Advanced Materials - 2019 - Zhang - Support and Interface Effects in Water Splitting Electrocatalysts

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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: [email protected]
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]
Adv. Mater. 2019, 31, 1808167 1808167 (1 of 19) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
15214095, 2019, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201808167 by Technische Universitat Darmstadt, Wiley Online Library on [24/02/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advmat.de
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.
Scheme 1. Schematic illustration of water-splitting electrolyzer and related reaction kinetics.
2.1. Support Effect
Simply changing the underlying support can greatly influence

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
Scheme 2. Schematic illustration of support effect and interface effect in and achieved 13.3 mA cm−2 at an overpotential of 280 mV
water-splitting electrocatalysts. in 1 m KOH aqueous solution. This current density was
significantly higher than that of NiCeOx supported on glassy 3. Electrocatalytic Water Splitting
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 3.1. Hydrogen Evolution Reaction
of magnitude higher than that of NiCeOx–GC. The density
functional theory (DFT) calculation revealed that Au support The HER process is a two-electron-coupled proton reduction
reduced the energy barrier of OER descriptor (ΔGOH* to ΔGO*) reaction.[46] As illustrated in Volcano plots, the electrocatalysts
on Au-supported NiCeOx films. Nevertheless, the intrinsic with a near-zero Gibbs free energies of H-adsorption (ΔGH)
interaction between gold support and active centers of surface may manifest the highest electrocatalytic HER activity.[46] Some
NiCeOx remained unclear. 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
2.2. Interface Effect much lower than Pt, which are mostly due to their poor
electrical conductivities and limited accessible active sites.[48]
The complexity of hybrid electrocatalysts makes the funda- Owing to the strong electronic or bonding interactions,
mental investigations on the structure–activity relationship support and interface effects can help to optimize the ΔGH of
extremely challenging. However, this complexity also brings electrocatalysts for enhancing the HER activity (Table 1).
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 3.1.1. Gold-Based Support Effects
hybrid electrocatalysts, but also their ensemble electrocatalytic
activity.[26] Unlike support effects, interface effects will result in MoS2 was predicted by theory to be a promising HER electro-
reconstructed active centers due to the strong bonding or elec- catalyst[49] and its active centers are experimentally proved to be
tronic interactions between two different active components. the uncoordinated edges.[50] Thus, MoS2 is a good model system
Thereby, the reconstructed active centers established at the for studying the influence of support effects on its HER activity.
interfaces can yield higher activity than individual compo- Accordingly, it has been found that the Mo-edge is the one that is
nents.[39] As we all know, the HER and OER kinetics are intrin- primarily exposed in single layer of MoS2 supported on Au(111),
sically dominated by the chemisorption of precursor molecules highly ordered pyrolytic graphite (HOPG), or graphitic carbon as
(H2O, OH−, or H+) and reaction intermediates (e.g., *H, substrates. The effects of substrate support on the HER activity at
*OH, *O, etc.).[5,40] Therefore, the interface effects provide a the MoS2 edge sites were systematically investigated for several
favorable strategy for accelerating the HER and OER kinetics by different systems in 2014: MoS2, MoS2-Au, and MoS2-graphene.[37]
optimizing the chemisorption of precursor molecules or/and As shown in Figure 1a, for the Mo-edge at 0.25 monolayer (ML)
reaction intermediates. H coverage, the H-adsorption free energies of MoS2-Au and
Toward this end, in 2011, a composite Ni(OH)2/Pt electro- MoS2-graphene were considerably increased by 0.56 and 0.18 eV,
catalyst was built up as a model HER system, where ultrathin respectively, in comparison with MoS2. When the multilayered
Ni(OH)2 clusters (height: 0.7 nm; size: 8–10 nm) were grown MoS2 was supported on Au(111) or graphene, the top layer MoS2
on Pt single-crystal surfaces.[41] The density of Ni(OH)2 clusters had a similar hydrogen binding with the unsupported MoS2,
reached a maximum at a Pt surface coverage of ≈35%. Inter- indicating that the support effect was in short range.
estingly, in comparison with the electrochemical cyclic voltam- Afterward in 2017, the support effect was utilized as an effective
metry (CV) curve of pure Pt electrode in alkaline conditions, the strategy for tuning the ΔGH of thiomolybdate [Mo3S13]2− cluster
Ni(OH)2/Pt hybrid presented an enhanced adsorption and irre- catalysts and thereby optimize their intrinsic HER activity.[51]
versible reduction of OHad under the negative sweep due to the Thin (≈1 × 1015 clusters cm−2) of [Mo3S13]2− cluster layers were
higher oxophilicity of the surface Ni(OH)2 clusters. As a result, deposited on gold, silver, copper, and glassy carbon supports. The
at an overpotential of −0.1 V, the electrocatalytic HER activity HER performance was evaluated using a three-electrode rotating
of Ni(OH)2/Pt in 1 a m KOH solution was approximately eight disk electrode (RDE) electrochemical system in acidic solutions.
times higher than that for pure Pt. The surface Ni(OH)2 clusters The onset HER overpotential of [Mo3S13]2−-Au was −0.15 V,
played a key role in promoting the initial water dissociation and which was much lower than −0.18 V for [Mo3S13]2−-Ag, −0.20 V
the alkaline HER kinetics. The DFT calculations unveiled that, at for [Mo3S13]2−-GC, and −0.24 V for [Mo3S13]2-Cu (Figure 1b). The
the interfaces between Ni(OH)2 and Pt, the strong interaction of TOF values per Mo atom are shown in Figure 1c. At −200 mV
Ni(OH)2 with O atoms and Pt with H atoms may synergistically versus RHE, the TOF value per Mo atom of [Mo3S13]2−-Au was
facilitate the initial adsorption of water molecules. Later, water 0.47 s−1, higher than Ag, GC, and Cu supports respectively,
dissociation occurred and the formed hydrogen intermediates which were 0.27 s−1 for [Mo3S13]2−-Ag, 0.15 s−1 for [Mo3S13]2−-GC,
bonded to neighboring Pt sites. Finally, two adsorbed H atoms and 0.045 s−1 for [Mo3S13]2-Cu. The near one order of magni-
on the Pt sites combined into a hydrogen molecule.[40] Sparked tude difference between the TOF values of [Mo3S13]2−Au and
by this pioneering work, a lot of hybrid electrocatalysts with [Mo3S13]2−-Cu strongly evidenced that the catalyst−gold interac-
abundant interfaces have been developed afterward.[42–45] How- tion substantially influenced the HER activity. In order to reveal
ever, their HER activities are still inferior to that for the Pt/C. the role of support effects in tuning the activity of [Mo3S13]2− clus-
Moreover, the fundamental mechanisms of synergistic effects ters, DFT calculations were carried out to calculate their ΔGH. As
between active components remain elusive due to the great chal- indicated in Figure 1d, the TOF values of all electrocatalysts at
lenges in experimentally characterizing interfacial structures. 200 mV were plotted versus the calculated ΔGH. The achieved plot
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 reduced graphene oxide (RGO) (Mo2C@NPC/NPRGO) was
showed the highest TOF value of 0.35 s−1 per Mo atom at 200 mV synthesized by pyrolysis of a PMo12 (H3PMo12O40)–polypyrrole/
due to its lowest |ΔGH|. These results highlight that gold-based RGO precursor at 900 °C in N2 atmosphere (Figure 2a).[56] Mo2C
support effects are a promising approach for optimizing the ΔGH nanoparticles (NPs) had an average size of about ≈2–5 nm and
of electrocatalysts toward high HER activity. 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
3.1.2. N-Doped-Carbon-Based Support Effects 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
Although the gold support can efficiently facilitate the HER exhibited outstanding electrocatalytic HER activity with a very
kinetics, but its broad utilizations are seriously hindered by the low onset overpotential of ≈0 mV, which was well comparable
high cost of gold. Lately, due to their superior electrical con- to that of Pt/C. The overpotential of the Mo2C@NPC/NPRGO
ductivity, high specific surface area, and existence of abundant at a current density of 10 mA cm−2 was only 34 mV, which was
nitrogen dopants, various N-doped carbon materials like 1D much lower than 260 mV for the Mo2C@NPC and very close to
carbon nanotubes,[52] 2D graphene,[53] and 3D porous carbon[54] 30 mV for the Pt/C (Figure 2b). The Tafel slope of the Mo2C@
have been widely composited with active electrocatalysts for NPC/NPRGO was about 33.6 mV per decade, indicating that
promoting the electron transfer and tuning the H-absorption the recombination of adsorbed H (Tafel step) is the rate-deter-
property during the HER. Since the conductive role of N-doped mining step (Figure 2c). The DFT results disclosed that the
carbon electrocatalysts has been broadly discussed in the pre- Mo2C (001), graphitic-N-doped graphene and pyridinic-N-doped
vious review articles,[26,55] here we will uniquely highlight their graphene had a ΔGH values of 0.82, 0.89, and −2.04 eV, respec-
support effects for tailoring the ΔGH of the HER electrocatalysts. tively, suggesting their strong binding ability toward H interme-
In 2016, a 2D composite electrocatalyst composed of Mo2C diate, which subsequently led to poor HER performance because
encapsulated by N,P-codoped carbon shells and N,P-codoped of the difficulty in hydrogen release. However, the Mo2C@
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.
pyridinic-N-doped graphene presented a near-zero ΔGH* value of energy filtered TEM showed that the Ru and Co contents in the
−0.22 eV, emphasizing the effective support effects of N-doped RuCo/NC were about 5.69 and 94.31 wt%. The nitrogen content
carbon for tailoring the H-absorption property of electrocatalysts. in the RuCo/NC was measured to be ≈3.51 at% using the XPS
Afterward, a RuCo alloy/nitrogen-doped porous carbon elec- analysis. The specific surface area of the RuCo/NC was about 41
trocatalyst (RuCo/NC) was prepared by annealing Ru-doped m2 g−1 and the corresponding pore size was narrowly distributed
Prussian blue analogs (Ru3+/Co3[Co(CN)6]2) at 600 °C for 4 h around ≈3 nm. In a 1 m KOH electrolyte, the RuCo/NC presented
under nitrogen atmosphere (Figure 3a).[57] The obtained sample an overpotential of ≈28 mV at a current density of 10 mA cm−2,
contained abundant alloy particles with a mean diameter of which was lower than 300 mV for Co/nitrogen-doped carbon
≈30 nm, which were encapsulated by supporting carbon shells and 58 mV for commercial Ru catalyst, and even 40 mV for Pt/C
with a thickness of ≈1–15 layers. The elemental analysis from (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.
decade, which was well comparable to that of Pt/C, indicating iridium–cobalt alloy encapsulated in N-doped carbon cages[58]
a rapid HER kinetics in alkaline solution (Figure 3c). In order and Co nanoparticles encapsulated in N,B-codoped carbon
to understand the role of Co in the HER activity, the RuCo/NC cages,[59] etc. Considering that some recent review papers have
was leached in 1 m HCl solution. The overpotentials at current systematically discussed the development of MOF-derived elec-
densities of 10 and 100 mA cm−2 considerably increased after the trocatalysts for water splitting, we will not emphasize here.[60]
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- 3.1.3. Conjugated-Organic-Framework-Based Support Effects
trated in Figure 3e, the Gibbs free energy of H-adsorption (ΔGH*)
of graphene was significantly reduced after nitrogen doping and Owing to their good electronic conjugation and the presence
the combination of metal Co with graphene. Alloying Ru atoms of abundant functional groups (like OH, O, COOH,
into Co metal could further decrease ΔGH* and Ru3Co-N-doped CN, etc.) and heteroatoms (N, S, P, etc.), conjugated organic
graphene model exhibited the lowest ΔGH* value of 0.31 eV. Very polymers can be employed as promising supporting materials
recently, various metal organic framework (MOF)-derived electro- for tailoring electrocatalytic HER of catalysts.[62] As schemed in
catalysts supported by N-doped carbon have been reported, e.g., 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.
(Ru@C2N) were fabricated using the polycondensation reaction interface while a nearby Ni site would facilitate H adsorption,
between hexaketocyclohexane (HKH) and hexaaminobenzene thus synergistically enhancing the HER catalytic activity of the
(HAB) trihydrochloride in the presence of ruthenium chloride NiO/Ni. In order to unravel the role of interfaces in composite
(RuCl3) and subsequent reduction reaction. As a result, the Ru electrocatalysts, a MoS2/CoSe2 hybrid was fabricated using a
nanoparticles were uniformly distributed in the C2N polymer solvothermal reaction in 2015, where MoS2 nanosheets were
matrix. The size of Ru nanoparticles was ≈1.6 ± 0.5 nm grown on the surface of CoSe2.[63] As shown in Figure 5c,d,
(Figure 4b). The thermogravimetric analysis (TGA) revealed the MoS2 nanosheets were uniformly anchored on CoSe2
that the Ru content in the Ru@C2N composite was about nanosheets, yielding abundant interfaces. In a 0.5 m H2SO4
28.7 wt%. The BET specific surface area of the Ru@C2N was electrolyte, the pristine CoSe2 showed an onset HER over-
measured to be 400.1 m2 g−1 with an average pore diameter of potential of ≈50 mV (Figure 5e). By contrast, the onset HER
3.37 nm. As a contrast, Co@C2N, Ni@C2N, Pd@C2N, and Pt@ overpotential of MoS2/CoSe2 hybrid reached as low as ≈11 mV.
C2N were also synthesized using the same method. In a 0.5 m The Tafel slope of MoS2/CoSe2 hybrid was determined to be
H2SO4 solution, the HER overpotentials of Co@C2N, Ni@ ≈36 mV per decade, which was close to 30 mV per decade
C2N, and Pd@C2N at 10 mA cm−2 were larger than 300 mV. for the Pt/C and lower than 48 mV per decade for CoSe2 and
The Pt@C2N delivered a current density of 10 mA cm−2 at an 101 mV per decade for MoS2 (Figure 5f). The XPS and theo-
overpotential of ≈43 mV. By contrast, Ru@C2N exhibited a retical investigations disclosed that the CoSe2 chemically inter-
very small onset HER overpotential of 9.5 mV, which was very acted with MoS2 by forming SCo bonds, which could further
close to 1.0 mV for commercial Pt/C (Figure 4c). Moreover, optimize the hydrogen adsorption.
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 3.2. Oxygen Evolution Reaction
a Volmer–Tafel mechanism (Figure 4d). Noticeably, in 1.0 m
aqueous KOH solution, Ru@C2N exhibited a HER overpoten- In contrast with the HER, the OER is more kinetically sluggish
tial of only 17.0 mV at 10 mA cm−2, which was even lower than as a result of its multistep oxidation pathway. According to
20.7 mV for the Pt/C (20.7 mV) (Figure 4e). Meanwhile, the the previously reported volcano plots for the OER, the change
TOF values of Ru@C2N were 0.76 s−1 at 25 mV and 1.66 s−1 of Gibbs free energy from *OH to *O intermediates is com-
at 50 mV, which were even larger than 0.47 s−1 at 25 mV and monly regarded as the rate-determining descriptor for theo-
0.95 s−1 at 50 mV for the Pt/C. DFT calculations were con- retically evaluating the inherent activity of OER catalysts.[5,9]
ducted to understand the origin of the high electrocatalytic Non-noble-metal-based electrocatalysts have shown much
activity of Ru@C2N. The Ru4, Ru13, and Ru55 models showed higher OER activity than Ir/C and RuO2 in alkaline electrolytes
the H-absorption energies of 0.44, 0.56, and 0.54 eV H−1, (Table 2).[14] However, because of their poor electrical conduc-
respectively. By contrast, hydrogen adsorbed on the surface tivities, low specific surface areas and poor intrinsic activities,
of Ru55@C2N was 0.55 eV H−1, which was the closest to the OER overpotential of noble-metal-free electrocatalysts is
0.6 eV H−1 for Pt(111). 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
3.1.4. Interface Effects HER process discussed above, support and interface effects
are also promising strategies for optimizing the chemisorption
In principal, the HER kinetics in acidic solutions was deter- properties of oxygen-containing intermediates to promote the
mined by the hydrogen adsorption on electrocatalyst surfaces OER kinetics.
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 3.2.1. Gold-Based Support Effects
different active components, constructing hybrid electrocata-
lysts with abundant interfaces provides a rational pathway for As previously demonstrated for the HER, owing to the strong
optimizing the H-adsorption and water dissociation kinetics, electronic interaction between electrocatalysts and electron-
eventually accelerating the sluggish HER kinetics. A nickel egative gold support, the H-absorption property of the active
oxide/nickel (NiO/Ni) composite electrocatalyst was fabricated centers will be preferentially optimized to promote the HER
on carbon nanotube (NiO/Ni@CNT) through a low-pressure kinetics. Sparked by these pioneering studies, gold support was
thermal reduction of nickel hydroxide.[44] Ni/NiO core–shell further explored for modulating the electronic properties of
nanoparticles were observed on the CNT (Figure 5a). The OER electrocatalysts. In 2011, Au@Co3O4 core–shell nanowires
size of NiO/Ni nanoparticles was about 10 nm. In a 1 m KOH were synthesized via colloidal polymerization of core–shell
aqueous solution, the resultant NiO/Ni@CNT exhibited a HER gold–cobalt NPs (AuCoNPs) and subsequent oxidation of pre-
overpotential of ≈80 mV at a current density of 10 mA cm−2, organized AuCoNPs.[81] Electrochemical specific capacitance
which was much lower than >200 mV for Ni@CNT and of the calcined Au@Co3O4 nanowire film was evaluated using
>450 mV for NiO@CNT (Figure 5b). Based on the achieved CV. In comparison with Co3O4 nanowire film, Au@Co3O4
experimental results, the authors tentatively proposed that at nanowire film exhibited a twofold enhancement of Faradaic
a NiO/Ni interface, the OH− generated from water dissocia- electrochemical activity based on the redox transitions at the
tion could preferentially bond to the Ni2+ sites of NiO at the active sites (i.e., CoO2 > CoOOH > Co3O4).
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 was in short range. Additionally, the TOF values of cobalt oxide
enhancement of OER activity of electrocatalysts, cobalt oxide supported by Pt, Pd, Cu, and Co were also evaluated (Figure 6c).
was deposited onto the surface of various supports including The achieved TOF values of cobalt oxide were dependent on the
Au, Cu, Co, Pd, and Pt.[36] The thickness of deposited cobalt metal supports: Au > Pt > Pd > Cu > Co. This result indicated
oxide was about ≈0.4 ML (monolayer). The oxygen evolution that the TOF values decreased as weakened electronegativity of
activity of pure Au, cobalt oxide, and Au electrodes with metal supports. The DFT calculations reported that the OER
different thicknesses of cobalt oxide was firstly measured overpotential on β-CoOOH (0 114) was 0.4 V.[82] However, when
in 0.1 m KOH aqueous solution. Figure 6a presents the OER the hydrogen transfer to AuO was considered, this value
polarization curves of the ≈0.4 ML cobalt oxide/Au, pure Au, decreased to 0.3 V (Figure 6d).
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 3.2.2. Metal-Oxide-Based Support Effects
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, To address these problems, antimony-doped tin oxide (ATO)
which was tenfold higher than 0.06 s−1 for ≈87 ML of cobalt was developed as a new type of supporting substrate.[84]
oxide/Au. The TOF values of pure Au and Co were only 0.007 Metallic Ir nanoparticles were synthesized on high-surface-area
and 0.05 s−1, respectively. Noticeably, the TOF values of ≈87 ML mesoporous ATO support composed of ATO nanoparticles, and
cobalt oxide/Au and bulk Co were almost the same, proving that then electrochemically oxidized into IrOx (Figure 7a).[83] ATO
the electronic interaction between cobalt oxide and gold support nanoparticles had a size of ≈3−5 nm while the average size of
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.
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 H- and O-containing intermediates, eventually speeding up the
Ir LIII-edge X-ray absorption near-edge spectroscopy (XANES) OER kinetics. For example, in 2012, through a polyol reduc-
region of the IrOx/ATO and IrOx/carbon electrocatalysts. tion approach, Mn3O4 nanoparticles with an average size of
The peak position of 2p3/2 to 5d white line was an indicator ≈15.7 nm were grown on CoSe2 nanobelts (Figure 8a,b).[85] The
of the number of electron vacancies in the 5d orbitals of Ir loading content of Mn3O4 on the CoSe2 was about 45.8 wt%.
atoms: IrOx/carbon ≈ IrO2 ≫ IrOx/commercial ATO ≈ IrOx/ The XPS binding energy of Co 2p3/2 in the CoSe2 located at
ATO > Ir foil. As further revealed in Figure 7d, the d vacancy 778.5 eV, which were principally responsible for the OER
of the ATO-supported IrOx was 4.2 holes, which was lower activity. By comparison, the XPS binding energy of Co 2p3/2 in
than that of bulk IrO2 (5 holes) and carbon-supported IrOx the Mn3O4/CoSe2 hybrid showed a negative shift of ≈0.84 eV,
(essentially 5 holes). In terms of average Ir oxidation states, which was attributed to the electron transfer from Mn3O4 to
IrOx/commercial ATO, IrOx/ATO, and IrOx/carbon were +3.3, CoSe2 because of their strong bonding or electronic interac-
+3.2, and +4.0, respectively. In 0.05 m H2SO4 solution, the elec- tions. The electron injection from Mn3O4 to CoSe2 might lead
trochemical OER activities of IrOx/ATO, IrOx/carbon, and IrOx/ to stronger acidity of Mn3O4 (Lewis acid), which promoted the
commercial ATO at a voltage 1.8 V (vs RHE) were basically sim- activation of water molecules (Lewis base) through such Lewis
ilar because the OER activity at this potential was mainly domi- acid−base interaction. In 0.1 m KOH aqueous solution, the
nated by ohmic resistances. Therefore, the reduced oxidation Mn3O4/CoSe2 hybrid exhibited an OER overpotential of ≈0.45 V
state of the ATO-supported IrOx particles did not change their at a current density of 10 mA cm−2, which was extremely
OER activity. However, after the stability tests, the OER activity lower than those of bare Mn3O4 and CoSe2 electrocatalysts
of IrOx/carbon seriously decreased by 99.7%. By contrast, the (Figure 8c). In 2016, the interface effects were further explored
activity decline of the IrOx/ATO catalyst was only 31.6%. These for improving the inherent activity of Ni centers. NiO/TiO2
results confirmed that the employment of ATO support greatly mixed metal oxide electrocatalysts (Mono-NiTi-MMO) were
enhanced the OER durability of IrOx electrocatalysts due to synthesized by thermal treatment of monolayer thick NiTi-
their strong electronic interaction. 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
3.2.3. Interface Effect in OER Electrocatalysts (Figure 8e). The elemental ratio of Ni to Ti in Mono-NiTi-
MMO was determined to be 1.6:1. The XANES spectroscopy
Regarding the multistep reaction nature of the water oxidation, revealed that the first Ni−O shell in Mono-NiTi-MMO showed
it is highly appealing to utilize the interface effects of hybrid a distance of ≈2.05 Å and a coordination number (N) of 5.70.
electrocatalysts for optimizing the chemisorption of both This Ni−O distance was smaller than 2.08 Å for both NiO
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 Bulk-NiTi-MMO, respectively. In addition, theoretical investi-
of Mono-NiTi-MMO was ≈2.98 Å, which was slightly larger gations indicated that NiO/TiO2 hybrid had an increased H2O-
than 2.96 Å for NiO and bulk NiTi-MMO. In comparison with adsorption energy of 1.09 eV in comparison with 0.73 eV for
Bulk-NiTi-MMO, Ti−O distance in Mono-NiTi-MMO short- NiO, which was associated with a facilitated OER kinetics.
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 3.3. Overall Water Splitting
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 In the past decade, although various HER and OER electrocata-
those for NiTi-LDH, NiO and Bulk NiTi-MMO respectively lysts have been developed, their optimal working environments
(Figure 8f). The TOF value of Mono-NiTi-MMO was about such as pH values are dissimilar. Specifically, the HER activity
0.068 s−1 at 500 mV, which was substantially higher than of some electrocatalysts, e.g., CoS|P[24] and atomic metal-
0.009 s−1 for NiTi-LDH, 0.002 s−1 for NiO and 0.003 s−1 for doped carbon,[23] is comparable to that of Pt/C in acidic media,
but still much lower than that of Pt/C in alkaline solutions. valence state of Co in the CoP/NCNHP was between 2+ and 3+.
Similarly, the current OER electrocatalysts such as NiFe-LDH Benefiting from the synergistic effects between highly active
and metal phosphides, show higher OER activity than the Ir/C CoP NPs and NCNHP, the CoP/NCNHP hybrid exhibited
under alkaline conditions, but not stable for acidic OER.[14,97] outstanding electrocatalytic water-splitting performances. As
For these reasons, pairing the HER and OER electrocatalysts shown in Figure 9a, in alkaline solution, the CoP/NCNHP cata-
together into a practical water-splitting electrolyzer is often lyst exhibited higher catalytic activity with a small HER over-
problematic due to the mismatch of their optimal pH environ- potential 115 mV at the current density of 10 mA cm−2 than
ments. Meanwhile, for the production of OER and HER elec- 148 mV for CoP/NCP, 168 mV for Co/NCNHP, 243 mV for
trocatalysts, different equipment and processes are essentially Co/NCP, and 628 mV for NCP. The Tafel slope of the CoP/
involved, which further increase the cost of the water-splitting NCNHP was estimated to be 66 mV per decade, suggesting
electrolyzers.[98,99] Hence, exploring overall water-splitting elec- a Volmer−Heyrovsky pathway. When the CoP/NCNHP was
trocatalysts with both high OER and HER activities is highly used as an OER electrocatalysts in 1 m KOH, a current density
attractive (Table 3). 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
3.3.1. N-Doped-Carbon-Based Support Effects IrO2 (Figure 9b). When the CoP/NCNHP was used as both
the anode and cathode for overall water splitting, a voltage of
Up to now, electrocatalysts based on 3d transition metals (3d 1.64 V was applied to achieve a current density of 10 mA cm−2
TMs; e.g., Fe, Co, Ni) have been broadly developed as bifunc- (Figure 9c). The DFT calculations revealed that the electron
tional electrocatalysts for overall water splitting.[101] However, transfer from NCNHP to CoP improved the electronic states
for electrochemical overall water splitting, the applied volt- of the Co d-orbital around the Fermi level, which increased the
ages of conventional 3d-TM-based materials are generally binding strength with H and thus enhanced the electrocatalytic
larger than 1.55 V due to their low specific surface areas, poor water-splitting activity (Figure 9d).
intrinsic activities, and poor electrical conductivities. Therefore,
compositing 3d-TM-based nanomaterials with a supporting
substrate with strong electronegativity is a promising approach 3.3.2. Interface Engineering for Bifunctional Electrocatalysts
for constructing high-activity bifunctional electrocatalysts. In
2017, a novel composite containing CoP NPs imbedded in a Under alkaline condition, the HER is principally a deoxygena-
N-doped carbon nanotube hollow polyhedron (NCNHP) was tion process of water molecules while the OER is a dehydro-
prepared from a core−shell ZIF-8@ZIF-67 using a pyrolysis− genation reaction of hydroxyl ion. Thus, if an electrocatalyst
oxidation−phosphidation strategy.[100] Based on the Co K-edge can facilitate the synergistic chemisorption of H* and oxygen-
XANES, the absorption edge position of the CoP/NCNHP was containing intermediates on the surface, the dissociation of
located between those of CoO and Co3O4, indicating that the 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
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 respectively (Figure 10d). By contrast, the HER onset overpo-
earth-abundant heterostructures with dense interfaces have tential of the MoS2/Ni3S2 heterostructures was substantially
been developed as bifunctional electrocatalysts for the HER and decreased to ≈50 mV, close to ≈0 V for the Pt catalyst. At a
OER.[103] In 2016, novel MoS2/Ni3S2 heterostructures featuring current density of 10 mA cm−2, the applied HER overpotential
abundant interfaces were synthesized using a commercial was about 110 mV, substantially lower than 193 mV for the Ni3S2
nickel foam and (NH4)2MoS4 through a one-pot solvothermal and 431 mV for the MoS2. When the MoS2/Ni3S2 heterostruc-
reaction at 200 °C in N,N-dimethylformamide.[42] (NH4)2MoS4 tures were employed as both the cathode and anode in an alka-
not only served as the precursor for MoS2 nanosheets but also line electrolyzer, a current density of 10 mA cm−2 was attained
provided the sulfur source for the in situ growth of Ni3S2 nano- at a low cell voltage of 1.56 V, which was noticeably lower than
particles on the nickel foam. The outer MoS2 nanosheets were the Ir/C-Pt/C couple. The DFT calculations confirmed that the
decorated on the surface of the supporting Ni3S2 nanoparticles, established interfaces between Ni3S2 and MoS2 as well as the
which formed abundant interfaces. The size of Ni3S2 nanopar- in situ formed interfaces between NiO (surface electrochemical
ticles was about several hundred nanometers (Figure 10a,b). oxidation of Ni3S2 under OER condition) and MoS2 facilitated
The size and thickness of the MoS2 nanosheets were 30–130 the synchronous chemisorption of hydrogen and oxygen-
and 5–15 nm, respectively. For bare MoS2 nanosheets, the containing intermediates, thus accelerating the electrochemical
Mo 3d5/2 and Mo 3d3/2 peaks appeared at 228.5 and 231.8 eV, overall water-splitting kinetics.
respectively. By contrast, the binding energies of Mo 3d5/2 and In 2018, Co-Ni3N composite nanowires were prepared on
Mo 3d3/2 in MoS2/Ni3S2 heterostructures had positive shifts of carbon cloth by annealing the beforehand synthesized NiCo2O4
≈0.1 and ≈0.3 eV, respectively. Meanwhile, the Ni 2p3/2 signal nanorods in ammonia atmosphere.[102] The Co-Ni3N nanowires
of the MoS2/Ni3S2 heterostructures also showed a positive consisted of Co and Ni3N nanoparticles, forming abundant
shift of ≈0.3 eV relative to that of bare Ni3S2 nanoparticles. interfaces (The insets in Figure 10e). The diameter and length
These results unraveled the existence of strong electronic of Co-Ni3N nanowires were ≈80 nm and ≈1 µm, respectively.
interaction between Ni3S2 nanoparticles and MoS2 nanosheets. Under basic condition (1.0 m KOH), the Co-Ni3N composite
In a 1 m KOH aqueous solution, the MoS2/Ni3S2 heterostruc- nanowires showed an HER overpotential of ≈194 mV at
tures demonstrated an OER onset potential of ≈175 mV, which 10 mA cm−2, which was much smaller than 305 mV for the
was considerably lower than 230 mV for Ni3S2 nanoparticles, Ni3N (Figure 10e). The TOF value of Co-Ni3N was estimated
280 mV for MoS2 nanosheets, and 250 mV for the Ir/C to be ≈0.1459 s−1 at 290 mV, which was ten times higher
(Figure 10c). Remarkably, the current density of MoS2/Ni3S2 than 0.0142 s−1 for Ni3N nanoarrays. For the OER, the
heterostructures reached 10 mA cm−2 at an overpotential of Co-Ni3N required an overpotential of 307 mV to deliver a current
≈218 mV, superior to the Ir/C (ca. 330 mV). For the HER, the density of 10 mA cm−2, while Ni3N necessitated a much larger
onset overpotentials of Ni3S2 and MoS2 were ≈120 and 236 mV, overpotential of 397 mV. In order to investigate the stability and
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 transfer and optimize the chemisorption of intermediates,
performed. The formed N–Co interfaces had the lowest inter- eventually enhancing the electrochemical overall water-splitting
facial energy of −181 to −178 meV Å−2, indicative of a better performance.
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- 4. Conclusion and Perspective
cial hybridizations among Co 3d, N 2p and Ni 3d. Moreover,
the Ni site close to the interface presented lower |ΔGH| than The water-splitting electrolyzer is a promising technology for
those sites far away from the interface. These results pointed dissociating water into high-purity hydrogen in a low-cost,
out that the strong interfacial interaction in the Co-Ni3N com- pollution-free, and high-efficiency way. As promising strategies
posite electrocatalysts could simultaneously promote the charge for designing high-performance water-splitting electrocatalysts
to substitute noble-metal-based catalysts, support and inter- electrolyzers with a low electrolyte resistance have been de-
face effects have been profoundly discussed in this review veloped, but earth-abundant overall water-splitting electro-
article. Noticeably, several types of achieved nanomaterials catalyst is still absent under acidic conditions. The support
have showed excellent electrocatalytic HER, OER, and overall effect remains unexplored for overall water-splitting electro-
water-splitting activities, which are comparable or superior to catalysts.
those for precious-metal-based catalysts (Pt/C and Ir/C). The
influence of support and interface on water-splitting kinetics, In the near future, the rapid development of experimental
particularly the binding properties of reaction intermediates methods, theoretical investigations, and characterization tech-
have been summarized up in this review article. Neverthe- niques will deepen the fundamental understandings on the
less, the utilization of support and interface effects for the support and interface effects between support and catalyst
fabrication of high-performance water-splitting electrocatalysts components, and advance the rapid exploration of novel, earth-
remains at the preliminary stage and future works are needed abundant, and high-performance electrocatalysts. Eventually,
to address some key challenges as detailed below: stable and low-cost nanomaterials with support and interface
effects should be prepared in a large scale and eventually cou-
1) For the HER in acidic solutions, hydrogen adsorption is the pled with practical electricity-generating plants, e.g., hydro-
rate-limiting step. With optimized hydrogen adsorption, power station and wind power plants.
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 Acknowledgements
hybrid electrocatalysts with strong support and interface
effects are still absent; 2) the decisive descriptors of support This work was financially supported by the EC under Graphene Flagship
(No. CNECT-ICT-604391), the European Science Foundation (ESF),
and interface effects between electrocatalysts and support-
National Natural Science Foundation of China (21720102002), and the
ing substrate remains unclear, like optimized chemisorp- MaxNet Energy. The authors also acknowledge the Center for Advancing
tion of intermediates, bonding interaction, charge injec- Electronics Dresden (cfaed), the Dresden Center for Nanoanalysis
tion/distribution, etc.; 3) the optimal support or interface (DCN) at TU Dresden.
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
Conflict of Interest
strategies for simultaneously optimizing the chemisorp- The authors declare no conflict of interest.
tion properties of hydrogen and oxygen-containing inter-
mediates, which eventually reduces the energy barrier of
Volmer step under alkaline or neutral conditions. However, Keywords
the intrinsic HER activity of noble-metal-free electrocata-
lysts with interface effect is still much lower than that of electrocatalytic water splitting, hydrogen evolution, interface effect,
oxygen evolution, support effect
Pt catalysts.
2) For the OER in alkaline environment, numerous nonpre- Received: December 19, 2018
cious materials exhibit superior activity to the Ir/C. First, Revised: January 29, 2019
besides gold and N-doped carbon, exploring novel and ef- Published online: March 6, 2019
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-
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15214095, 2019, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201808167 by Technische Universitat Darmstadt, Wiley Online Library on [24/02/2023].

Support and Interface Effects in Water-Splitting

carrier for the sustainable energy systems

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

2.1. Support Effect

Simply changing the underlying support can greatly influence

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

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