Hydrogen Production From Water Electrolysis: Role of Catalysts

Wang
et al. Nano Convergence (2021) 8:4

https://doi.org/10.1186/s40580-021-00254-x
REVIEW Open Access
Hydrogen production from water

electrolysis: role of catalysts
Shan Wang, Aolin Lu and Chuan‑Jian Zhong*
Abstract
As a promising substitute for fossil fuels, hydrogen has emerged as a clean and renewable energy. A key challenge is
the efficient production of hydrogen to meet the commercial-scale demand of hydrogen. Water splitting electrolysis
is a promising pathway to achieve the efficient hydrogen production in terms of energy conversion and storage in
which catalysis or electrocatalysis plays a critical role. The development of active, stable, and low-cost catalysts or
electrocatalysts is an essential prerequisite for achieving the desired electrocatalytic hydrogen production from water
splitting for practical use, which constitutes the central focus of this review. It will start with an introduction of the
water splitting performance evaluation of various electrocatalysts in terms of activity, stability, and efficiency. This will
be followed by outlining current knowledge on the two half-cell reactions, hydrogen evolution reaction (HER) and
oxygen evolution reaction (OER), in terms of reaction mechanisms in alkaline and acidic media. Recent advances in
the design and preparation of nanostructured noble-metal and non-noble metal-based electrocatalysts will be dis‑
cussed. New strategies and insights in exploring the synergistic structure, morphology, composition, and active sites
of the nanostructured electrocatalysts for increasing the electrocatalytic activity and stability in HER and OER will be
highlighted. Finally, future challenges and perspectives in the design of active and robust electrocatalysts for HER and
OER towards efficient production of hydrogen from water splitting electrolysis will also be outlined.
Keywords: Electrocatalysts, Water splitting electrolysis, Hydrogen production, Energy storage and conversion,
Oxygen evolution reaction, Hydrogen evolution reaction
1 Introduction storage system is required in conjunction with the explo-

Energy and environment are two key issues in mod- ration of renewable energy sources for large scale utiliza-
ern society which are necessities for the economic and tion [1]. This need constitutes a major driving force for
social sustainable development of the world [1, 2]. In numerous innovations in energy conversion and storage
2018, there is 79.5% energy economy that relies on con- systems. Indeed, systems such as hydrogen production
ventional energy sources such as coal, petroleum oil, and from water splitting by electrolysis, fuel cells for convert-
natural gas, which are not renewable and environmen- ing hydrogen to electricity, and lithium-ion or metal-
tally benign [3]. To deal with this problem, there has been air batteries for energy storage have drawn a great deal
a global drive seeking renewable and clean alternatives of attention in recent decades [5]. For the battery-based
to fossil fuels. Nature offers various renewable sources energy storage, it is increasingly difficult to store excess
such as solar energy, wind energy, tidal energy, biomass electricity from a large-scale production facility, which is
energy, etc. However, such energy sources suffer from very expensive and needs a large facility area. With the
intermittent availability due to regional or seasonal fac- large-scale solar or wind produced excess electricity, an
tors [4]. As a result, an efficient energy conversion and alternative pathway for energy storage is needed. Hydro-
gen production by electricity-driven water splitting has
become a promising strategy to convert the large excess
*Correspondence: cjzhong@binghamton.edu
Department of Chemistry, State University of New York at Binghamton, amount of electrical energy from the renewable energy
Binghamton, NY 13902, USA resources in the form of a clean fuel—hydrogen (H2). As
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Wang et al. Nano Convergence (2021) 8:4 Page 2 of 23
a clean and sustainable energy carrier, hydrogen has the required to minimize the overpotentials for OER and
highest gravimetric energy density. When it is used as the HER towards efficient H2 and O2 production.
fuel in a fuel cell, it features not only high efficiency in The design of catalysts or electrocatalysts depends
energy conversion, but also produces zero pollution as on the operating conditions of the water electrolysis
it emits only water as a byproduct. Therefore, the devel- cell. Currently, there are three main types of electroly-
opment of water splitting cells for hydrogen production sis technologies: (1) proton exchange membrane (PEM)
from renewable sources and fuel cells for effective con- electrolysis (2) alkaline electrolysis (3) high-temperature
version of hydrogen to electricity has become a global solid oxide water electrolysis. The solid oxide water elec-
drive towards a sustainable power package of the future trolysis requires high energy consumption because of the
(Fig. 1). This development is leading its way to address high temperature. For the PEM based electrolysis cell, the
many of the challenging issues facing energy and envi- water splitting is performed under acidic condition and
ronmental sustainability. Significant progress has been using PEM. This condition has some advantages over
made in the fronts of electrolysis water-splitting cells [1, other conditions such as lower gas permeability and high
2, 5–11] and fuel cells [12–18], offering hopes for a sus- proton conductivity. It features high energy efficiency and
tainable transition to carbon–neutral operations. fast hydrogen production rate [8]. However, the require-
Among many aspects of the progress in the development of acidic media limits the OER electrocatalysts to
ment of the sustainable power package of the future, noble metal and noble metal oxide catalysts, which are
catalysis, or electrocatalysis, has played a major role the state-of-the-art OER electrocatalysts in the acidic
in overcoming the kinetic energy barriers for electro- media. This requirement leads to a high cost for the cell
chemical reactions of water, oxygen, and hydrogen in [27]. For the alkaline electrolysis cell, water splitting
water-splitting cells and fuel cells (Fig. 1). It is the role is performed under alkaline condition. In comparison
of catalysis in electrolysis water-splitting cells that is the with cells using acidic media, water splitting in alkaline
focal point of this review. The readers are referred to sev- media broadens the selection of the electrocatalysts to
eral recent reviews for the role of catalysis in fuel cells non-noble metals or metal oxides. However, the activity
[15, 19–26]. of HER in alkaline media is usually 2–3 orders of magni-
Generally, the overall reaction of water electrolysis can tude lower than the activity of HER in acidic media [28].
be divided into two half-cell reactions: hydrogen evo- Therefore, the design of optimal electrocatalysts suitable
lution reaction (HER) and oxygen evolution reaction for the different media with low-cost, high catalytic activ-
(OER). HER is the reaction where water is reduced at the ity, and good durability for electrolytic water splitting is
cathode to produce H2, and OER is the reaction where very challenging.
water is oxidized at the anode to produce O2. One of Because of the surge of recent interest in hydrogen pro-
the critical barriers that keep water splitting from being duction from water electrolysis, there have been many
of practical use is the sluggish reaction kinetics of OER excellent reviews describing the progress of research in
and HER due to high overpotentials[5], a measure of the HER and OER [4, 8, 29]. Many of the reviews focused on a
kinetic energy barriers. Therefore, catalysis plays a major comprehensive overview in terms of the half-cell reaction
role in both OER and HER. Highly effective catalysts are mechanisms in alkaline media, and the progress in the
Fig. 1 a An illustration of the evolution of fuels in terms of hydrogen to carbon ratio. b Illustrations of a dual cell functioning as an electrolysis water
splitting cell for hydrogen production from solar energy and a fuel cell for the conversion of hydrogen to electricity, highlighting the sustainable
power package of the future and the role of catalysis
preparation of noble metal-free electrocatalysts which in the design of nanostructured electrocatalysts for HER
exhibit excellent catalytic activity and durability for HER and OER towards efficient production of hydrogen from
and OER. There is a relatively limited number of reviews water splitting by electrolysis will also be outlined.
discussing insights into mechanistic details in terms of
catalysts’ structure, morphology, composition, active site, 2 Performance evaluation index
and their correlation with activity and stability for HER for electrocatalysts
and OER in both acidic and alkaline media, which con- Electrolytic water splitting is not only an uphill reac-
stitutes the focus of the present review. This focus stems tion, as reflected by the positive value of ΔG (Gibbs free
from the increasing need of active, stable, and low-cost energy), but also has to overcome a significant kinetic
electrocatalysts for the efficient production of hydrogen barrier. Catalysts play a crucial role in lowering the
from electrocatalytic water splitting. There are several kinetic barrier (Fig. 2a). The evaluation of the perfor-
challenging areas for the development of active, stable, mance of a catalyst for the electrocatalytic water splitting
and low-cost electrocatalysts. First, while most of the is based on several key parameters for activity, stability,
efficient OER catalysts such as Ir and Ru based electro- and efficiency (Fig. 2). The activity is characterized by
catalysts exhibit a high dissolution resistance in acidic overpotential, Tafel slope, and exchange current den-
condition, most of the non-noble metal-based electro- sity, which can be extracted from the polarization curves
catalysts cannot survive under such condition. Thus, (Fig. 2b). The stability is characterized by the changes
the challenge is to develop stable and robust non-noble of the overpotential or current over time (Fig. 2c). The
metal OER electrocatalysts with high activity and long- efficiency is characterized by the faradaic efficiency and
term stability performance in acidic media. Second, while turnover frequency in terms of experimental results vs.
non-noble-metal-based electrocatalysts such as carbides, theoretical predictions (Fig. 2d).
phosphides, and chalcogenides have drawn great atten-
tion due to their high performance for OER in alkaline 2.1 Activity in terms of overpotential, Tafel slope,
media, the catalysts undergo composition and struc- and exchange current density
tural transformation during OER condition. Thus, the For electrochemical water splitting reaction, the ther-
identification of the real active sites remains elusive, modynamic potential is 1.23 V at 25 °C and 1 atm. How-
and it is challenging to develop techniques to detect the ever, due to the kinetic barrier for the reaction, water
real active sites to guide the design and preparation of electrolysis requires a higher potential than thermody-
optimal catalysts. Third, the knowledge on the catalytic namic potential (1.23 V) to overcome the kinetic barrier.
mechanisms of many electrocatalysts, especially transi- The excess potential is also known as overpotential (η)
tion metal-based catalysts for HER in alkaline condition, which mainly comes from the intrinsic activation barri-
is rather limited in comparison with HER in acidic con- ers present on both anode and cathode. Overpotential
dition. Thus, an important challenge is to determine the is a very important descriptor to evaluate the activity of
factors that govern the catalytic mechanism of HER in the electrocatalysts. Usually, the overpotential value cor-
alkaline media. responding to the current density of 10 mA cm−2 is used
In this review, we start with an introduction of the to compare the activities among different catalysts. This
performance index used to evaluate the electrocata- current density corresponds to a 12.3% solar-to-hydrogen
lysts’ activity, stability, and efficiency. It is followed by efficiency.
discussions of HER reaction pathways and mechanisms The Tafel slope and exchange current are two other
in acidic and alkaline media. We will discuss the recent parameters to assess the activity from the overpotential
advances in developing strategies for performance vs. kinetic current relationship, which is expressed by the
improvement of HER electrocatalysts derived from noble equation: η = a + b log j, where η is the overpotential, and
metal and non-noble-metal-based metal carbides, metal j is the current density. In the Tafel plot, the linear cor-
phosphides, and metal chalcogenides. In the subsequent relation yields two important kinetic parameters. One is
section, we discuss recent insights into the mechanistic the Tafel slope b, and the other is the exchange current
details of the catalysts and possible reaction pathways density j0 which can be obtained by extracting the current
in acidic media and alkaline media. This discussion is at zero overpotential. The Tafel slope b is related to the
followed by highlighting some recent development in catalytic reaction mechanism in terms of electron-trans-
increasing the intrinsic activity of active sites on nano- fer kinetics. For example, a smaller Tafel slope means that
structured noble-metal-based and non-noble-metal- there is a significant current density increment as a func-
based catalysts for OER. Some of the recent insights into tion of the overpotential change, or in other words, faster
the lattice oxygen mediated mechanism (LOM) will also electrocatalytic reaction kinetics. The exchange current
be highlighted. Finally, future challenges and perspectives density describes the intrinsic charge transfer under
Fig. 2 a Schematic illustration of the catalyst’s role in lowering the activation energy barrier; b–d schematic illustrations of the performance
evaluation parameters of electrocatalyst, including, b activity in terms of overpotential, Tafel slope, and exchange current density, c stability in terms
of current- and potential-time curves, and d efficiency in terms of faradaic efficiency and turnover frequency
equilibrium conditions. A higher exchange current den- cycles of run at a scan rate (e.g. 50 mV s−1). Linear sweep
sity means a greater charge transfer rate and a lower reac- voltammetry (LSV) is typically applied to examine the
tion barrier. A lower Tafel slope and a higher exchange overpotential shift before and after CV cycling at a spe-
current density are expected for a better electrocatalyst. cific current density. The smaller the change of overpo-
tential is, the better the electrocatalyst’s stability.
2.2 Catalyst stability in terms of current‑
and potential‑time curves 2.3 Efficiency in terms of faradaic efficiency and turnover
Stability is an important parameter to evaluate whether frequency
the catalyst has the potential for use in water split- Faradaic efficiency is a quantitative parameter used to
ting cells in practical applications. There are two typical describe the efficiency of electrons in the external circuit
methods for characterizing the stability of electrocata- that is transferred to the electrode surface for the elec-
lysts. One method is chronoamperometry (I–t curve) or trochemical reaction. The definition of faradaic efficiency
chronopotentiometry (E–t curve) which measures the is the ratio of the experimentally detected quantity of
current variation with time under a fixed potential or H2 or O2 to the theoretically calculated quantity of H2
measure the potential change with time at a fixed current. or O2. The theoretical values can be calculated from the
For this measurement, the longer the tested current or integration of the chronoamperometric or chronopoten-
potential remains constant, the better the stability of the tiometric analysis. The experimental values are measured
catalyst. For the comparison with the different research by analyzing the gas production using the water–gas dis-
groups, people usually set a current density larger than placement method or gas chromatography method.
10 mA cm−2 for at least 10 h test. Another method is Turnover frequency (TOF) is a useful parameter to
cyclic voltammetry (CV) which measures the current by describe the reaction rate in terms of the catalytic sites
cycling the potential, usually requiring more than 5000 which is the intrinsic catalytic activity of the catalyst. In
general, TOF describes how many reactants can be con- 3 Electrocatalysts for hydrogen evolution reaction
verted to the desired product per catalytic site per unit (HER)
time. However, it is usually difficult to calculate the pre- 3.1 Reaction steps in HER
cise TOF value for most heterogeneous electrocatalysts HER is the key half-reaction to produce hydrogen at
since the precise number of active sites per electrode area the cathode in water electrolysis which involves a two-
is often an estimate. Despite being relatively imprecise, electron transfer process. The mechanism of this HER is
TOF still is a useful way to compare the catalytic activi- highly dependent on the environmental condition. For
ties among different catalysts, especially within a similar the HER reaction in acidic media, there are three possible
system or under a similar condition. reaction steps.
The choice of the techniques for the analysis of activ-
ity, stability, and efficiency of the catalysts depends on the H+ + e− = Had , (1a)
specific focus of the research and development. In addi-
tion to synthesis and preparation of the electrocatalysts, H+ + e− + Had = H2 , (1b)
the current studies of the activity, stability, and efficiency
can be grouped in three areas in terms of the specific 2Had = H2 . (1c)
focus: performance evaluation, structural characteriza-
tion, and mechanistic determination. While the analysis The first step is Volmer step (1a) to produce adsorbed
of the current- or potential-time curves provides infor- ydrogen. Then, the hydrogen evolution reaction can
h
mation for assessing the catalyst’s durability performance, proceed by Heyrovsky step (1b) or the Tafel step (1c) or
which is very important for practical applications, the both to produce H 2 [30]. For the HER reaction in alkaline
determination of the overpotential, Tafel slope, exchange media. There are two possible reaction steps, i.e., Volmer
current density, faradaic efficiency, turnover frequency, step (2a) and Heyrovsky step (2b) [31], as shown in the
and provides the basic parameters for assessing the following equations, respectively:
electrocatalytic mechanism. Importantly, coupling of
H2 O + e− = OH− + Had , (2a)
these electrochemical techniques to spectroscopic and
microscopic techniques (ex-situ or in-situ) enables the
structural characterization, which is crucial for gaining H2 O + e− + Had = OH− + H2 . (2b)
insights into the design of the active and stable catalysts. It is vital to trade-off H
ad, hydroxy adsorption (OHad),
Examples in terms of the rationale of applying the differ- and water dissociation for HER activity in alkaline media.
ent techniques for the specific research and development Theoretical simulations have revealed that HER activ-
focus will be highlighted in the following subsections. ity was related to hydrogen adsorption (Had). The free
energy of hydrogen adsorption (ΔGH) is widely accepted
to be a descriptor for a hydrogen evolution material. A
moderate value of hydrogen binding energy will benefit
HER process. As shown in Fig. 3a [32, 33], and Fig. 3b
[34], the volcano curve provides a quick comparison of
Fig. 3 Volcano plots: a exchange current density vs. the M–H bond energy for each metal surface (for acidic media) (Figure reprinted with
permission from Refs. [32, 33]); b exchange current density on monometallic surfaces vs. the calculated HBE (for alkaline media) (Figure reprinted
with permission from Ref. [34])
the activities of different metals in acidic media and alka- the alkaline HER activities which is very meaningful for
line media, respectively. Pt appears to be the best catalyst industry practical use. For non-noble metal based HER
for HER in both media which have the optimal hydrogen electrocatalysts, a great deal of attention has been drawn
adsorption energy showing the highest exchange current to their development largely based on the considerations
density. The activity of HER in alkaline media is usually of the low-cost and earth-abundant characteristics. In
lower than that in acidic media [28]. This largely stems the following sections, we will start with a discussion of
from the fact that the reaction is hindered by the sluggish selected examples of noble metal catalysts. We will then
water dissociation step, which leads to a reduction of the focus on several categories of non-noble metal based
reaction rate by 2–3 orders of magnitude. However, alka- electrocatalysts such as transition metal carbides, tran-
line electrolysis is more preferable in industrial plants. sition metal phosphides, and transition metal chalcoge-
The rational design of electrocatalysts with high alkaline nides which have gone through great development in the
HER performance requires the catalysts to have the char- field of electrocatalytic HER.
acteristics of binding hydrogen species and dissociating
water. 3.2.1 Noble‑metal based electrocatalysts
Noble metals, such as Pt group metals (PGMs, includ-
3.2 HER electrocatalysts ing Pt, Pd, Ru, Ir, and Rh) show outstanding catalytic
Table 1 lists some of the recent examples of studies in performance for HER. Pt ranks at the top of the volcano
developing effective catalysts for HER. These catalysts are curve in Fig. 3. However, the commercial application of
compared in terms of the electrocatalytic performance these noble-metal based catalysts is hindered by their
and kinetic parameters under different reaction condi- scarce storage and high cost. To overcome this challenge,
tions. There are two main types of HER electrocatalyst: a rational design of catalysts with low metal loading and
noble-metal based electrocatalysts and non-noble metal high metal utilization is necessary.
based electrocatalysts. For the noble-metal based elec- Alloying Pt with transition metal can significantly
trocatalyst, especially Pt-based catalysts, several strate- improve the Pt utilization and the synergistic effect of
gies are being developed to increase HER performance alloy could modify the electronic environments which
and lower the electrocatalyst price. For example, alloy- significantly promote the HER electroactivity. Sun et al.
ing Pt with other low-cost transition metal which could reported in situ growth of ultrafine PtNi nanoparticle-
improve Pt utilization and the synergistic effect of alloy decorated Ni nanosheet array on carbon cloth (PtNi-Ni
could modify the electronic environments to improve NA/CC) with ultralow loading Pt content (7.7%) which
the activity. Also, coupling Pt with other water disso- show better HER activity with low overpotential 38 mV
ciation promoters is an important strategy to improve in 0.1 M KOH at the current density of 10 mA cm−2 than
Table 1 Summary of the HER performance of the reported electrocatalysts

Catalysts Electrolyte η (mV) I (mA cm−2) Tafel slope Stability Refs.
(mV dec−1)
PtNi–Ni NA/CC 0.1 M KOH 38 10 42 90 h [35]

PtNi–O/C 1 M KOH 39.8 10 78.8 10 h [36]
PtNi(N) NW 1 M KOH 13 10 29 10 h [37]
Mo2C-R 1 M KOH 200 30 45 [38]
0.5 M H2SO4 200 32 58 2000 cycle
Mo2C-GNR 0.5 M H2SO4 167 10 63 3000 cycles [39]
1 M NaOH 217 10 64 3000 cycles
1 M PBS 266 10 74 3000 cycles
Ni2P/Ti 0.5 M H2SO4 130 20 46 500 cycles [40]
NiCo2Px 1 M KOH 58 10 34.3 5000 cycles [41]
1 M PBS 63 10 63.3 5000 cycles
0.5 M H2SO4 104 10 59.6 5000 cycles
Defect-rich MoS2 0.5 M H2SO4 200 13 50 10,000 s [42]
CoS2 NW 0.5 M H2SO4 145 10 51.6 3 h [43]
CoS2 MW 0.5 M H2SO4 158 10 58 41 h
Oxygenated MoS2 0.5 M H2SO4 120 Onset 55 3000 cycles [44]
the benchmark Pt/C (20%). Remarkably, it also shows hydrogen electrode (RHE), the PtNi–O/C present the
long-term durability with a 90 h catalytic activity test. highest activity of 7.23 mA/µgpt in comparison with those
The superior HER performance of PtNi–Ni NA/CC could obtained for PtNi (5.35 mA/µgpt) and commercial Pt/C
be rationally attributed to the downshift of the d-band (0.92 mA/µgpt).
center of Pt, which weakens the adsorption energy of Doping of Pt-based materials with different metal com-
oxygenated species (OH*) on the surface Pt atom [35]. ponents is another effective way to improve the catalytic
As a benchmark for Pt electrocatalyst, the activity of ability for HER while reducing the use of Pt. Wang et al.
HER in alkaline media is usually lower than the activity [37] reported a catalyst derived from N modified PtNi
of HER in acidic media [3]. The reason is the water dis- nanowires, which was shown to boost water dissociation
sociation on the Pt surface is inefficient which results in kinetics by N-induced orbital tuning of the catalyst, deliv-
poor HER activity. To this end, coupling Pt with water ering an ultralow overpotential of 13 mV at 10 mA cm−2
dissociation promoters is the commonly used strategy to in alkaline media. Figure 5a–d shows the HER catalytic
boost the alkaline HER activities [37]. performance of PtNi(N) NWs in alkaline media in terms
Among different Pt-based electrocatalysts for HER, of linear sweep voltammogram (LSV) curves (a) for Pt–
[35, 45–47] the ability to control the metal composition Ni, Pt–Ni(N), Pt–Ni/Ni4N, and commercial Pt/C. Pt–
on the surface is critical for enhancing the electrocata- Ni(N) NWs exhibit the lowest overpotential of 13 mV
lytic activity. Recently, Markovic et al. [48] demonstrated at a current density of 10 mA cm−2. The Tafel slopes, as
a controlled preparation of nanometer-scale Ni(OH)2 shown in Fig. 5b, provide information for probing the
clusters on Pt electrode surface, showing a factor of rate-determining steps in the alkaline HER process. The
8 in the enhancement of HER activity compared with Tafel slope for Pt-Ni (N) reaches 29 mV dec−1, suggest-
state-of-the-art Pt. Figure 4A shows the proposed HER ing that the Volmer step is not the rate-determining step
mechanism. The edges of Ni(OH)2 cluster promote water for Pt–Ni(N) in the alkaline media. Further, the analy-
dissociation to form M–Had intermediates on Pt surface. sis of the TOF data provides information for unraveling
The adsorbed hydrogen intermediates combine to pro- the intrinsic activity of catalysts, as shown in Fig. 5c.
duce H2. Inspired by the synergy between Ni(OH)2 and Pt–Ni(N) exhibits a higher TOF than that for Pt/C and
Pt(111), Huang et al. demonstrated the formation of sur- Pt–Ni NWs under various potentials. Lastly, as shown in
face-engineered PtNi–O nanoparticles with an enriched Fig. 5d, the durability test of Pt–Ni(N) by chronopotenti-
NiO/PtNi interface. This interface structure transforms ometry shows that there is no obvious potential change
to Ni(OH)2 in alkaline media, creating Ni(OH)2/Pt(111)- after 10 h at the current density of 40 mA cm−2. Density
like interface on the surface. The catalyst showed a low function theory (DFT) calculation (Fig. 5e–g) was used
HER overpotential of 39.8 mV at 10 mA cm−2 with only to study the modulation essence of nitrogen dopants in
5.1 µgpt cm−2 loading of Pt [36]. The annealing-induced the PtNi nanowire. The analysis of the surface electron
transformation of the PtNi/C to PtNi–O/C structure density difference (Fig. 5e) shows that the introduction of
is shown in Fig. 4B(a). As shown in Fig. 4B(b), the mass N could decrease the electron density around Ni site by
activity at overpotential of 70 mV versus reversible strong interaction between N and Ni. The orbital analysis
Fig. 4 A Schematic illustration of the mechanism of HER on nanometer-scale Ni(OH)2 clusters on Pt electrode surface (Figure reprinted with
permission from Ref. [48]). B (a) Schematic illustration of the transformation of PtNi/C to PtNi–O/C via annealing in air, and (b) comparison of HER
mass activities at − 0.07 V vs RHE (Figure reprinted with permission from Ref. [36])
Fig. 5 a–d HER performance, a LSV curves comparing different catalysts in 1.0 M KOH with IR correction, b Tafel plots, c TOF curves, d
Chronopotentiometric curve of Pt–Ni(N) NWs. Insets: SEM images of Pt–Ni(N) NWs before and after the stability test. e–g DFT calculation results:
e electron density difference for slices of Pt–Ni and Pt–Ni(N), f, g top-view and side-view of orbitals above the Fermi level for Pt–Ni and Pt–Ni(N)
(Figure reprinted with permission from Ref. [37])
(Fig. 5f, g) further confirms the strong Ni–N coupling and alkaline media. However, there is a relatively large
generated in the direction perpendicular to empty d z2 overpotential (190–230 mV) to achieve a cathodic cur-
with an optimal orientation for water dissociation and rent of 10 mA cm−2. Inspired by the pioneering studies,
activation. researchers pursued different approaches for the optimi-
zation of M o2C catalyst by nanoengineering the materials
3.2.2 Non‑noble metal based electrocatalysts to expose more active sites. Wang et al. [38] have success-
Transition metal carbides (TMCs) TMCs have received fully synthesized M o2C nanorods with a porous structure
extensive interest in the development of non-noble metal by facile carburization of anilinium molybdate in hydro-
based electrocatalysts. For example, Mo2C and WC are gen, as shown in Fig. 6A. The nanorod morphologies with
shown to exhibit high catalytic activity toward HER. In a smooth surface and a porous structure are revealed by
addition to the high electrical conductivity, their prop- field emission scanning electron microscope (FE-SEM)
erties of hydrogen adsorption and d-band electronic and transmission electron microscopy (TEM) images
density state (similar to that of Pt) exhibit an optimal (Fig. 6A(a, b)). Enhanced HER electrocatalytic perfor-
combination that is considered to be the main factor for mance is shown for M o2C nanorod catalyst. Figure 6A(c)
the observed high HER activity. Back to 1973, Levy and shows the linear scan voltammetry (LSV) results in 0.5 M
Boudart first discovered that tungsten carbide possessed H2SO4 which exhibits the M o2C nanorods has a better
d-band electronic density states similar to that of Pt spe- activity than the commercial Mo2C. The stability test of
cies and thus exhibited platinum-like catalytic behavior the Mo2C is also shown in Fig. 6A(d). The results show
[49]. Further, Chen et al. employed DFT calculation to that the activity is stable after 2000 cycles, demonstrating
investigate the physical, chemical, and electronic struc- an excellent cycling life. The Mo2C nanorod is also stud-
ture properties of a series of transition metal carbides. ied in alkaline media, showing an advantage in perfor-
Their results show that the incorporation of carbon atoms mance over commercial Mo2C in 1 M KOH. The Mo2C
into the lattice interstitials afford them with d-band elec- nanorods display a competitive performance for HER
tronic density states similar to the Pt benchmark [50]. in both acidic and alkaline media, which stem from the
The theoretical result was first supported by experimen- high conductivity and well-defined, and porous morphol-
tal data in 2012. Hu et al. [51] reported that commercially ogy. The catalytic activity could be further improved by
available molybdenum carbide microparticles (com- loading Ni nanoparticles. The deposition of molybdenum
Mo2C) possess good HER catalytic activity in both acidic carbides on carbon-based materials is another method
Fig. 6 A (a) FESEM image of Mo2C-R, (b) SEM image of M o2C-R, (c) polarization curves in 0.5 M H2SO4, and (d) stability test of Mo2C-R in 0.5 M
H2SO4 (Figure reprinted with permission from Ref. [38]). B (a) Preparation of molybdenum carbide ( Mo2C) nanoparticles anchored on graphene
nanoribbons (GNRs), and (b–d) activity and durability of Mo2C-GNR in acidic, basic, and neutral media, respectively (Figure reprinted with
permission from Ref. [39])
to further improve the performance of HER as an effec- would lead to an increased desorption energy for the
tive hybrid nano-electrocatalyst. Liu et al. [39] prepared hydrogen species from the metal surface. The presence
molybdenum carbide (Mo2C) nanoparticles anchored of P atoms dilutes the concentration of highly active Ni
on graphene nanoribbons (GNRs) by in situ growth of sites, leading to a moderate bonding to the intermedi-
carbides on GNR template through hydrothermal syn- ates and products, i.e., the so-called “ensemble effect”.
thesis and subsequent high-temperature calcination, as The first direct experimental evidence supporting the
shown in Fig. 6B(a). The M o2C-GNR hybrid exhibits out- catalytic synergy was provided by Popczun et al., who
standing electrocatalytic activity and durability in all the demonstrated that Ni2P nanoparticle deposited onto a
acidic, basic, and neutral media (Fig. 6B(b–d)). The use Ti foil substrate for excellent HER activity, showing an
of GNRs as templates for the in situ growth of carbides exchange density of 3.3 × 10–5 mA cm−2 and a Tafel slope
is an intriguing approach since the interconnected GNR of 46 m V dec−1 [40]. However, the stability of the Ni2P/
network structure may provide multiple conductive path- Ti electrode was not satisfactory especially in alkaline
ways for fast electron transport and large accessible sur- electrolyte. Further investigation was carried by Hu et al.
face area with increased exposed active sites, leading thus [41] by developing a bimetallic-structured phosphide
to enhanced catalytic activity in all the acidic, basic, and electrocatalyst, NiCo2Px. This catalyst shows excellent
neutral media. durability and long-term stability in different electrolytes,
Transition metal phosphides The exploration of tran- an efficient pH-universal catalyst performance for HER.
sition metal phosphides (TMP) is one of the rapidly The self-supported NiCo2Px nanowire arrays were fabri-
growing areas in developing electrocatalysts with high cated on commercial carbon felt (CF) by a wet chemical-
catalytic activity and stability in both acid and basic hydrothermal route combined with subsequent in situ
(pH universal). It has been proposed that P atom plays phosphorization reaction. Figure 7a shows that N iCo2Px
a significant role in TMP due to the excellent conduc- exhibits excellent HER performance in acidic, alkaline,
tivity and unique electronic structure. The discovery and neutral media. In the alkaline electrolyte, NiCo2Px
of Ni2P catalysts as one of the best practical catalysts has the lowest overpotential of 58 mV at a current den-
for HER dates back to 2005. Liu and Rodriguez investi- sity of 10 mA cm−2 compared with C oPx (94 mV), NiPx
gated a series of electrocatalysts by density functional (180 mV), and commercial Pt (70 mV). Figure 7b shows
theory (DFT) [52]. The results show the HER activity in the morphology of NiCo2Px after the long term HER
the trending of [NiFe] hydrogenase > [Ni(PNP)2]2+ > Ni2P activity test, demonstrating that the catalyst structure of
(001) > [Ni(PS3*)(CO)]1− > Pt > Ni. The reason that Ni2P NiCo2Px is still well-preserved after 5000 cycles under
displays a superior activity over the bulk Pt and Ni is different conditions. A synergistic effect is proposed for
because hydrogen formed in the HER process strongly NiCo2PX in alkaline electrolyte, as shown in Fig. 7c. There
bonds on metal (Pt, Ni) hollow site. The strong bonding are two important interactions: the interaction between
Fig. 7 NiCo2PX catalyst: a HER performance in 1 M KOH and PBS and 0.5 M H2SO4, b SEM images before and after HER long-term stability test in
different media, c schematic illustration of water dissociation over NiCo2PX in alkaline solution (Figure reprinted with permission from Ref. [41])
the under-coordinated metal center (Mδ+, M = Ni, Co) ultrathin nanosheets, which was shown to dramatically
and O atom, and the interaction between the dangling improve the electrocatalytic HER performance of MoS2.
P atom (Pδ−) and H atom. The combination of these This high activity was attributed to additional active edge
two interactions weakens the H–OH bond, leading to sites of the rich-defect structure synthesized by partial
water molecule dissociate into H atom and OH−. The H cracking of the catalytically inert basal plane. In another
atom is then transferred onto a nearby vacant metal site study, Jin et al. [43] successfully synthesized CoS2 with
anchored as adsorbed H, and the adsorbed H atoms com- controllable film, microwire (MW), and nanowire (NW)
bine to form molecular H2. morphologies (Fig. 8A(b–d)). They systematically stud-
Transition metal chalcogenides (sulphides and sele- ied their structures, activities, and stabilities and demon-
nides) By DFT calculation in 2005, Nørskov et al. [53] strated the morphology-dependent enhancement of both
showed that the free energy of atomic hydrogen bond- activity and stability. Among the three different morphol-
ing to the M oS2 edge is close to that of Pt. This finding ogies, CoS2 NWs show the highest HER catalytic perfor-
identifies MoS2 as a promising electrocatalyst for HER. mance and stability (Fig. 8A(a)), which is attributed to the
To further identify the actual active site of MoS2 struc- high effective electrode surface area and high speed to
ture, Chorkendorff et al. [54] prepared triangular MoS2 release of evolved gas bubbles from the electrode surface
single crystals with different sizes on Au(111) substrate. (Fig. 8A(e)). In addition to engineering active sites, con-
They demonstrated that the electrocatalytic HER activity siderable efforts have been devoted to engineering the
is linearly dependent on the number of edge sites of the electronic conductivity of metal chalcogenides to opti-
MoS2 catalyst. The edge sites of the MoS2 are highly cata- mize the HER electrocatalytic activity. Heteroatom dop-
lytically active sites. Inspired by this understanding, vari- ing is an effective method to enhance HER activity. Xie
ous strategies have been proposed to expose the active et al. [44] found that incorporation of oxygen atom and
sites to improve HER activity, including nanostructure controllable disorder engineering can effectively regulate
tailoring and morphology tuning. For example, Xie et al. the electronic structure of MoS2 ultrathin nanosheets,
[42] reported a strategy to engineer the defects in MoS2 leading to the enhancement of conductivity and HER
Fig. 8 A (a) Polarization curves of CoS2 film, MW array, and NW array electrode for HER, (b–d) SEM images of CoS2 film, NW array, and MW array
on graphite, (e) schematic depictions of CoS2 film, C
oS2 NWs, and MWs surface along with the produced H2(g) bubbles (Figure reprinted with
permission from Ref. [43]). B (a) XRD pattern of the products obtained at various temperatures, (b) HER performance of the catalysts with different
oxygen-incorporated MoS2 ultrathin nanosheets. (c, d) Structural models of the oxygen-incorporated M oS2 with enlarged interlayer spacing and
the pristine 2H–MoS2. (e, f ) Schematic representation of the disordered structure in oxygen-incorporated M oS2 ultrathin nanosheets. The blue lines
represent the fast electron transport between the quasi-periodically aligned nanodomains; the purple shadings indicate the enrichment effect of
active sites arising from the disordered structure (Figure reprinted with permission from Ref. [44])
activity. As shown in Fig. 8B(a) with a series of XRD pat- (120 mV), suggesting the superior HER activity. Fig-
terns for the catalysts obtained at various temperatures, ure 8B(e, f ) shows schematic representation of the disor-
the MoS2 ultrathin nanosheets obtained at high tem- dered structure in oxygen-incorporated M oS2 ultrathin
perature (220 °C) exhibit rich defects. When the synthe- nanosheets. There is a fast electron transport between
sis temperature decreases to 200 °C and below, two new the quasi-periodically aligned nanodomains (Fig. 8B(e)).
peaks emerge at the low-diffraction angle region, indi- The enrichment effect of active sites is derived from the
cating the presence of a new lamellar structure with an disordered structure (purple shading). The excellent HER
enlarged interlayer spacing of 9.5 Å compared with that electrocatalytic activity is attributed to the disordered
of 6.15 Å in pristine 2H–MoS2. The proposed structure structure which offers large amounts of unsaturated sul-
models are shown in Fig. 8B(c, d). HRTEM images and fur atoms as active sites for HER and provides quasiperi-
corresponding FFT patterns of the MoS2 structures from odic arrangement of nanodomains for a fast interdomain
the different temperatures reveal a controllable disorder electron transport.
engineering with the degree of disorder depending on the
temperature. The electrochemical measurements of the
oxygen-incorporate MoS2 ultrathin nanosheets with dif-
ferent degrees of disorder were performed in Fig. 8B(b).
The catalyst labeled as S180 exhibits the lowest potential
4 Electrocatalysts for oxygen evolution reaction recent development of the understanding of OER mecha-
(OER) nism for the rational design of OER electrocatalysts. It is
As stated earlier, OER is the other key half-reaction widely accepted that OER can proceed through two dif-
in water-splitting reaction. This reaction occurs at the ferent mechanisms conventional adsorbate evolution
anode and involves a four-electron transfer process which (AEM) and lattice oxygen-mediated mechanism (LOM),
requires a remarkably high overpotential compared which are discussed in two of the following subsections.
to HER. OER is known to be the major bottleneck in
improving the overall efficiency of electrochemical water 4.1 Reaction steps in OER—adsorbate evolution
splitting. Therefore, it is imperative to seek highly effi- mechanism (AEM)
cient OER catalysts that can effectively reduce the kinetic For OER, adsorbate evolution mechanism (AEM) have
limitation. Significant progress has been made in the conventionally been used to describe the various reaction
steps. In AEM, the reaction typically involves four con-
certed proton and electron transfers with the metal cent-
ers as active site (M), producing oxygen molecules from
water in acidic and alkaline media (Fig. 9a) [5]. The reac-
tion pathway of alkaline OER (in red line) includes the
following steps (3a–3d):
Fig. 9 a OER mechanisms in acidic (blue line) and alkaline (red line) electrolytes (Figure reprinted with permission from Ref. [5]). b Free energy
diagram at U = 0 and U = 1.23 V for OER on the ideal catalyst (Figure reprinted with permission from Ref. [55]). c Relationship between the
adsorption energies of *OOH and *OH on a series of oxide OER catalysts (Figure reprinted with permission from Ref. [56]). d Volcano-shaped
relationship between OER activities on metal oxide surfaces vs. enthalpy for the transition metal oxides in acidic (black square) and basic solution
(white square) (Figure reprinted with permission from Ref. [57])
step with the most positive reaction free energies (ΔG)

OH− + M → M − OH + e− , (3a)
in the four steps. Based on a database of diverse oxide
catalyst model, there is a scaling relationship (linear cor-
M − OH + OH− → M − O + H2 O + e− , (3b)
relation) established in the AEM in terms of the bind-
M − O + OH− → M − OOH + e− / 2M − O → 2M + O2 + 2e− , (3c)
ing energies of these intermediates (M–OH, M–OOH,

M − OOH + OH− → O2 + H2 O + e− + M. (3d)
and M–O), as shown in Fig. 9c. The binding energies of
the adsorbed M–OH and M–OOH exhibit a constant
Firstly, hydroxide anions are adsorbed on the metal difference of 3.2 eV(ΔGHOO* − ΔGHO*). This is because
active site to form M–OH. Then M–OH forms M–O after both HOO* and HO* bind with catalyst surface through
deprotonation. Thereafter, there are two different path- similar adsorption configurations with an oxygen atom
ways to form O 2 molecules. One way is that M–O reacts via a single bond [56]. According to the scaling rela-
with OH− to form M–OOH intermediate, producing O 2 tion, there is a minimum theoretical overpotential of
through the deprotonation of M–OOH with the regener- 0.37 eV((3.2 − 1.23*2 eV)/2) which represents the differ-
ation of the active site. The other way, as illustrated by the ence between the constant difference in binding energy
green route as in Fig. 9a, involves two M–O species being (3.2 eV) and the ideal value of 2.46 eV.
combined and converted into O2 along with the regen- Moreover, since the second (the formation of M–O)
eration of the M active site, which is considered to have and third steps (the formation of M–OOH) are consid-
a large activation barrier. For the mechanism of acidic ered as the RDS in most OER catalyst, the difference
OER, the common consensus is that the same interme- between ΔGO* and ΔGHO* is used as a universal descrip-
diates such as M–OH, M–O, and M–OOH are involved. tor to predict their OER activity. This is represented by
For electrocatalysis of OER, a detailed understanding of the Sabatier’s volcano-shaped relationship which has
the binding strength of the reaction intermediates on the been traditionally used to explain the OER activity trends
electrode surface is crucial for the enhancement of the on metal oxides in both acidic and alkaline media. The
overall OER performance because the binding strength is best catalysts in terms of the lowest theoretical overpo-
a key parameter governing the reaction overpotential. tential for OER are I rO2 and R
uO2, which exhibit optimal
As shown by the ideal free energy diagram of the dif- binding strength on the catalyst surface, i.e., neither too
ferent reaction steps in OER in Fig. 9b, there is no over- strong nor too weak, as shown in Fig. 9d [57].
potential needed for OER to occur if the free energy gap
for each of the elementary steps would remain the same 4.2 OER electrocatalysts
at 1.23 eV [55]. However, this ideal case is almost impos- Table 2 lists some selected OER electrocatalysts in terms
sible to achieve. The OER overpotential is determined by of their performance descriptors, which will be fur-
the rate-determining step (RDS) which comes from the ther discussed in later sections under different reaction
Table 2 Summary of the OER performance of the reported electrocatalysts

Catalysts Electrolyte η (mV) I (mA cm−2) Tafel slope Stability Refs.
(mV dec−1)
Cu-doped RuO2 0.5 M H2SO4 188 10 43.96 10,000 cycles [58]

IrNi NPNW 0.1 M HClO4 283 10 56.7 200 min [59]
IrCo NPNW 0.1 M HClO4 295 10 60.3
IrFe NPNW 0.1 M HClO4 302 10 68.5
IrNiCu DNF 0.1 M HClO4 300 10 48 2500 cycles [60]
IrO2 NN 1 M H2SO4 313 10 57 200 h [61]
Au40Co60 NPs 0.1 M KOH 175 10 65 1 h [62]
G-FeCoW 1 M KOH 191 10 500 h [63]
Plasma-engraved Co3O4 0.1 M KOH 153 10 68 2000 cycles [64]
NiFe-LDH NPs 0.1 M KOH 151 30 50 10 h [65]
Ni0.83Fe0.17(OH)2 1 M KOH 245 10 61 10 h [66]
NixFe1−xSe2-DO 1 M KOH 195 10 28 24 h [67]
conditions. There are two main types of OER electro- electrocatalyst activity and stability and reduce the high
catalysts, noble-metal based electrocatalysts, and non- cost.
noble metal based electrocatalysts. For the noble-metal Heteroatom doping for tuning the composition of
based electrocatalysts, Ru and Ir-based catalysts are con- IrO2-based OER electrocatalysts has generated a great
sidered as the state-of-the-art electrocatalyst for OER, deal of interest. However, different guest atoms generated
especially in the acidic electrolyte, which has a larger distinct energy domains for the host system. Chen et al.
dissolution resistance compared with other metals. To prepared Cu-doped RuO2 with hollow porous polyhe-
reduce the high price, improve the electrocatalyst activ- dral morphology composed of ultrasmall nanocrystals by
ity, stability, and even enforce the dissolution resistance thermal decomposition of Ru-exchanged metal–organic
in acidic media, there are several strategies to engineer framework (MOF) derivatives. The catalyst displays a
and optimize the catalyst composition, structure, and remarkable OER performance with a low overpotential of
morphology. Other than Ir and Ru, other noble metals 188 mV at 10 mA cm−2 in acidic electrolyte and excellent
such as Rh, Au, Pt, and Pd-based catalysts have also been stability in durability testing for 10,000 cycles [58]. High-
developed as bi- or tri-functional electrocatalysts which resolution TEM (HRTEM) and XRD data reveal the Cu
show promising performance for OER, HER, and oxygen is incorporated into the RuO2 lattice to form Cu-doped
reduction reaction (ORR). For the non-noble metal based RuO2 rutile phase, as shown by the high-index surface
catalysts, the earth-abundant oxide and (oxy)hydroxide facets in Fig. 10a. The high OER activity is attributed to
electrocatalysts have received a great deal of interest for the high-index surface which contains highly under-
OER, especially Ni–Fe based oxide and (oxy)hydroxide, coordinated Ru (CN = 3) sites that can effectively reduce
some of which are the most common OER catalyst being the OER overpotential, as shown by DFT calculation in
employed in the industry-scale development. In the fol- Fig. 10b. The formation of *OOH on R uO2(110) (Fig. 10b)
lowing subsections, we will highlight different strategies was found to be the RDS, with an energy barrier of
that are applied to further improve the activity and stabil- 0.78 eV. For other high-index facets of the RuO2(111)
ity of NiFe-based electrocatalysts. surface, only 0.66 eV is needed to overcome the energy
barrier, which contributes to the decreased overpotential
4.2.1 Noble‑metal based electrocatalysts of 120 mV. The Cu-dopant R uO2 not only can induce the
Noble metal and metal oxide electrocatalysts have long formation of unsaturated Ru sites by Cu dopant gener-
been considered as the most powerful electrode materi- ated O vacancies on the surface, but also can modulate
als in OER. Examples include R uO2 and IrO2, which are the electronic structure which exhibits a broad binding
usually considered as the state-of-the-art electrocatalysts region closer to the Fermi level of p-band center, leading
for OER. However, the high price and serious dissolution to the enhancement of the OER activity.
of RuO2 and IrO2 are the major concerns, which bring Alloying Ru or Ir with other transition metals is an
great attention to the modification of the catalysts to ena- intriguing strategy to engineer the OER catalysts, which
ble composition and structure/morphology optimization. can effectively modify the electronic structure and opti-
Several strategies have been proposed to improve the mize the adsorption energy of the reaction intermediates.
Zhang et al. [59] designed a class of IrM (M=Ni, Co, Fe)
Fig. 10 a High-resolution TEM (HRTEM) of Cu-doped R uO2 with high-index surface facets being indicated. b Free energy profile of OER on (110)
and (111) surfaces (Figure reprinted with permission from Ref. [58])
Fig. 11 a Projected DOS of Ir 5d bands of IrO2 and IrMOx model. b–d Relationship between the activity (indicated by the logarithm of the
as-measured current density at 1.55 V vs. RHE) and the binding energies of different intermediate species: b O, c OH, and d OOH (Figure reprinted
with permission from Ref. [59])
catalysts with a unique network structure composed of depends on the binding energies of O, OH, and OOH
intertwining nonporous nanowires by a eutectic-directed species. Consequently, the introduction of 3d transition
self-templating strategy. The results show a transition- metals can shift down the Ir d-band center and weaken
metal dependent feature. Compared with IrFe NWs and the adsorption strength of the reaction intermediate spe-
IrCo NWs, IrNi NWs exhibit the best OER activity with cies, leading to the exhibition of the 3d transition-metal
the lowest overpotential of 283 mV at 10 mA cm−2. The dependent OER activity.
high activity of IrNi NW was explained by DFT calcu- Surface structure modifications play an extremely impor-
lation results (Fig. 11). During the OER process, Ir and tant role in exposing catalytically active sites and taking
M are oxidized at a high potential to form IrMOx. The advantage of the interfacial effect. Morphology regulation,
d band centers for IrO2, IrFeOx, IrCoOx and
IrNiOx as one aspect of the surface structure modification, has
are − 3.61, − 3.72, − 4.09, and − 4.34 eV, respectively received increasing attention. For example, hollow nanopar-
(Fig. 11a). There is a negative shift of density of state ticles such as nanocages, nanoshells, and nanoframes have
(DOS). The downshift for Ir’s d band center indicates been proved effective for the enhanced catalytic activity,
that the d-band electrons distribute away from the Fermi reflecting their most open structure with increased cata-
level, which is caused by the ligand effect after alloy- lytically active sites. Lee et al. [60] demonstrated that an
ing. As shown in Fig. 11b–d, the OER activity strongly Ir-based multimetallic double-layered nanoframe (DNF)
Fig. 12 A The HAADF-STEM, TEM, HRTEM, and elemental mapping of desired IrNiCu DNF structure (Figure reprinted with permission from Ref. [60]).
B (a, b) TEM images of IrO2 nanoparticles and IrO2 nanoneedles, (c, d) OER performance before and after 2 h galvanostatic operation, (c) LSV curves
of IrO2 NN and unshaped nanoparticles, (d) Tafel slope (Figure reprinted with permission from Ref. [61])
electrocatalyst can be formed by a simple one-step synthe- Nobel metals other than Ir and Ru, such as Rh, Au,
sis. The HAADF-STEM, TEM, HRTEM, and elemental Pt, and Pd, have also been emerging as viable OER elec-
mapping data revealed that the desired IrNiCu DNF struc- trocatalysts. The design of Pt, Pd, Ru, and Au catalysts
ture preserves a rhombic dodecahedral morphology after involves the construction of bi- or tri-functional electro-
strong acid etching and has a uniform component distribu- catalysts for OER, oxygen reduction reaction (ORR), and
tion in the entire DNF structure (ternary alloy), as shown in hydrogen evolution reaction (HER). Because Rh, Pt, Au,
Fig. 12A. The excellent electrocatalytic activity and durabil- and Pd have smaller dissolution resistances than Ir and
ity of the IrNiCu catalyst for OER are attributed to a frame Ru in an acidic electrolyte with a large overpotential,
structure that prevents the coarsening and agglomeration the evaluation of their OER behaviors has usually been
of particles and in situ formation of robust rutile I rO2 phase conducted in alkaline solution. The ability to control the
during OER process. Morphology control is also shown morphology and composition of the catalysts is critical
to affect the electrical conductivity of the catalyst, which for achieving the desired electrocatalytic properties. Lu
improves the OER electrocatalytic activity. Lee et al. synthe- et al. [62] demonstrated the design of AuCo nanopar-
sized ultrathin IrO2 nanoneedles (Fig. 12B(a, b)) by a scal- ticles as catalysts for OER in alkaline media. The AuCo
able molten salt method which show a better OER activity nanoparticles exhibit a uniform size distribution with
and stability compared with IrO2 nanoparticle. As shown a core–shell structure (Fig. 13a). The catalysts showed
by the electrochemical performance of IrO2 NPs and IrO2 a composition dependence of the activity, displaying a
nanoneedles for OER in Fig. 12B(c, d), the I rO2 nanoneedles maximum OER activity for Au:Co ratio of 2:3, as shown
exhibit better activity and stability than those for IrO2 NPs. in Fig. 13c [62]. The AuCo nanoparticles are partially
In comparison with the electrical conductivity, 25.9 S cm−1, alloyed with segregated phases of fcc Au, hcp Co, and
for IrO2 unshaped nanoparticles, the conductivity for fcc Co, as detected by XRD. The surface partially phases
ultrathin IrO2 nanoneedles is 318.3 S cm−1, suggested the segregated sites of the AuCo nanoparticles are shown to
shape of the catalyst plays an important role in the electron exhibit a bifunctional synergy of Co and Au where Co
transfer induced high activity for OER [61]. acts as active center in a higher valent state whereas the
Fig. 13 a TEM images of AuCo core–shell nanoparticles (inset: high-magnification TEM showing the lattice fringes corresponding to fcc Au and fcc
Co), b schematic illustration of OER on the partially phase segregated AuCo nanoparticles, c comparison of catalytic activities at 1.67 V in 0.1 M KOH.
Inset: polarization curves of (a) Au23Co77/C, (b) A
u40Co60/C, (c) Au71Co29/C, (d) Au95Co5/C, (m) C
oOx/C, (n) Au/C in 0.1 M KOH (Figure reprinted with
permission from Ref. [62])
surface Au serves as a strong electron sink promoting supported by density function theory (DFT) plus Hub-
various steps of OER (Fig. 13b). bard U correction, i.e., the DFT + U calculation, which is
widely used in first-principles studies of some strongly-
4.2.2 Non‑noble metal based electrocatalysts correlated systems (Fig. 14b). The calculated theoretical
Noble-metal-free OER electrocatalysts have attracted OER overpotential, as presented in the two-dimensional
considerable research interest because of their low-cost (2D) volcano plot (Fig. 14c), exhibits a significantly
and abundant supplies. Increasing efforts have been enhanced catalytic activity toward OER. A theoretical
devoted to looking for efficient noble-metal-free OER overpotential of only 0.4 V is derived by modulating the
electrocatalysts. Significant progress has been made local electronic and geometrical environments.
in the past decades in demonstrating superb catalytic Defect engineering is another effective pathway to
activity comparable to the noble metal catalyst. In this regulate the structural and electronic properties of the
subsection, we will highlight some recent strategies in electrocatalysts. The enhancement of the OER activity
terms of increasing active sites by controlling the mor- can be achieved by modulating the intermediate adsorp-
phology, manipulating the composition, tuning the tion energy, which sometimes leads to unexpected active
electronic structure and binding energy of the inter- sites. Dai et al. reported a method to generate suffi-
mediates through elemental doping, defect engineer- cient oxygen vacancies by plasma engraving strategy on
ing, and enhancing electroconductivity and electron Co3O4 nanosheet. SEM and TEM analysis of the cata-
transport through incorporating hybrid structures into lysts revealed that the plasma engraved C o3O4 nanosheet
composites for the rational design highly efficient OER has a rough, discontinuous, and loose surface with
electrocatalysts. enhanced exposure of the surface area. Furthermore,
Recently, Zhang et al. [63] prepared a gelled FeCoW Co3+ is partially reduced to C o2+ by Ar plasma treat-
oxyhydroxide (W, Fe-doped CoOOH, G-FeCoW) with ment, producing oxygen vacancies, as confirmed by the
homogeneous metal distribution by sol–gel fabrication. X-ray photoelectron spectroscopy (XPS). This method
The FeCoW oxyhydroxide exhibited the lowest overpo- not only can produce high surface area, but also modify
tential of 191 mV at a current density of 10 mA cm−2 and its electronic structure by controlling C o2+/Co3+ ratio,
500 h cycle stability. This performance is superior to that leading to excellent OER catalytic activity with an over-
of the benchmark Ni–Fe based catalyst. In Fig. 14a, the potential of 153 eV at a current density of 10 mA cm−2
overpotentials at the current density of 10 mA cm−2 for [64]. Besides the intrinsic alteration for the optimal
Au(111), GCE (glass carbon electrode), and gold-plated absorption energy of intermediate species, the ability to
Ni foam are compared. The result shows that the cata- tune the electron transport is crucial for improving the
lytic activity of G-FeCoW is much higher than that of the OER activity. Duan et al. performed in situ growth of
annealed A-FeCoW, gelled FeCo without W (G-FeCo), 3D porous films of vertically aligned NiFe-LDH (layered
and LDH FeCo on different substrates. The synergistic double hydroxide) nanoplates (NiFe-LDH NPs) on nickel
effect of Fe and W co-doped Co oxyhydroxide allowed foams (Fig. 15a). The catalyst exhibits a small overpoten-
the optimal adsorption energy of intermediate OH, as tial of 151 mV at 30 mA cm−2 better than 20 wt% Ir/C
Fig. 14 a Overpotentials obtained from OER polarization curves on Au(111), GCE (glass carbon electrode), and gold-plated Ni foam at 10 mA cm−2.
b Illustration of tuning the energetics of OER intermediates on CoOOH via alloying with Fe and W. c Map of OER activities for pure Fe, Co
oxyhydroxides and W, Fe-doped Co oxyhydroxides, cobalt tungstate, and W oxides calculated with DFT + U (Figure reprinted with permission from
Ref. [63])
catalyst and prominent durability [65]. The observed Dou et al. [66] synthesized Fe-doped Ni(OH)2 nanosheet
high electrocatalytic activity was attributed to the syner- possessing a nanoporous surface structure with abundant
gistic effect of the 3D porous structure which provides a defects by a facile and universal cation-exchange process
large surface area with a high density of active sites. The which shows enhanced OER activity. In comparison with
nickel foam substrate, as shown in Fig. 15A(b), is consid- typical NiFe layered double hydroxide (LDH) nanosheets,
ered as an ideal substrate based on its porous structures the defect-rich Ni0.83Fe0.17(OH)2 nanosheets show the
and metallic electronic conductivity which acceler- lowest overpotential of 245 mV at the current density of
ates the electron transport involved within OER. In situ 10 mA cm−2. The excellent OER activity is attributed to
Raman technique was employed to probe the active a combination of the enriched active surface sites, abun-
phase (Fig. 15A(c)). At an oxygen evolution potential, the dant defects, and enhanced surface wettability. The suc-
detected new bands indicate the conversion of LDH into cess in using the cation-exchange process to prepare the
NiOOH, demonstrating NiOOH was the active phase for active Fe-doped Co(OH)2 nanosheet has demonstrated a
OER. The Fe incorporation into active site Ni hydroxide new pathway for the fabrication of highly effective OER
could create a more active site to enhance OER activity. catalysts.
Fig. 15 A (a) Schematic illustration of NiFe-LDH nanoplates grown on nickel foam, (b) SEM image of Ni foam, (c) in situ Raman spectra of NiFe-LDH
films with and without OER operation (Figure reprinted with permission from Ref. [65]). B iR-corrected LSV polarization curves of Ni0.83Fe0.17(OH)2,
NiFe LDH and Ni(OH)2 (Figure reprinted with permission from Ref. [66]). C SEM images of (a) NixFe1−xSe2 and (b) NixFe1−xSe2-Do (c) comparison of
NixFe1−xSe2 and NixFe1−xSe2-Do in elemental mapping images (Figure reprinted with permission from Ref. [67])
The majority of non-precious metal catalysts include partially transformed in situ into the corresponding
metal oxides and (oxy)hydroxides. Recently, many other metal hydroxides at the catalyst surface under OER
promising electrocatalysts are exhibiting excellent OER conditions, which correspond to the real active OER
catalytic activities, which consist of transition-metal sites.
phosphides, sulfides, and selenides. However, these
compounds show unsatisfied stability under highly 4.3 OER mechanism involving lattice oxygen species
oxidative potential in alkaline solution. Therefore, In the conventional AEM, the entire reaction proceeds
the understanding of the chemical nature of the true on a single metal site and there is a limitation by the scal-
active sites has attracted a great deal of attention in ing relation among the OER intermediates where the
the development of OER-related catalysts. Hu and co- minimum theoretical overpotential is 0.37 eV. Recently,
worker synthesized nanostructured nickel iron disele- a new OER mechanism involving lattice oxygen species
nide (NixFe1−xSe2) as a templating precursor for in situ is proposed, i.e., lattice oxygen mediated mechanism
generations of a highly active nickel iron oxide catalyst. (LOM) [68–71]. In LOM, the lattice oxygen on the cata-
This catalyst showed excellent OER activity with an lyst directly participates in the oxygen evolution reac-
overpotential of only 195 mV for 10 mV cm−2 [67]. The tion. The participation of lattice oxygen is a phenomenon
SEM image analysis of N ixFe1−xSe2 as-synthesized and recently demonstrated for alloy catalysts in gas-phase
NixFe1-xSe2 derived oxide (NixFe1−xSe2-Do) after OER catalytic oxidation reactions [72]. It is intriguing that
test, as shown in Fig. 15C(a, b), indicate that NixFe1− this phenomenon is considered as an alternative reaction
xSe2-Do has an overall morphology similar to NixFe1− pathway, and sometimes the most favorable one, in the
Se
x 2 nanoparticles grown on the nanoplates. The OER electrocatalysis.
elemental mapping of the change of composition after Indeed, progress has been made by several key studies
the in situ transformation from NixFe1−xSe2 to NixFe1− of the mechanism involving lattice oxygen species. Ste-
xSe2-Do (Fig. 15C(c)) showed that Se content was venson et al. [73] proposed a primary reaction pathway
removed, the oxygen was incorporated in the structure, where the lattice oxygen participate in OER reaction via
and Ni and Fe remained homogeneously distributed reversible formation of surface oxygen vacancies based
in the structure. Powder XRD and XPS analysis of the on a DFT study. They presented a series of cobaltite per-
structure and composition of NixFe1−xSe2 and NixFe1− ovskites structure and demonstrated the relationship
xSe2-Do confirmed the hypothesis that NixFe1−xSe2 is between oxygen vacancies, metal–oxygen covalency,
Fig. 16 A (a) Illustration of oxygen vacancy concentration and Co–O bond covalency. (b) Relationship between oxygen vacancies, oxygen
diffusivity, and the OER activity. (c) The proposed LOM mechanism (Figure reprinted with permission from Ref. [73]). B Possible OER mechanisms
involving concerted proton-electron transfer on surface oxygen sites to yield (a) 34O2(16O18O), and (b) 36O2(18O18O), respectively (Figure reprinted
with permission from Ref. [68]). C Volcano plot for OER on some perovskites with AEM and LOM (Figure reprinted with permission from Ref. [70])
and OER activity. Figure 16A(a) shows the relationship key to determining if the OER proceeds via the AEM or
between oxygen vacancy concentration and Co–O bond LOM is the relative stabilities of these two intermediates.
covalency. DFT studies have shown that by substitut- It is predicted that there is a transition from the AEM to
ing Co3+ with S r2+, the Fermi level (EF) moves closer to LOM upon increasing x in La1−xSrxCoO3−δ system which
the O 2p band which is accompanied with an increase will reduce the O vacancy formation energy and reduce
in the overlap between the M 3d band and O 2p band, the bulk stability.
indicating an enhanced covalency between metal–oxy- Using in situ 18O-isotope-labeling mass spectrom-
gen bond. At the same time, it creates ligand holes. The etry, Shao-Horn et al. provide direct experimental
structural arrangement is followed to reduce the energy evidence that the lattice oxygen is involved in the pro-
reaching a stable state by formation and release of O2, duction of oxygen molecules during the OER. They
resulting in oxygen vacancies. Therefore, the enhanced demonstrated that in highly covalent metal oxides such
covalency between metal–oxygen bond exhibits a higher as La0.5Sr0.5CoO3−δ and SrCoO3−δ (δ represents the
vacancy concentration in the catalyst which can be con- vacancy parameter), the lattice oxygen enables to oxide
trolled by substitution of the lower valence Sr2+ into formation during the OER process which involves non-
La1−xSrxCoO3−δ(LSCO) structure. The DFT modeling concerted proton-electron transfer steps and exhibits
and experimental data results show a direct relationship pH-independent OER activity [68]. Therefore, the OER
between oxygen vacancies, oxygen diffusion rate, and mechanism is triggered when metal–oxygen covalency
the OER activity (Fig. 16A(b)). The data indicate that the is increased. On-line electrochemical mass spectrom-
increased vacancy and surface exchange kinetics correlate etry (OLEMS) is used to detect the participation of lat-
with the increased OER activity. Based on the correla- tice oxygen in the oxidation reaction by 18O-labelled
tion, a LOM mechanism is proposed as a parallel reac- Co-based perovskites La0.5Sr0.5CoO3−δ, SrCoO3−δ, and
tion mechanism to AEM, which is shown in Fig. 16A(c). Pr0.5Ba0.5CoO3−δ which have different metal–oxygen
The lattice oxygen reacts with the adsorbed oxygen on covalency. Oxygen gas was measured in situ by mass
the metal site to form adsorbed –OO intermediates and spectroscopy in terms of different molecular weights such
leave an oxygen vacancy in the lattice. This is different as 32O2(16O16O), 34O2(16O18O), and 36O2(18O18O). There
from AEM mechanism involving the generally-proposed are two different possible lattice oxygen species involved
adsorbed –O species. For a given LSCO composition, the in the oxidation mechanism, which are proposed to
explain the formation of 34O2(16O18O) and 36O2(18O18O), the development of non-noble metal OER electrocatalysts
as shown in Fig. 16B. These steps all involved a chemi- with high activity and long-term stability performance in
cal step to produce molecular O 2 and the oxygen vacancy acidic media remains a challenging area of research and
activity happening on the surface oxygenated sites. Fur- development. This challenge stems from the increasing use
thermore, Kolpak et al. constructed AEM and LOM of proton exchange membrane (PEM) electrolysis is prom-
activity volcano plots as shown in Fig. 16C. The LOM ising water electrolysis because of PEM’s high energy effi-
exhibits a higher OER activity than AEM by minimiz- ciency and fast hydrogen production rate. PEM electrolysis
ing the thermodynamically required overpotential [70]. for water splitting is operated under acidic conditions. For
For AEM, based on the scaling relation, there is a mini- HER, there is various efficient non-noble metal electrocata-
mum theoretical overpotential of 0.37 eV. However, for lyst available in acid media. However, for OER, most of the
LOM, the relative constant ΔG around 1.4 to 1.6 eV for efficient OER catalyst is Ir and Ru based electrocatalysts
VO + OO* → VO + OH* is much smaller than the AEM- which have higher dissolution resistance in acidic condi-
based ΔG, which is 3.2 eV. Therefore, the minimum OER tion. For non-noble metal-based electrocatalysts, most of
overpotential is only 0.17 eV for LOM, demonstrating a them, cannot survive under such conditions. Thus, there
new avenue for the design of better OER electrocatalysts. is a clear need for the development of stable and robust
non-noble metal OER electrocatalysts. Recently, Nocera
5 Summary and perspectives et al. demonstrated a rational approach for designing non-
Taken together, significant progress has been made in the noble metal based electrocatalysts that exhibit high activ-
design of electrocatalysts for water splitting for the pro- ity and stability in acidic media by treating activity and
duction of hydrogen by advancing the atomic, molecular, stability as a decoupled elements of mixed metal oxides.
and nanoscale materials engineering strategies. Hydro- For example, manganese is used as a stabilizing structural
gen is a promising substitute for fossil fuel as its highest element which is coupled to the catalytically active Co
gravimetric energy density and zero pollution emission, center in CoMnOx film [29]. Secondly, there is a limited
which provides a clean and renewable energy as an alter- knowledge of the detailed catalytic mechanisms especially
native to fossil fuels. The development of water splitting for transition-metal-based HER and OER electrocata-
cells as an efficient energy conversion and storage system lysts. The intrinsic active site of electrocatalysts cannot be
play an important role in hydrogen production. How- completely determined based on the descriptor of TOF.
ever, the energy efficiencies of water electrolysis are hin- Recently, non-noble-metal-based carbides, phosphides,
dered by the sluggish reaction kinetics of OER and HER and chalcogenides have drawn great attention due to their
due to high overpotentials which lead to only 4% of the high performance for OER in alkaline media. However, the
word’s hydrogen generation from water splitting at pre- nanostructured electrocatalysts undergo composition and
sent. To facilitate the practical use of water splitting in structural transformations during the reaction under OER
industries, the design of efficient catalysts plays a major conditions. Therefore, understanding the structural trans-
role in both OER and HER to minimize the overpoten- formation is required to determine the real active phases
tial and improve the energy efficiencies. In this review, and sites. Gaining insight into the detailed mechanism,
we highlighted some of the significant advances in the structural transformation, real active sites is critical for the
development of nanostructured noble-metal-based and rational design of the optimal performance catalysts. Inte-
non-noble-metal-based electrocatalysts for HER and gration of in situ characterization techniques and theoreti-
OER (see Tables 1, 2), which show high performance cal modeling is an advanced approach to gain insights into
approaching benchmark catalysts Pt and IrO2/RuO2 for the structural transformation, reaction intermediates, and
the HER and OER with low cost. Fundamental insights reaction pathways of the catalysts. Thirdly, it is difficult to
have been gained into the mechanistic details of the syn- directly compare various nanostructured catalyst materi-
ergistic structure, morphology, and composition of the als based on the performance descriptors due to the differ-
catalysts for HER and OER in different media. The cur- ent mass loadings of the catalysts on the electrode and the
rent understanding of the reaction mechanisms for HER different materials of substrate which may affect the elec-
and OER, especially the emerging LOM for OER, could tron transfer rate by different electrochemical measure-
lead to new advances in overcoming the limitation of ment methods. More effective electrocatalysts screening
the traditional AEM by providing a new avenue for the strategies are needed to establish the standard evaluation
design of better OER electrocatalysts. protocol for effective comparisons of the performances
Despite the significant progress in understanding the of catalysts from different research groups. Nevertheless,
electrocatalytic processes of the OER and HER, several the surge of recent interests in nanostructure and lattice
challenges remain for the ultimate commercial large-scale oxygen engineering of catalysts is expected to lead to new
production of hydrogen by water splitting electrolysis. First, advances in the design of active, stable, and low-cost OER
and HER electrocatalysts for the mass commercialization 23. Y. Xie, Y. Yang, D.A. Muller, H.D. Abruña, N. Dimitrov, J. Fang, ACS Catal.
10(17), 9967–9976 (2020)
of water-splitting based hydrogen production. 24. Z.P. Wu, S. Shan, S.Q. Zang, C.J. Zhong, Acc. Chem. Res. 53, 1287–1299
(2020)
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