REVIEW
Electrocatalysis
Electrochemical Water Splitting: Bridging the Gaps Between
Fundamental Research and Industrial Applications
Hainan Sun, Xiaomin Xu, Hyunseung Kim, WooChul Jung , Wei Zhou*, and Zongping Shao*
Electrochemical water splitting represents one of the most promising
technologies to produce green hydrogen, which can help to realize the goal
of achieving carbon neutrality. While substantial efforts on a laboratory scale
have been made for understanding fundamental catalysis and developing
high-performance electrocatalysts for the two half-reactions involved in
water electrocatalysis, much less attention has been paid to doing relevant
research on a larger scale. For example, few such researches have been done
on an industrial scale. Herein, we review the very recent endeavors to bridge
the gaps between fundamental research and industrial applications for water
electrolysis. We begin by introducing the fundamentals of electrochemical
water splitting and then present comparisons of testing protocol, figure of
merit, catalyst of interest, and manufacturing cost for laboratory and
industry-based water-electrolysis research. Special attention is paid to
tracking the surface reconstruction process and identifying real catalytic
species under different testing conditions, which highlight the significant
distinctions of corresponding electrochemical reconstruction mechanisms.
Advances in catalyst designs for industry-relevant water electrolysis are also
summarized, which reveal the progress of moving the practical applications
forward and accelerating synergies between material science and engineering.
Perspectives and challenges of electrocatalyst design strategies are proposed
finally to further bridge the gaps between lab-scale research and large-scale
electrocatalysis applications.
1. Introduction
Electrochemical water splitting with high purity hydrogen production
without CO2 emission is a promising technique to realize a sustainable
energy landscape.[1–3] Due to the abundant sources of raw materials
(e.g., electricity and water), electrochemical water splitting has
Dr. H. Sun, H. Kim, Prof. W. Jung
Department of Materials Science and Engineering, Korea Advanced Institute
of Science and Technology (KAIST), Daejeon 34141, Korea
Dr. X. Xu, Prof. Z. Shao
WA School of Mines: Minerals Energy and Chemical Engineering (WASM-
MECE), Curtin University, Perth, Western Australia 6102, Australia
E-mail: shaozp@njtech.edu.cn
Prof. W. Zhou, Prof. Z. Shao
State Key Laboratory of Materials-Oriented Chemical Engineering, College of
Chemical Engineering, Nanjing Tech University, Nanjing 211816, China
E-mail: zhouwei1982@njtech.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/eem2.12441.
DOI: 10.1002/eem2.12441
Energy Environ. Mater. 2022, 0, e12441 1 of 21
advantages over coal gasification and steam-
methane reformation associated with large
hydrogen production.[3–6] In particular, alkaline
water electrolysis has received considerable
attention owing to its characteristics of simple
architecture and low-cost electrode materials
(non-precious metal-based electrocatalysts with
high performance).[7–9] In addition, due to the
advantages it has in terms of lower resistance
losses and less gas crossover, proton exchange
membrane (PEM) water electrolysis can provide
much higher current densities and purer gas
production compared to alkaline water electrol-
ysis.[10–15] The viability of these technologies
relies largely on the electrochemical perfor-
mance of the two half-reactions involved,
namely the oxygen evolution reaction (OER) at
the anode and the hydrogen evolution reaction
(HER) at the cathode.[16,17] Moreover, the OER
is a thermodynamically uphill reaction that
involves a complex, stepwise, and electron-
proton-coupled process.[18–20] Thus, the OER is
a bottleneck in the whole process and requires a
high overpotential to obtain a desired current
density compared with that of the HER pro-
cess.[20–24] Therefore, considerable efforts have
been made on designing high-performance and
low-cost electrocatalysts, especially the OER cat-
alysts.
Ir/Ru and Pt-based materials are commonly regarded as the bench-
mark electrocatalysts for OER and HER, respectively.[25–32] However,
the high cost, low abundance, and poor stability associated with these
materials under harsh reaction conditions hinder their large-scale
applicability within the framework of sustainable energy-use technolo-
gies. Therefore, materials based on transition metals, which are abun-
dant on Earth, such as metal/alloys, metal oxides, (oxy)hydroxides,
single-atom catalysts, and carbon-based materials, have all attracted sub-
stantial attention from us as electrocatalysts for OER and HER.[33–47]
However, it remains a great challenge for people to use materials
based on non-precious metals as efficient electrocatalysts in acidic con-
ditions.
Searching for OER/HER electrocatalysts with high-current density,
low overpotential, and superior long-term stability is highly impor-
tant yet challenging for commercial water-electrolysis systems. Signifi-
cant breakthroughs have been made recently in designing high-
performance electrocatalysts for the OER and HER in fundamental
research, some of which even meet the requirements for commercial
use.[48–59] Despite the significant efforts that have been made for
conducting water electrolysis in the past 100 years, and for the
© 2022 Zhengzhou University.
development of material science in the past several decades, currently
95% of hydrogen is still produced through reforming fossil fuels,
and only 4% of it is produced by performing water electrolysis each
year.[60] The gaps between the fundamental research on administer-
ing water electrolysis and its practical applications hinder its leapfrog
development. In addition to the above criteria for ideal electrocata-
lysts, other testing protocols such as high operating temperatures in a
highly corrosive electrolyte and applied devices are also distinguished
from those under industrial conditions. For example, the catalytic
performance evaluation from a laboratory for the designed alkaline
OER catalysts is usually performed at room temperature with low
concentrations of alkaline electrolytes (e.g., 0.1 and 1.0 M KOH),
while a commercial alkaline water electrolyzer operates at industrial
temperatures (at 50–80 °C) with a highly corrosive electrolyte (20–
40 wt.% KOH in water).[16,19,61]
In this review, we discuss the main gaps between doing fundamen-
tal research and making practical applications for water electrolysis,
including testing protocols, figure of merits, catalysts of interest, and
manufacturing cost (Figure 1). Special attention is paid to making com-
parisons between real catalytic species and reconstruction mechanisms
under laboratory testing conditions and industrial conditions. Recent
progress is further summarized to highlight the critical need for evalu-
ating catalysts under harsh industrial conditions through doing funda-
mental research. Finally, perspectives, challenges, and strategies
associated with designing electrocatalysts are proposed to bridge the
gap between doing laboratory-scale research and making larger-scale
applications.
2. Electrochemical Water Splitting
2.1. Fundamentals
Water electrolysis is able to split water molecules into H2 and O2 at the
cathode and anode, respectively, as products. According to the opera-
tional temperature and electrolyte, water electrolysis can be classified as
PEM water electrolysis, alkaline water electrolysis, anion exchange mem-
brane (AEM) water electrolysis, and solid oxide electrolysis.[16,62–64]
The last of the four types of solid oxide electrolysis requires high
Figure 1. Main gaps in existence between doing fundamental research and making practical applications alkaline electrolyte is different from the
for electrochemical water splitting.
Energy Environ. Mater. 2022, 0, e12441 2 of 21
operational temperatures (700–800 °C), while the other three, which
belong to the electrolysis techniques type with aqueous electrolytes,
are operated at significantly lower temperatures (i.e., typically lower
than 100 °C).[5,63]
Although a solid oxide electrolyzer has an ideal theoretical efficiency
(up to 100% vs. 70–80% for a PEM water electrolyzer and 60–70% for
an alkaline water electrolyzer), the higher working-temperature-
induced safety issues and operational durability make up a great chal-
lenge for its practical applications.[63] For the PEM, alkaline, and AEM
water electrolyzers, two electrodes are immersed into the aqueous elec-
trolyte and connected to an external circuit.[64] A suitable voltage can
drive the OER and HER simultaneously at the anode and cathode,
respectively; see Eqns (1)–(5).[16–18,65]
Anode : 2H2 O ! 4Hþ þ O2 þ 4e ðacidÞ (1)
4OH ! O2 þ 2H2 O þ 4e ðalkalineÞ (2)
Cathode : 2Hþ þ 2e ! H2 ðacidÞ (3)
2H2 O þ 2e ! 2OH þ H2 ðalkalineÞ (4)
Total reaction : 2H2 O ! 2H2 þ O2 (5)
2.2. Lab-Scale Research
The electrochemical reaction is commonly comprised of two pro-
cesses, namely an interface charge transfer reaction and a mass transfer
reaction. Under steady-state testing conditions, the use of electrodes at
the millimeter level is often limited by mass transfer, in which it is
difficult to study the kinetics of fast electrochemical reactions. The
rotating disk electrode (RDE) technology has been demonstrated as an
effective strategy which can be used to strengthen the mass trans-
fer.[66–68] Moreover, the evenly distributed current densities and the
short time necessary to reach the steady state also make it a good tech-
nology for measuring the steady state. In addition, the thickness of
the mass transfer diffusion layer decreases with an increase in rotation
speed. For the conventional acid and base electrolytes at a rotational
speed of 1600 rpm, the thickness of the diffusion layer is approxi-
mately 12 μm, which is about one order
smaller in magnitude than the typical diffu-
sion layer thickness of 100 μm in a static
electrolyte.
2.3. Industrial-Scale Research
Currently, the leading low-temperature water
electrolysis technologies include PEM, alka-
line, and AEM water electrolysis. Figure 2
shows the configurations of these three
water electrolyzers and their design consider-
ations for activity and long-term stability.[60]
Table 1 compares the main characteristics
that are displayed by alkaline, PEM, and AEM
water electrolyzers.[5,62–64] Taking the alka-
line water electrolyzer as an example, the
configurations during the evaluation at the
© 2022 Zhengzhou University.

Figure 2. Configurations of current low-temperature water electrolyzers, including a) alkaline, b) PEM, c) employed as the [74] electrolyte for the AEM
AEM water electrolyzers, d) Crucial factors to be considered for designing electrolyzers with superior water electrolyzer.
activity and long-term stability. Reproduced with permission from Ref. [24] Copyright 2021, CellPress.
laboratory-scale, and it is continuously pumped through the electrol-
ysis stack, where the H2 and O2 gases are formed (Figure 2a).[60]
The main advantages of the mature alkaline water electrolyzer can
be summarized as follows: 1) starting up faster, 2) having higher-
purity hydrogen production, 3) being more of a compact system
design, and 4) undergoing lower resistance losses. The key
component of this device is the diaphragm,
which enables ion transportation toward the
anode and cathode. In addition, heat
exchangers are commonly required to main-
tain an optimal range of temperatures of the
electrolyte. In terms of the PEM water elec-
trolyzer, the membrane electrode assembly is
involved, which contains the catalysts and
the PEM (Figure 2b). For the membrane
electrode assembly, the ionomer ensures liq-
uid or gas management, ionic conductivity,
and mechanical stability of the catalysts.[69]
The AEM water electrolyzer has been consid-
ered as an emerging third-generation tech-
nology, which combines the merits of
alkaline and PEM water electrolysis.[62,70–73]
AEM water electrolysis uses transition-metal-
based materials, as in alkaline water electrol-
ysis, and a solid polymer electrolyte architec-
ture, as in PEM water electrolysis
(Figure 2c). The alkaline water electrolyzer
uses concentrated KOH/NaOH solutions,
while distilled water or a low-concentration
alkaline aqueous solution can also be
Therefore, the AEM
water electrolyzer with a hydrocarbon AEM
and low-cost electrodes is expected to show
promising hydrogen performances, though it
needs more studies on its applicable catalysts and electrolyzer
designs. In addition to exploiting high-performance catalysts, the
efficiency and product yields of the water electrolyzer are also influ-
enced by the selection and design of the membrane, support, bin-
der/ionomer, gas diffusion, operational conditions, local pH values,
and impurities (Figure 2d).[24]

Table 1. Comparison of the main characteristics displayed by alkaline, PEM, and AEM water electrolyzers.

Alkaline water electrolyzer PEM water electrolyzer AEM water electrolyzer

Separator Diaphragm (Zirfon Perl 500 μm) Nafion 117 AEM (20–100 μm)
Catalysts Anode: Ni, Ni-Co alloys Anode: Ru/IrO2 Cathode: Pt, Pt-Pd Anode: Ni, Fe, Co oxides Cathode: Ni and Ni alloys
Cathode: Ni, Ni-Mo alloys
Electrolyte KOH (20–40 wt.%) High-purity deionized water (18 MΩcm) Alkaline solution or deionized water
Ion transport OH− H+ OH−
Temperature (°C) 50–80 50–80 50–70
Pressure (bar) 1–30 30–76 1–30
Current density (A cm−2) 0.2–0.6 0.6–2.0 0.2–0.4
Cell voltage (V) 1.8–2.4 1.8–2.2 1.8–2.2
Efficiency (%) 60–70 70–80 –
Gas purity (vol%) >99.5 >99.9999 >99.99
Developing status Mature technology Mature for small scale Under development
Advantages Non-noble metal catalysts, Compact design, fast response/start-up, Combined advantages of alkaline
great durability, low capital cost high-purity production and PEM water electrolysis
Disadvantages Slow dynamics, corrosive electrolyte, Noble metal catalysts, poor durability, Low OH− conductivity in polymeric membranes
further purification stage high capital cost

Energy Environ. Mater. 2022, 0, e12441 3 of 21 © 2022 Zhengzhou University.

3. Identifying the Gaps circulated in and out of the electrochemical cells (Figure 3d).[13,60]
The two electrodes are also immersed in the electrolyte but are sepa-
3.1. Testing Protocols rated by a diaphragm to prevent the cross-diffusion of generated
oxygen and hydrogen gases. The membrane is the core that is inde-
3.1.1. Equipment pendent of the water electrolyzers and ensures ion transportation
toward the two electrodes. The membrane needs to be stable under
For the evaluation of electrochemical performance, including activity and operational conditions. Asbestos was used as the separating material
stability, a conventional three-electrode setup is the most frequently used for the alkaline water electrolyzer due to its excellent durability, but
equipment in the laboratory.[19,75] As shown in Figure 3a, the three- it was later substituted by microporous polymers or ceramic materi-
electrode configuration consists of a working electrode, a counter elec- als, given its toxicity and carcinogenicity.[5,82] Currently, the materi-
trode, and a reference electrode as well as a gas inlet for oxygen or argon/ als commonly used as separators are Zirfon PERL, Ryton, and Ni
nitrogen.[61] The mass transport limitation is partially avoided by applying oxides.[83–85] For PEM and AEM water electrolyzers, a membrane
a rotation, where a rotational speed of 1600 rpm is commonly adopted. electrode assembly (Figure 3e) coupled with the sandwiching porous
For the evaluation of overall water splitting performance, two electrodes transporting layer and bipolar plates is used, making the alkaline
are immersed into the electrolyte, and high-performance electrocatalysts water electrolyzer device a simple architecture.[60]
for the OER and HER are attached to the anode and cathode, respectively.
Currently, considerable efforts have been made to design bifunctional
electrocatalysts for the OER and HER to accelerate the overall water elec- 3.1.2. Working Electrode Designing
trolysis and simplify the device (Figure 3b).[29,76–80] Figure 3c is a repre-
sentative photograph of the overall water electrolysis device used at the Many differences in testing protocols lead to great discrepancies in elec-
laboratory scale.[81] trode design and electrochemical performances. For fundamental
The equipment of a large-scale water electrolyzer involves open research, a thin film containing the studied electrocatalysts and Nafion
systems, in which reaction products and reactants are continuously (a binder to ensure mechanical stability during testing) is loaded on a
conductive RDE (i.e., a glassy carbon substrate)
to act as a working electrode.[61] Such a config-
uration usually suffers from low electrical con-
ductivity, which can effectively be mitigated
by the inclusion of conductive carbon in the
working electrode. The typical catalyst loading
is in the range of 0.1–0.3 mg cm−2 with cur-
rent densities in the order of ≈10 mA cm−2.
The low catalyst loading with a thin catalyst
layer aims to decrease the mass transfer; the
liquid electrolyte thus can efficiently access the
catalyst layer.[86] Moreover, the thin layer facil-
itates the diffusion and release of generated
gases such as oxygen and hydrogen.[21] In
contrast, for the industrial setups, measure-
ments at the cell, stack, and system levels are
required due to a limitation by the liquid and/
or gas management. What is different is that
for the membrane electrode assembly configu-
ration, the catalyst loading can be up to 1–
2 mg cm−2 with current densities in the order
of several hundreds of mA cm−2.[87] The
higher catalyst loading and thicker catalyst
layer bring about large mass-transfer resistance
from electrolyte access and gas diffusion.[61]
To accelerate the mass transfer, thin catalyst
layers are coated on the membrane for the
Figure 3. a) A schematic diagram of a three-electrode configuration containing a working electrode, PEM water electrolyzer and on highly porous
reference electrode, counter electrode, and gas inlet used for lab-scale evaluation of electrocatalytic conductive substrates for the alkaline water
performances. Two distinguished areas of the electrified interface and the free liquid environment are electrolyzer. Therefore, optimizing the mem-
also represented. Reproduced with permission from Ref. [60] Copyright 2020, Nature Publishing Group. brane electrode assembly is more complex than
b) A schematic illustration of the overall alkaline water electrolyzer at the lab scale. c) A photograph of optimizing the three-electrode configuration,
the overall water electrolysis device powered by an AAA battery. Reproduced with permission from Ref.
[81] Copyright 2019, Wiley-VCH. d) Membrane electrode assembly for proton and anion exchange
which leads to an easier electrocatalytic perfor-
membrane water electrolyzers. Reproduced with permission from Ref. [13] Copyright 2021, Wiley-VCH. mance collection via a three-electrode configu-
e) An open system for alkaline water electrolyzer architectures and designs. Reproduced with permission ration than that via membrane electrode
from Ref. [60] Copyright 2020, Nature Publishing Group. assembly configurations.

Energy Environ. Mater. 2022, 0, e12441 4 of 21 © 2022 Zhengzhou University.

3.1.3. Testing Conditions One open question is that when an electrocatalyst, which is deemed
to make high performances at the laboratory scale as reported in the lit-
There is also a huge difference in testing conditions between funda- erature, is applied for usage under industrial conditions, “Would it still
mental research and practical application. Taking the alkaline water show good activity with superior stability?” What are the differences
electrolysis analyzed in this study as an example, we present the and similarities of reaction mechanisms under these two evaluation
detailed differences in testing conditions. Designing efficient OER elec- conditions? In addition, how to bridge the gaps between fundamental
trocatalysts with a high current density and superior long-term stability research and industrial application seems particularly important. Fig-
at elevated temperatures (50–80 °C) in a high corrosive electrolyte ure 4d shows the illustrations of the main gaps between laboratory
(20–40 wt.% KOH in water) is needed for commercial alkaline water research and industrial applications of alkaline water electrolysis.
electrolyzer systems. The alkaline electrolytes supply the reagent of the
reaction while also providing ions that improve electrical conduction
inside the electrolysis cell. The relationship between electrolyte concen- 3.2. Figures of Merit
tration and conductivity shows that when the concentration of the
electrolytes for KOH and NaOH reaches approximately 32 wt.% and The past decade has witnessed the development and prosperity of the
18 wt.% (by weight in water), respectively, their conductivities are material sciences. Thus, it is necessary to establish a standard measure-
close to the maximum value (Figure 4a).[85] In particular, the maxi- ment protocol based on conventional electrochemical techniques, which
mum conductivity can be obtained at 30–35 wt.% KOH when the will enable a reasonable evaluation of designed materials and fair activity
temperature increases to 80 °C. As we can see from Figure 4b, which comparison with the reported electrocatalysts. McCrory et al. recom-
was reported in the literature, with an increase in the electrolyte tem- mended a benchmark measurement protocol of heterogeneous catalysts
perature (from room temperature to approximately 50 °C), the elec- for the OER and HER mainly based on the RDE technique.[75] Many criti-
trocatalytic activities of NiMoO4 also increased.[88] Additionally, a new cal properties for evaluating the catalytic activity and stability have been
peak corresponding to the transformation of Ni2+ and Ni3+ emerged suggested. In particular, the overpotential corresponding to the current
only at a high temperature of 51.9 °C, indicating that the reaction pro- density per geometric area of 10 mA cm−2 (testing conditions: room
cess and related reaction mechanism depended on the electrolyte tem- temperature under 1 atm O2) is a widely used parameter to assess the
perature, especially at high temperatures. Moreover, high-performance activity. Specifically, the calculation of the overpotential for the OER at
electrocatalysts exhibited further improvement of electrocatalytic activi- room temperature can be seen as follows: η = E – 1.23 V, where E rep-
ties in high-concentration electrolytes. Notably, the current density for resents the potentials vs. RHE. The value of 10 mA cm−2geo is a metric
the Co-doped NiO-Fe3O4@NiCo2O4 hierarchical nano-array electrode relevant to solar fuel synthesis.[89] The reliability of using this value to
could even reach 2000 mA cm−2 at approximately 1.53 V vs. the evaluate the intrinsic properties of the catalyst has been challenged.[90]
reversible hydrogen electrode (RHE) in a 30 wt.% (≈7.6 M) KOH Therefore, additional parameters such as those geared for specific activity,
solution (Figure 4c).[50] mass activity, and turnover frequency are also recommended for activity
evaluation. Commercial-scale water electrolysis
is usually operated under a high current den-
sity and voltage. For example, PEM water elec-
trolysis operates at current densities greater
than 1.6 A cm−2 while alkaline water electroly-
sis operates at around 0.5 A cm−2.[5] Thus, a
driving large current density (>0.5 A cm−2) at
a low overpotential (<300 mV) is required of
the designed alkaline OER catalysts. However,
as mentioned above, it remains a great chal-
lenge in terms of developing simple and effec-
tive strategies to synthesize electrocatalysts that
meet these requirements.
The chronoamperometry and chronopo-
tentiometry tests are straightforward ways of
assessing long-term stability of electrocatalysts,
and they serve as a direct indicator of practical
applications.[19,61,91] A chronopotentiometry
test under 10 mA cm−2geo has been adminis-
tered to demonstrate electrolysis as a testing
protocol to benchmark the OER stability on a
Figure 4. a) Relationship between electrolyte concentration (KOH and NaOH aqueous solutions) and laboratory scale.[92–94] For example, pro-
conductivity at temperatures of 25 and 80 °C. Reproduced with permission from Ref. [85] Copyright longed durability tests on PEM water electrol-
2021, Academic Press: London. b) LSV curves of NiMoO4 at different electrolyte temperatures for the
ysis which take more than 50 000 h under a
OER. Reproduced with permission from Ref. [88] Copyright 2020, Wiley-VCH. c) LSV curves of Co-doped
NiO-Fe3O4@NiCo2O4 hierarchical nano-arrays, NiO-Fe3O4, NiCo2O4, IrO2, and nickel foam in 30 wt.% high −2
current density (i.e., in the order of A
(≈7.6 M) KOH solutions for the OER. Reproduced with permission from Ref. [50] Copyright 2020, cm ) cannot be realized in the typical three-
Elsevier. d) Comparisons of alkaline water electrolysis that operate under laboratory conditions and electrode configurations because there are
industrial conditions. mechanical and chemical stability issues

Energy Environ. Mater. 2022, 0, e12441 5 of 21 © 2022 Zhengzhou University.

associated with loaded catalysts and glassware, respectively, which
might hinder the tests.[24,69,95]
3.3. Catalysts of Interest
3.3.1. Materials Used in Industrial Applications
For designing electrocatalysts toward practical applications, the most
important factors to be considered are activity, stability, and cost. In
other words, cost and electrochemical performances of materials are
equally important in the designing process.[24] For example, require-
ments of electrodes for commercial alkaline water electrolysis include
good resistance to corrosion, abundantly available active sites, high con-
ductivity, and excellent structural integrity.[61] Cathode materials are
commonly made of Ni or Raney Ni. However, with a high initial HER
electrocatalytic activity, the overpotential increases due to nonconduc-
tive Ni-hydride formation under cathodic conditions. Therefore, Ni is
usually used in alloys with metals (e.g., W, Mo, Cr, Co, Fe, and Zn)
and metallic oxides (e.g., MoO2, MoO3, and CeO2).[96] The anode
materials are also commonly made of Ni to reduce the cost of industrial
alkaline electrolyzers.[61,85] The materials mentioned above exhibit
good corrosion in alkaline conditions and engage in good activities
with a low cost. From this perspective, the cost of alkaline water
electrolyzers is relatively lower than that of other water electrolyzers.
The electrode materials that work well in industrial alkaline water
electrolysis cannot survive in an acidic electrolyzer. For PEM electrolysis,
precious metal-based materials are commonly used for the cathodic
HER (i.e., Pt and Pt-Pd) and the anodic OER (i.e., IrO2 and RuO2).[5,87]
3.3.2. Emerging Materials in Fundamental Research
Aimed at enhancing the overall efficiency and reducing the fabrication
cost of water electrolysis, considerable attempts have been made to
exploit more promising material systems in fundamental research, such
as metal oxides, (oxy)hydroxides, single-atom catalysts, and carbon-
based materials.[97–100] More investigations have also been made with a
focus on developing high-performance bifunctional electrocatalysts for
the OER and HER.[29,77,101,102] Here, we present a brief summary on the
emerging catalytic materials for applications for fundamental research.
Metals/alloys: Metals and alloys with high conductivity are potential
electrocatalysts in water electrolysis.[103] Under alkaline OER conditions,
phase transition from an alloy to (oxy)hydroxide could easily occur, and
surface (oxy)hydroxide is identified as the real active site.[88,104–106] To
protect the metal/alloy phase, a surface carbon-coating strategy is usually
used.[107–110] The catalytic activity is also optimized by modulating the
electronic structure via interactions with the internal components. For
example, hcp-NiFe alloy nanoparticles were encapsulated in an N-doped
carbon shell (hcp-NiFe@NC), which exhibited low overpotentials of
226 and 263 mV at 10 and 100 mA cm−2, respectively.[111] That work
further demonstrated the reactive mechanism under metal@graphene
catalysts, where the metal core changes the electronic state of external N-
doped carbon. The optimized N-doped carbon is also a direct active site.
What is different is that surface carbon can be destroyed by the harsh oxi-
dation condition during the long-term and accelerated tests of degrada-
tion.[112] Similarly, Ir and Ru with their metal state inevitably
transformed into the oxide state (+3, +4, or >+4) act as the direct and
active species during the acidic OER process. The high activities of in
Energy Environ. Mater. 2022, 0, e12441 6 of 21
situ-formed sites during the OER process generally contributed to the
abundant electronic defects, flexible structures, modulated electronic
structures, and so on and so forth. Several problems need to be solved
before larger-scale applications of metal and alloy catalysts can be
launched. It is challenging to design the targeted metallic precursors pre-
cisely. It remains unclear as to whether phase transformation occurs
under electrochemical testing at different temperatures. Additionally,
even though the carbon-coating strategy enhances catalytic activity and
creates higher stability, the state in which surface carbon emerges is clo-
sely related to the material structure and testing conditions (e.g., testing
temperature, solution concentration, applied potential, and testing time).
Metal oxides: Metal oxides (e.g., precious metal oxides, transition-
metal oxides, spinel oxides, and perovskite oxides) have been studied
extensively as electrocatalysts toward electrochemical water split-
ting.[34,36,113–122] Moreover, transition metal oxides or (oxy)hydrox-
ides can be directly synthesized or derived from metal nitrides, sulfides,
phosphides, and selenides due to their surface reconstruction during
the OER process.[123–125]
Among precious metal oxides, Ru- and Ir-based oxides are regarded
as benchmark materials for the OER in an acidic medium. Chen et al.
summarized the strategies for improving performances of Ru/Ir oxides,
including doping, defect/facet engineering, crystallinity/morphology
control, and surface-oxidation-state modulation.[69] Transition-metal-
based oxides are good candidates for alkaline OER electrocatalysts owing
to their low cost and superior OER activities. Remarkably, the electro-
chemical activities of transition-metal oxides in the OER are comparable
or even superior to those of noble metal-based benchmark materials.
Taking perovskite oxides as an example, due to their great flexibility in
chemical composition and electronic structure, perovskite-type oxides
are good candidates for water electrolysis catalysts.[126–132] Simple per-
ovskite oxides (ABO3−δ), double perovskite oxides (AA’B2O5+δ and
A2BB’O6−δ), and Ruddlesden-Popper-type oxides (An+1BnO3n+1) are
the most frequently studied materials, especially as OER electrocatalysts
in alkaline solutions.[47,127,133–136] The high intrinsic activities of per-
ovskite oxides are attributed to their optimized bulk physicochemical
properties, on the basis of which various descriptors have been pro-
posed, such as eg occupation, d-band center, metal-oxygen covalency,
and generalized electronegativity.[137–139] Further studies have found
that their ability to initiate superior activity is also strongly related to the
surface reconstruction species under electrochemical conditions, which
calls for the rational designing of initial materials.[140–143] Li et al. sum-
marized the roles of initial bulk chemistry in the surface reconstruction
process of perovskite-type oxides under OER conditions.[144] Their
report provided designing principles and guidance for developing
advanced electrocatalysts based on perovskite oxides. It has widely been
reported that the surface rearrangements of perovskite oxides are cou-
pled with leaching of cation elements under working conditions of the
OER/HER at room temperatures in alkaline solutions.[145–148]
In acidic conditions, the promising perovskite oxides for OER elec-
trocatalysts are limited to Ir-based perovskite oxides, and the active spe-
cies are identified as IrOx with nanocrystallites or amorphous states
after surface reconstruction.[146,149–152] For instance, Seitz et al.
reported that IrOx/SrIrO3, which is created by Sr-leaching from the sur-
face layers of SrIrO3, exhibited superior OER activity in an acidic solu-
tion (0.5 M H2SO4). Notably, the surface reconstruction process takes
approximately 30 h to complete at room temperature.[147] Additionally,
Ru-based perovskite oxides, such as SrRuO3, Na-SrRuO3, and
CaCu3Ru4O12 (quadruple perovskite), have been reported as acidic OER
electrocatalysts with high performances.[153–155] Notably, the thicker
© 2022 Zhengzhou University.
surface active layer contributed to enhanced catalytic activity. However,
little is known about the level and rate of the reconstruction under
industry-evaluation conditions, which calls for further in-depth studies.
(Oxy)hydroxides: (Oxy)hydroxides are promising catalyst candidates
for water splitting. The reconstructed species after undergoing alkaline
OER are commonly (oxy)hydroxides, which suggests their high activ-
ity.[145] In particular, layered double hydroxides (LDHs) have been
demonstrated to be one of the best-performing electrocatalysts for the
alkaline OER. It is worth noting that NiFe LDHs show the highest cat-
alytic activity among the non-noble metal-based OER electrocatalysts in
alkaline media. By tuning the composition and electronic structure,
adjusting the morphology, and designing novel synthesis methods, the
electrocatalytic performance of LDHs will far exceed that of
noble-metal-based electrocatalysts, which enables the low-cost feature
of alkaline water electrolyzers.[156–160] Although ultra-low overpoten-
tials have been achieved for LDHs (e.g., overpotential of 130 mV at
10 mA cm−2 for NiFe LDH/FeNi foil for the OER in 0.1 M KOH),[161]
metal dissolution and phase segregation reduce their activeness and
shorten their lifetime. Moreover, under continuous operations at high
current density and elevated temperature, structural defects induced by
structural degradation and amorphization form the main challenges for
the development of LDH catalysts.[162]
Single-atom catalysts: Single-atom catalysts (SACs) with well-distributed
transition-metal atoms and noble-metal atoms anchored onto the support-
ing matrix have received enormous attention for both scientific research
and industrial applications because they are remarkably active and highly
efficient in utilizing atoms (100%).[163–167] As a typical example, Li et al.
explained the nature of Pt single atoms under realistic HER conditions
(laboratory scale: 0.5 M H2SO4 at room temperature) by an operando X-
ray absorption spectroscopy technique.[168] It was found that the total
unoccupied density of states of Pt 5d orbitals of Pt1 atoms was higher than
that of Pt nanoparticles under the HER conditions, which contributed to a
higher level of HER activity for SACs.
One of the greatest challenges to a wide range of applications for
SACs lies in their stabilization under realistic working conditions. The
diffusion of single atoms on the supporting matrix and reconstruction
of SAC structures under different reaction conditions are urgently
needed for understanding the reaction mechanisms of SACs, which is
Figure 5. a) Technical characterization of the alkaline water electrolysis plant and system boundaries. electrolyzer must all be taken into account
b) Indicative system cost breakdowns for alkaline water electrolysis systems. c) Stack cost breakdown when considering the overall cost of this
for alkaline electrolyzers. Reproduced with permission from Ref. [9] Copyright 2017, Frontiers.
Energy Environ. Mater. 2022, 0, e12441 7 of 21
important for the stabilization of SACs. In addition, one of the key
approaches to stabilizing single metal atoms is through initiating a
strong interaction between metals and supports.[169] Therefore, in-
depth understanding on both the sintering and structural reconstruc-
tion mechanisms would provide guidance for designing efficient cat-
alytic systems and offering meaningful criteria for developing
promising industrial electrocatalysts.
Carbon-based materials: Carbon-based materials with high electrical
conductivity have been extensively investigated for electrocatalysts.
They are promising and cost-effective alternatives to noble-metal elec-
trocatalysts.[170–172] Although great progress has been made in design-
ing high-performance carbon-based electrocatalysts, there are several
issues that are challenging and awaiting to be solved before carbon-
based materials can be widely used in electrocatalysts. Remarkably, the
OER activity of some carbon-based materials is comparable to those of
noble-metal materials.[173] However, the HER activity of the former is
yet to be improved greatly to complete with the latter. Moreover, theo-
retical calculations have revealed that the electrocatalytic activity of
carbon-based materials is still inferior to that of metal-based materials
in most cases. Therefore, effective designing strategies are highly
desired to break the scaling relationships which limit the improvement
in the activities of carbon-based electrocatalysts. Moreover, carbon-
based materials are thermodynamically unstable under acidic OER con-
ditions, which leads to poor stability among mechanical and chemical
reactions in the process of electrocatalysis.[174]
3.4. Manufacturing Cost
Although water electrolysis has already had a long history of develop-
ment over many decades, only 4% of today’s hydrogen is produced
via water electrolysis, and most of it still comes about through reform-
ing fossil fuels.[175] Moreover, the costs of hydrogen per kg are US
$1.3–1.5 from the production of reforming fossil fuels and over US
$4 from renewable-powered water electrolysis. The high cost prevents
the prices being charged for green-water-electrolyzed hydrogen from
staying competitive in the commercial markets. Here, we would like
to highlight the fact that in addition to the cost incurred in the prepara-
tion of electrocatalysis, its manufacturing cost
is also a key factor to considering whether or
not to launch hydrogen production. For exam-
ple, Figure 5a illustrates some technical system
boundaries for an alkaline water electrolysis
plant.[9] It was found that the stack largely
determines the system’s cost, which accounts
for 50% of the overall cost (Figure 5b). A
breakdown of the stack cost revealed that most
of this cost is incurred by the anode and the
cathode (altogether accounting for 50% of the
stack cost) (Figure 5c). The rest of the cost is
incurred by other parts, although at a relatively
lower percentage. For instance, membranes
contribute to 7% of the stack cost, which
accounts for 3.5% of the total system cost. This
analysis suggests that the impact of cost from
the electrode and from the components of the
device.
© 2022 Zhengzhou University.
4. Bridging the Gaps Table 2. Summary of typical high-performance OER and HER electrocata-
lysts with low overpotentials.
4.1. Improving Catalyst’s Performance
Electrocatalysts Current Overpotential Electrolyte References
density (mV)
4.1.1. Reducing Overpotentials (mA cm−2)
OER electrocatalysts
Reducing the overpotentials of the OER and the HER is a crucial step in
improving the competitiveness of water electrolysis. Generally, this step NiFe LDH/FeNi foil 10 130 0.1 M KOH [161]
is challenged by initial adsorption and subsequent desorption steps to NiFe-NM@G 100 208 1.0 M KOH [192]
achieve an optimal level of the OER/HER process. Integrating functional NiFe(OH)x/(Ni,Fe)Se2/ 10 180 1.0 M KOH [190]
materials is an effective strategy through which to reach a synergistic CC
effect.[59,176–185] For example, it was discovered that NiFe LDH was NiFeS/NF 10 65 1.0 M KOH [193]
highly active but unstable, while birnessite was fairly stable but lacking
100 189
in activity. Chen et al. fabricated a 2D LDH(+)-Birnessite(−) hybrid
with success, and it exhibited outstanding OER performance under CoV-Fe0.28 10 215 1.0 M KOH [194]
close-to-industrial-evaluation conditions over 20 h at current densities Ni-Fe-W LDH/NF 100 247 1.0 M KOH [195]
of being greater than 100 mA cm−2.[186] The enlarged interlayer dis- 1000 329
tance, modulated electronic structure of layered MnO2 by flexible inter-
12Ru/MnO2 10 161 0.1 M HClO4 [196]
layer NiFe LDH(+), and an electric filed created between NiFe(+) LDH
and Birnessite(−) jointly contributed to the greatly decreased overpo- RuO2 nanosheets 10 199 0.5 M H2SO4 [197]
tential. Sargent’s group reported CrOx/Cu-Ni catalysts with multiple Etched Ru/Fe oxide 10 238 0.5 M H2SO4 [198]
active sites that can accelerate water dissociation.[187] Metallic Ni and Pt, La co-doped IrO2 10 205 0.5 M H2SO4 [199]
CrOx sites have strong hydrogen and hydroxyl binding energy, respec-
Co2MnO4 1000 <770 0.5 M H2SO4 [200]
tively, whereas Cu has a weak hydrogen binding energy that concur-
HER electrocatalysts
rently promotes hydrogen formation. The proposed multi-active site by
destabilization of water molecules contributed to a low overpotential of Ru/Ni/WC@NPC 10 3 1.0 M KOH [201]
48 mV to reach a current density of 10 mA cm−2 for the HER in a pH Ni-CeF3-VN 10 33 1.0 M KOH [202]
7 buffer electrolyte. Very recently, Fu et al. used hydrogen spillover to Ni3S2/Cr2S3@NF 3500 251 1.0 M KOH [188]
bridge Volmer/Tafel processes at the hybridized Ni3S2/Cr2S3 sites to
FeIr/NF 10 6.2 1.0 M KOH [203]
simultaneously promote water dissociation/OH* desorption steps.[188]
At the same time, they incapacitated the adsorbed H*- and/or OH*- 3500 471
induced inhibition effects. Through these actions, they achieved an Ni2P/NF 1500 368 1.0 M KOH [204]
ultralow HER overpotential of 251 mV to drive a high current density Pt/Ni-Mo 1000 33 1.0 M KOH [205]
of 3.5 A cm−2 in a 1.0 M KOH electrolyte.
2000 42
For the OER in alkaline solutions, multi-metal-based (oxy)hydrox-
ides, especially NiFe LDHs, exhibited low overpotentials.[5,17,33,189] For RuNi-alloy@SC 10 34 0.5 M H2SO4 [206]

example, a core-shell heterostructure containing amorphous NiFe Ru/RuS2 10 45 0.5 M H2SO4 [207]
(OH)x (shell) and crystalline (Ni,Fe)Se2 (core) showed an excellent Mn-NiCoP/NF 10 37 0.5 M H2SO4 [208]
OER activity with a low overpotential of 180 mV at 10 mA cm−2.[190] α-Ni(OH)2@Ir 10 20 0.5 M H2SO4 [209]
Moreover, Xiang et al. synthesized FeNi LDH nanosheet arrays on FeNi
V-doped CoP2/CC 10 50 0.5 M H2SO4 [210]
foil.[161] DFT calculations demonstrated that the formation of a hydrox-
ide interfacial layer between the FeNi foil and the LDH facilitated the 100 181
adsorption of an OH intermediate during the OER process. As a result, 2H Nb1.35S2 5000 420 0.5 M H2SO4 [211]
FeNi LDH/FeNi foil needed a mere 130 mV to obtain 10 mA cm−2 in CoS¦Ni¦P 100 88 0.5 M H2SO4 [212]
0.1 M KOH. For self-supported electrodes, besides achieving a low
1000 150
overpotential, an assessment of comprehensive parameters such as
exchange current density, turnover frequency value, and Faradaic effi- Co-NC-AF 1000 343 0.5 M H2SO4 [213]
ciency is also necessary.[5,53,191] Table 2 summarizes the recent pro-
gress made on the development of high-performance electrocatalysts
with low overpotentials. Some electrocatalysts with low overpotentials abundantly and actively available sites, good electron conductivity, great
that drive high current densities are also highlighted in the table. surface permeability, and excellent durability under harsh oxidizing
conditions to meet these requirements.[218–220] Furthermore, the
exposed active sites must also be homogeneously distributed under
4.1.2. Yields of Large Current Density such catalytic conditions at high temperatures. The influence induced
by continuously produced hydrogen and oxygen gas bubbles should
Commercial water electrolysis with large-scale production of hydrogen also be considered.[38,53,58,219] Directly growing functional materials
requires the designing of cost-effective and durable electrocatalysts. on a three-dimensional and conductive substrate is an effective strategy
Such electrocatalysts should also drive a large current density at a low to meet the above-mentioned requirements.[39,53,221–223] A substrate
overpotential.[52,54,58,214–217] An ideal electrocatalyst should have that provides a widely open hierarchical-channel network and

Energy Environ. Mater. 2022, 0, e12441 8 of 21 © 2022 Zhengzhou University.

 4.1.3. Enhancing Operational Stability

What is equally important to electrolysis is its

long-term operational stability.[24,226] Good
electrocatalytic performance on a laboratory
scale does not necessarily guarantee good activ-
ity and high stability on an industrial scale. Tak-
ing the bulk NiFe LDH as an example, its high
activity originates from its interlayer basal plane,
and possibly decreases with time due to its slow
diffusion of proton acceptors within its interlay-
ers under OER conditions. To enhance the OER
stability of NiFe LDH, especially under industrial
conditions such as raised temperatures and large
current densities, Liu’s group designed delami-
nated NiFe LDH with a morphology of atomi-
cally thin nanosheets. This facilitated diffusion
of proton acceptors, making it a potential mate-
rial for alkaline water electrolyzers.[186] Aimed
at commercialization of technology for electro-
chemical water splitting, operational stability
testing (including testing the testing time and
conditions) is required to approach the indus-
Figure 6. a) Scanning electron microscopy images of Ni foam, Ni microfiber felt, and Ni-Cu nanowire
felt. b) LSV curves of Ni foam, Ni microfiber felt, and Ni-Cu nanowire felt for OER. c) Cell potential as a trial level. For instance, a firm named Fuel Cells
function of time at constant current densities for the Ni microfiber felt. d) Water electrolysis and Hydrogen Joint Undertaking in Europe pro-
performance of the Ni microfiber belt as a function of cell potential. Reproduced with permission from posed the goal that a current density of
Ref. [224] Copyright 2020, Wiley-VCH. e) LSV curves of different transition metal dichalcogenides and 2500 mA cm−2 for PEM water electrolysis and
Pt. f) Water electrolysis performance with 2H Nb1.35S2 as a cathode and Pt as an anode. g) Calculated 800 mA cm−2 for alkaline water electrolysis
free-energy diagram for hydrogen evolution under standard conditions. Reproduced with permission should be achieved by 2030. More importantly,
from Ref. [211] Copyright 2019, Nature Publishing Group.
activity degradations by 0.12% and 0.1% per
1000 h of catalysts are also required of PEM and
functional catalysts, with the latter referring to nanosized materials with alkaline water electrolysis.[227] For a comprehensive understanding about
pores, could allow more active sites to be exposed. For example, Ni recent advances already achieved regarding overall water electrolysis
foam, Ni microfiber felt, and Ni-Cu nanowire felt were tested with in a under current densities which are industry relevant and about the long-
flow-cell configuration to study the effects of surface area and pore size term stability evaluation, a summary of representative electrocatalysts is
on the performance of alkaline water electrolysis (Figure 6a).[224] The provided in Figure 7. For example, Li et al. reported that the self-
nanowire felt initially exhibited an up-limit current density, but the supported porous Co-P foam could act as bifunctional electrocatalysts for
performance dramatically decreased as the generated bubbles were an alkaline water electrolyzer, requiring an overpotential of 380 and
trapped in the electrode. Ni foam with an open structure exhibited 290 mV to reach 1000 mA cm−2 for the OER and HER, respectively
good stability for bubble removal, yet its low surface area limited its (testing conditions: 1.0 M KOH at room temperature). The electrolyzer
current density. The microfiber felt demonstrated an optimal level of required a cell voltage of 1.98 V at 1000 mA cm−2 with an extraordinary
activity and durability due to its balanced surface area and capability to stability of 4000 h.[228]
get rid of bubbles. Notably, the Ni microfiber felt maintained an ultra-
high current density of 25 000 mA cm−2 for at least 100 h without
significant decay, which is far superior compared to the performances
of conventional alkaline and PEM electrolyzers (Figure 6b–d). This
work provides a strategy which modifies the electrode’s ability to
remove the gas bubbles and designs electrodes of the next-generation
for use in conducting practical water electrolysis.
Transition-metal dichalcogenides with a metallic property are good
candidates for HER.[225] Yang et al. reported a metallic 2H phase of
Nb1.35S2 as a high-performance HER catalyst, which can drive a high
current density of 5000 mA cm−2 at an overpotential of ≈420 mV in
0.5 M H2SO4 (Figure 6e).[211] The two-electrode electrolyzer
(commercial Pt as the anode) needed an ultra-low cell voltage (1.3 V)
to initiate the reaction and 2.0 V to obtain 1000 mA cm−2 (Figure 6f).
The theoretical calculations revealed that 2H Nb1+xS2 with an Figure 7. Summary of the electrolyzer’s performances in terms of their cell
Nb-terminated surface exhibited free energy for hydrogen adsorption voltages and stability testings.
that is close to thermoneutral (Figure 6g).

Energy Environ. Mater. 2022, 0, e12441 9 of 21 © 2022 Zhengzhou University.

4.2. Operations Under Industrial-Relevant Conditions
The above studies have focused on evaluating OER and HER perfor-
mances at room temperature. In addition, it was necessary to evaluate
electrocatalytic activity of water electrolysis under industrial conditions.
In this part, we shall provide a summary on recent advances that have
been made regarding this topic.
4.2.1. Testing Conditions at Elevated Temperatures
The RDE technique is a quick and effective method for screen checking
the intrinsic activity and durability of electrocatalysts that have been
designed. In terms of doing fundamental research on a laboratory scale,
raising the temperature of the electrolyte from room temperature to a
higher level is a simple and easy task to simulate realistic industrial test- ure 8c,d). Notably, the onset overpotential and overpotentials at a
ing conditions.[229] Therefore, more studies have focused on testing
conditions at elevated temperatures.
Figure 8. LSV curves of various catalysts for the OER evaluated at a) 25 °C and c) 50 °C. Stability
evaluation of FeMOFs-SO3 at a fixed current density of 1000 mA cm−2 for 100 h at b) 25 °C and d)
50 °C. Reproduced with permission from Ref. [231] Copyright 2020, Wiley-VCH. e) LSV curves for the authors did not evaluate its durability under
different electrolyzers and f) Chronpotentiometric curve at 1000 mA cm−2 for NiFe(OH)x/Ni3S2/NiǀǀNiMo harsh conditions.
electrolyzer for overall water electrolysis in 30 wt.% KOH electrolyte at 80 °C. Reproduced with
permission from Ref. [232] Copyright 2022, Wiley-VCH.
Research on OER in alkaline solutions to produce hydrogen via a
water electrolysis technique has witnessed prosperity with development
of efficient catalysts. In particular, transition-metal-based materials are
regarded as state-of-the-art OER electrocatalysts, which are superior to
noble-metal-based catalysts in terms of their lower cost and higher cat-
alytic performances. Fe, which is the second most abundant metal on
Earth, is a promising block to construct cost-effective electrocatalysts
when compared to Co and Ni.[230] For example, utilizing the method of
sulfur treatment of Fe-based MOFs, Feng et al. designed a promising
OER catalyst that could reach current densities of 10, 500, and
1000 mA cm−2 at ultralow overpotentials of 218, 289, and 330 mV at
room temperature with superior stability (Figure 8a,b).[231] Impor-
tantly, this catalyst could achieve 1000 mA cm−2 at an overpotential of
296 mV (which is even lower than 300 mV at such a large current den-
sity) along with a satisfactory level of stability at 50 °C for 100 h (Fig-
current density of 10 mA cm−2 at 50 °C for this Fe-based catalyst were
superior to those of noble metal oxide (RuO2) and nickel foam. To fur-
ther approach the testing conditions for a com-
mercial alkaline water electrolyzer, Wang et al.
studied the overall water splitting performance
of NiFe(OH)x/Ni3S2/Ni(anode)ǀǀNiMo(cath-
ode) in 30 wt.% KOH electrolyte at
80 °C.[232] Remarkably, this two-electrode
device required a cell voltage of 1.61 V to
achieve 1000 mA cm−2 (Figure 8e), which is
much lower than what is required for the elec-
trolyzers in 1.0 M KOH at room temperature.
Moreover, the catalytic durability of this pair
was verified through a long-term chronopo-
tentiometric measurement at a high current
density of 1000 mA cm−2. This measurement
showed a steady cell-voltage of approximately
1.61 V over 1500 h (Figure 8f).
Additionally, a bifunctional electrocatalyst
showing both exceptional OER and HER per-
formances in the same electrolyte is urgently
needed. Such an electrocatalyst can simplify
the water electrolysis system and operational
procedures and then reduce the manufactur-
ing cost and energy consumption. Macrop-
orous CoFeP triangular plate arrays have been
demonstrated as remarkable bifunctional elec-
trocatalysts for the OER and the HER.[233] In
addition to evaluating their activities for over-
all water electrolysis at 30 °C, the authors fur-
ther tested the catalyst’s water splitting
performances at an industrial temperature of
60 °C to demonstrate its potential in practical
applications. When the temperature reached
60 °C, the overall performance was enhanced
greatly. This was demonstrated by the fact that
low cell voltages of 1.34 and 1.70 V delivered
10 and 100 mA cm−2, respectively. Although
such low voltages had not been reported, the
In addition to alkaline water electrolysis,
electrolysis in acidic electrolytes is also a

Energy Environ. Mater. 2022, 0, e12441 10 of 21 © 2022 Zhengzhou University.

promising technique for hydrogen production. State-of-the-art OER elec- thermodynamically stable lead oxide matrix. Notably, this method was
trocatalysts under acidic conditions still rely on noble-metal-based materi- unsuitable for up-scaled situations due to the low concentrations of metal
als, which are not ideal for industrial applications due to their high cost ions in the acidic electrolyte. Further modifications were necessary to tai-
and instability, the problem of which remains unsolved. Few studies have lor it for use in devices for water electrolysis.
paid enough attention to designing both thermodynamically stable and
electrocatalytically active OER electrocatalysts for use in acidic electrolyzers
at elevated temperatures. As a typical example, having benefited from the 4.2.2. Performance in Industrial Electrolyzer Systems
study of self-healing mechanisms, Chatti et al. designed OER catalysts
based on non-noble metals (e.g., Fe, Co, Ni, and Pb), which formed in Our ultimate goal in designing superior electrocatalysts for the OER
situ in its electrochemical process under acidic conditions. These catalysts and HER is to incorporate them into overall water electrolysis devices.
exhibited high operational durability.[234] Notably, the OER activity of However, the working conditions of industrial electrolyzer systems are
the CoFePbOx system even outperformed that of noble-metal-based cata- quite different from those of the RDE beyond the working temperatures
lysts, such as SrIrO3/IrOx. Moreover, the CoFePbOx catalyst, which is and electrolyte concentration. For example, significant mechanical pres-
self-healing, possessed robust stability under strong acidic conditions at sure from gas bubbles that have been produced can build up in the
industrial temperatures. Specifically, the above electrode could provide a flow reactor at elevated temperature and with high current density dur-
stable current density of up to 500 mA cm−2 with overpotentials of ing operation. These factors cause rapid degradation of performances
lower than 700 mV and at temperatures of up to 80 °C with essentially on the devices and complicated reaction mechanisms over practical
a flat support. The key factors for exercising a robust operation are active applications when compared with those under the RDE technique in
and homogeneously distributed active dopants as well as a fundamental research. Therefore, assessing catalysts’ performances
among industrial electrolyzer systems is neces-
sary for evaluating large-scale applications for
designed catalysts.[92,235–237]
The precatalyst of NiMoO4 is a potential
water electrolysis anode which demonstrates
OER mechanisms and dynamic reconstruction
processes at high temperatures. MoO2-Ni-
heterostructured nanowires grown on com-
mercial nickel foam showed Pt-like HER activ-
ity at room temperature.[88] Furthermore, its
durability was evaluated at industrial tempera-
tures. Remarkably, the catalyst could tolerate
such harsh conditions for at least 115 h and
still maintain its high catalytic activity at
51.9 °C. The activity and durability of both of
those electrodes were excellent when coupled
with MoO2-Ni and cat.-51.9 as anode and
cathode electrodes, respectively, while operat-
ing in a water electrolysis device at 51.9 °C
(Figure 9a). That work showcased that the
rational designs of OER and HER electrocata-
lysts made high-performance. Those designs
were applied to water electrolysis under oper-
ation at high temperatures. Recently, Zhang et
al. designed an OER catalyst which displayed
high performance and could be used at room
temperature. They designed it by reprogram-
ming transition metals in the first row (e.g.,
Fe, Co, and Ni) and incorporating high-
valence transition-metal modulators (e.g., W,
Mo, MoW, Nb, Ta, and Re) into it.[236] When
this optimized catalyst was utilized under
industrial conditions (Figure 9b,c), they had
managed to enhance its mass activity by a
Figure 9. a) Stability evaluation of MoO2-Ni nano-arrays/nickel foam at a constant current density of ≈ 17-fold relative to a commercial catalyst,
10 mA cm−2 at 51.9 °C. Reproduced with permission from Ref. [88] Copyright 2020, Wiley-VCH. b)
and still make it stable (Figure 9d,e).
Schematic illustration of the composites of an electrolyzer cell. c) Photograph of industrial water
electrolyzer equipment. d) Polarization curves of overall water electrolysis with a NiFeMo catalyst and a To achieve high activity and retain it for an
Raney Ni electrode as the anode and a Ru electrode as the cathode. e) Stability evaluation of the high- extended period of time (e.g., 50 000 h) for
temperature overall water electrolysis at a constant current density of 300 mA cm−2 at 80–85 °C and a PEM water electrolyzer under commercial
2 MPa for 12 h. Reproduced with permission from Ref. [236] Copyright 2020, Nature Publishing Group. use, platinum-group catalysts such as Pt and Ir

Energy Environ. Mater. 2022, 0, e12441 11 of 21 © 2022 Zhengzhou University.

have been used.[238] Reducing the usage of precious metals and design-
ing catalysts in the non-platinum group are two of the methods via
which to lower the cost of the device. For example, through use of a
pyrolysis-synthesis method and a co-doping strategy, torsion-strained
TaxTmyIr1-x-yO2-δ nanoparticles with abundant trigeminal grain bound-
aries were obtained.[92] In addition to achieving a low overpotential of
198 mV at 10 mA cm−2 for the OER in 0.5 M H2SO4, a PEM water
electrolyzer using Ta0.1Tm0.1Ir0.8O2-δ as the anode and Pt/C as the cath-
ode was constructed (Figure 10a). The polarization curves showed that
cell voltages of 1.868 and 1.894 V could drive current densities of 1.5
and 2 A cm−2, respectively (0.5 M H2SO4 at 50 °C) (Figure 10b).
Moreover, the PEM electrolyzer could be operated at 1.5 A cm−2 for
500 h without experiencing significant performance decay (Fig-
ure 10c). Remarkably, the estimated cost for this device was only US $1
per kilogram of hydrogen, which is much lower than the targeted cost
set by the US Department of Energy (US $2 per kilogram of hydrogen).
King et al. demonstrated the practicability of using an efficient HER cata-
lyst from a non-platinum group (cobalt phosphide, CoP) in a commer-
cial PEM electrolyzer.[239] Over the course of laboratory-scale testing
(i.e., through use of a liquid electrode, with an electrode area of 1 cm2,
and under ambient temperature and pressure), the CoP showed excel-
lent HER activity and stability. Even though the activity of the CoP was
not superior to that of platinum, the CoP exhibited little activity degra-
dation revealed by the CV testing. For evaluations on a commercial scale,
a tailor-made electrolyzer was constructed to approach the realistic test-
ing conditions (with an electrode area of 86 cm2, a pressure of 400 psi,
and a temperature of 50 °C) (Figure 10d). The total loading of the cata-
lyst (including the carbon support) was 4.5 mg cm−2, with a CoP
loading of 1.0 mg cm−2 on the cathode gas diffusion electrode. The
electrolyzer with the CoP membrane electrode assembly delivered cur-
rent densities of 0.1 and 1.86 A cm−2 at a cell voltage of 1.54 and
2.27 V, respectively (Figure 10e). In comparison, the platinum mem-
brane electrode assembly needed 2.05 V to obtain 1.86 A cm−2. This
comparison revealed operating efficiencies for CoP- and platinum-based
electrolyzers to be 55% and 61%, respectively. CoP exhibited promising
catalytic performance with continuous production of hydrogen under
operation at 1.86 A cm−2 for at least 1700 h (Figure 10f). More impor-
tantly, utilization of catalysts selected from non-precious metals reduced
the cost of resources significantly compared to the use of platinum as
the catalyst. However, studies on HER performance under industrial
conditions are still limited. Similar to the OER, the HER’s surface recon-
struction mechanisms under room and industrial temperatures may dif-
fer from each other as well. Thus, there is yet work to be done amid
provision of specific reaction mechanisms of HER under industrial con-
ditions.
Designing AEMs and ionomers which possess superior mechanical
properties, high ion conductivity, and high durability under alkaline
conditions is a prerequisite for AEM water electrolyzers to achieve
remarkable performances.[240–243] Chen et al. reported anhydrous cath-
ode AEM water electrolyzers which made outstanding performances with
its rational design of an electrode that was based on poly(fluorenyl-co-
aryl piperidinium) (PFAP) ionomers and AEMs (Figure 11a,b).[237] A
record-high current density of 7.68 A cm−2 at 2.0 V with a 1.0 M KOH
electrolyte was obtained for AEM water electrolyzers (where most of the
current density was below 4 A cm−2 at 2.0 V) with platinum-group
metal catalysts, which surpassed the state-of-the-art PEM water

Figure 10. a) Schematic diagram of PEM water electrolyzer. b) Polarization curves of IrO2-δ-based materials as anode catalysts. c) Durability tests for the
PEM electrolyzer operated at 1.5 A cm−2. Reproduced with permission from Ref. [92] Copyright 2021, Nature Publishing Group. d) Photograph of the 86 cm2
electrolyzer set-up. e) Polarization curves of CoP and commercial platinum at industrial scale. f) Durability tests for the polymer electrolyte membrane
electrolyzer. Reproduced with permission from Ref. [239] Copyright 2019, Nature Publishing Group.

Energy Environ. Mater. 2022, 0, e12441 12 of 21 © 2022 Zhengzhou University.

electrolyzers (6 A cm−2 at 2.0 V) (Figure 11c). Meanwhile, platinum-
group metal-free AEM water electrolyzers exhibited a high current den-
sity of 1.62 A cm−2 at 2.0 V (Figure 11d). A high stability of operation
was observed under a current density of 0.5 A cm−2 for more than
1000 h without experiencing voltage decay (Figure 11e,f). This
achievement highlighted the potential application of anhydrous cathode
AEM water electrolyzers and advanced the progress that AEM water elec-
trolyzers could make. Yang et al. deigned a Pt/Ni-Mo electrocatalyst
which required only an overpotential of 113 mV to reach a high current
density of 2000 mA cm−2 in a 1.0 M KOH solution at room tempera-
ture.[205] Up-scaled production and larger-scaled applications were con-
ducted afterwards (Figure 11g). The Pt/Ni-Mo catalyst was used in a
membrane electrode assembly electrolyzer, and one membrane electrode
assembly stack consisted of two OER cells in the middle and two HER
cells on the sides (Figure 11h). The electrolyzer systems utilized nickel
foam as the anode and Pt/Ni-Mo as the cathode, and required a cell volt-
age of 2.06 V to reach 600 mA. The voltage was much lower than
2.63 V, which was required of the original commercial electrolyzer sys-
tem that used Pt and Ir/Ru as materials. More importantly, the price of
Pt/Ni-Mo is much lower than that of other platinum-group metal-based
catalysts and comparable with non-platinum-group metal catalysts (Fig-
ure 11i).
4.3. Understanding the Catalyst’s Reconstruction Under
Different Testing Conditions
4.3.1. Thermal-Induced Reconstruction Without Electrochemical Treat-
ments
Most studies have focused on designing advanced catalysts by incorpo-
rating various strategies, such as substituting foreign elements and engi-
neering a defective/interface/crystal structure. Different from this focus,
some studies have looked into the scenario where precatalysts interact

Figure 11. a) Schematic diagram of the AEM water electrolyzer used in this work. b) Chemical structure and physical parameters of PFTP-13 AEMs. c)
Polarization curves of the AEM water electrolyzer at 80 °C based on platinum-group metal catalysts. d) Polarization curves of the AEM water electrolyzer at
60 and 80 °C based on Ni-Fe composite. e) Platinum-group metal AEM water electrolyzer based on the PFTP-13 AEM under 0.5 A cm−2 at 60 °C. f) Ni-Fe
AEM water electrolyzer based on the PFTP-13 AEM under 0.5 A cm−2 at 60 °C. Reproduced with permission from Ref. [237] Copyright 2021, Royal Society
of Chemistry. g) A photo of the TH-1000 Hydrogen Generator. h) Stack structure for AEM water electrolyzer. i) Comparison of the price and activity for Pt/
Ni-Mo catalyst and other catalysts. Reproduced with permission from Ref. [205] Copyright 2021, Wiley-VCH.

Energy Environ. Mater. 2022, 0, e12441 13 of 21 © 2022 Zhengzhou University.

 made among evolutions of the phase struc-
ture, morphology, and microstructure
between room temperature (25 °C in this
study, denoted cat.-25.0) and industrial
temperature (51.9 °C in this study,
denoted cat.-51.9).[88] HRTEM images
revealed that the dense surface reconstruc-
tion layer was ≈6 nm for the cat.-25.0
after the OER process (Figure 14a). When
the electrolyte temperature was increased, the
degree of reconstruction expanded (e.g., as
large as ≈19 nm of the amorphous layer for
cat.-32.4) (Figure 14b,c). When the elec-
trolyte temperature reached 51.9 °C, there was
no apparent boundary between the NiMoO4
precatalyst and surface reconstruction-induced
NiOOH (Figure 14d). Notably, an ≈5 nm
orthorhombic NiOOH nanoparticle-
interconnected structure with considerable
Figure 12. a) XRD patterns of pristine NiFe-layered double hydroxide and pristine materials after immersion for
grain boundaries was observed, which was
60 h in 1.0 M KOH at room temperature and 7.5 M KOH at 80 °C. b) HRTEM and STEM-EDS images of NiFe- attributed to the full leaching of Mo ions and
layered double hydroxide after immersion for 60 h in 7.5 M KOH at 80 °C. c) LSV curves and d) Tafel plots of complete surface reconstruction of the
the three materials for the OER. Reproduced with permission from Ref. [244] Copyright 2018, Wiley-VCH. NiMoO4 precatalyst, as confirmed by in situ

with an electrolyte at high temperatures (>80 °C) and without electro-

chemical polarization, and they in turn undergo phase transformations,
thus impacting the catalytic performance of the catalyst. For example,
Andronescu et al. found that the phase structure of NiFe LDH trans-
formed into a mixed structure consisting of β-Ni(OH)2 and amorphous
FeOOH under the conditions of 7.5 M KOH solution at 80 °C for 60 h
without undergoing electrochemical treatment (Figure 12a,b).[244]
Although no noticeable structural changes were observed after the pris-
tine sample was treated in 1.0 M KOH at 25 °C for 60 h, there was still
a decline in the catalytic activity. Clearly, the high-temperature-treated
sample exhibited a substantial decline in OER activity and reaction
kinetics (Figure 12c,d). Based on these findings, the authors
recommended that when evaluating the OER activity of designed cata-
lysts, concurrently evaluating their stability under realistic industrial
conditions is necessary.

4.3.2. Thermal- and Electrochemical-Induced Reconstruction

The surface self-reconstruction of electrocatalysts occurs commonly in

materials when they are tested at room temperature. Due to the dense
reconstruction layer and limited mass transportation, a limited depth of
reconstruction (<10 nm) is usually observed (Figure 13a).[245] For
example, Xie’s group reported that the vibronic superexchange interaction
facilitated the surface formation of active species (Ni/Mn oxide/hydrox-
ide) for double perovskite La2NiMnO6 nanoparticles.[246] Specifically, after
50 CV tests, an amorphous layer with a thickness of approximately 1 nm
was generated on the catalyst surface. As the electrochemical process pro-
ceeded, the thickness of the amorphous active species increased, and
reached a steady level gradually (5–8 nm) (Figure 13b).
However, the electrochemical surface reconstruction of precatalysts Figure 13. a) Summary of surface and complete reconstruction results for
some reported precatalysts in one dimension. Reproduced with permission
is accelerated and expanded at industrial temperatures. The true cat-
from Ref.[245] Copyright 2020, CellPress. b) HRTEM images of pristine
alytically active sites and surface reconstruction mechanism between La2CoMnO6 and samples after 50, 100, and 500 CV cycles for OER tested at
room temperature and industrial conditions may differ from each room temperature. Reproduced with permission from Ref. [246] Copyright
other. For example, Liu et al. presented a comprehensive comparison 2018, American Chemical Society.

Energy Environ. Mater. 2022, 0, e12441 14 of 21 © 2022 Zhengzhou University.

Figure 14. a–d) HRTEM images of cat.-25, cat.-32.4, cat.-39.6, and cat.-51.9 after the OER tests. In situ e) low-temperature and f) high-temperature Raman
spectra along with the chronopotentiometric curves. g) Comparison of overpotentials and h) Tafel plots of cat.-25, cat.-32.4, cat.-39.6, and cat.-51.9 for the
OER. i) Schematic illustration for the comparison of surface reconstruction of NiMoO4 under room temperature and industrial temperature electrooxidation
conditions. Reproduced with permission from Ref. [88] Copyright 2020, Wiley-VCH.

high-temperature Raman spectra and high-angle annular dark-field scan-
ning transmission electron microscopy (Figure 14e,f). In addition, the
completely reconstructed catalyst featured abundant vacancy or boundary
properties, which brought about a vacancy-boundary coeffect that could
efficiently lower the reaction energy barrier and promote OER kinetics.
This was demonstrated by both experimental data and theoretical analyses.
Cat.-51.9 exhibited significantly improved OER activity given the com-
pletely reconstructed catalyst, as evidenced by the low overpotential corre-
sponding to 10 mA cm−2 and small Tafel slopes (Figure 14g,h). Thus,
the commonly reported surface reconstruction at room temperature
might be different from that done under high-temperature conditions
(Figure 14i). The industrial application of a designed catalyst must take

Energy Environ. Mater. 2022, 0, e12441 15 of 21 © 2022 Zhengzhou University.

into account the reconstruction effect that thermal and electrochemical co- 5.2. Material Designs for the Next-Generation
induced.
When designing electrocatalysts in the process of doing fundamental
research, there are diverse criteria that should be considered: 1) The
5. Conclusion and Perspectives catalyst should be highly efficient, have a high current density, and pos-
sess a low overpotential; 2) This catalyst should be durable with no
In this review, we have pointed out the substantial gaps in existence in observable loss of performance during a long period of testing time; 3)
water electrolysis between its fundamental research and industrial appli- The catalysts for alkaline and AEM water electrolysis must be based on
cation, and summarized recent efforts that have been made to bridge earth-abundant elements; 4) Reducing usage of noble metals, improv-
these gaps. It is demonstrated that the surface self-reconstruction mecha- ing electrochemical performance of catalysts, and developing non-
nism and related real catalytic species may differ from each other under precious metal catalysts form the main tasks for launching PEM water
ambient (laboratory scale) and industrial conditions (industrial scale). electrolysis; 5) The catalysts used should be recyclable.
We also highlighted the critical importance in evaluating catalysts under It was demonstrated that an ultrahigh current density of
harsh industrial conditions. In addition to material design, some other 1500 mA cm−2 is the default value for the hydrogen produced via water
key factors that determine the cost and efficiency of practical applications electrolysis. Using self-standing electrodes (i.e., electrodes that are pre-
should also be considered. Great efforts still urgently need to be made pared by hydrothermal, electrospinning, and filtration methods, and so
for designing the next-generation electrocatalysts so as to meet the on and so forth) which contain functional active species anchored on a
requirements set forth under industrial conditions. Here, we provide the conductive substrate (such as metal foam or carbon paper) and are free
future perspectives and strategies needed to bridge the gaps between of a binder and current collector, we identified an effective approach to
material science and engineering. improving the current density and maintaining long-term stability.
However, the currently explored and self-supported electrodes exhibited
remarkable performance only through alkaline water electrolysis. Such
5.1. Electrocatalytic Performance and Evaluation Principles efficient electrodes have rarely been reported using acidic media, and it
is especially so for the overall water electrolysis under industrial testing
As mentioned above, the industrial temperatures used in commercial conditions. This is mainly due to the poor OER performance and unsta-
water electrolyzers typically range from 50 to 80 °C. From the test condi- ble chemical and structural properties of transition-metal-based materials
tions summarized in conjunction with the industrial alkaline water elec- in the acid solutions. To address these issues, we need to consider select-
trolysis (Table 3), various temperatures and different concentrations of ing materials with great inherent corrosion resistance and developing
electrolytes have been adopted. This makes direct comparisons among anti-corrosion coating strategies. Additionally, special attention should
reported materials a challenge. Therefore, when evaluating electrocatalysts be paid to the deposited nanostructured catalysts, though there have
under industrial conditions, it is strongly recommended to establish test- been few studies on substrates. Nickel foam, iron foam, and copper
ing criteria. For example, the elevated temperature of 60 °C and a high- foam are commonly used metal foams for self-supported electrode
concentration electrolyte of 6.0 M KOH are recommended as criteria for designs. One critical issue is how to deal with the unsatisfactory mechan-
evaluating the practical alkaline water electrolysis performance. An extra- ical strength of metal foams under industrial testing conditions and with
long stability testing (lasting more than 1000 h) under a high current large current density and high temperature. Therefore, more efforts
density (with at least 500 mA cm−2) is the prerequisite for turning elec- should be made to develop advanced substrates.
trocatalysis into a potential industrial application. In addition to designing electrocatalysts capable of making high per-
formances in their practical applications, it is essential to develop eco-
nomical ways of producing electrocatalysts on a large scale. This is
Table 3. Comparison of different alkaline OER/HER electrocatalysts with because physicochemical properties and electrocatalytic activities of the
respect to different industrial testing conditions.
catalysts depend strongly on the methods of synthesis.[118,256,257] For
Electrocatalysts Applications Electrolyte Temperature (°C) References
example, an industrial alkaline water electrolyzer usually requires the
electrodes to have an area larger than 500 cm2 or even reaching several
NiFeMo OER/HER 30 wt.% KOH 85 [236]
square meters in a cylindrical vessel.[205]
NiFe(OH)x/Ni3S2/Ni OER 30 wt.% KOH 80 [232]
FeIr alloy OER/HER 30 wt.% KOH 60 [247]
5.3. Improved Theoretical Insights
LDH-Bir OER 6.0 M KOH 85 [159]
FeNi2S4@NiFe-LDH OER 6.0 M KOH 70 [229] Use of recently developed descriptors that link the structure to perfor-
Ni/MoO2@CN OER/HER 6.0 M KOH 60 [248] mances of catalysts promotes our understanding of the physics and
F, P-Fe3O4/IF HER 6.0 M KOH 60 [249] chemistry underlying OER/HER catalysts. However, while these descrip-
tors have been successful, they are based on room temperature, and are
NiFe@GO/NF OER 6.0 M KOH 50 [250]
not necessarily applicable to industrial conditions. Advanced descriptors
CoFe/Co-BF OER/HER 5.0 M KOH 70 [251] suitable for industrial conditions should be developed so that designing
NiFe LDH-MoSx OER 5.0 M KOH 65 [252] next-generation electrocatalysts can be tailored to practical applications.
WC-Mo2C@CC HER 10.0 M KOH 70 [253] The currently established theoretical calculations are also based on room
3D-O2-Cat-1 OER 10.0 M KOH Room temperature [254]
temperature. In addition to the difficulty of choosing physical models
and computational parameters, it is also difficult to consider the effects
F-Co2P/Fe2P/IF HER 6.0 M KOH Room temperature [255]
that industrial conditions (such as the temperature and concentration of

Energy Environ. Mater. 2022, 0, e12441 16 of 21 © 2022 Zhengzhou University.

the electrolyte and the testing time) have on catalysts’ screening and pre-
diction.[258] Therefore, it is a tremendous challenge for us to precisely
model the different work conditions and rationally establish a correlation
between the structure and the observed activities at industrial levels. This
is a challenge that we need to urgently overcome.
Acknowledgement
H.S. and X.X. contributed equally to this work. This work was financially sup-
ported by the Priority Academic Program Development of Jiangsu Higher Educa-
tion Institutions (PAPD). This research was supported by National R&D Program
through the National Research Foundation of Korea (NRF), grant number
2021M3H4A1A01079300, and the Korea Research Institute of Chemical Technol-
ogy Core Research Program funded by the Korea Research Council for Industrial
Science and Technology, grant number KS2222-10.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
electrocatalyst design, electrochemical water splitting, gaps and bridges,
laboratory scale and industrial scale
Received: February 7, 2022
Revised: April 26, 2022
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