspartic acid-intercalated MgAl LDH and mechanism of chloride binding, SEM image of MgAl-ASP LDH, and polarization
curves for different operational times.319 Reproduced with permission from ref 319. Copyright 2019 Elsevier.
inorganic network that can form a physical corrosion resistive
film by the accumulation of dense nanoparticles. Zhang et al.313
prepared a protective film of MgAl LDH by hydrothermal
crystallization of an anodic layer on a AZ31 Mg alloy. The anodic
oxidation layer mainly improves the stability of the structural
arrangement and adhesion of LDH. Besides, LDH and the anion
oxidation layer help in sealing the pores and cracks, resulting in a
sealed pathway for chloride ion aggression. The boiling water
sealing characteristic technique also favors the corrosion
inhibition mechanism by reduction of the anion oxidation
layer porosity. The EDS experiments analyze the composition of
MgAl LDH nanoparticles and confirm the perfect synthesized
material. Similarly, Mata et al.314 developed the LiAl LDH layer
on AA2024 Al alloys by modification of the anodic oxidation
layer. The thickness of the oxidation layer is around 3 μm as a
result of the tartaric-sulfuric bath treatment. The LiAl LDH
protective film is synthesized under alkali conditions (NaOH
and NaNO3) with LiNO3 as the additional metal salt. The
synergetic sealing mechanism of the inner anion oxidation layer
and outer LDH layer helps in enhancing anticorrosion
properties. There are two methods available to date for
developing a physical protective film of LDH, namely, in situ
conversion of anodic oxide to a LDH layer and in situ or ex situ
growth of LDH on alloy material by hydrothermal or
coprecipitation techniques.
6.4.3. Corrosion Inhibitors. As mentioned earlier, anions in
the interlayer gallery of LDH can be replaced by other
extraneous anions through physical or chemical treatment
techniques for specific applications. This corrosion-resistant
mechanism involves the intercalation of unique application-
specific anions by the anion exchange method and is released
whenever necessary (slow-release effect). The anion-based
corrosion inhibitor has exhibited excellent anticorrosion proper-
ties at a low cost. Hence, the combination of characteristic
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properties of LDH and the inhibitor can have higher corrosion
inhibition for long-term usage. For example, Liu et al.315
synthesized 5-methyl-1,3,4-thiadiazole-2-thiol (MMT)-interca-
lated ZnAl LDH by the exfoliation of ZnAl-NO3 LDH in
formamide and then reassembled in a MMT aqueous solution
(LDH-MTT-(R)). The presence of MMT in the gallery of ZnAl
LDH is analyzed by XRD experiments, in which the character-
istic peaks of the (003) plane shift to the small diffraction angle.
Alibakhshi et al.316 developed ZnAl-NO3 LDH and ZnAl-PO43−
LDH. ZnAl-NO 3 LDH is synthesized by a one-step
coprecipitation technique, and ZnAl-PO43− LDH is prepared
by a direct anion exchange treatment between NO3− and PO43−.
Anjum et al.317 prepared MgAl LDH on an AZ31 Mg alloy with
an 8-hydroxy quinolone (8HQ) as a specific corrosion inhibitor
anion by an in situ hydrothermal synthesis technique in different
proportions. Serdechnova et al.318 fabricated NO3− and VOx
intercalated ZnAl LDH film by manipulating the plasma
electrolytic oxidation layer of an AA2024-T3 Al alloy. The
VOx intercalated LDH film exhibits a better corrosion inhibition
activity than that of the precursor LDH film. Similarly, Tang et
al.246 designed a ZnAl LDH physical protective film with
different anion compositions on an AZ31 Mg-alloy. The
corrosion inhibition capacity of ZnAl LDH with different
anion intercalations is found to be in the following order: ZnAl-
VO43− LDHs > ZnAl-MoO42− LDHs > ZnAl-PO43− LDHs >
ZnAl-Cl−LDHs > ZnAl-NO3− LDHs, where ZnAl-VO43− LDH
exhibits the best corrosion. Chen et al. developed MgAl LDH on
an AZ31 magnesium alloy substrate with aspartic acid (ASP) as
the corrosion inhibitor incorporated at an interlayer geometry of
LDH and found that it shows better corrosion resistance than
MgAl LDH nanoparticles.319
The schematic of MgAl LDH with intercalation of ASP,
mechanism of corrosion resistance by exchanging chloride ions,
morphological structure of MgAl ASP LDH, and polarization
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Figure 20. Schematic of self-healing mechanism of ZnAl LDH.
Figure 21. Schematic of removal of sulfate ions present in wastewater through adsorption processes using LDH catalyst.
curves of MgAl-ASP LDH soaked in 0.6 M NaCl solution are
shown in Figure 19.
6.4.4. Self-Healing (Memory Effect). Developing an insoluble
protective film on the metal surface to avoid the interaction of
chloride ions and the metal layer is the main approach to
avoiding corrosion, but failure is probably due to external forces
during industrial operations. The damaged corrosion inhibition
layer instead of protecting the metal surface from metal
oxidation initiates the reaction mechanism. To deal with
external forces, we should modify the system to develop a self-
healing mechanism for corrosion-resistant applications. Re-
cently, certain studies have shown that even though there is
damage to the protective layer due to external forces, the slow
release of corrosion inhibitor ions can rebuild the layer through
the complexion of dissolved metal ions and inhibitor anions. For
example, Chen et al.320 developed MgAl LDH with intercalation
of aspartic acid (MgAl-ASP-LDH) on an AZ31 Mg alloy. Nitrate
ion-intercalated MgAl LDH was also prepared in the same
manner for comparing the corrosion resistance property of
LDH. These results show that MgAl-ASP LDH exhibits more
corrosion inhibition activity when compared to pure ASP and
the MgAl-NO3 LDH because of the coexisting protective film of
LDH and corrosion inhibitor. The self-healing mechanism on an
erupted portion of the metal surface can be observed during the
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immersion of a Mg alloy in a 3.5 wt % NaCl solution for 20 days.
The aspartic acid anion adsorbs on the dented portion of the
metal and thus hinders any further corrosion reactions. The self-
healing property of the magnesium alloy enhances corrosion
resistance and can be useful for long-term operation even in a
chloride environment. Chen et al.287 developed methionine
intercalated MgAl LDH (Met-LDHs) and CO32‑-intercalated
MgAl LDH. Met LDH has shown better resistance to corrosion
due to the methionine intercalation. When Met LDH is in the
epoxy coating and sprayed on a Mg alloy surface, the epoxy resin
binds to Met LDH in the interior portion of the coating and
enables the slow release of the inhibitor from the interlayer
gallery and also exhibits long-term stability. Chen et al.
synthesized ZnAl LDH by the in situ growth method and
studied the performance of the catalyst in a simulated salt water
medium (0.6 M NaCl solution); however, the self-healing
mechanism was observed by electrochemical impedance
spectroscopy (EIS) and DC polarization curves. Figure 20
illustrates the self-healing mechanism of developed ZnAl LDH
in seawater.321
6.4.5. Sulfate Ion Adsorption. LDH has gained an
appreciation for anticorrosion properties due to its anion
exchange capability. The removal of SO42− ions by LDH was
studied by batch adsorption experiments, where a Na2SO4
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Figure 22. Schematic of green hydrogen production by using seawater electrolysis technique.
solution was used as the adsorbate and LDH nanomaterial as the
adsorbent. The sulfate removal rate is determined based on the
initial and final concentrations of the sodium sulfate solution and
was tested by ion chromatography.322
Sulfate removal rate = (Cin − Cout)/Cin, here Cin and Cout refer
to the initial and final equilibrium concentrations of SO42−.
Maziarz et al.323 investigated the removal of sulfate ions from
acid mine drainage (AMD) wastewater (Cin is 5301 mg/L) by
adsorbing or precipitation using calcium hydroxide and MgAl
LDH. The results in Figure 21 show the adsorption data of
sulfate using a LDH catalyst.
The preliminary experiments by introducing a particular
amount of LDH in wastewater are performed, and the amount of
sulfate ion removal from wastewater by LDH nanoparticles is
calculated. These studies reveal that 2g/L LDH can remove only
19.3% of sulfate, and it reaches 63.2% for 20 g/L LDH dosage.
However, the equilibrium concentration of sulfates reduces from
4380 to 1944 mg/L, and pH also increases from 2.5 to 4.51.323
6.5. Factors Affecting Corrosion Inhibition. The
corrosion inhibition mechanism of LDH mainly depends on
two key parameters, namely, structural influence and chemical
properties.122 Compactness, thickness, and porosity are the
characteristics of synthesized protective films that have strong
influences on LDH corrosion applications. Chemical properties
of LDH include exchangeability of interlayer anions for binding
corrosion resist ions. Manipulation of physical structural
parameters depends on the synthesis conditions of nano-
particles.
Layered double hydroxides protect metallic substrates by a
physical barrier, anion exchange mechanism, and hydro-
phobicity. The physical barrier helps in resisting the movement
of aggressive chloride ions to the substrate and decreases the
interaction with the metallic layer. LDH exchanges the
intercalated anions with the corrosion-responsible ions present
in the electrolyte medium, traps aggressive Cl− ions in the
interlayer geometry, and helps in corrosion resistance of the
substrate.324 The intercalated anions react with the substrate
ions due to prolonged immersion and form chelates. These
chelates deposit on the surface of LDH and also block the active
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sites. The chelates formed due to the substrate and intercalated
anions having self-healing capabilities.317,325,326 The reaction
products may precipitate and seal the defects. The intercalated
anions may have hydrophobicity and may induce hydro-
phobicity of the resulting LDH coating. The hydrophobicity is
increased due to the modification of morphology and water
replant nature of intercalated anions such as 8-hydroxyquino-
line.245Figure 22 describes the seawater electrolysis in a PEM
electrolytic cell by using renewable sources and an ion-exchange
mechanism in the LDH structure.
7. DIRECT SEAWATER SPLITTING VS DESALINATION
FOLLOWED BY SEAWATER ELECTROLYSIS
Seawater contains various salts, which are responsible for higher
ionic conductivity. These salts pose problems during the
electrolysis process for hydrogen production by blocking the
electrodes and also reducing the activity of the electrocatalyst.
The saline water can be utilized for hydrogen production in two
different ways. One method is desalination followed by
electrolysis in a conventional electrolyzer, and the other
technique involves direct seawater electrolysis. The main
challenges for direct seawater splitting include thermodynamic
requirements, energy consumption, complexity and size of the
devices, capital cost, and operational costs.327 The energy
requirements, capital, and operational costs of seawater
desalination are marginal compared to direct seawater splitting,
so the benefits of direct water electrolysis are insignificant. The
electrolyzer’s operational lifetime is threatened by various
impurities, corrosive Cl− oxidative species, precipitation, and
blocking of electrolyzer assembly parts and reducing the
efficiency by adding resistance. The direct seawater electrolyzer
should be operated with higher velocities and an efficient design
model for washing deposited species and frequent acid cleaning,
which may increase the cost of the electrolyzer.30 The water feed
quality, maintenance, and capital costs, and lower efficiency of a
direct seawater electrolyzer compared to a conventional
electrolyzer limits industrial application; however, it has the
advantage of a single-step process rather than a two-step
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purification and electrolysis process in a conventional electro-
lyzer.30
The comparative study of direct seawater electrolysis with
conventional purification followed by the water electrolysis
process was done from an energy and economic perspective by
evaluating energy consumption and price for producing 1 kg of
hydrogen and splitting 1 kg of water. The thermodynamic
estimation of the two processes can be done by simplified
reactions (shown by eqs 23 and 24); however, both processes
are endergonic, thus requiring additional energy to drive the
reaction. The process (indicated by eq 23) is exothermic with
standard Gibbs free energy of 5.4 kJ/kg H2O. However, the
electrolysis of a 0.6 M NaCl solution does not produce salt
crystals rather it produces a concentrated brine solution, so the
Gibbs free energy is even lower (2.73 kJ/kg). The water-splitting
process shown in eq 24 is endothermic, so it requires 15,888 kJ/
kg. These show that it requires 3000 times more energy than for
desalination of seawater, which illustrates the specific energy
consumption and capital cost for both processes.
1.035 kg 0.6 M NaCl(aq) 1 kg H 2O + 0.035 kg NaCl(s)
(23)
1 kg H 2O 0.11 kg H 2 + 0.89 kg O2 (24)
Seawater can be purified by using the reverse osmosis (RO)
process; however, the specific energy consumption for modern
RO plants is 9.0−14.4 kJ/kg H2O, which constitutes 71% of the
total energy consumption. The efficiencies of acidic and alkaline
electrolyzer systems are around 62%−82% based on the heating
value of hydrogen; thus, the direct seawater electrolysis process
requires 1350−2897 times more energy compared to the
conventional process. The capital cost estimation for the water
electrolyzer and RO plants is quite challenging as RO
technology is well adapted, but electrolyzers are newly built
technology as per hydrogen-based energy economy require-
ments. The average capital cost of a RO plant for producing 1 kg
of fresh water per day is US$2.07, whereas the capital cost for
water electrolyzers utilizing 1 kW electricity consumption and
voltage efficiency of 62%−82% is 203−838 US$/kg water per
day. Therefore, the capital cost is around 50−420 times higher
than that of desalination equipment proving fresh water is best
for the production of hydrogen fuel.30 The international energy
agency estimated the price of hydrogen from renewable sources
as 2.5−6 US$/kg and the price of desalinated water from
seawater as 0.2−3.2 US$/m3 (conventional energy is used for
desalination) during the G20 summit in 2019; this indicates that
hydrogen produced is 87−3332 times costlier than desalinated
seawater. The electrolyzer should be placed at the proper
location to reduce energy cost, however, the energy supply
might be varied based on the hydrogen production capacity. The
water desalination process increases the cost of hydrogen
production by 1%, but the capital cost increase can be neglected.
The disposal of concentrated brine obtained after desalination
from RO plants is one of the major challenges due to the
presence of several contaminants/chemicals added during the
treatment process. The RO plants situated in coastal areas utilize
seawater as feed to produce fresh water resources and dispose of
the brine solution into the ocean, which has adverse effects on
the marine environment. The hydrogeological characteristics of
the sea such as waves, currents, and depth of the column
determine the extent of mixing of brine and geographical range
of impact. The concentrated brine has potential applications like
the production of caustic soda and hydrochloric acid in chloro-
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alkali industries, recycling the softener brine, usage as cooling
liquid in chemical plants, agricultural and irrigation purposes,
and recovering and selling solid salt.328 The pure water
production cost from the reverse osmosis process (US$1.23/
m3) is quite high compared to the nanofiltration (NF) (US
$0.49/m3) technique; however, it mainly depends on water
recovery and feedwater flow rate, temperature, and pressure.329
The above-mentioned factors illustrate that direct seawater
electrolysis is quite expensive and energy consuming. The
reduction in capital cost by using seawater feed compared to
freshwater feed is less than 1%. So direct seawater electrolysis is
less promising in the current situation, but promising catalysts
like LDH can help in dealing with serious problems of chloride
oxidation by trapping chloride ions. Purification of seawater
followed by seawater electrolysis helps for the long-term stability
of the electrolyzer. The capital costs of the entire seawater
electrolysis process should be optimized at a later stage after
dealing with the numerous challenges faced due to the presence
of different ions in seawater.
8. CHALLENGES, GAPS, AND PERSPECTIVES
The global hydrogen energy demand has increased from 255.3
billion cubic meters in 2013 to 324.8 billion cubic meters in
2020;330 however, hydrogen energy produced from natural gas
reforming and water is considered a secondary energy source.
Industrial-scale hydrogen applications should consider various
factors such as operational and capital costs, environmental
impact, investment, source of raw materials, and availability. The
production cost and initial investment of the steam reforming
process are lower than the water electrolysis process for large-
scale hydrogen production plants, whereas the investment for
the water-splitting process is lower than the natural gas steam
conversion process for small-scale H2 production plants.331
Hydrogen fuel demand has been increasing gradually to deal
with energy and environmental problems, and new technologies
such as photocatalytic water electrolysis, solar energy water
electrolysis, sodium borohydride electrolysis, and photo-
chemical cells are used for producing hydrogen and oxygen
fuels at optimum energy consumption.332 These technologies
are not advanced enough for industrial adaptability, but there is
significant scope for research and improving them for long-term
development. Another major research area is the development
of inexpensive, highly active, stable, corrosion-resistant electro-
catalysts to replace expensive noble metal catalysts for hydrogen
production by the water electrolysis process; however, Cu-, Fe-,
and Ni-based electrocatalysts have been considered as potential
catalysts for better HER and OER activities and long-term
stability in seawater electrolysis. Seawater electrolysis is always a
challenging task due to the presence of various ions, so the
developed electrocatalysts should be stable in a complex saline
water environment.333 The catalyst materials with better
performances can be obtained by appropriate selection of
materials and structural design; however, there are some
important challenges for future research such as screening of
materials with better anticorrosion properties, mechanism of
competitive reactions such as OER and CLER, evaluation of
anticorrosion materials, industrial-scale electrolysis, optimiza-
tion of experimental conditions, and novel integrated electro-
lyzer design. Artificial intelligence (Al) technology-enabled
simulations and theoretical calculations provide us a lot of data
for selecting potential materials, and advanced operando
techniques are helpful to probe real reaction mechanisms.
Industrial-scale seawater electrolysis adaptability is limited by
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selectivity, corrosion, and high current density maintenance for
the long-term stabilities of electrolyzer systems. The depend-
ence of local cations, pH, ionic conductivity, and magnetic fields
on the catalytic process may offer new insights for optimized
catalytic performances. The electrolyzer design can help in the
improvement of reaction efficiency; however, these are major
research areas to be investigated thoroughly and deep
exploration of catalyst materials is necessary for saline
environments.334 Seawater electrolysis is mainly used in
chloro-alkali industries for producing chlorine gas; however,
the importance of hydrogen fuel in the growing market across
the world exceeds the chlorine demand. The researchers have
developed different kinds of electrodes to deal with numerous
problems during seawater electrolysis for the production of H2
or Cl2. The industrial adaptability of efficient electrocatalysts for
seawater electrolysis is under development and can be achieved
in the future. Green H2 production using seawater electrolysis
has multiple advantages, and commercialization requires
meeting challenges for future research perspectives, which
includes the following: (1) Strategies for designing catalysts on
theoretical studies are limited, but catalysts with multilayer
hierarchical structures can reduce the mass transport and
stability, so density functional theory (DFT) is used for the
development of novel catalysts based on adsorption energies of
active sites and intermediates for optimum OER activity. (2)
Pretreatment of seawater is necessary for high efficiency and
long-term stability of the catalyst. (3) Present technologies for
deposition of catalysts is also a concern; however, the spraying
method is superior to surface growth of a catalyst. The spraying
technique is always followed by high-temperature treatment,
which might reduce efficiency and damage the hierarchical
structure of the electrocatalyst. (4) The intermittent renewable
resources limit the vast usage of power grids. However, large-
scale seawater splitting requires vast power resources, and
adoption of renewable energy such as wind turbines and
photovoltaic cells for energy conversion is a great choice. The
industrialization of seawater electrolysis technology prefers
coastal areas because of seawater availability, strong wind
patterns, and intense solar radiation.335
9. CONCLUSION
Modern society is more dependent on nonrenewable sources for
fulfilling the demand for energy across the globe, which also have
some harsh effects on the environment. Hydrogen fuel has been
considered as an alternative source to replace existing
technology, but still, there are certain limitations to a reduction
in energy consumption for the production process and also
corrosion problems during seawater electrolysis. In this review,
we have focused on hydrogen production from seawater
electrolysis, the main challenges for the electrolysis of saline
water, and different electrocatalysts used for hydrogen
generation from seawater splitting. A comparative study has
been done for improving the performance activity of catalysts. In
addition, we have briefly described several 2D nanoparticles
such as graphene, phosphorene, layered double hydroxide, and
their derivatives synthesized for electrolysis application. Among
these catalysts, LDH has many advantages including flexible
morphology, memory effect, easy synthesis, and corrosion-
resistant property, and it also has the potential for industrial
scale-up. The main challenge for electrocatalyst industrial
adaptability includes corroding electrodes during seawater
electrolysis and considerable reduction in energy consumption.
This review provides information regarding the anticorrosion
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properties of LDHs and their mechanism of inhibiting species
responsible for the corrosion of electrodes. We have also
discussed briefly the various photoelectrocatalysts and key
factors responsible for the modification of catalyst activity. The
comparative study of direct seawater electrolysis and desalina-
tion followed by the conventional electrolysis process has been
discussed as per energy and economic requirements. This review
helps researchers across the globe by providing vast knowledge
on seawater electrolysis and the challenges, synthesis
techniques, and performance of different catalysts and also
assists them to focus on the direct seawater-splitting mechanism
to reduce the capital and operational costs and energy
requirements. The researchers can also focus on improving
the efficiency of the electrochemical reaction and electrolyzer by
modifying the parameters like feed temperature, flow rate,
electrolyte circulation, and ionic conductivity.
■ AUTHOR INFORMATION
Corresponding Author
Rohit Srivastava − Catalysis & Hydrogen Research Lab, School
of Petroleum Technology, Pandit Deendayal Energy
University, Gandhinagar 382007 Gujarat, India;
orcid.org/0000-0002-9957-8499; Email: rohit.s@
spt.pdpu.ac.in
Author
Sankhula Lokesh − Catalysis & Hydrogen Research Lab,
School of Petroleum Technology, Pandit Deendayal Energy
University, Gandhinagar 382007 Gujarat, India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.2c02013
Author Contributions
R.S.: conceptualization, project administration, supervision,
writing�review and editing. S.L.: investigation, visualization,
writing�original draft.
Notes
The authors declare no competing financial interest.
Biographies
Sankhula Lokesh: Mr. Lokesh earned his bachelor’s degree (B.Tech)
in chemical engineering from Andhra University College of Engineer-
ing (A), Visakhapatnam Andhra Pradesh, India. He completed his
master’s of technology (chemical engineering) from the Indian
Institute of Technology (IIT), Guwahati, India, in 2018. At present,
he is working as a junior research fellow (JRF) in catalysis and hydrogen
research at Pandit Deendayal Energy University, Gandhinagar, Gujarat,
India. His research interests include electro/photocatalysts for water
splitting and electrochemical CO2 reduction into valuable fuels.
Rohit Srivastava: Dr. Rohit Srivastava earned his Ph.D. degree from the
Birla Institute of Technology, Mesra, Ranchi, India, in 2015. He worked
as a postdoctoral fellow at Harvard University USA. At present, Dr.
Srivastava holds the position of assistant professor at the School of
Petroleum Technology, Pandit Deendayal Energy University, Gan-
dhinagar, Gujarat, India, since August 2018 and works in the area of
green hydrogen energy and CO2 reduction into green fuels. He is also a
member of the origin of life initiative, Harvard University, United
States.
■ ACKNOWLEDGMENTS
R.S. and S.L. would like to thank PDEU, India, for providing the
required infrastructure and start-up research grant. This research
work was funded by Shell Energy India Private Limited.
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■ ABBREVIATIONS:
LDH, layered double hydroxide; 2D, two-dimensional; H2,
hydrogen; NOx, oxides of nitrogen; SOx, oxides of sulfur;
NaOH, sodium hydroxide; KOH, potassium hydroxide; TW,
terawatts; K, Kelvin; MPa, megapascal; TMDC, transition metal
dichalcogenides; S, sulfur; Se, selenium; Te, tellurium; HER,
hydrogen evolution reaction; OER, oxygen evolution reaction;
CNT, carbon nanotubes; DOS, density of states; NS, nano-
sheets
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