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REVIEW
Electrocatalytic Water Splitting www.advmat.de

Support and Interface Effects in Water-Splitting

Electrocatalysts
Jian Zhang, Qiuyu Zhang, and Xinliang Feng*

carrier for the sustainable energy systems

Water-splitting electrolyzers that can convert electricity into storable hydrogen in future.[2] Considering the abundance
are a fascinating and scalable energy conversion technology for the utilization and accessibility of water resources on
of renewable energies. To speed up the sluggish hydrogen and oxygen evolu- the earth, water-splitting electrolyzers that
tion reactions (HER and OER), electrocatalysts are essential for reducing their can convert the generated electricity into
storable hydrogen are such a fascinating
kinetic energy barriers and eventually improving the energy conversion effi-
and scalable energy conversion technology
ciency. As efficient strategies for modulating the binding ability of water-­splitting (Scheme 1).[3,4]
intermediates on electrocatalyst surface, the support effect and interface effect Principally, the water dissociation
are drawing growing attention. Herein, some of the recent research progress on process comprises two half-reactions:
the support and interface effects in HER, OER, and overall water-splitting hydrogen evolution reaction (HER) and
oxygen evolution reaction (OER) that
electrocatalysts is highlighted. Specifically, the correlation between the
occur on the cathode and anode of a
electronic interaction of the constituent components and the electrocatalytic water-splitting electrolyzer, respectively.[5]
water-splitting performance of electrocatalysts is profoundly discussed, with The water-splitting process is a thermody-
the aim of advancing the development of highly efficient water-splitting namically uphill reaction and requires a
electrocatalysts, which may eventually replace the noble-metal-based thermodynamics Gibbs free energy (ΔG)
electro­­catalysts and bring the practically widespread utilization of of ≈237.2 kJ mol−1, corresponding to a
standard potential (ΔE) of 1.23 V versus
water-splitting electrolyzers into a reality.
reversible hydrogen electrode (RHE).[6]
Nevertheless, the two-electron transfer
(HER) and four-electron–proton coupled
1. Introduction reaction (OER) pathways kinetically cause large energy barriers
and thus seriously slow down the electrocatalytic water-splitting
Considering the rapidly growing global energy demand and kinetics. In practice, the water-splitting electrolyzers afford a
environmental concerns, it is urgent to search for renewable very high input voltage of >1.45 V as a result of high overpoten-
and environmentally friendly energy sources to replace the tials of the HER (>30 mV) and OER (>190 mV) processes.[6–8] In
traditional fossil fuels. Although abundant solar energy and order to speed up the sluggish HER and OER kinetics, electro-
wind energy are such sustainable energy sources and can be catalysts are essential for reducing their kinetic energy barriers
converted into electricity, they are intermittent and dependent and eventually improving the energy conversion efficiency of
on weather conditions. For the all-weather utilization of electricity to hydrogen.[4,9] Currently, Pt-based electrocatalysts
these renewable energies, it is of paramount significance to exhibit benchmark HER activity while Ir-based electrocatalysts
efficiently store them.[1] Due to its high gravimetric energy are widely utilized as OER electrocatalysts because of their
density, zero CO2 emission and pollution-free advantages, long-term durability. However, the scarce reserves and high
hydrogen has been commonly regarded as a potential energy price of these noble-metal-based catalysts severely hamper
their universal utilization in the commercial water-splitting
electrolyzers.
Dr. J. Zhang, Prof. Q. Zhang In the past decade, great efforts have been devoted to devel-
Department of Applied Chemistry oping water-splitting electrocatalysts with high activity and
School of Applied and Natural Sciences low cost.[5,10] In general, three strategies have been adopted
Northwestern Polytechnical University
Xi’an 710129, P. R. China for enhancing the electrocatalytic water-splitting activity of
Dr. J. Zhang, Prof. X. Feng catalysts: 1) boosting charge transfer from conductive support to
Center for Advancing Electronics Dresden (cfaed) catalyst surfaces; 2) improving the intrinsic activity of the elec-
and Department of Chemistry and Food Chemistry trocatalysts through engineering the structure of surface active
Technische Universität Dresden centers; 3) increasing the density of accessible active centers by
01062 Dresden, Germany
E-mail: xinliang.feng@tu-dresden.de
structural design of electrocatalysts, such as balanced porosity
and high surface area. Accordingly, various earth-abundant
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201808167. water-splitting electrocatalysts, e.g., carbon materials,[11] carbon
nitride,[12] as well as transition-metal-based oxides,[13] oxyhy-
DOI: 10.1002/adma.201808167 droxides,[14] sulfides,[15] selenides,[16] carbides,[17] nitrides,[18]

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phosphides,[19] phosphates,[20] layered double hydroxides,[21]

and alloys[22] have been developed as alternatives to Jian Zhang received his
precious-metal-based catalysts. Therein, benefiting from Ph.D. degree from the
large surface areas and high inherent activity, several HER Institute of Coal Chemistry,
electrocatalysts (e.g., Ni,N-codoped carbon[23] and CoP|S[24] in University of Chinese
acidic solution; MoNi4[22] in basic solution) show excellent HER Academy of Science in 2014.
performance approaching to the Pt/C while a majority of OER Then he joined Professor
electrocatalysts have higher activity than the Ir/C in alkaline Xinliang Feng’s group as
environment.[25] Nevertheless, the intrinsic activity of above a postdoctoral research
water-splitting electrocatalysts, e.g., turnover frequency (TOF) associate at Technische
per active site, is still much lower than those for precious- Universität Dresden. In
metal-based catalysts. December 2017, he was
For the development of high-activity water-splitting elec- appointed as a research
trocatalysts, the above three strategies have been extensively group leader in Prof. Feng’s group. From 2019, he will
utilized. In particular, several review articles have systematically be a Professor in Northwestern Polytechnical University
summarized the development of Strategies 1 and 3.[8,26] in Xi’an, China. His research interests focus on the
Nevertheless, the Strategy 2 for modulating the intrinsic development of 2D nanomaterials and carbon-rich mate-
activity of water-splitting electrocatalysts are less explored. In rials for energy conversion processes including water
the past decades, support effect and interface effect have been splitting, oxygen reduction, CO2 reduction, and metal–air
widely explored to enhance the catalytic activity of traditional batteries.
heterogeneous catalysts for CO oxidation,[27] Fischer–Tropsch
synthesis,[28] water–gas shift reaction,[29] etc. Very recently,
Qiuyu Zhang obtained
support and interface effects are drawing rising attention
her Ph.D. degree in 1999.
because of their strong modulation ability toward chemisorp-
Since 2004, she has been a
tion of reaction intermediates on electrocatalysts surface,
Professor at Northwestern
which can efficiently accelerate the water-splitting kinetics
Polytechnical University.
(Scheme 2). Regarding the support effects, the underlying sup-
She is a member of the
port or substrate has rather poor catalytic activity, but it can
Polymer Division, Chinese
considerably enhance the catalytic performance of supported
Chemical Society, a member
active materials due to their strong electronic interactions like
of the Polymer Materials
electronegativity. For the interface effect, the formed interfaces
and Engineering Society of
between two types of active materials can constitute more
China, and the Executive
active centers than individual component as a result of their
Director of the Shaanxi
strong bonding, electronic interactions, or synergistic effects.
Provincial Chemical Society. Her research interests focus
In this context, we like to highlight some recent progress of
on micro-/nanoscale polymer/inorganic composite
support and interface effects in the HER, OER, and overall
materials and functional polymer materials Surface and
water-splitting electrocatalysts. Specifically, the influence of
interface of materials.
mutual interaction of constituent components on catalytic per-
formance of electrocatalysts will be profoundly discussed. We
hope that this review article will advance the development of Xinliang Feng received
highly efficient water-splitting electrocatalysts, and eventually his Bachelor’s degree in
replacing the noble-metal-based electrocatalysts and bringing 2001 and Master’s degree
the practically widespread utilization of the water-splitting elec- in 2004. Then he joined
trolyzers into a reality. Prof. Klaus Müllen’s group at
the Max Planck Institute for
Polymer Research (MPIP) and
2. Support and Interface Effects in Water-Splitting obtained his Ph.D. degree
in April 2008. In December
Electrocatalysts
2007, he was appointed as a
As discussed above, three strategies have been employed for group leader at the MPIP, and
improving the activity of water-splitting electrocatalysts, e.g., in 2012 he became a distin-
nanostructuring to increase the number of accessible active guished group leader at the MPIP. In 2014, he became a
sites,[8,30] alloying/hybridizing to improve intrinsic activity, W3 Chair Professor at Technische Universität Dresden. His
compositing to enhance charge transfer/intrinsic activity.[22,31] current scientific interests include graphene, 2D nano-
Therein, catalyst support and catalyst–catalyst electronic inter- materials, organic conjugated materials, and carbon-rich
actions have been suggested to modify the binding energy of molecules and materials for electronic and energy-related
the water-splitting intermediates through either electronic applications.
structure perturbation of the active sites or direct participation
in the reaction.

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Scheme 1.  Schematic illustration of water-splitting electrolyzer and related reaction kinetics.

2.1. Support Effect

Simply changing the underlying support can greatly influence

Scheme 2.  Schematic illustration of support effect and interface effect in
water-splitting electrocatalysts.
the associated electronic properties of surface catalysts, which,
in turn, result in significant effects on catalytic activity.[27]
Support effects, particularly metal–metal oxide electronic inter-
actions like Au/TiO2,[32] have been widely investigated in heter-
ogeneous catalytic reactions such as water–gas shift reaction,[33]
hydrogenation reaction,[34] methane oxidation,[35] etc. In the
last several years, support effect emerges as a facile approach
to optimize the bonding properties of water-splitting interme-
diates and thus improve the electrocatalytic performance.[36,37]
For example, in 2016, a Ce-doped NiOx electrocatalyst film was
fabricated by electrodeposition of Ni- and Ce-nitrate precursors
onto an Au-coated glassy carbon disk (NiCeOx–Au).[38] Here,
Au layer acted as the support. The depth X-ray photoelectron
spectroscopy (XPS) profile of NiCeOx–Au indicated that Au
potentially diffused into the top NiCeOx film. Meanwhile, the
electrodeposition could form a porous structure with abundant
active sites. Benefiting from the strong electronic interaction
between the gold support and NiCeOx film, the NiCeOx–Au
required only an overpotential of 271 mV to reach 10 mA cm−2
and achieved 13.3 mA cm−2 at an overpotential of 280 mV
in 1 m KOH aqueous solution. This current density was

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significantly higher than that of NiCeOx supported on glassy
carbon (GC; <1 mA cm−2 at 280 mV). The TOF of NiCeOx–Au
at 280 mV was determined to be 0.08 s−1, which was one order
of magnitude higher than that of NiCeOx–GC. The density
functional theory (DFT) calculation revealed that Au support
reduced the energy barrier of OER descriptor (ΔGOH* to ΔGO*)
on Au-supported NiCeOx films. Nevertheless, the intrinsic
interaction between gold support and active centers of surface
NiCeOx remained unclear.
2.2. Interface Effect
The complexity of hybrid electrocatalysts makes the funda-
mental investigations on the structure–activity relationship
extremely challenging. However, this complexity also brings
diverse structural features that can be favorably modulated. For
instance, the selection of active component materials is crucial,
which can affect not only the growth and morphology of
hybrid electrocatalysts, but also their ensemble electrocatalytic
activity.[26] Unlike support effects, interface effects will result in
reconstructed active centers due to the strong bonding or elec-
tronic interactions between two different active components.
Thereby, the reconstructed active centers established at the
interfaces can yield higher activity than individual compo-
nents.[39] As we all know, the HER and OER kinetics are intrin-
sically dominated by the chemisorption of precursor molecules
(H2O, OH−, or H+) and reaction intermediates (e.g., *H,
*OH, *O, etc.).[5,40] Therefore, the interface effects provide a
favorable strategy for accelerating the HER and OER kinetics by
optimizing the chemisorption of precursor molecules or/and
reaction intermediates.
Toward this end, in 2011, a composite Ni(OH)2/Pt electro-
catalyst was built up as a model HER system, where ultrathin
Ni(OH)2 clusters (height: 0.7 nm; size: 8–10 nm) were grown
on Pt single-crystal surfaces.[41] The density of Ni(OH)2 clusters
reached a maximum at a Pt surface coverage of ≈35%. Inter-
estingly, in comparison with the electrochemical cyclic voltam-
metry (CV) curve of pure Pt electrode in alkaline conditions, the
Ni(OH)2/Pt hybrid presented an enhanced adsorption and irre-
versible reduction of OHad under the negative sweep due to the
higher oxophilicity of the surface Ni(OH)2 clusters. As a result,
at an overpotential of −0.1 V, the electrocatalytic HER activity
of Ni(OH)2/Pt in 1 a m KOH solution was approximately eight
times higher than that for pure Pt. The surface Ni(OH)2 clusters
played a key role in promoting the initial water dissociation and
the alkaline HER kinetics. The DFT calculations unveiled that, at
the interfaces between Ni(OH)2 and Pt, the strong interaction of
Ni(OH)2 with O atoms and Pt with H atoms may synergistically
facilitate the initial adsorption of water molecules. Later, water
dissociation occurred and the formed hydrogen intermediates
bonded to neighboring Pt sites. Finally, two adsorbed H atoms
on the Pt sites combined into a hydrogen molecule.[40] Sparked
by this pioneering work, a lot of hybrid electrocatalysts with
abundant interfaces have been developed afterward.[42–45] How-
ever, their HER activities are still inferior to that for the Pt/C.
Moreover, the fundamental mechanisms of synergistic effects
between active components remain elusive due to the great chal-
lenges in experimentally characterizing interfacial structures.
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3. Electrocatalytic Water Splitting
3.1. Hydrogen Evolution Reaction
The HER process is a two-electron-coupled proton reduction
reaction.[46] As illustrated in Volcano plots, the electrocatalysts
with a near-zero Gibbs free energies of H-adsorption (ΔGH)
may manifest the highest electrocatalytic HER activity.[46] Some
earth-abundant-metal-based HER electrocatalysts such as
MoS2 show a |ΔGH| close to that of Pt with a near-zero ΔGH.[47]
However, their experimentally measured HER activities are
much lower than Pt, which are mostly due to their poor
electrical conductivities and limited accessible active sites.[48]
Owing to the strong electronic or bonding interactions,
support and interface effects can help to optimize the ΔGH of
electrocatalysts for enhancing the HER activity (Table 1).
3.1.1. Gold-Based Support Effects
MoS2 was predicted by theory to be a promising HER electro-
catalyst[49] and its active centers are experimentally proved to be
the uncoordinated edges.[50] Thus, MoS2 is a good model system
for studying the influence of support effects on its HER activity.
Accordingly, it has been found that the Mo-edge is the one that is
primarily exposed in single layer of MoS2 supported on Au(111),
highly ordered pyrolytic graphite (HOPG), or graphitic carbon as
substrates. The effects of substrate support on the HER activity at
the MoS2 edge sites were systematically investigated for several
different systems in 2014: MoS2, MoS2-Au, and MoS2-graphene.[37]
As shown in Figure 1a, for the Mo-edge at 0.25 monolayer (ML)
H coverage, the H-adsorption free energies of MoS2-Au and
MoS2-graphene were considerably increased by 0.56 and 0.18 eV,
respectively, in comparison with MoS2. When the multilayered
MoS2 was supported on Au(111) or graphene, the top layer MoS2
had a similar hydrogen binding with the unsupported MoS2,
indicating that the support effect was in short range.
Afterward in 2017, the support effect was utilized as an effective
strategy for tuning the ΔGH of thiomolybdate [Mo3S13]2− cluster
catalysts and thereby optimize their intrinsic HER activity.[51]
Thin (≈1 × 1015 clusters cm−2) of [Mo3S13]2− cluster layers were
deposited on gold, silver, copper, and glassy carbon supports. The
HER performance was evaluated using a three-electrode rotating
disk electrode (RDE) electrochemical system in acidic solutions.
The onset HER overpotential of [Mo3S13]2−-Au was −0.15 V,
which was much lower than −0.18 V for [Mo3S13]2−-Ag, −0.20 V
for [Mo3S13]2−-GC, and −0.24 V for [Mo3S13]2-Cu (Figure 1b). The
TOF values per Mo atom are shown in Figure 1c. At −200 mV
versus RHE, the TOF value per Mo atom of [Mo3S13]2−-Au was
0.47 s−1, higher than Ag, GC, and Cu supports respectively,
which were 0.27 s−1 for [Mo3S13]2−-Ag, 0.15 s−1 for [Mo3S13]2−-GC,
and 0.045 s−1 for [Mo3S13]2-Cu. The near one order of magni-
tude difference between the TOF values of [Mo3S13]2−Au and
[Mo3S13]2−-Cu strongly evidenced that the catalyst−gold interac-
tion substantially influenced the HER activity. In order to reveal
the role of support effects in tuning the activity of [Mo3S13]2− clus-
ters, DFT calculations were carried out to calculate their ΔGH. As
indicated in Figure 1d, the TOF values of all electrocatalysts at
200 mV were plotted versus the calculated ΔGH. The achieved plot
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Table 1.  The HER performance of the electrocatalysts with support and interface effects.

Electrocatalysts Onset overpotential Overpotential at 10 mA cm−2 TOF [s−1] Tafel slope [mV per decade] Electrolyte
Interface effect
MoS2/Cu2S hybrid[65] ≈0 mV ≈50 mV − ≈39 0.5 m H2SO4
MoS2(1−x)Se2x/NiSe2[66] − ≈69 mV − 42.1 0.5 m H2SO4
Platinum-nickel/nickel sulfide ≈0 mV ≈25 mV − − 0.5 m H2SO4
nanowires[67]
Ni-S/MOF[68] − >200 mV 34 at 210 mV 111 0.1 m HCl
Pt/FeCo alloy/Cu/CNTs[69] ≈0 mV ≈18 mV 7.22 24 0.1 m HClO4
MoS2/black phosphorus[70] ≈0 mV ≈90 mV − 68 0.5 m H2SO4
MoxC-Ni@N-doped carbon[71] ≈0 mV 75 mV − 45 0.5 m H2SO4
Ni@Ni2P−Ru heterostructures[72] ≈0 mV 51 mV 0.78 at 10 mV 35 0.5 m H2SO4
Polyaniline/CoP[73] 15 mV ≈55 mV − 34.5 0.5 m H2SO4
Cu7S4@MoS2 [45]
− 133 mV − 48 0.5 m H2SO4
Mo2N–Mo2C/graphene[53] 11 mV 157 mV − 55 0.5 m H2SO4
18 mV 154 mV − 68 1 m KOH
Co–Mo–Sx chalcogels [74]
− >200 mV at 5 mA cm−2 − − 0.1 m KOH
Ni/NiO/CNTs[44] ≈0 mV <100 mV − 82 1 m KOH
Ni/CeO2[75] ≈0 mV ≈90 mV − − 1 m KOH
Cu nanodots/Ni3S2 nanotubes[76] 60 mV 128 mV − 76.2 1 m KOH
Support effect
Coupled molybdenum carbide and ≈0 mV 34 mV − 33.6 0.5 m H2SO4
reduced graphene oxide[56]
Mo2C/Nitrogen-doped carbon[77] 60 mV ≈120 mV − 60 0.5 m H2SO4
RuCo/N-doped graphene[57] ≈0 mV 28 mV − 31 1 m KOH
Co(OH)2@polyaniline hybrid[78] 50 mV ≈95 mV − 91.2 1 m KOH
Ru/C2N[61] ≈0 mV 17.0 mV 0.75 38 1 m KOH
≈0 mV 13.5 0.67 30 0.5 m H2SO4

suggested a volcano-like trend in HER activity. The [Mo3S13]2−-Au
showed the highest TOF value of 0.35 s−1 per Mo atom at 200 mV
due to its lowest |ΔGH|. These results highlight that gold-based
support effects are a promising approach for optimizing the ΔGH
of electrocatalysts toward high HER activity.
3.1.2. N-Doped-Carbon-Based Support Effects
Although the gold support can efficiently facilitate the HER
kinetics, but its broad utilizations are seriously hindered by the
high cost of gold. Lately, due to their superior electrical con-
ductivity, high specific surface area, and existence of abundant
nitrogen dopants, various N-doped carbon materials like 1D
carbon nanotubes,[52] 2D graphene,[53] and 3D porous carbon[54]
have been widely composited with active electrocatalysts for
promoting the electron transfer and tuning the H-absorption
property during the HER. Since the conductive role of N-doped
carbon electrocatalysts has been broadly discussed in the pre-
vious review articles,[26,55] here we will uniquely highlight their
support effects for tailoring the ΔGH of the HER electrocatalysts.
In 2016, a 2D composite electrocatalyst composed of Mo2C
encapsulated by N,P-codoped carbon shells and N,P-codoped
reduced graphene oxide (RGO) (Mo2C@NPC/NPRGO) was
synthesized by pyrolysis of a PMo12 (H3PMo12O40)–polypyrrole/
RGO precursor at 900 °C in N2 atmosphere (Figure 2a).[56] Mo2C
nanoparticles (NPs) had an average size of about ≈2–5 nm and
were homogeneously deposited on the graphene sheets. The
Brunauer–Emmett–Teller (BET) surface area of the Mo2C@
NPC/NPRGO was 190 m2 g−1, which was much higher than
55 m2 g−1 for the Mo2C/N,P-codoped carbon (Mo2C@NPC).
In a 0.5 m H2SO4 aqueous solution, the Mo2C@NPC/NPRGO
exhibited outstanding electrocatalytic HER activity with a very
low onset overpotential of ≈0 mV, which was well comparable
to that of Pt/C. The overpotential of the Mo2C@NPC/NPRGO
at a current density of 10 mA cm−2 was only 34 mV, which was
much lower than 260 mV for the Mo2C@NPC and very close to
30 mV for the Pt/C (Figure 2b). The Tafel slope of the Mo2C@
NPC/NPRGO was about 33.6 mV per decade, indicating that
the recombination of adsorbed H (Tafel step) is the rate-deter-
mining step (Figure 2c). The DFT results disclosed that the
Mo2C (001), graphitic-N-doped graphene and pyridinic-N-doped
graphene had a ΔGH values of 0.82, 0.89, and −2.04 eV, respec-
tively, suggesting their strong binding ability toward H interme-
diate, which subsequently led to poor HER performance because
of the difficulty in hydrogen release. However, the Mo2C@

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Figure 1.  a) The change of Gibbs free energy of H-absorption on the Mo-edge at each coverage of MoS2 supported by different support. Reproduced
with permission.[37] Copyright 2014, American Chemical Society. b) The HER polarization curves of electrocatalysts and c) related TOF plots. d) The
TOF values at η = 200 mV as a function of ΔGH. b–d) Reproduced with permission.[51] Copyright 2017, American Chemical Society.

Figure 2. a) Schematic illustration of the synthetic process of Mo2C@NPC/NPRGO. b) Polarization curves and c) Tafel plots of Mo2C@NPC,
Mo2C@NPC/NPRGO and Pt/C catalysts. The inset in (b) is a photograph of the production of H2 bubbles on the surface of Mo2C@NPC/NPRGO).
a–c) Reproduced with permission.[56] Copyright 2016, Nature Publishing Group.

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pyridinic-N-doped graphene presented a near-zero ΔGH* value of
−0.22 eV, emphasizing the effective support effects of N-doped
carbon for tailoring the H-absorption property of electrocatalysts.
Afterward, a RuCo alloy/nitrogen-doped porous carbon elec-
trocatalyst (RuCo/NC) was prepared by annealing Ru-doped
Prussian blue analogs (Ru3+/Co3[Co(CN)6]2) at 600 °C for 4 h
under nitrogen atmosphere (Figure 3a).[57] The obtained sample
contained abundant alloy particles with a mean diameter of
≈30 nm, which were encapsulated by supporting carbon shells
with a thickness of ≈1–15 layers. The elemental analysis from
energy filtered TEM showed that the Ru and Co contents in the
RuCo/NC were about 5.69 and 94.31 wt%. The nitrogen content
in the RuCo/NC was measured to be ≈3.51 at% using the XPS
analysis. The specific surface area of the RuCo/NC was about 41
m2 g−1 and the corresponding pore size was narrowly distributed
around ≈3 nm. In a 1 m KOH electrolyte, the RuCo/NC presented
an overpotential of ≈28 mV at a current density of 10 mA cm−2,
which was lower than 300 mV for Co/nitrogen-doped carbon
and 58 mV for commercial Ru catalyst, and even 40 mV for Pt/C
(Figure 3b). The Tafel slope of the RuCo/NC was ≈31 mV per

Figure 3.  a) Schematic illustration of the synthesis procedures for the RuCo/CN. b) The HER polarization curves and c) related Tafel plots of RuCo@NC
samples with different Ru contents (S-0, S-1, S-2, S-3, S-4, S-5, and S-6. d) The HER polarization curves of RuCo@NC before and after etching in 1 m HCl
solution. e) The diagram of calculated ΔGH* on different catalyst models. a–e) Reproduced with permission.[57] Copyright 2017, Nature Publishing Group.

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decade, which was well comparable to that of Pt/C, indicating
a rapid HER kinetics in alkaline solution (Figure 3c). In order
to understand the role of Co in the HER activity, the RuCo/NC
was leached in 1 m HCl solution. The overpotentials at current
densities of 10 and 100 mA cm−2 considerably increased after the
etching, proving the key role of Co in HER activity of RuCo/NC
(Figure 3d). Subsequently, DFT calculations were carried out to
probe the origin of excellent HER activity of RuCo/NC. As illus-
trated in Figure 3e, the Gibbs free energy of H-adsorption (ΔGH*)
of graphene was significantly reduced after nitrogen doping and
the combination of metal Co with graphene. Alloying Ru atoms
into Co metal could further decrease ΔGH* and Ru3Co-N-doped
graphene model exhibited the lowest ΔGH* value of 0.31 eV. Very
recently, various metal organic framework (MOF)-derived electro-
catalysts supported by N-doped carbon have been reported, e.g.,
iridium–cobalt alloy encapsulated in N-doped carbon cages[58]
and Co nanoparticles encapsulated in N,B-codoped carbon
cages,[59] etc. Considering that some recent review papers have
systematically discussed the development of MOF-derived elec-
trocatalysts for water splitting, we will not emphasize here.[60]
3.1.3. Conjugated-Organic-Framework-Based Support Effects
Owing to their good electronic conjugation and the presence
of abundant functional groups (like OH, O, COOH,
CN, etc.) and heteroatoms (N, S, P, etc.), conjugated organic
polymers can be employed as promising supporting materials
for tailoring electrocatalytic HER of catalysts.[62] As schemed in
Figure  4a, Ru/conjugated polymer composite electrocatalysts

Figure 4. a) Schematic illustration of the synthesis process of the Ru@C2N electrocatalyst. b) The TEM image of Ru@C2N. Inset: particle size
distribution of the Ru nanoparticles. Scale bar, 20 nm. c) The polarization curves and d) corresponding Tafel plots of Co@C2N, Ni@C2N, Pd@C2N,
Pt@C2N, and Pt/C electrocatalysts in 0.5 m H2SO4 aqueous solution. e) The polarization curves of Co@C2N, Ni@C2N, Pd@C2N, Pt@C2N, and Pt/C
electrocatalysts in 1.0 m KOH aqueous solution. a–e) Reproduced with permission.[61] Copyright 2017, Nature Publishing Group.

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(Ru@C2N) were fabricated using the polycondensation reaction
between hexaketocyclohexane (HKH) and hexaaminobenzene
(HAB) trihydrochloride in the presence of ruthenium chloride
(RuCl3) and subsequent reduction reaction. As a result, the Ru
nanoparticles were uniformly distributed in the C2N polymer
matrix. The size of Ru nanoparticles was ≈1.6  ± 0.5 nm
(Figure 4b). The thermogravimetric analysis (TGA) revealed
that the Ru content in the Ru@C2N composite was about
28.7 wt%. The BET specific surface area of the Ru@C2N was
measured to be 400.1 m2 g−1 with an average pore diameter of
3.37 nm. As a contrast, Co@C2N, Ni@C2N, Pd@C2N, and Pt@
C2N were also synthesized using the same method. In a 0.5 m
H2SO4 solution, the HER overpotentials of Co@C2N, Ni@
C2N, and Pd@C2N at 10 mA cm−2 were larger than 300 mV.
The Pt@C2N delivered a current density of 10 mA cm−2 at an
overpotential of ≈43 mV. By contrast, Ru@C2N exhibited a
very small onset HER overpotential of 9.5 mV, which was very
close to 1.0 mV for commercial Pt/C (Figure 4c). Moreover,
for the Ru@C2N, the HER overpotential at 10 mA cm−2 was
≈22 mV, which was only 6 mV higher than 16 mV for the Pt/C.
The Tafel slope of Ru@C2N was 30 mV per decade, indicating
a Volmer–Tafel mechanism (Figure 4d). Noticeably, in 1.0 m
aqueous KOH solution, Ru@C2N exhibited a HER overpoten-
tial of only 17.0 mV at 10 mA cm−2, which was even lower than
20.7 mV for the Pt/C (20.7 mV) (Figure 4e). Meanwhile, the
TOF values of Ru@C2N were 0.76 s−1 at 25 mV and 1.66 s−1
at 50 mV, which were even larger than 0.47 s−1 at 25 mV and
0.95 s−1 at 50 mV for the Pt/C. DFT calculations were con-
ducted to understand the origin of the high electrocatalytic
activity of Ru@C2N. The Ru4, Ru13, and Ru55 models showed
the H-absorption energies of 0.44, 0.56, and 0.54 eV H−1,
respectively. By contrast, hydrogen adsorbed on the surface
of Ru55@C2N was 0.55 eV H−1, which was the closest to
0.6 eV H−1 for Pt(111).
3.1.4. Interface Effects
In principal, the HER kinetics in acidic solutions was deter-
mined by the hydrogen adsorption on electrocatalyst surfaces
while by the initial water dissociation step in alkaline elec-
trolytes.[5,64] In this respect, taking advantage of the strong
bonding or electronic interactions at the interfaces between two
different active components, constructing hybrid electrocata-
lysts with abundant interfaces provides a rational pathway for
optimizing the H-adsorption and water dissociation kinetics,
eventually accelerating the sluggish HER kinetics. A nickel
oxide/nickel (NiO/Ni) composite electrocatalyst was fabricated
on carbon nanotube (NiO/Ni@CNT) through a low-pressure
thermal reduction of nickel hydroxide.[44] Ni/NiO core–shell
nanoparticles were observed on the CNT (Figure  5a). The
size of NiO/Ni nanoparticles was about 10 nm. In a 1 m KOH
aqueous solution, the resultant NiO/Ni@CNT exhibited a HER
overpotential of ≈80 mV at a current density of 10 mA cm−2,
which was much lower than >200 mV for Ni@CNT and
>450 mV for NiO@CNT (Figure 5b). Based on the achieved
experimental results, the authors tentatively proposed that at
a NiO/Ni interface, the OH− generated from water dissocia-
tion could preferentially bond to the Ni2+ sites of NiO at the
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interface while a nearby Ni site would facilitate H adsorption,
thus synergistically enhancing the HER catalytic activity of the
NiO/Ni. In order to unravel the role of interfaces in composite
electrocatalysts, a MoS2/CoSe2 hybrid was fabricated using a
solvothermal reaction in 2015, where MoS2 nanosheets were
grown on the surface of CoSe2.[63] As shown in Figure 5c,d,
the MoS2 nanosheets were uniformly anchored on CoSe2
nanosheets, yielding abundant interfaces. In a 0.5 m H2SO4
electrolyte, the pristine CoSe2 showed an onset HER over-
potential of ≈50 mV (Figure 5e). By contrast, the onset HER
overpotential of MoS2/CoSe2 hybrid reached as low as ≈11 mV.
The Tafel slope of MoS2/CoSe2 hybrid was determined to be
≈36 mV per decade, which was close to 30 mV per decade
for the Pt/C and lower than 48 mV per decade for CoSe2 and
101 mV per decade for MoS2 (Figure 5f). The XPS and theo-
retical investigations disclosed that the CoSe2 chemically inter-
acted with MoS2 by forming SCo bonds, which could further
optimize the hydrogen adsorption.
3.2. Oxygen Evolution Reaction
In contrast with the HER, the OER is more kinetically sluggish
as a result of its multistep oxidation pathway. According to
the previously reported volcano plots for the OER, the change
of Gibbs free energy from *OH to *O intermediates is com-
monly regarded as the rate-determining descriptor for theo-
retically evaluating the inherent activity of OER catalysts.[5,9]
Non-noble-metal-based electrocatalysts have shown much
higher OER activity than Ir/C and RuO2 in alkaline electrolytes
(Table 2).[14] However, because of their poor electrical conduc-
tivities, low specific surface areas and poor intrinsic activities,
the OER overpotential of noble-metal-free electrocatalysts is
still higher than 200 mV in alkaline media.[9,79] Additionally,
under acidic condition, precious-metal Ir-based materials
remain the benchmark OER electrocatalysts.[80] Similar to the
HER process discussed above, support and interface effects
are also promising strategies for optimizing the chemisorption
properties of oxygen-containing intermediates to promote the
OER kinetics.
3.2.1. Gold-Based Support Effects
As previously demonstrated for the HER, owing to the strong
electronic interaction between electrocatalysts and electron-
egative gold support, the H-absorption property of the active
centers will be preferentially optimized to promote the HER
kinetics. Sparked by these pioneering studies, gold support was
further explored for modulating the electronic properties of
OER electrocatalysts. In 2011, Au@Co3O4 core–shell nanowires
were synthesized via colloidal polymerization of core–shell
gold–cobalt NPs (AuCoNPs) and subsequent oxidation of pre-
organized AuCoNPs.[81] Electrochemical specific capacitance
of the calcined Au@Co3O4 nanowire film was evaluated using
CV. In comparison with Co3O4 nanowire film, Au@Co3O4
nanowire film exhibited a twofold enhancement of Faradaic
electrochemical activity based on the redox transitions at the
active sites (i.e., CoO2 > CoOOH > Co3O4).
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Figure 5.  a) Atomic resolution STEM bright-field image showing the structure of a typical NiO/Ni particle on a CNT. Scale bar, 2 nm. b) The polarization
curves of NiO@CNT, Ni@CNT, and NiO/Ni@CNT catalysts. a,b) Reproduced with permission.[44] Copyright 2014, Nature Publishing Group. c) TEM
and d) HRTEM images of MoS2/CoSe2 hybrid. e) The polarization curves and f) related Tafel plots of MoS2/CoSe2 hybrid, pure MoS2, pure CoSe2, and
Pt/C catalyst. c–f) Reproduced with permission.[63] Copyright 2015, Nature Publishing Group.

To further probe the unique role of Au support in the
enhancement of OER activity of electrocatalysts, cobalt oxide
was deposited onto the surface of various supports including
Au, Cu, Co, Pd, and Pt.[36] The thickness of deposited cobalt
oxide was about ≈0.4 ML (monolayer). The oxygen evolution
activity of pure Au, cobalt oxide, and Au electrodes with
different thicknesses of cobalt oxide was firstly measured
in 0.1 m KOH aqueous solution. Figure  6a presents the OER
polarization curves of the ≈0.4 ML cobalt oxide/Au, pure Au,
pure Co, and a curve plotted by simple addition of currents
of pure Au and cobalt oxide. The large enhancement of cobalt
oxide/Au in anodic currents pointed out that Au undoubtedly
improved the activity of surface cobalt oxide. The ≈0.4 ML cobalt
oxide/Au showed the highest TOF value of 1.8 s−1 at 351 mV,
which was tenfold higher than 0.06 s−1 for ≈87 ML of cobalt
oxide/Au. The TOF values of pure Au and Co were only 0.007
and 0.05 s−1, respectively. Noticeably, the TOF values of ≈87 ML
cobalt oxide/Au and bulk Co were almost the same, proving that
the electronic interaction between cobalt oxide and gold support
was in short range. Additionally, the TOF values of cobalt oxide
supported by Pt, Pd, Cu, and Co were also evaluated (Figure 6c).
The achieved TOF values of cobalt oxide were dependent on the
metal supports: Au > Pt > Pd > Cu > Co. This result indicated
that the TOF values decreased as weakened electronegativity of
metal supports. The DFT calculations reported that the OER
overpotential on β-CoOOH (0 114) was 0.4 V.[82] However, when
the hydrogen transfer to AuO was considered, this value
decreased to 0.3 V (Figure 6d).
3.2.2. Metal-Oxide-Based Support Effects
To address these problems, antimony-doped tin oxide (ATO)
was developed as a new type of supporting substrate.[84]
Metallic Ir nanoparticles were synthesized on high-surface-area
mesoporous ATO support composed of ATO nanoparticles, and
then electrochemically oxidized into IrOx (Figure  7a).[83] ATO
nanoparticles had a size of ≈3−5 nm while the average size of

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Table 2.  The OER performance of electrocatalysts with support and interface effects.

Electrocatalysts Onset overpotential Overpotential at 10 mA cm−2 TOF Electrolyte

Interface effects
Fe(PO3)2/Ni2P[87] − 177 mV 0.12 s−1 at 300 mV 1 m KOH
NiO/TiO2 hybrid[86] − 320 mV 0.068 s−1 at 500 mV 1 m KOH
Au/CoSe2 [88]
176 mV 430 mV − 0.1 m KOH
Co@Co3O4/carbon nanotubes[89] 330 mV 410 mV − 0.1 m KOH
FeCo Alloys/Co4N hybrid[90] 230 mV 280 mV 0.19 s−1 at 300 mV 1 m KOH
Carbon-confined NiCo@ − 366 mV at 20 mA cm−2 0.022 s−1 at 450 mV 1 m KOH
NiCoO2[91]
FeOOH/CeO2 nanotube[92] 210 mV − − 1 m KOH
Support effect
Ce-doped NiOx/Au[38] − ≈270 mV 0.08 s−1 at 280 mV 1 m KOH
NiO/Fe, N-doped carbon [93] 230 mV 390 mV 0.2 s−1 at 350 mV 0.1 m KOH
NiCo-LDH/N-doped graphene[94] 350 mV − − 0.1 m KOH
Co(OH)2 encapsulating conduc- − 296 mV at 25 mA cm−2 0.95 s−1 at 450 mV 1 m KOH
tive nanowires array[95]
NiFe hydroxides/N-doped − 264 mV − 0.1 m KOH
graphene[96]

Figure 6.  a) The OER polarization curves of the ≈0.4 ML cobalt oxide@Au, pure Au and Co electrodes in 0.1 m KOH. The inset in (a) is the SEM image
of ≈0.4 ML of cobalt oxide supported by Au substrate. b) The TOF values of the different cobalt oxide/Au electrodes as a function of the number of
monolayers of cobalt oxide. c) The TOF values of cobalt oxide deposited on Au, Pt, Pd, and Cu support. a–c) Reproduced with permission.[36] Copyright
2011, American Chemical Society. d) The theoretically achieved OER Volcano plot. Reproduced with permission.[82] Copyright 2015, Wiley-VCH.

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Figure 7.  a) Low-resolution and b) high-resolution TEM images of Ir nanoparticles supported on ATO. The insets in (a,b) are the EDX pattern of
Ir/ATO and the Ir nanoparticle size distribution, respectively. c) Normalized XANES spectra and b) integrated white-line versus d vacancy and Ir
oxidation state of the IrOx/C, IrOx/Com. ATO, and IrOx/ATO. a–d) Reproduced with permission.[83] Copyright 2016, American Chemical Society.

Ir nanoparticle was 2.5 nm (Figure 7b). Figure 7c shows the
Ir LIII-edge X-ray absorption near-edge spectroscopy (XANES)
region of the IrOx/ATO and IrOx/carbon electrocatalysts.
The peak position of 2p3/2 to 5d white line was an indicator
of the number of electron vacancies in the 5d orbitals of Ir
atoms: IrOx/carbon ≈ IrO2 ≫ IrOx/commercial ATO ≈ IrOx/
ATO  > Ir foil. As further revealed in Figure 7d, the d vacancy
of the ATO-supported IrOx was 4.2 holes, which was lower
than that of bulk IrO2 (5 holes) and carbon-supported IrOx
(essentially 5 holes). In terms of average Ir oxidation states,
IrOx/commercial ATO, IrOx/ATO, and IrOx/carbon were +3.3,
+3.2, and +4.0, respectively. In 0.05 m H2SO4 solution, the elec-
trochemical OER activities of IrOx/ATO, IrOx/carbon, and IrOx/
commercial ATO at a voltage 1.8 V (vs RHE) were basically sim-
ilar because the OER activity at this potential was mainly domi-
nated by ohmic resistances. Therefore, the reduced oxidation
state of the ATO-supported IrOx particles did not change their
OER activity. However, after the stability tests, the OER activity
of IrOx/carbon seriously decreased by 99.7%. By contrast, the
activity decline of the IrOx/ATO catalyst was only 31.6%. These
results confirmed that the employment of ATO support greatly
enhanced the OER durability of IrOx electrocatalysts due to
their strong electronic interaction.
3.2.3. Interface Effect in OER Electrocatalysts
Regarding the multistep reaction nature of the water oxidation,
it is highly appealing to utilize the interface effects of hybrid
electrocatalysts for optimizing the chemisorption of both
H- and O-containing intermediates, eventually speeding up the
OER kinetics. For example, in 2012, through a polyol reduc-
tion approach, Mn3O4 nanoparticles with an average size of
≈15.7 nm were grown on CoSe2 nanobelts (Figure 8a,b).[85] The
loading content of Mn3O4 on the CoSe2 was about 45.8 wt%.
The XPS binding energy of Co 2p3/2 in the CoSe2 located at
778.5 eV, which were principally responsible for the OER
activity. By comparison, the XPS binding energy of Co 2p3/2 in
the Mn3O4/CoSe2 hybrid showed a negative shift of ≈0.84 eV,
which was attributed to the electron transfer from Mn3O4 to
CoSe2 because of their strong bonding or electronic interac-
tions. The electron injection from Mn3O4 to CoSe2 might lead
to stronger acidity of Mn3O4 (Lewis acid), which promoted the
activation of water molecules (Lewis base) through such Lewis
acid−base interaction. In 0.1 m KOH aqueous solution, the
Mn3O4/CoSe2 hybrid exhibited an OER overpotential of ≈0.45 V
at a current density of 10 mA cm−2, which was extremely
lower than those of bare Mn3O4 and CoSe2 electrocatalysts
(Figure 8c). In 2016, the interface effects were further explored
for improving the inherent activity of Ni centers. NiO/TiO2
mixed metal oxide electrocatalysts (Mono-NiTi-MMO) were
synthesized by thermal treatment of monolayer thick NiTi-
layered double hydroxide nanosheets (NiTi-LDH) at 500 °C
(Figure 8d).[86] The sizes of the NiO and TiO2 nanoparticles in
Mono-NiTi-MMO were about ≈4.0 and 11.0 nm, respectively
(Figure 8e). The elemental ratio of Ni to Ti in Mono-NiTi-
MMO was determined to be 1.6:1. The XANES spectroscopy
revealed that the first Ni−O shell in Mono-NiTi-MMO showed
a distance of ≈2.05 Å and a coordination number (N) of 5.70.
This Ni−O distance was smaller than 2.08 Å for both NiO

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Figure 8.  a) Synthesis scheme of Mn3O4/CoSe2 hybrid. b) TEM image hybrid and related selected area electron diffraction (SAED) pattern (inset) of
Mn3O4/CoSe2. c) The OER polarization plots of various electrocatalysts. a–d) Reproduced with permission.[85] Copyright 2012, American Chemical
Society. d) Schematic illustration for the synthesis of Mono-NiTi-MMO. e) HRTEM image of Mono-NiTi-MMO. f) The OER polarization plots of
as-fabricated electrocatalysts. e,f) Reproduced with permission.[86] Copyright 2016, American Chemical Society.

and bulk NiTi-MMO. Meanwhile, the average Ni−Ni distance
of Mono-NiTi-MMO was ≈2.98 Å, which was slightly larger
than 2.96 Å for NiO and bulk NiTi-MMO. In comparison with
Bulk-NiTi-MMO, Ti−O distance in Mono-NiTi-MMO short-
ened. These results evidenced that existence of strong bonding
or electronic interactions between NiO and TiO2 in Mono-NiTi-
MMO. In 1.0 m KOH aqueous solution, the Mono-NiTi-MMO
delivered a current density of 10 mA m−2 at an OER overpo-
tential of 320 mV, which was ≈3-, 15- and 34-fold larger than
those for NiTi-LDH, NiO and Bulk NiTi-MMO respectively
(Figure 8f). The TOF value of Mono-NiTi-MMO was about
0.068 s−1 at 500 mV, which was substantially higher than
0.009 s−1 for NiTi-LDH, 0.002 s−1 for NiO and 0.003 s−1 for
Bulk-NiTi-MMO, respectively. In addition, theoretical investi-
gations indicated that NiO/TiO2 hybrid had an increased H2O-
adsorption energy of 1.09 eV in comparison with 0.73 eV for
NiO, which was associated with a facilitated OER kinetics.
3.3. Overall Water Splitting
In the past decade, although various HER and OER electrocata-
lysts have been developed, their optimal working environments
such as pH values are dissimilar. Specifically, the HER activity
of some electrocatalysts, e.g., CoS|P[24] and atomic metal-
doped carbon,[23] is comparable to that of Pt/C in acidic media,

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but still much lower than that of Pt/C in alkaline solutions.
Similarly, the current OER electrocatalysts such as NiFe-LDH
and metal phosphides, show higher OER activity than the Ir/C
under alkaline conditions, but not stable for acidic OER.[14,97]
For these reasons, pairing the HER and OER electrocatalysts
together into a practical water-splitting electrolyzer is often
problematic due to the mismatch of their optimal pH environ-
ments. Meanwhile, for the production of OER and HER elec-
trocatalysts, different equipment and processes are essentially
involved, which further increase the cost of the water-splitting
electrolyzers.[98,99] Hence, exploring overall water-splitting elec-
trocatalysts with both high OER and HER activities is highly
attractive (Table 3).
3.3.1. N-Doped-Carbon-Based Support Effects
Up to now, electrocatalysts based on 3d transition metals (3d
TMs; e.g., Fe, Co, Ni) have been broadly developed as bifunc-
tional electrocatalysts for overall water splitting.[101] However,
for electrochemical overall water splitting, the applied volt-
ages of conventional 3d-TM-based materials are generally
larger than 1.55 V due to their low specific surface areas, poor
intrinsic activities, and poor electrical conductivities. Therefore,
compositing 3d-TM-based nanomaterials with a supporting
substrate with strong electronegativity is a promising approach
for constructing high-activity bifunctional electrocatalysts. In
2017, a novel composite containing CoP NPs imbedded in a
N-doped carbon nanotube hollow polyhedron (NCNHP) was
prepared from a core−shell ZIF-8@ZIF-67 using a pyrolysis−
oxidation−phosphidation strategy.[100] Based on the Co K-edge
XANES, the absorption edge position of the CoP/NCNHP was
located between those of CoO and Co3O4, indicating that the
valence state of Co in the CoP/NCNHP was between 2+ and 3+.
Benefiting from the synergistic effects between highly active
CoP NPs and NCNHP, the CoP/NCNHP hybrid exhibited
outstanding electrocatalytic water-splitting performances. As
shown in Figure 9a, in alkaline solution, the CoP/NCNHP cata-
lyst exhibited higher catalytic activity with a small HER over-
potential 115 mV at the current density of 10 mA cm−2 than
148 mV for CoP/NCP, 168 mV for Co/NCNHP, 243 mV for
Co/NCP, and 628 mV for NCP. The Tafel slope of the CoP/
NCNHP was estimated to be 66 mV per decade, suggesting
a Volmer−Heyrovsky pathway. When the CoP/NCNHP was
used as an OER electrocatalysts in 1 m KOH, a current density
of 10 mA cm−2 was delivered at an OER overpotential of
310 mV, which was lower than 360 mV for CoP/NCP, 580 mV
for Co/NCNHP, and 610 mV for Co/NCP, and 560 mV for
IrO2 (Figure 9b). When the CoP/NCNHP was used as both
the anode and cathode for overall water splitting, a voltage of
1.64 V was applied to achieve a current density of 10 mA cm−2
(Figure 9c). The DFT calculations revealed that the electron
transfer from NCNHP to CoP improved the electronic states
of the Co d-orbital around the Fermi level, which increased the
binding strength with H and thus enhanced the electrocatalytic
water-splitting activity (Figure 9d).
3.3.2. Interface Engineering for Bifunctional Electrocatalysts
Under alkaline condition, the HER is principally a deoxygena-
tion process of water molecules while the OER is a dehydro-
genation reaction of hydroxyl ion. Thus, if an electrocatalyst
can facilitate the synergistic chemisorption of H* and oxygen-
containing intermediates on the surface, the dissociation of
water molecules or hydroxyl ions will be favored, eventually

Table 3.  The overall water-splitting performance of electrocatalysts with support and interface effects.

Electrocatalysts HER overpotential at a current OER overpotential at a current Cell voltage at a current density Electrolyte
density of 10 mA cm−2 density of 10 mA cm−2 of 10 mA cm−2
Support effect
CoP nanoparticle-embedded 115 mV 310 mV 1.64 V 1 m KOH
N‑doped carbon nanotube hollow
polyhedron[100]
Cobalt−cobalt oxide/N-doped 235 mV 260 mV 1.55 V 1 m KOH
carbon hybrids[104]
Ni@N-doped graphene[105] 70 mV 280 mV 1.6 V 1 m KOH
Nickel sulfide/ nitrogen-doped 370 mV 380 mV − 1 m KOH
graphene oxide[106]
Interface effect
Cu@NiFe-LDH[98] 116 mV 199 mV 1.54 V 1 m KOH
MoS2/Ni3S2 heterostructures[42] 110 mV 218 mV 1.56 V 1 m KOH
Co-Ni3N heterostructure array[102] 194 mV 307 mV − 1 m KOH
[43]
Cu@CoSx 134 mV 160 mV 1.5 V 1 m KOH
NiFe LDH/NiCoP hybrids[107] 120 mV 220 mV 1.57 V 1 m KOH
NiFe/NiCo2O4 composite[108] 105 mV ≈240 mV 1.67 V 1 m KOH
CoS-doped Co(OH)2@MoS2+x[109] 143 mV 380 mV 1.58 V 1 m KOH
NiO@Ni/MoS2[110] 40 mV <347 mV 1.42 V 1 m KOH

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Figure 9. a) The HER and b) OER polarization curves of different electrocatalysts. c) The overall water-splitting polarization curve of the CoP/
NCNHP∥CoP/NCNHP electrode. d) Calculated free energy diagram of the HER on CoP, surface-oxidized 50% CoP, and surface-oxidized 100% CoP,
respectively. Electrolyte is 1 m KOH aqueous solution. a–d) Reproduced with permission.[100] Copyright 2017, American Chemical Society.

leading to enhanced HER and OER activities.[5] Thus, some
earth-abundant heterostructures with dense interfaces have
been developed as bifunctional electrocatalysts for the HER and
OER.[103] In 2016, novel MoS2/Ni3S2 heterostructures featuring
abundant interfaces were synthesized using a commercial
nickel foam and (NH4)2MoS4 through a one-pot solvothermal
reaction at 200 °C in N,N-dimethylformamide.[42] (NH4)2MoS4
not only served as the precursor for MoS2 nanosheets but also
provided the sulfur source for the in situ growth of Ni3S2 nano-
particles on the nickel foam. The outer MoS2 nanosheets were
decorated on the surface of the supporting Ni3S2 nanoparticles,
which formed abundant interfaces. The size of Ni3S2 nanopar-
ticles was about several hundred nanometers (Figure  10a,b).
The size and thickness of the MoS2 nanosheets were 30–130
and 5–15 nm, respectively. For bare MoS2 nanosheets, the
Mo 3d5/2 and Mo 3d3/2 peaks appeared at 228.5 and 231.8 eV,
respectively. By contrast, the binding energies of Mo 3d5/2 and
Mo 3d3/2 in MoS2/Ni3S2 heterostructures had positive shifts of
≈0.1 and ≈0.3 eV, respectively. Meanwhile, the Ni 2p3/2 signal
of the MoS2/Ni3S2 heterostructures also showed a positive
shift of ≈0.3 eV relative to that of bare Ni3S2 nanoparticles.
These results unraveled the existence of strong electronic
interaction between Ni3S2 nanoparticles and MoS2 nanosheets.
In a 1 m KOH aqueous solution, the MoS2/Ni3S2 heterostruc-
tures demonstrated an OER onset potential of ≈175 mV, which
was considerably lower than 230 mV for Ni3S2 nanoparticles,
280 mV for MoS2 nanosheets, and 250 mV for the Ir/C
(Figure 10c). Remarkably, the current density of MoS2/Ni3S2
heterostructures reached 10 mA cm−2 at an overpotential of
≈218 mV, superior to the Ir/C (ca. 330 mV). For the HER, the
onset overpotentials of Ni3S2 and MoS2 were ≈120 and 236 mV,
respectively (Figure 10d). By contrast, the HER onset overpo-
tential of the MoS2/Ni3S2 heterostructures was substantially
decreased to ≈50 mV, close to ≈0 V for the Pt catalyst. At a
current density of 10 mA cm−2, the applied HER overpotential
was about 110 mV, substantially lower than 193 mV for the Ni3S2
and 431 mV for the MoS2. When the MoS2/Ni3S2 heterostruc-
tures were employed as both the cathode and anode in an alka-
line electrolyzer, a current density of 10 mA cm−2 was attained
at a low cell voltage of 1.56 V, which was noticeably lower than
the Ir/C-Pt/C couple. The DFT calculations confirmed that the
established interfaces between Ni3S2 and MoS2 as well as the
in situ formed interfaces between NiO (surface electrochemical
oxidation of Ni3S2 under OER condition) and MoS2 facilitated
the synchronous chemisorption of hydrogen and oxygen-
containing intermediates, thus accelerating the electrochemical
overall water-splitting kinetics.
In 2018, Co-Ni3N composite nanowires were prepared on
carbon cloth by annealing the beforehand synthesized NiCo2O4
nanorods in ammonia atmosphere.[102] The Co-Ni3N nano­wires
consisted of Co and Ni3N nanoparticles, forming abundant
interfaces (The insets in Figure 10e). The diameter and length
of Co-Ni3N nanowires were ≈80 nm and ≈1  µm, respectively.
Under basic condition (1.0 m KOH), the Co-Ni3N composite
nanowires showed an HER overpotential of ≈194 mV at
10 mA cm−2, which was much smaller than 305 mV for the
Ni3N (Figure 10e). The TOF value of Co-Ni3N was estimated
to be ≈0.1459 s−1 at 290 mV, which was ten times higher
than 0.0142 s−1 for Ni3N nanoarrays. For the OER, the
Co-Ni3N required an overpotential of 307 mV to deliver a current
density of 10 mA cm−2, while Ni3N necessitated a much larger
overpotential of 397 mV. In order to investigate the stability and

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Figure 10.  a) SEM and b) HRTEM images of MoS2/Ni3S2 heterostructures. c) The OER CV and d) HER polarization curves of the nickel foam, MoS2
nanosheets, Ni3S2 nanoparticles, MoS2/Ni3S2 heterostructures, and IrO2. a–d) Reproduced with permission.[42] Copyright 2016, Wiley-VCH. e) The
HER and OER curves of the Co-Ni3N and Ni3N nanorod arrays. The insets are the low- and high-resolution TEM images of Co-Ni3N. Reproduced with
permission.[102] Copyright 2018, Wiley-VCH.

charge transfer at the Co/Ni3N interface, DFT calculations were
performed. The formed N–Co interfaces had the lowest inter-
facial energy of −181 to −178 meV Å−2, indicative of a better
stability relative to Ni–Co interfaces. The difference of charge
densities indicated the electron transportation from Co to
Ni3N at the interfaces, which was attributed to the interfa-
cial hybridizations among Co 3d, N 2p and Ni 3d. Moreover,
the Ni site close to the interface presented lower |ΔGH| than
those sites far away from the interface. These results pointed
out that the strong interfacial interaction in the Co-Ni3N com-
posite electrocatalysts could simultaneously promote the charge
transfer and optimize the chemisorption of intermediates,
eventually enhancing the electrochemical overall water-splitting
performance.
4. Conclusion and Perspective
The water-splitting electrolyzer is a promising technology for
dissociating water into high-purity hydrogen in a low-cost,
pollution-free, and high-efficiency way. As promising strategies
for designing high-performance water-splitting electrocatalysts

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to substitute noble-metal-based catalysts, support and inter-
face effects have been profoundly discussed in this review
article. Noticeably, several types of achieved nanomaterials
have showed excellent electrocatalytic HER, OER, and overall
water-splitting activities, which are comparable or superior to
those for precious-metal-based catalysts (Pt/C and Ir/C). The
influence of support and interface on water-splitting kinetics,
particularly the binding properties of reaction intermediates
have been summarized up in this review article. Neverthe-
less, the utilization of support and interface effects for the
fabrication of high-performance water-splitting electrocatalysts
remains at the preliminary stage and future works are needed
to address some key challenges as detailed below:
1) For the HER in acidic solutions, hydrogen adsorption is the
rate-limiting step. With optimized hydrogen adsorption,
Ru-based electrocatalysts have demonstrated excellent HER
activity that was comparable to Pt/C. However, several is-
sues await further investigations: 1) the noble-metal-free
hybrid electrocatalysts with strong support and interface
effects are still absent; 2) the decisive descriptors of support
and interface effects between electrocatalysts and support-
ing substrate remains unclear, like optimized chemisorp-
tion of intermediates, bonding interaction, charge injec-
tion/distribution, etc.; 3) the optimal support or interface
for accelerating the HER kinetics is unknown. For the HER
process, under alkaline or neutral conditions, is domi-
nated by the initial water dissociation step (Volmer step).
Therefore, the support and interface effects are promising
strategies for simultaneously optimizing the chemisorp-
tion properties of hydrogen and oxygen-containing inter-
mediates, which eventually reduces the energy barrier of
Volmer step under alkaline or neutral conditions. However,
the intrinsic HER activity of noble-metal-free electrocata-
lysts with interface effect is still much lower than that of
Pt catalysts.
2) For the OER in alkaline environment, numerous nonpre-
cious materials exhibit superior activity to the Ir/C. First,
besides gold and N-doped carbon, exploring novel and ef-
ficient support materials like covalent organic frameworks,
conjugated polymers, and metallic-phase metal-based
oxides/sulfide/nitrides/phosphides is particularly promising.
Second, regarding the nature of the OER as a multistep reac-
tion, support and interface effects will be an appealing way
to synergistically optimize the binding energies of interme-
diates at different oxidation stages. Third, although the OER
intrinsically is a dehydrogenation process, the influence of
proton transfer on the OER kinetics is less studied. More­
over, the exploration of stable and high-activity noble-metal-
free OER electrocatalyst falls far behind in acidic solutions.
Therefore, the exploration of stable hybrid electrocatalysts
featuring strong support and interface effects are desirable
for the acidic OER.
3) For the overall water splitting, many noble-metal-free elec-
trocatalysts have shown higher activity than the Pt/C-Ir/C
couple in alkaline or neutral media. However, in acidic
solutions, these bifunctional electrocatalysts will be gradu-
ally oxidized and dissolved into the acidic electrolyte. Up
to now, proton-exchange-membrane-based water-splitting
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www.advmat.de
electrolyzers with a low electrolyte resistance have been de-
veloped, but earth-abundant overall water-splitting electro-
catalyst is still absent under acidic conditions. The support
effect remains unexplored for overall water-splitting electro-
catalysts.
In the near future, the rapid development of experimental
methods, theoretical investigations, and characterization tech-
niques will deepen the fundamental understandings on the
support and interface effects between support and catalyst
components, and advance the rapid exploration of novel, earth-
abundant, and high-performance electrocatalysts. Eventually,
stable and low-cost nanomaterials with support and interface
effects should be prepared in a large scale and eventually cou-
pled with practical electricity-generating plants, e.g., hydro-
power station and wind power plants.
Acknowledgements
This work was financially supported by the EC under Graphene Flagship
(No. CNECT-ICT-604391), the European Science Foundation (ESF),
National Natural Science Foundation of China (21720102002), and the
MaxNet Energy. The authors also acknowledge the Center for Advancing
Electronics Dresden (cfaed), the Dresden Center for Nanoanalysis
(DCN) at TU Dresden.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
electrocatalytic water splitting, hydrogen evolution, interface effect,
oxygen evolution, support effect
Received: December 19, 2018
Revised: January 29, 2019
Published online: March 6, 2019
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