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Layered double hydroxide-based electrocatalysts

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for the oxygen evolution reaction: identification

Cite this: Chem. Soc. Rev., 2021,
Open Access Article. Published on 23 June 2021. Downloaded on 10/17/2022 2:13:24 AM.
50, 8790 and tailoring of active sites, and superaerophobic

nanoarray electrode assembly
Daojin Zhou,a Pengsong Li,a Xiao Lin, b Adam McKinley,c Yun Kuang,*a Wen Liu,a
Wen-Feng Lin, *c Xiaoming Sun *a and Xue Duana
The electrocatalytic oxygen evolution reaction (OER) is a critical half-cell reaction for hydrogen
production via water electrolysis. However, the practical OER suffers from sluggish kinetics and thus
requires efficient electrocatalysts. Transition metal-based layered double hydroxides (LDHs) represent
one of the most active classes of OER catalysts. An in-depth understanding of the activity of LDH based
electrocatalysts can promote further rational design and active site regulation of high-performance
electrocatalysts. In this review, the fundamental understanding of the structural characteristics of LDHs
is demonstrated first, then comparisons and in-depth discussions of recent advances in LDHs as highly
active OER catalysts in alkaline media are offered, which include both experimental and computational
methods. On top of the active site identification and structural characterization of LDHs on an atomic
scale, strategies to promote the OER activity are summarised, including doping, intercalation and
defect-making. Furthermore, the concept of superaerophobicity, which has a profound impact on the
performance of gas evolution electrodes, is explored to enhance LDHs and their derivatives for a large
scale OER. In addition, certain operating standards for OER measurements are proposed to avoid
Received 18th February 2021 inconsistency in evaluating the OER activity of LDHs. Finally, several key challenges in using LDHs as
DOI: 10.1039/d1cs00186h anode materials for large scale water splitting, such as the issue of stability and the adoption of
membrane–electrode-assembly based electrolysers, are emphasized to shed light on future research
rsc.li/chem-soc-rev directions.
a
State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical
Technology, Beijing, 100029, China. E-mail: [email protected], [email protected]
b
Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, CB3 0AS, UK
c
Department of Chemical Engineering, Loughborough University, Loughborough, Leicestershire, LE11 3TU, UK. E-mail: [email protected]
Dr Daojin Zhou received his PhD Professor Yun Kuang joined the
degree in 2019 from Beijing College of Chemistry, Beijing
University of Chemical Technology University of Chemical Technology,
and currently works as a post- in 2015. His recent work focuses on
doctoral researcher in collabo- nanomaterials and interface design
ration with Prof. Xiaoming Sun. for active and stable water/seawater
He focuses on the design of novel splitting for hydrogen production,
catalysts for electrochemical water and environmental related electro-
splitting and solid–gas catalysis. He catalytic reactions. He has co-
has published 16 original research authored over 40 scientific papers.
papers in chemistry, materials and
energy related journals in the last
Daojin Zhou 4 years. Yun Kuang
8790 | Chem. Soc. Rev., 2021, 50, 8790–8817 This journal is © The Royal Society of Chemistry 2021
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Review Article Chem Soc Rev
1. Introduction of the oxygen evolution into green chemical fuels. Water splitting for hydrogen production
reaction in water splitting via electrocatalysis consists of two half-cell reactions, known as the
hydrogen evolution reaction (HER) at the cathode,16–18 and the
Production of hydrogen is of significance in promoting the oxygen evolution reaction (OER) at the anode.4,19 The cathodic HER
development of clean and low-carbon economies since hydrogen involves a two-electron transfer, whereas the anodic OER involves a
has the highest energy density and serves as an ideal energy four-electron transfer,20 suggesting that the OER is kinetically
carrier.1–9 The US,10 Europe11 and China have published roadmaps unfavourable when compared to the HER.21 Therefore, extensive
for hydrogen and fuel cell vehicles recently; and the efficient efforts have been made in seeking efficient electrocatalysts for the
production of hydrogen has gained popularity worldwide.12 To OER.22–24 The OER traditionally relies heavily on the use of iridium
date, the main and conventional method for hydrogen production oxide25–27 (IrO2) or ruthenium oxide28–30 (RuO2) based catalysts.
has been coal gasification which involves CO contamination and However, this is economically unfavourable due to their limited
still relies on fossil fuels.13–15 reserves and high cost for industrial use.31,32 To overcome this
Electrocatalytic water splitting to produce hydrogen represents challenge, investigations of low-cost transition metal-based catalysts
a clean and sustainable technology converting renewable energy used in alkaline media, which have both satisfactory intrinsic
activity and stability for the OER, have attracted significant attention
in recent years.33–38 In fact, investigations into Co-, Ni-, Fe-,
and Mn-containing spinels,39–43 perovskites,44–48 oxides49–53 or
Professor Wen-Feng Lin, FRSC, is hydroxides54–56 for catalysing the OER in alkaline media could
the Professor of Chemical date back to more than half a century ago, demonstrating the
Engineering and the Departmental potential of replacing noble metal-based catalysts. In Fig. 1,
Director of Research at Lough- some classical and popular electrocatalysts for the OER are
borough University. He has summarized, including Ruddlesden–Popper oxides,57–60 rock
expertise in physical chemistry, salt oxides,61 rutiles,62 high-entropy alloys,63–65 perovskites,66,67
electrochemistry and electro- metal oxides,62,68–73 spinels41,74–78 and LDHs,62,79–88 from which
chemical engineering. The primary it can be deduced that LDH species have shown the most
themes of his research are related outstanding OER performance, with small Tafel slopes and
to clean energy, the environment, relatively low overpotentials at a given current density. Therefore,
and water. He collaborates the use of LDHs for designing advanced OER electrocatalysts has
internationally and has led a attracted sufficient attention from researchers across the globe.
Wen-Feng Lin significant number of externally Initially, a-Ni(OH)2 was the first metal hydroxide identified
funded projects, ranging from to exhibit OER electrocatalytic activity,89 then it was further
fundamental understanding of electro-catalysis at the atomic and revealed that doping it with other metal cations with variable
molecular levels to applied R&D in energy materials, fuel cells, oxidation states can boost the OER activity of a-Ni(OH)2.90,91
batteries, hydrogen production, carbon dioxide utilization, ozone Since then, transition metal (e.g., Co-, Ni-, Fe-, and Mn-)
generation, and advanced oxidation technologies. He has over 170 containing layered double hydroxides69,92,93 (LDHs) and their
publications and his research contributed to 2 high tech spin-offs.
Professor Xiaoming Sun joined the Professor Xue Duan, Academician

State Key Laboratory of Chemical of the Chinese Academy of
Resource Engineering, Beijing Sciences, is the Executive Vice-
University of Chemical Technology, Chair of the Academic Committee
in 2008. His research interests focus of the State Key Laboratory of
on active site design and controlled Chemical Resource Engineering.
synthesis of inorganic nano- He established a distinctive
materials, and their utilization in research program covering the
gas-involving electrocatalytic reac- assembly of layered materials
tions, including water electrolysis, and their applications, developed
fuel cells, and metal–air batteries. a novel method for separating
He proposed the concept of gas- aging and nucleation steps for
Xiaoming Sun super-wetting electrodes (superaero- Xue Duan preparation of layered materials
phobic or superaerophilic electrodes) and employed it to synthesize a
based on nanoarray architecture and employed them to enhance gas wide range of new intercalated materials. He led the establishment
transfer in gas-involving electrocatalysis. He has co-authored over 200 of a portfolio of independent IPs with 65 patents, and won many
scientific papers which have been cited over 24 000 times. prizes including the National Scientific and Technological Innovation
Prize and the National Scientific and Technological Progress Prize.
This journal is © The Royal Society of Chemistry 2021 Chem. Soc. Rev., 2021, 50, 8790–8817 | 8791
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Fig. 1 Comparison of the OER performance of classical electrode/catalyst materials. Benchmarks are IrO2 and RuO2; the different types of catalyst
materials are categorized by using different colours.
topotactic derivatives94,95 have been documented to exhibit

outstanding performance towards the OER, originating from
their highly controllable structure,96–98 intensive host–guest
interactions99–101 and highly dispersed single-atomic sites.102
There are already several review articles which have summarized
the development of LDHs for the OER from material and char-
acterization perspectives. For example, exfoliating LDHs,62 doping
LDHs103 and introducing defects84 into LDH nanosheets, as well as
compositing LDHs with carbon nanotubes (CNTs),104 have been
chosen as methods to improve the understanding of LDHs for the
OER. However, there is a lack of an overall comprehension and
recognition of OER kinetics on LDHs; in particular, there is a gap
regarding design and optimization of LDHs based on their atomic
structure characteristics and larger scale electrode assembly to Fig. 2 Structure of LDHs and typical distribution of the metal sites in LDHs
promote mass transportation for further development towards for the OER. (a) A schematic illustration of the layered structure of LDHs.
(b) Arrangements of the metal cations in LDH nanosheets upon increasing
applications in industrial water electrolysers.
the MII/MIII ratio from 2.0 to 4.0. MIII exhibits single atom dispersion
In this review, identification of active sites, at the atomic characteristics.
level, of LDHs for the OER is introduced and discussed in detail,
based on the OER mechanism in alkaline medium. The current
strategies for active site optimization to enhance the OER perfor- anions are confined between the layers.105,106 A general formula
mance of LDHs are summarised. Furthermore, the development of unveiling the composition of LDHs is MII1 xMIIIx(OH)2(An )x/n
superaerophobic electrodes based on LDHs for a large-scale OER is yH2O,107 where MII and MIII are divalent and trivalent metallic
explored. Finally, we offer perspectives into challenges faced by cations, respectively, and An is the intercalated anion (e.g.,
industrial-scale water splitting for hydrogen production, and CO32 ) neutralizing the positive charge of the nanosheets.108,109
point out the enormous potential of using LDHs in addressing A wide variety of divalent, trivalent, or even higher valence state
these challenges. cations can be selected to construct the nanosheets, while
multiple anions can be intercalated between the layers, leading
to the highly flexible and controllable composition and structure
2. Fundamental characteristics of LDHs of LDHs.110
The structure recognition of LDHs can be traced back to
LDHs are a series of two-dimensional nanomaterials as shown 2008. Nielsen et al.111 used 1H–27Al double-resonance and 25Mg
in Fig. 2a, in which MO6 (where M stands for the metallic cation) triple-quantum MAS NMR to study the local configuration of
octahedra constitute the nanosheets, and the intercalated Mg and Al in LDH nanosheets. The results showed that the
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cations were fully ordered for a Mg : Al ratio of 2 : 1, and at a It can be clearly seen that NiFe-LDHs show a superior OER
lower aluminum content, a non-random distribution of cations catalytic performance over other binary LDHs; therefore,
persists with no Al3+–Al3+ close contacts. We thus propose to NiFe-LDHs can be identified as the optimal framework for
consider LDHs as ‘‘hydroxide solid solutions’’ with single- compositional modulation. In NiFe-LDHs, both metal elements
atomic dispersion of MIII (or MIV) in the matrix of MII(OH)2 are redox-active, and Ni2+ is used as a ‘‘solvent’’ to isolate Fe3+
nanosheets based on previous structure investigations.111,112 ions. During the OER process, a pre-oxidation of metal ions to
That is, the MII and MIII cations in the LDH nanosheets can higher oxidation states can be observed. Fig. 3b shows the
replace each other as long as no M(III)–O–M(III) is formed. The typical OER polarization curves of NiFe-LDHs in an alkaline
MII/MIII cation ratio can be widely tuned without restructuring medium. The oxidation and reduction of Ni2+/Ni3+ occur in the
the layered structure. This is the feature of a solid solution that overpotential range of 0.1–0.2 V, while the OER overpotential is
forms after the dissolve–precipitate ripening process, to arrive located after 0.2 V. As shown in the inset, two locations (edge or
in a thermodynamically stable state. In the LDH nanosheets, bulk) and two species (Ni or Fe) of metal sites in the LDHs are all
MII (or MIV) cations can be regarded as the matrix (or solvents), potentially responsible for the OER activity. Therefore, the
while MIII can be considered as ‘‘solute’’ or dopant species to identification of OER active sites in LDHs is of significant
replace MII sites. Due to the high electrostatic force existing importance for the design and preparation of the next generation
between high valence MIII (or MIV) cations in the LDH of efficient OER catalysts based on LDHs.
nanosheets, MIII (or MIV) cations could not bridge each other
by sharing oxygen atoms (unless, in some cases, M(III)–O–M(III)
forms due to insufficient crystallization or ripening), but only 3. OER pathways and identification of
existed randomly and single-atomically in the nanosheets, active sites on LDHs for the OER in
regardless the MII/MIII ratios (Fig. 2b). However, to well isolate alkaline media
the MIII ions, much more MII ions are required, which makes the
MII/MIII ratio larger than 2 in most cases. It has been observed that 3.1 OER pathways on LDHs in alkaline media
the MII/MIII ratio = 3 : 1 results in slightly higher stability, according LDHs as transition metal hydroxide materials will inevitably dis-
to repeated experiments. This unique structure provides opportu- solve in acidic media. Therefore, the OER on LDHs has always
nities for modulation of the MIII (or MIV) coordination environment been conducted under alkaline conditions, where the OER may
and synergistic interaction between MIII (or MIV) and MII to enhance occur via (a) an adsorbate evolution mechanism (AEM)123,124 or (b)
the electrocatalytic oxygen evolution activities of LDHs. Further- a lattice oxygen oxidation mechanism as shown in Fig. 4.
more, two or even more species of high valent metallic cations can The adsorbate evolution mechanism (AEM), a well-known
also be single atomically dispersed in the M2+–OHx matrix, due mechanism that involves successive adsorption and desorption of
to the electrostatic repulsion, and synergic effects within the oxygenated intermediates on the unsaturated coordinated metal
M3+/4+–O–M2+ couple can have a profound influence on the ion (M*) as active sites, has already been verified by simulation and
corresponding properties of LDHs. experiments.126 The process consists of the continuous adsorption
In Fig. 3a, we summarize the representative studies on of oxygenated intermediates (M* - M–OH; M–O - M–OOH), the
preparing and applying LDHs for the OER.62,79–82,85,86,97,113–122 deprotonation of hydrogen (M–OH - M–O), and the desorption of
Fig. 3 Comparison of the performance of various LDHs for the OER in terms of Tafel slope. (a) The bar charts show that OER on Fe-containing/NiFe-
LDHs exhibits a smaller Tafel slope. The error bar corresponds to the different Tafel slopes of NiFe-LDHs reported in different studies. The blue numbers
in the brackets in Fig. 3a correspond to the cited references. (b) Typical polarization curves of NiFe-LDHs for the OER and the corresponding distribution
of metal sites in the LDHs.
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other LDHs (e.g. NiFe-LDHs as we discussed in detail) for the

OER needs further verification; therefore our discussion will be
mainly based on the AEM.
3.2 Identification of the active sites on LDHs for the OER in

alkaline media
Besides the revelation of the working pathway of LDHs in the
OER, the identification of active sites in LDHs, by which we can
Fig. 4 Proposed OER mechanism on LDHs in alkaline medium. (a) Adsorbate
rationally modulate the binding strength of intermediates to
evolution mechanism (AEM). Reproduced with permission.123 Copyright 2019,

The Royal Society of Chemistry. (b) Lattice oxygen oxidation mechanism metal sites, is also indispensable for preparing efficient OER
(LOM). Reproduced with permission.125 Copyright 2019, the authors. catalysts. Binary transition metal cations with high redox
activity are always preferred for the OER,106,127 so the combinations

of Ni2+/3+, Co2+/3+, Fe2+/3+ metal cations in LDH nanosheets are the
oxygen (M–O–OH - M*) on active sites, although some reports most extensively researched objects among all the LDH species.
argue that two M–O species get combined and converted into O2 Thus, identification of the active sites using experimental126,128 and
and M active sites at the surface. According to the scaling relation- computational tools has been carried out mostly on Ni-, Co- and Fe-
ship (DGOOH DGOH = 3.2 0.2 eV) in the AEM, if DGO DGOH 4 containing LDHs. NiFe-LDHs show the highest activity among the
1.6 0.1 eV, then the formation of DGO would be the rate binary LDHs and are substantially more cost-effective for future
determining step with an overpotential of 40.38 V; by contrast, large-scale utilization. Despite the fact that only two metals exist in
if DGOOH DGO 4 1.6 0.1 eV, the formation of DGOOH would be plane, the origin of the high OER activity is still ambiguous. The
the rate determining step with an overpotential of 40.37 V. Thus, controversial assumption of active sites being Ni sites on the
according to the Sabatier principle, the optimal Gibbs free energy NiFe-LDHs started from the early 21st century and then turned
change for every single step in the OER is 1.6 0.1 eV. to be Fe sites; while more recent studies, based on the full
Consequently, the identification of active sites of LDH-based utilization of advanced research techniques available, have
OER electrocatalysts, by spectroscopic study of the binding proposed that the synergy between Ni and Fe sites was respon-
energy of active metallic sites to OER intermediates, is critical sible for OER activity.
for further optimization or atomic structure design. A pioneering study was reported by Bell’s group as shown in
Besides the AEM mechanism, some recent findings propose Fig. 5a. They tracked the electrode surface transformation from
that the lattice oxygen oxidation mechanism (LOM), which Ni(OH)2 into NiOOH using in situ Raman spectra129 recorded at
involves O–O coupling during the OER and is similar to some a potential of 0.47 V vs. Hg/HgO.130 The band in the range of
recently reported OER processes on perovskites, may also be 445–465 cm 1 in the lower potential region in Fig. 5a can be
possible for LDH catalysed OERs.125 However, only a few LDHs attributed to the Ni–O vibration of Ni(OH)2. Upon increasing
have been studied, and in most cases, Co was involved (e.g., the potential to 0.47 V and above, a new pair of bands appeared
Co–Zn oxyhydroxide),123 so the applicability of the LOM on at 474 and 554 cm 1, respectively, which were attributed to
Fig. 5 Identification of the active sites for the OER on Ni oxide and NiFe-LDHs in alkaline medium using in situ Raman spectra and XAS. (a) In situ Raman
spectra collected from the Ni oxide electrode, as a function of potential in 0.1 M KOH at potentials of 0 V to 0.7 V vs. Hg/HgO (1 M KOH). Reproduced
with permission.130 Copyright 2013, The American Chemical Society. (b) and (c) Complementary operando EXAFS measurements confirmed the
potential-induced bond contraction at both Fe and Ni sites. The structure model of Fe doped g-NiOOH. Ni K-edge XAS shows shifts in both oxidation
state-sensitive and structure-sensitive features due to the oxidation of Ni2+ sites. Reproduced with permission.137 Copyright 2015, The American
Chemical Society. (d) The k2-weighted Fourier transformed in situ EXAFS data of Fe2+-NiFe-LDHs under OER working conditions, demonstrating the
Fe–O bond-length variation. Reproduced with permission.82 Copyright 2018, Wiley-VCH.
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Ni–O vibrations in NiOOH. This work suggested that the OER the potential was set at 0 V. These studies have expanded further
was catalysed by Ni3+ in NiOOH, leading to a significant on previous findings and pointed out that Fe was the active site in
enhancement in the potential at which the Ni(OH)2/NiOOH LDHs for the OER with the support of in situ XAS data.
redox reaction occurred. Also, XAS was applied by Nocera et al. To elucidate the role and evolution of Fe cations in hydro-
to identify the OER active sites on NiFe-LDHs.131 The authors xides during the whole process of the OER, Jin et al. developed
identified Ni4+ ions as the active sites, while the Lewis acid operando Mössbauer spectroscopy to probe the valence states
Fe3+ in NiFe-LDHs served to increase the acidity of OHx (aqua/ of Fe cations in NiFe-LDHs during the OER process.138 Fig. 6a
hydroxo) moieties that are coordinated to nickel, thereby low- shows the CV curve collected prior to Mössbauer spectral
ering the reduction potential for the Ni4+/3+ redox couple and measurement. The Mössbauer spectra were recorded initially at
thus generating a greater population of Ni4+ in the Fe-doped the open circuit potential, then at various potentials of
catalysts, and, correspondingly, benefited the enhancement of 1.49 V, 1.62 V and 1.76 V, and finally returned to the open circuit
OER activity. In situ X-ray absorption spectroscopy (XAS), which potential. Under open circuit conditions, a doublet with an isomer
is capable of revealing the valence state and coordination shift of 0.34 mm s 1 and a quadrupole splitting of 0.46 mm s 1
environment132–134 of active sites on LDHs during the OER were observed for the NiFe-LDHs, which remained relatively stable
process, was also employed to provide direct information on until 1.49 V. With increasing working potential, a shoulder
the evolution of both the electronic and atomic structures of appeared at 0.27 mm s 1, and the intensity reflected the
LDHs.135,136 The work by Bell and Friebel as shown in Fig. 5b oxidation of approximately 12% (at 1.62 V) and 21% (at 1.76 V)
and c unveiled that the Fe–O bond length contracted from of Fe species in LDHs, which corresponded to the assignment of
2.01 Å at 1.12 V to 1.90 Å at 1.92 V, indicating that the Fe localized species as Fe4+. When the potential returned to 1.49 V or
hydroxides were actively transformed during the OER and the to the open circuit potential for a short period of time, Fe4+ was
interaction between Fe and lattice oxygen at the OER potential still detected. This work provided clear evidence for the formation
was noticeably stronger than that of Ni.137 The phase evolution of Fe4+ in NiFe-LDHs during the OER, and the role of Fe species in
differences between Ni–OH and Fe–OH may indicate that Fe catalysing oxygen evolution began to be recognized.
played a more significant role in NiFe-LDHs for the OER. Since both Ni and Fe cations are redox active sites on LDH
Cai et al. reported the synthesis of Fe2+ doped NiFe-LDHs nanosheets, the precise roles of Ni and Fe in the OER activity of
(NiFe2+Fe3+-LDHs) and presented the structural evolution during LDHs need to be clarified. Friebel et al. constructed several
the OER by employing in situ XANES, which can identify both Fe2+ models to identify the role of Fe in Fe doped NiOOH for the
and Fe3+.82 As shown in Fig. 5d, the Fe species in the NiFe2+Fe3+- OER as shown in Fig. 7. It was shown that subsurface Fe sites in
LDHs without applied potential showed mixed valence states of g-NiOOH increased the OER overpotential at surface Ni sites
both +2 and +3. The valence state increased to +3.22 at 1.5 V with (0.56 V to 0.59 V)137 by weakening the binding strength of oxyge-
a shortened Fe–O bond (partial Fe4+ among all Fe species), and nated intermediates to the Ni site (the Fe doping results in the
remained in the +3.22 state for a short period of time even when anodic shift of the Ni2+ oxidation peak prior to the OER onset).
Fig. 6 Identification of Fe4+ in NiFe-LDHs during the OER using Mössbauer spectra. (a) Cyclic voltammograms of NiFe layered oxyhydroxide (blue) and
hydrous Fe oxide (green) electrocatalysts employed in the operando experiments with Mössbauer spectra collected at the open circuit potential (grey),
1.49 V (purple), 1.62 V (yellow), and 1.76 V (red). (b–g) Mössbauer spectra at different applied potentials. Reproduced with permission.138 Copyright 2015,
The American Chemical society.
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which was very close to the experimental value (0.3–0.4 V). The
authors unveiled that the high spin d4 Fe(IV) led to the efficient
formation of the O radical intermediate (M–O), while the closed
shell d6 Ni(IV) catalysed the subsequent O–O coupling; thus, it
was the synergy between Fe and Ni rather than any single active
site that delivered the optimal performance for the OER. This
work provided insights into the OER activity on NiFe-LDHs
from the computational viewpoint, and for the first time, both
Ni and Fe were suggested to play an important role synergistically
in influencing the OER activity of NiFe-LDHs.

Recently, Strasser et al. combined operando wide-angle X-ray
scattering (WAXS) and absorption spectroscopy, differential

electrochemical mass spectrometry (DEMS), and DFT calculations
to elucidate the catalytically active phase, reaction centre and OER
mechanism.140 From the perspective of crystallinity, their data
showed that Fe-containing bimetallic LDHs were oxidized from the
as-prepared a-phases to activated g-phases with around 8% lattice
spacing contraction (Fig. 8b). From the active site identification
perspective, their data revealed that the OER progressed via a
Mars–van Krevelen mechanism,139 where the synergy between
surface Fe sites and the nearest-neighbour M sites worked through
the formation of O-bridged Fe–M reaction centres, stabilizing OER
intermediates and fundamentally accounting for the high catalytic
activity of MFe LDHs (Fig. 8c). In a recently published study, Wang
et al. applied DFT calculation first and then used an acid-etching
Fig. 7 Identification of the active sites for the OER on metal hydroxides by experimental method to verify that the edge Fe sites showed
theoretical methods. Theoretical OER overpotentials at Ni and Fe surface superior OER activity in the presence of Ni atoms; while Fe–O–
sites in pure and doped g-NiOOH and g-FeOOH model structures. Fe in Fe(OH)3, bulk metal sites and Ni sites were less active.141
Reproduced with permission.137 Copyright 2015, The American Chemical
Society.
These findings are in line with the calculation work by Goddard III
and Xiao,139 where a conclusion was reached that Ni–O–Fe jointly
functioned as the active centre on NiFe-LDHs.
However, the surface Fe exhibited a lowered overpotential for the To further probe and compare the exact contributions from
OER (Z = 0.43 V), which was close to the experimental result (nearly Ni, Fe and even lattice oxygen in NiFe-LDHs for OER activity,
0.3 V), indicating that Fe rather than Ni has a higher OER activity. Hu et al. studied different reaction sites on the LDHs, using
18
Although a growing number of published studies claim that Fe has O-labeling experiments in combination with in situ Raman
a higher OER activity than Ni, Fe-doped NiOOH with high Fe spectroscopy to probe whether lattice oxygen was involved
content (55 at% Fe)126 fails to show attractive OER electrocatalytic during the OER (Fig. 9a and b).142 In pure Ni-LDHs, the Raman
activity, and the overpotential for the OER on a single Fe site peak changed from Ni–18O to Ni–16O as the OER proceeded,
revealed by density functional theory (DFT) calculations is consider- illustrating that the lattice oxygen in Ni-LDHs was actively
ably higher than that presented by the polarization curve obtained involved in the OER. However, the NiFe-LDHs showed steady
experimentally. This implies that not all the Fe atoms, but only the d(NiIII–O), n(NiIII–O) and n(O–O) peaks in the Raman spectra
Fe atoms chemically surrounded by Ni atoms are potentially OER regardless of the change of electrolyte (whether labelled with
18
active. Thus, a synergistic interaction between Ni and Fe in NiFe- O or 16O). In other words, O2 evolved through an active oxygen
LDHs has been recognised and has attracted increasing attention. species (Ni–O–O ) on the Ni sites and with lattice oxygen
Goddard III and Xiao used grand canonical quantum participation; whereas on Fe sites, O2 evolved neither with
mechanics and DFT with exact atomic exchange to check the lattice oxygen participation, nor through an active oxygen
OER activity of g-(Ni,Fe)OOH: the OER overpotential decreased species. When the OER occurs through Ni sites, the lattice O
from 1.22 V on pure g-NiOOH to 0.83 V on the 1/3 surface Fe should exchange with the O atoms of the OH electrolyte
doped g-(Ni,Fe)OOH and 0.42 V on the 1/3 surface plus 1/3 (Fig. 9c). On the other hand, when the OER occurs through
subsurface Fe doped g-(Ni,Fe)OOH (Fig. 8a).139 The substitution Fe sites, there is no exchange of lattice O with OH , suggesting
of Ni by Fe had an obvious impact on the reactivity for the OER. that only the Fe sites were OER active in NiFe-LDHs142,143
As shown in Fig. 8a, the free energy required for O radical (Fig. 9d). Hu et al. also used the procedure to study the OER
formation was reduced from 2.04 eV to only 1.20 eV (as activity on individual Ni or Fe in NiFe-LDHs by comparing the
compared with pristine NiOOH), while the barrier for O–O degree of O exchange on them during the OER.144 The turnover
coupling increased slightly to 0.60 eV. The combination of O frequency (TOF) on Fe was found to be 20–200 times higher
radicals with O–O coupling led to an overpotential of 0.42 V, than that on Ni when the Fe content accounted for 4.7%.
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Fig. 8 Synergy between Ni and Fe sites identified on NiFe-LDHs during the OER. (a) The mechanistic cycles for the OER on one-third surface Fe doped
plus one-third subsurface Fe doped g-(Ni,Fe)OOH catalysts. The free energy input required for O radical formation is reduced drastically to 1.2 eV, while
the barrier for O–O coupling increases slightly to 0.6 eV. This combination leads to an overpotential@10 mA cm 2 of 0.42 V. Reproduced with
permission.139 Copyright 2018, the authors. (b) Waterfall plots of normalized and background-subtracted (003) peaks obtained during in situ WAXS and
potential steps for NiFe-LDHs in 0.1 M KOH. (c) Reaction free-energy diagrams for the OER on g-NiOOH, g-NiFe LDHs, and g-CoFe LDHs; the potential
limiting steps and the OER overpotentials are also given. Reproduced with permission.140 Copyright 2020, the authors.
Fig. 9 Identification of the active sites by isotope labelling experiments. (a and b) In situ Raman spectra of 18O labelled Ni-LDHs (a) and NiFe-LDHs (b)
recorded at 1.65 V in 0.1 M KOH in H216O. The models illustrating the different roles of lattice oxygen in OER catalysis: (c) participation of lattice oxygen in
NiNi- and NiCo-LDHs; and (d) nonparticipation of lattice oxygen in NiFe-LDHs. M = Ni or Co. Reproduced with permission.142 Copyright 2019, Wiley-VCH.
This indicated that Fe was considerably more active than Ni line with computational results, and suggested that Fe sites had
on the NiFe-LDHs for the OER. The experimental data were in superior OER activity to Ni sites.
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4. Strategies to enhance the OER on have previously been achieved and resulted in a further
LDHs by tailoring active sites on an improvement in OER activity.
According to the AEM mechanism (Fig. 4a), metal sites with
atomic scale an electron-rich structure can be easily oxidized, which are
The abovementioned experimental and computational studies highly active towards the OER. Cai et al. constructed Fe2+–O–
focused on identifying the active sites at the atomic level and Fe3+ motifs as the active sites, showing simultaneously high
shedding light on the future design of efficient OER catalysts. stability and high activity for the OER as shown in Fig. 10a.82
Since Ni and Fe are both indispensable sites accounted for the Doping with Fe2+ first modified the electronic structure of Ni
and Fe, resulting in an electron-rich structure at all metal sites
boosted OER performance, the modulations of the Ni–O–Fe

motif with an optimized electronic structure are one of the key available on NiFe-LDHs; at the same time, the specially
designed Fe2+–O–Fe3+ significantly increased the adsorption
goals for active site tailoring. Some strategies have been attempted
to enhance the OER performance of NiFe-LDHs. These include the of OER intermediates on NiFe2+Fe3+-LDHs. The latter can be
following 4 aspects: (1) compositional optimization, i.e., substitut- confirmed by the cathodic shift of the Ni2+/Ni3+ redox potential
ing Ni2+ with other M2+ to modulate the electronic structure of and the boosted OER performance with a smaller overpotential
Fe2+, or replacing Fe3+ with other M3+ to optimize the electronic of 249 mV at 10 mA cm 2 (Fig. 10b). However, excessive Fe2+
structure of Ni2+; (2) coordination environment modulation, i.e., doping weakens the interaction between Ni and Fe, resulting in
from making metal vacancies to tailoring the number of edge sites, the OER onset potential on Fe2+–NiFe-LDHs being shifted
and introducing oxygen vacancies to generate more unsaturated anodically. In another case, Co2+ and Co3+ were doped into
metal sites; (3) host–guest interaction, i.e., intercalating different NiFe-LDH nanosheets to substitute Ni2+ and Fe3+, respectively,
anions to tailor the basal spacing or induce electron transfer as shown in Fig. 10c;147 the Volcano plot correlated the over-
between metal sites in nanosheets and intercalated species; potential with DE*O, and the effect of Co doping on the OER
and (4) noble metal loading, i.e., adding noble metal cations as activity of NiFe-LDHs was summarised, specifically, from the
both active sites and electronic structure mediators to metal viewpoints of the M2+/M3+ ratio and doping Co cation valence
sites in nanosheets. state. The results shown in Fig. 10d showed that at a fixed
M2+/M3+ ratio, the replacement of Fe3+ with Co3+ had a more
positive effect on the overall OER activity. The Co3+ modified
4.1 Modulation of the compositions of LDH nanosheets the electronic structure of the Ni site (enlarged Ni2+ oxidation
Modulation of the compositions of LDH nanosheets can be peak in the blue curve) and benefited the electron transfer in
achieved in large varieties, e.g., M2+ in the nanosheets can be NiCo3+Fe-LDHs.
selected from Mn2+, Co2+, Fe2+, Mg2+, etc., and M3+ in the Li et al. reported doping V into NiFe-LDHs for enhanced
nanosheets can be selected from Fe3+, Co3+, Cr3+, V3+, OER activity.150 XPS spectra revealed that the binding energy of
etc.145,146 Taking NiFe-LDHs as the benchmark for the OER, Fe 2p3/2 shifted negatively from 713.1 to 712.4 eV after V doping,
and the Ni–O–Fe motif serving as the active centre, there are indicating the charge compensation between metal cations
several representative studies that involve doping with a third induced by differences in electronegativity (EN). V3+ had
metal cation. Heterovalent metal cations in LDH nanosheets a lower EN than Fe3+ and tended to donate electrons to the
Fig. 10 Modulation of the compositions of LDH nanosheets for improving OER activity. (a) A schematic atomic arrangement of NiFe2+Fe3+-LDHs. (b) CV
curves of NiFe2+Fe3+-LDHs with different Fe2+/Fe3+ ratios. Reproduced with permission.82 Copyright 2018, the authors. (c) Schematic atomic
arrangement of Co3+-doped NiFe-LDHs. (d) Linear sweep voltammetry polarization curves of the as-prepared NiCo2+Fe211, NiCo3+Fe611, and
NiFe31-LDH. Reproduced with permission.147 Copyright 2018, Elsevier Ltd. (e) Scheme of Ru3+ doped NiFe-LDHs. (f) Polarization curves of
the NiFeRu-LDHs, NiFe-LDHs, nickel foam, and Ir/C electrocatalysts. Reproduced with permission.148 Copyright 2018, Wiley-VCH. (g) SEM image of
NiFeCr-LDHs. (h) OER polarization curves for various LDH samples deposited on GC electrodes at a constant loading of 0.2 mg cm 2. Reproduced with
permission.149 Copyright 2018, Wiley-VCH.
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surrounding Fe3+, resulting in the oxidation of V3+ to V4+ and Fig. 11 shows the modulation of the compositions of
V5+, accompanied by the reduction of Fe3+. The corresponding NiFe-based LDH nanosheets, in which most of the reductive
NiFeV-LDHs exhibited enhanced OER activity over NiFe- metal cations, such as Fe2+, Mn2+, Cr3+ and V3+, can largely
LDHs and RuO2, and it only required a small overpotential of improve the OER activity of NiFe-LDHs by donating electrons to
195 mV to reach an OER current density of 20 mA cm 2. On top the parental Ni2+ and Fe3+. Specifically, the electronic structure
of the active site modulation, the high valence states of V4+ and of Ni2+ and Fe3+ will evolve from electron-equilibrium to
V5+ also benefited the electron transport in NiFeV-LDHs; for electron-rich, benefiting the de-protonation step in the OER
example, the resistivity decreased from (2.4 0.3) 103 O sq 1 by enhancing the binding strength between the adsorbates and
(NiFe-LDHs) to (1.3 0.2) 103 O sq 1 (NiFeV-LDHs) by the active sites. Notably, recent research has reported that Mo5+
changing the conducting band state of the LDHs, which is in and W6+ can also improve the OER activity of NiFe-LDHs by
accordance with the results of Co3+ doped materials.151 Similar lowering the valence state of Ni and Fe prior to the OER.154 On
activity enhancement was observed on NiV-LDHs,79 in which V the other hand, redox inert homovalent metal cations such
played key roles in modulating the electronic structure of as Mg2+ and Ca2+ can reduce the intrinsic OER activity of NiFe-
metal sites and contributed collectively to the enhanced OER LDHs due to the decreased number of available active sites,
performance.152 Relying on single atomic dispersion of Fe3+ although some recent reports show that doping Mg2+ and
and the function-oriented replacement of high valence state Ca2+ into NiFe-LDHs can improve the OER activity in neutral
metal ions in LDH nanosheets, a strategy for accelerating the medium by enhancing the water dissociation process.
oxygen evolution kinetics of the NiFe-LDHs by partially Doping Cu2+ into NiFe-LDH nanosheets can induce structural
substituting Fe3+ ions with Ru3+ was proposed by Feng et al. disorder due to the Jahn–Teller effect, which can modulate the
(Fig. 10e).148 The NiFeRu-LDHs showed an exceptionally low OER activity from a crystallinity perspective (the amorphous
overpotential of 225 mV for the OER at 10 mA cm 2 as depicted structure can lead to more exposed uncoordinated sites). Doping
in Fig. 10f. with Zn2+ and Al3+ hardly benefits the electronic structure of
In 2017, Jin et al. prepared Cr-doped NiFe-LDHs for catalysing active sites but reduces the number of active sites, which may be
the OER (Fig. 10g).149 The XPS binding peak corresponded to Fe2+ comparable to that of Ca2+ and Mg2+; however, the solubility of
that emerged with Cr3+ doping, proving that the interaction Zn2+ and Al3+ in alkaline medium may also influence the OER
between Cr3+ and Fe3+ led to the electronic structure change performance of NiFe-LDHs by tailoring the coordination environ-
from electron-equilibrium to electron-rich, which can also be ment of the metal sites. From the above findings, a bold
described as the Fe3+ sites being partially reduced. This tuned perspective can be put forward for discussion: as long as the
electronic structure led to the improved OER activity of NiFeCr- radius of doping metal cations fits in the LDH matrix, the
6 : 2 : 1-LDHs as confirmed in Fig. 10h, where the onset potential modulation of the compositions of LDH nanosheets for enhan-
shifted much earlier for the OER on NiFeCr-6 : 2 : 1-LDHs. cing their OER activity can always be explored. The factors to
Furthermore, the synergy between NiFe-LDHs and substrates consider are: the selection of doping cations, location and
can also lead to electronic structure modulation of both Ni and arrangement of doping cations in the nanosheets, whether the
Fe sites. Recently, Hu et al. decorated Co3O4 with NiFe-LDHs and doping cations work alone or as an integration to affect the OER
correlated the electronic states of LDHs to the OER activity.153 performance, etc.
After the decoration of Co3O4, the XPS binding energy of Ni
and Fe shifted negatively compared with pristine NiFe-LDHs. 4.2 Modulation of the coordination environment of metal
Similarly, Co3O4@NiFe LDHs with electron-rich Ni and Fe sites in LDH nanosheets
showed superior OER activity over pristine NiFe-LDHs. This work Two types of coordination environment modulation in LDH
may also provide guidance for the further design of improved nanosheets are commonly used. The first one is the introduction
LDHs for catalysing oxygen evolution. of oxygen or metal vacancies into LDH nanosheets, and the second
one is the exfoliation of LDH nanosheets into mono/few layers. In
the process of vacancy introduction, approaches include plasma
treatment, reducing flame treatment, hydrothermal treatment
with the use of reducing reactants and acidic/alkaline etching.
Wang’s group reported a series of impressing and advancing
vacancy engineering studies to enhance the OER activity of
LDHs. As shown in Fig. 12a, the authors prepared CoFe-LDHs
by a hydrothermal method and then subjected the intact
CoFe-LDHs to a dielectric barrier discharge (DBD) plasma
reactor for 5 min to obtain vacancy-rich CoFe-LDH nanosheets.119
The OER on the water-plasma exfoliated CoFe-LDH nanosheets
required a low overpotential of 290 mV to reach a current density of
Fig. 11 Summary of the Tafel slope values of the oxygen evolution
reaction on NiFe-based LDH nanosheets with different doping cations.
10 mA cm 2, while the pristine CoFe-LDHs needed an overpotential
Elements with a white background correspond to the cations that can be of 332 mV, highlighting the promoting role of vacancies in
potentially doped into the LDH nanosheets. enhancing the OER performance of LDHs.
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electron-rich state was responsible for the improved OER activity.

In the same year, Jin et al. introduced Al3+ into NiFe-LDHs
(Fig. 12c);156 they found that etching of Al3+ species in strong
alkaline solution during an OER test would greatly benefit the
formation of Ni3+ species as active sites. Despite the Al3+ and
Fe3+ being bridged by O in the precursor, the above process
was possibly because of the fast nucleation. The prepared
Ni3FeAlx-LDHs exhibited high activity and favourable kinetics.
The etching of Al3+ tailored the coordination environment of
Ni2+ as evidenced by the earlier transformation from Ni(OH)2

into NiOOH in the forward CV scan. The defect rich LDHs not
only improved the intrinsic activity but also increased the

electrochemical surface area of Ni3FeAlx-LDHs.
The exfoliation of LDH nanosheets into a monolayer (few
layers) serves as another approach to tailor the coordination
environment of the metal sites in LDHs. The strong electro-
static interaction between LDH nanosheets leads to ordered
stacking along the (001) direction;157,158 hence the majority of
active sites are inhibited by hydroxyl groups and intercalated
anions, resulting in a weakened exposure of active sites in
LDHs. Previous studies showed that low-coordinated metal
sites in disordered or amorphous structures can serve as the
Fig. 12 Modulation of the coordination environment of metal sites in LDH active sites for the OER;159–161 therefore, it is promising to
nanosheets for improving OER activity. (a) A schematic illustration of the further improve the OER activity of LDHs by increasing the
water-plasma-enabled exfoliation of CoFe-LDH nanosheets and the
proportion of low-coordinated active sites and manipulating
corresponding OER performance. Reproduced with permission.119 Copy-
right 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) Schematic
the electronic structure of the metallic sites.162 Hence, a large
illustration of selective defect engineering of NiFe-LDHs. Polarization curves of amount of work has focused on the modulation of the active
Zn2+ doped NiFe-LDHs and Al3+ doped NiFe-LDHs before and after alkaline sites via exfoliation/delamination of LDH nanosheets.163–165 Hu
etching. Reproduced with permission.155 Copyright 2018, Tsinghua University et al. prepared a single layer/few layers of LDHs through an
Press and Springer-Verlag GmbH Germany, part of Springer Nature.
anion exchange-exfoliation method. Firstly, Br intercalated CoCo-/
(c) A schematic illustration of the preparation of Ni3FeAlx–LDH nanosheets.
Reproduced with permission.156 Copyright 2017 Elsevier Ltd. (d) OER polariza-
NiCo-LDHs and Cl intercalated NiFe-LDHs were prepared.62 Later
tion curves of LDHs prior to and after exfoliation in 1 M KOH. Reproduced with on, the anion exchange was applied for the substitution of Br with
permission.62 Copyright 2014 Macmillan Publishers Limited. NO3 in CoCo-/NiCo-LDHs, and Cl with ClO4 in NiFe-LDHs. The
anion exchanged LDHs were then dispersed in degassed formamide
to be exfoliated into a single layer or few layers. Fig. 12d shows the
In addition to oxygen vacancies, introduction of metal exfoliation process of LDH nanosheets and the OER performance of
vacancies via alkaline etching could selectively create M2+ or different LDHs before and after exfoliation. Obviously, a significant
M3+ vacancies in LDH nanosheets. In a recent study, Sun et al. decrease in the overpotential can be observed after exfoliation.
proposed a strategy that uses doping and then etching to selectively The authors further prepared ultrathin CoMn-LDHs by a one
construct M2+ or M3+ defects into NiFe-LDH nanosheets. As shown pot co-precipitation method; the Co(IV) species in the ultrathin
in Fig. 12b, the authors deliberately introduced base-soluble Zn2+ and amorphous LDH layer contributed to the boosted OER
and Al3+ cations into NiFe-LDHs, in which the Zn2+ substituted Ni2+ activity, with a low overpotential of 324 mV at 10 mA cm 2,
in the nanosheets and the subsequent etching of Zn2+ created a small Tafel slope of 43 mV dec 1 and 2.8 times higher current
M2+ defects and left nearby unsaturated Fe3+ exposed. In contrast, density at an overpotential of 350 mV as compared with
doping Al3+ would substitute Fe3+ in the nanosheets and the benchmark IrO2.118 Jin et al. also exfoliated NiCo-LDHs with
subsequent etching of Al3+ created M3+ defects and left nearby formamide in a N2 atmosphere.166 The exfoliation procedure
unsaturated Ni2+ exposed.155 The results illustrated that the resulted in more metal sites with dangling bonds exposed and
doping with Zn2+ and Al3+ in NiFe-LDHs both had a negative electron-rich structures of active sites, which benefited the
effect on the OER activity of NiFe-LDHs. However, the enhanced adsorption of oxygenated intermediates, leading to the overall
OER activities of NiFe-LDHs were observed after the etching enhanced OER activity of LDH nanosheets.
process. Also shown in Fig. 12b, to reach the same current
density, the applied potentials on D-NiFeZn and D-NiFeAl-LDHs 4.3 Decoration of noble metal atoms into LDH nanosheets
were 80 and 48 mV lower, respectively, than those of pristine The single atomic dispersion of redox active elements in LDHs
NiFeZn and NiFeAl LDHs, with that of D-NiFeZn-LDHs even makes the nanosheet structure an ideal substrate for loading
surpassing that of pristine NiFe-LDHs. The electronic structure noble metal atoms that also exhibit atomic dispersion. On one
evolution for both Ni and Fe from an electron-equilibrium to hand, noble metal atoms can act as mediators to tailor the
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electronic structure of transition metal sites in LDHs to further electron microscope (AC-STEM) (Fig. 13c) showed clearly that
enhance the OER activity; on the other hand, the noble metal– single-atomically dispersed Ru existed on the surfaces of the
oxygen–metal motif in LDHs enables noble metal atoms to act CoFe-LDHs. The elaborated structural characterization by
as the active sites for the OER. EXAFS revealed that only the first-shell Ru–O bond and some
Zhang et al. first prepared Au decorated NiFe-LDHs by an weak Ru–O–M (M = Co or Fe) can be identified, while the Ru–Cl
electrodeposition method, and took advantage of single-atom bond, metallic Ru–Ru bond and Ru–O–Ru bond from clustered
Au decoration to facilitate the in situ generation of OER active ruthenium oxides cannot be identified, confirming the single-
NiFe oxyhydroxide from LDHs.167 The electronic interaction atom dispersion of Ru on the CoFe-LDHs (Fig. 13d). The
between Fe and the anchored Au (Fig. 13a) yielded a net Au-to- host–guest interaction between the CoFe-LDH substrate and
LDH charge redistribution, which facilitated the adsorption of monatomic Ru improved the intrinsic activity of Ru, and
OH and modified the adsorption energy of O* and OOH* facilitated the oxidation of Co and Fe, resulting in the high
intermediates on Fe sites, resulting in a low overpotential OER activity of the Ru/CoFe-LDHs with as low as 198 mV
required in the rate-limiting step. Ir species can be seen as overpotential needed to drive a current density of 10 mA cm 2
the benchmark for OER catalysts and have also been used to in alkaline medium. Furthermore, the interaction between Ru
decorate the surfaces of metal hydroxides as shown in Fig. 13b. and Co enhanced the stability of Ru against dissolution in a
Co and Ir precursors were mixed under vigorous stirring to high valence state compared to commercial RuO2 catalysts. It is
prepare 3D CoIr hierarchical structure samples by Song et al. in noted that the loading of single atomic noble metals onto LDHs
2018.168 The optimized CoIr with 9.7 wt% Ir content displayed should be performed under relatively mild conditions. For
an efficient OER performance with an overpotential of 373 mV instance, Au was loaded onto NiFe-LDHs by electrodeposition
to achieve a current density of 10 mA cm 2 in 1.0 M phosphate for only a short period of time, and Ru was loaded onto CoFe
buffer solution and an overpotential of 235 mV at a current LDHs by diluted KOH induced precipitation. In some other
density of 10 mA cm 2 in 1.0 M KOH, outperforming commer- cases, when chloroplatinic acid and borohydride solution were
cial IrO2 catalysts. The interaction between Ir and Co(OH)2 mixed to anchor Pt onto NiFe-LDHs, the fast formation of Pt
facilitates the oxidation of Co(OH)2 to CoOOH and at the same metal would induce quick nucleation and growth into nano-
time maintains the unsaturated coordination of Co atoms. particles as reported by Kundu170 as shown in Fig. 13e.
Other than electronic structure modulation, noble metal A study by Liang and Liu provided additional guidance from
atoms can also serve as active sites in LDHs. Li et al. prepared the computational perspective on the bonding sites to immobilize
Ru anchored CoFe-LDHs via a mechanical stirring procedure.169 noble metal atoms.171 A model consisting of Pt and NiFe-LDHs, as
The spherical aberration corrected scanning transmission shown in Fig. 13f, was constructed to elucidate the trend of the Pt
Fig. 13 Decoration of noble metal atoms into LDH nanosheets for improving OER activity. (a) Differential charge densities of NiFe-LDHs with and
without Au atoms, while one O atom adsorbed onto the Fe site. The iso-surface value is 0.004 e Å 3. Yellow and blue contours represent electron
accumulation and depletion, respectively. Reproduced with permission.167 Copyright 2018, The American Chemical Society. (b) The mechanistic diagram
of the OER on the CoIr-0.2 sample surface and the transformation of the a-Co(OH)2 into b-CoOOH phase. Reproduced with permission.168 Copyright
2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) The AC-STEM image of Ru/CoFe-LDH nanosheets shows the monoatomic ruthenium
dispersed on the surfaces of the LDHs (some of the isolated Ru atoms are marked with red circles). Scale bar, 2 nm. Reproduced with permission.165
Copyright 2018, Springer Nature. (d) Model-based fittings of Ru EXAFS for Ru/CoFe-LDHs and simulated EXAFS spectra from Ru–O and Ru–O–M
(M = Co or Fe) bonds (the inset shows the magnified local structure of Ru/CoFe-LDHs), showing the exclusive existence of Ru–O–M bonds in the
Ru/CoFe-LDH sample. Reproduced with permission.169 Copyright 2019, The Springer Nature. (e) Polarization curves showing the OER on NiFe LDH
crystalline sheets, Pt NP tethered NiFe LDH crystalline sheets, Pt NP tethered co-precipitated NiFe LDHs and IrO2 modified CC interfaces. Reproduced
with permission.170 Copyright 2017, Elsevier Ltd. (f) Atomic structure of the Pt atom bonding to the ferric site in NiFe-LDHs. Reproduced with
permission.171 Copyright 2018, the authors.
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OER activity. The effectiveness of the proposed strategies

towards tailoring active sites for improving the OER activity
of LDHs is compared and highlighted in Fig. 14, where it can be
seen that the noble metal anchoring yields the best results.
4.4 Host–guest interaction in LDHs

The host–guest interaction in LDHs172–174 serves as a significant
characteristic and can be used to modulate the electronic structure
of LDHs. By using an inert atmosphere (normally N2) and a
precisely controlled synthetic environment (e.g., in boiled water),

the carbonate in the LDH interlayers can be substituted with other
Fig. 14 Summary of the representative studies on tailoring active sites on anions, although the carbonate intercalated LDHs are thermo-
NiFe-LDHs for improving OER activity.
dynamically more favourable. Thus, it provides rich opportunities
to study the effect of host–guest interaction between the layers and
atom being anchored on LDH nanosheets. The adsorption energy the intercalated anions in LDHs for the OER.
Ead of the Pt atom on the NiFe-LDH nanosheets (via the Fe3+–O(H)– Based on the different radii of the intercalated anions, a
Pt bonding) was 2.87 eV, which was stronger than that of the Pt common host–guest interaction in LDHs for the OER was
atom adsorbed onto Ni(OH)2 nanosheets (via the Ni2+–O(H)–Pt studied and the relationship between basal spacing and OER activity
bonding, 2.08 eV). The theoretical calculation revealed that Pt was revealed. Xu and Hao prepared NO3 and CO32 intercalated
tended to bond with Fe3+; therefore, the interaction between Fe3+ NiFe-LDHs and compared the OER activity differences. They
and Pt was responsible for the site-specific loading and enhanced showed that the larger the basal spacing of the NiFe-LDHs, the
electrocatalytic activity of Pt–NiFe-LDHs. lower the charge transferring resistance (Rct) at the corresponding
The representative studies focusing on tailoring active sites electrode/electrolyte interface, and the more the favourable OER
on NiFe-LDHs for improving OER performance are summarized kinetics.175 Later, Guan et al. intercalated formamide molecules into
in Fig. 14, in terms of Tafel slope and overpotential needed to the interlayers of NiFe-LDHs by ultrasonic irradiation,176 which
drive the OER at a current density of 10 mA cm 2. Starting from increased the basal spacing of the NiFe-LDHs from 7.8 Å to 9.5 Å.
pristine NiFe-LDHs, the strategies include cation doping, exfo- As a result, the overpotential for the OER to reach 10 mA cm 2
liation/vacancy engineering and noble metal anchoring; all of current density reduced from 256 mV to 210 mV. Jin et al. proposed
them have successfully modulated the electronic structure of dodecyl sulfate (DS ) intercalated NiFe-LDHs which could protect
LDHs towards electron-rich and thus enhanced the adsorption the LDHs from carbonate attacking to some extent (Fig. 15a).177
of OER intermediates onto the active sites, leading to boosted The DS -intercalated NiFe-LDHs with 2.39 nm interlayer spacing
Fig. 15 Effect of host–guest interaction between the LDH nanosheets and intercalated anions on OER activity. (a) Schematic description of the synthetic
procedures and anion exchange route with structural illustrations of NiFe-LDH products containing carbonate, chloride, sulfate, and dodecyl sulfate
anions in the interlayer gallery, which eventually convert to carbonate-intercalated LDHs. Reproduced with permission.177 Copyright 2018, The American
Chemical Society. (b) Overpotential (Z) of the OER on NiFe-LDHs with different interlayer anions at 1 mA cm 2 in virtually carbonate-free electrolyte as a
function of anion basicity. Reproduced with permission.179 Copyright 2016, The Royal Society of Chemistry. (c) Schematics of NiFe-LDHs intercalated
with different redox active anions. (d) Relationship between the OER onset potential measured at 1 mA cm 2 on the as-prepared NiFe-LDHs and the
corresponding standard redox potential of the intercalated anions. Reproduced with permission.180 Copyright 2018, Springer.
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(significantly larger than that of CO32 –NiFe-LDHs, 0.79 nm) 4.5 Compositing LDHs with carbon nanomaterials for the OER
exhibited 41 mV lower overpotential at 10 mA cm 2 than that Besides the intrinsic activity modulation of LDHs, integrating
of CO32 –NiFe-LDHs, which can be attributed to the increased LDHs with nanostructured carbon materials (graphene oxide,
electrochemical surface area. Komarneni et al. intercalated dicar- carbon nanotubes, carbon quantum dots) can also benefit the
boxylic acids, adipic acid and succinic acid into the interlayer OER performance of the hybrid catalysts by exposing more
spaces of NiFe-LDHs and studied the effect of basal spacing on active sites and facilitating electron transfer, which are indispen-
the OER activity.178 Their findings suggested that the pillaring of sable for eletrocatalysts. Dai et al. used mildly oxidized multiwalled
NiFe-LDHs with large organic anions was a promising method to CNTs as the substrate for the growth of NiFe-LDHs; the electro-
create LDH-type high-performance catalysts for the OER in a
static force between negatively charged functional groups on the

pH-near-neutral electrolyte. The enlarged basal spacing in the CNTs can adsorb positively-charged metal cation precursors
above studies benefited the OER performance of the LDHs by
(Fig. 16a).104 Then the composites prepared by solvothermal

providing more space for mass diffusion and exposing more treatment exhibited outstanding OER performance due to more
inner active sites for oxygen evolution. This conclusion agrees exposed active sites and the faster electron transfer (Fig. 16b).
well with the studies on LDH exfoliation, as the infinite increase Sun et al. reported the in situ growth of NiCoFe-LDHs on
of the basal spacing of LDHs would mean a full exfoliation of nitrogen-doped graphene oxide (GO), also assisted by electro-
LDH nanosheets. However, these studies only placed emphasis static force; array-like LDHs on graphene oxide composites,
on the mass transfer during oxygen evolution, and the effect of with highly open channels for electrolyte penetration and gas
host–guest interaction on the intrinsic OER activity of NiFe-LDHs evolution, were prepared and they showed excellent OER
was less well understood. In 2016, Hunter et al. introduced performance.181 Yang et al. fabricated NiFe-LDH/rGO compo-
various anions into the interlayers of NiFe-LDHs via the ion- sites as shown in Fig. 16c and d, and by virtue of the high
exchange method and studied the relationship between the electron conductivity of rGO, the overall OER performance of
intercalated anions and the corresponding OER activity of the the composites was improved, achieving an onset potential as
NiFe-LDHs (Fig. 15b).179 First of all, the authors indeed found a low as 1.425 V (vs. RHE) as shown in Fig. 16e.182
linear correlation of the measured basal spacing with anionic
radius, confirming the successful intercalation into the NiFe-
LDHs. However, different from the positive relationship between 5. Long-term stability of LDHs for the
the enlarged basal spacing and enhanced OER activity, the
authors discovered a strong correlation between the OER activity
OER
and the pKa values of the conjugated acids of the interlayer Although significant efforts have been made in the fields of active
(anions’ Brønsted or Lewis basicity), e.g., the larger the pKa, the site identification, OER mechanistic study and efficient catalyst
higher the OER activity of the corresponding NiFe-LDHs. preparation, the bottlenecks hindering the application of LDHs for
Later on, Sun and Zhou correlated the intercalated anions industrial scale water splitting are the phase transformation183,184
and the OER performance of NiFe-LDHs from a different
viewpoint.180 In consideration of the facts that the OER
depends highly on the redox activity of metal sites on LDHs,
and that the redox activity of metal sites can be modulated via
electronic effects between intercalated anions and metal sites
on the nanosheets, the authors intercalated sixteen species of
anions with distinct redox activities (SO32 , SO42 , S2O82 ,
HPO32 , Cl , NO3 , CO32 , C2O42 , PO43 , ClO4 ) into the
interlayers of the NiFe-LDHs, separately (Fig. 15c). The intercalated
anions with a strong reducing ability can donate electrons to metal
sites on the LDH nanosheets, while anions with an oxidizing ability
would withdraw electrons from metal sites on the LDH nanosheets
via electronic effects. The OER activity of the NiFe-LDHs was plotted
as a function of the standard redox potential of the intercalated
anions, as shown in Fig. 15d. It shows that the lower the standard
Fig. 16 Compositing LDHs with carbon nanomaterials for enhancing OER
redox potential (i.e., the stronger reducing ability), the higher the
activity. (a) Schematic showing the hybrid architecture and LDHs’ crystal
OER activity of the NiFe-LDHs. The enhanced OER activity can be structure. (b) IR-corrected polarization curves of the NiFe-LDH/CNT
attributed to the high electron-density of metal sites in the laminate, hybrid and Ir/C catalyst on a glassy carbon electrode in 0.1 and 1 M
which can facilitate the de-protonation and adsorption of oxyge- KOH. Reproduced with permission.104 Copyright 2013, The American
nated intermediates on the active sites. These two studies provided Chemical Society. (c) Schematic showing of compositing NiFe-LDHs with
GO. (d) Morphology of the LDH/GO hybrid; the arrows point to LDH
theoretical insights, from a ‘‘chemical perspective’’, into design of
nanosheets. The scale bar is 200 nm. (e) The onset potential (Eonset) and
efficient OER catalysts based on LDHs, showing that the host–guest the potential required to reach 10 mA cm 2 (Ej = 10 mA cm 2) of the OER
interaction can serve as a new dimension to tailor the deprotonation catalysed by the catalysts employed. Reproduced with permission.182
step of the OER on the NiFe-LDHs. Copyright 2014, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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and dissolution184 of LDHs at high working potentials. The decay structural evolution as revealed by X-ray diffraction. The (003)
and dissolution mechanisms have been studied by several groups reflection peak shifted to higher values due to the decrease in
and the progress achieved can be helpful in designing stable OER the basal spacing caused by restructuring of the material or
catalysts based on LDHs and overcoming the intrinsic weakness. replacement of the NO3 with CO32 ; however, the diffraction
Liu et al. studied the dissolution mechanism of LDHs during peaks at 2y = 11.28 and 22.481 disappeared and new peaks
oxygen evolution by both operando electrochemical and isotope- emerged, corresponding to b-Ni(OH)2 isomorphous with
labelling characterization studies,185 finding that the interlayer brucite. Further revealed by TEM, minor non-homogeneously
OH in bulk NiFe-LDHs was involved in the oxygen evolution distributed crystalline domains of a-FeOOH were also observed.
process and the sluggish diffusion of proton acceptors (e.g., Thus, how to maintain or protect the structure of LDHs against
OH ) into the NiFe-LDH interlayers during the OER caused the high temperatures and high concentrations of electrolyte is a
dissolution of the NiFe-LDHs, resulting in a decrease in OER matter of great urgency.
activity with time. As shown in Fig. 17a, in a high concentration Aiming to solve the above stability issue of NiFe-LDHs for
of alkaline medium, the fast penetration of OH from electro- the OER, Schuhmann et al. prepared NiFe-LDH/pBO (poly-
lyte would compensate for the consumption of interlayer OH , benzoxazine) nanocomposites via a calcination approach (resulting
leading to a less significant decrease of local pH; however, in in NiFe/C).187 As shown in Fig. 17d, the XRD pattern of NiFe/C
neutral electrolyte, the large size of HPO42 ions (as an example) before potential cycling (BC) showed four major reflections indexed
would make it hard for them to diffuse into the NiFe-LDH inter- to the NiFe2O4 and NiO. However, the NiFe-LDHs recovered the
layers, resulting in a significantly decreased local pH (from basic to layered structure with OH as the interlayer anion with typical (003),
acidic) and the corresponding dissolution of the NiFe-LDHs. (006), and (012) reflections, respectively, which is due to the memory
Andronescu and Schuhmann evaluated the chemical and effect of NiFe-LDHs. The carbon matrix derived from pBO served as
structural stability of NiFe-LDHs under conditions akin to a stabilizer to NiFe-LDHs for the OER against high temperature
practical electrolysis and tracked the decay of the OER activity (60 1C), high working current density (200 mA cm 2) and a
of LDHs under working conditions.186 As shown in Fig. 17b, no saturated KOH (5 M) conducting environment; nevertheless,
significant electrochemical performance changes were detected further consideration is still needed to see if carbon materials
for the NiFe-LDHs immersed in 1.0 M KOH at 25 1C for 60 h. would be stable in the high oxidation potential range.
After working at 25 1C for 60 h, only an additional 30 mV From the above work we may draw the conclusion that
overpotential was required to achieve 10 mA cm 2 current the fast exchange of interlayer OH with electrolyte and the
density compared to pristine NiFe-LDHs. However, once the protection of NiFe-LDHs using additional matrices or substrates
NiFe-LDH electrode was immersed in 7.5 M KOH at 80 1C and from phase or structural transformation are the two key factors
worked for 60 h, around 90 mV higher overpotential was in solving the stability issue of the LDHs in applying them as
required to deliver the same current density. Then the XRD catalysts for the OER. These two requirements can naturally
patterns were collected to trace the OER activity decay of the guide us to combine another merit in designing efficient LDH-
NiFe-LDHs. Also shown in Fig. 17c, NiFe-LDHs that worked in based electrodes for the OER, the nanoarray electrode structure;
1 M KOH for 60 h at ambient temperature exhibited a small and more than that, the nanoarray offers a further advantage which
will be elaborated in the following section.
6. Superaerophobic nanoarrays of
LDHs for enabling a rapid current
increase during the OER
The OER involves tri-phase participation: electrode as the solid
phase, electrolyte as the liquid phase, and oxygen bubbles as
the gas phase. In a gas evolution reaction, the generated oxygen
gas bubbles tend to adhere onto the electrode surface until
Fig. 17 Structural evolution of LDHs for the OER. (a) A schematic illustration the buoyancy is large enough to overcome the adhesion force.
showing the NiFe-LDHs on the substrate with different accessibility to These strongly adhered bubbles will cover a large area of the
proton acceptors. Blue balls represent OH and yellow balls represent
electrode surface, the diffusion of the electrolyte through the
HPO42 . Reproduced with permission.185 Copyright 2019, Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim. (b) Linear sweep voltammograms at a scan
bubble film will be very difficult with an enlarged diffusion
rate of 5 mV s 1 and 1600 rpm. (c) X-ray diffractograms for NiFe-LDHs resistance, and consequently the OER will be inhibited, leading
(black), and NiFe-LDHs after immersion for 60 h in 1.0 M KOH at 25 1C (blue) to a slow current increase rate with a high overpotential. In
and 7.5 M KOH at 80 1C (red) (K = NiFe-LDHs, ’ = b-Ni(OH)2). Reproduced Sections 3 and 4, we discussed the identification and regulation
with permission.186 Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA,
of active sites on LDHs regarding charge transfer between active
Weinheim. (d) XRD patterns of the calcined NiFe SDS/pBO composite (NiFe/
C) before (BC) and after (AC) potential cycling in 0.1 M KOH, NiO (1) and
sites and adsorbents, while the mass transport onto the electrode
NiFe2O4 (*) are reference patterns. Reproduced with permission.187 was almost untouched as efforts from a new perspective are
Copyright 2017, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. required, e.g., how to accelerate gas release/detachment from the
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electrode surface? In this section, assembling LDHs into nano- where gSV, gSL, and gLV represent the solid/gas, solid/liquid, and
array electrodes with superwetting behaviours, to facilitate liquid/gas interface tension, respectively. a is the intrinsic
electrolyte (liquid) penetration and, at the same time, benefit contact angle (CA) of the bubble to the electrode surface.
oxygen bubble (gas) release, will be highlighted and thoroughly Based on this hypothesis, the Cassie–Baxter equation (eqn (2)
discussed. Then, the corresponding characterization and appli- and Fig. 18c)192 is introduced to investigate the influence of
cations of the LDH nanoarray electrodes with superwetting surface architectures, which is essential for achieving super-
properties for enhancing OER performance will be summarized. aerophobicity underwater.
6.1 Design of LDH based superaerophobic nanoarrays cos a* = r cos a (2)

For gas evolution reactions, a high-performance electrode surface cos a* = 1 + fs(cos a + 1) (3)
requires a strong affinity to liquid electrolyte while being capable
where a is the apparent CA, a* is the apparent CA on the rough

of repelling the gas phase. Therefore, a superaerophobic surface
solid surface, r is the surface roughness factor, and fs is the solid
with a high bubble contact angle (usually a 4 1501), accompanied
fraction of the contact area. According to the Cassie–Baxter
by a low bubble adhesion force, is an ideal candidate. For instance,
equation, a low solid fraction and a high surface roughness of
MoS2 nanosheet arrays188 and CoS2 microwire arrays189 reported
an electrode would be suitable for constructing a superaerophobic
in 2014 both showed superaerophobicity for hydrogen evolution
surface; thus, materials with oriented growth directions have been
(Fig. 18a). In the same year, a superaerophobic nanoarray of NiFe-
studied for preparing superaerophobic electrodes.
LDHs was demonstrated to be highly effective for oxygen evolution
and adopted for achieving the world-record performance towards 6.2 Construction of LDH nanoarrays
solar-to-hydrogen conversion190,191 (Fig. 18b). A common point
It is known that a suspension of LDH nanosheets can be directly
that can be observed from the above studies is that the nano-
introduced onto an electrode by the traditional dipping or spin-
structured electrodes had high surface roughness, which can
coating methods. However, these approaches usually led to the
cut three-phase contact lines (TPCL) at the bubble/electrode
aggregation of nanoparticles and stacking of nanosheets on the
interface into discontinuous dots and benefit the bubble release.
electrode surface, which in turn weakened the superaerophobicity
Afterwards, a series of studies concerning superaerophobic
of the electrode and limited its electrochemical performance
electrodes were reported.
towards the OER. At the same time, physical contact of the LDHs
Several factors for constructing designed superaerophobic
with the electrode substrate could not ensure a stable loading of
surfaces need to be clarified. Young’s equation was used to
the LDH catalyst materials on the substrate, as the detachment of
describe hydrophobicity under ideal conditions, by balancing
bubble films during the OER would cause a severe dragging force
the forces at the three-phase contact lines; thus a model
and peel off the catalyst layer consequently, resulting in the
(eqn (1)) is proposed for (super)aerophobicity analysis:
deterioration of the durability. Therefore, the accomplishment of
gSL = gSV + gLV cos a (1) LDH nanoarray electrodes can not only benefit efficient mass
Fig. 18 Concepts and models for designing a superaerophobic nanoarray as an enabling electrode for gas evolution reactions. (a) A schematic illustration
of a bubble on a superaerophobic electrode surface. Inset: b stands for bubble, l stands for liquid, and s stands for solid. Reproduced with permission.188
Copyright 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) NiFe-LDH nanoarrays prepared on nickel foam. The SEM image below shows a
porous electrode. Reproduced with permission.190 Copyright 2014, The Royal Society of Chemistry. A schematic illustration of (c) aerophobic and
(d) superaerophobic surfaces based on the nanoarray structure. Reproduced with permission.192 Copyright 2018, The American Chemical Society.
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transport but will also be suitable for maintaining electrode be used to prepare NiFe-LDHs via the hydrothermal in situ
integrity and stability. On the other hand, LDH nanoarrays can growth method.195
be grown directly on the surfaces of conducting substrates (e.g.,
ITO, carbon or metals) by an in situ growth approach. The key 6.3 Characterization of superaerophobic nanoarrays
strategies to build LDH nanoarrays are through interfacial reaction The typical surface bubble behaviour measurements include
engineering and avoiding self-nucleation in the bulk solution. To gas bubble contact angles, adhesion force, advancing/receding
prepare the nanoarrays by chemical bath deposition, the surfaces angles and contact angle hysteresis.196,197 These are commonly
of substrates should be well cleaned (e.g., acid washing on Ni foam used to characterise the superaerophobicity of an electrode.
or plasma treatment on ITO glass). Urea was used as a pH adjustor, Among all the reported approaches, the bubble attachment
which would release ammonia by hydrolysis and increase the pH behaviour (adhesion force) on an electrode and the contact
value slowly. The slowly increased OH concentration leads to angle of the bubble on the electrode can be obtained by using a
mild oversaturation and favours the interfacial precipitation of high-speed camera.

LDHs. The in situ growth of LDHs usually results in an oriented As shown in Fig. 20a, Yu et al. reported the study of super-
and rigid nanoplatelet array architecture, which allows for easy wetting behaviour between a bubble and an electrode.198 As can
access of the electrolyte onto the nanosheets and thus improves be clearly observed, a bubble is readily pinned on the surface of
the overall performance of LDH based electrodes. For instance, bare nickel foam (NF) and without shape evolution within the
Wei et al. reported the synthesis of NiMn-LDHs on CNTs modified time range studied, i.e., 69.3 to 207.9 ms; whereas a bubble on a
with functional groups (e.g., –OH, –COO) (Fig. 19a). The electro- superaerophobic electrode has a larger contact angle than that
negative –OH and –COO served as nucleation sites capable of on the NF and can bounce on and gets released more rapidly
anchoring Ni and Mn ions and guaranteed the in situ growth of from the electrode surface. The schematic illustration below
NiMn-LDHs.193 revealed that the generated bubbles adhered onto the surface of
Electrodeposition or interfacial etching can also be used for the bare NF and induced an isolated zone, in contrast to a
the construction of LDH nanoarrays with a high efficiency. The limited covered area induced by a bubble on a superaerophobic
electrodeposition method can shorten the preparation time for electrode. Pang et al. studied both the bubble and electrolyte
LDH nanoarrays to hundreds of seconds. Li et al. prepared Fe- droplet contact angle on bare NF and [email protected]
containing LDHs with different divalent metal ions by using the As shown in Fig. 20b, the NF exhibited both hydrophobicity and
electrosynthesis method (Fig. 19b). This was achieved by con- aerophobicity (CA 4 1201), while NiFe-LDH@Ni3N-NF showed
trolling the reduction reactions occurring on the working superhydrophilicity (01) and superaerophobicity (153.61). The
electrode, in which the resulting OH leads to the precipitation electrochemical data showed that the superhydrophilicity and
of MxFe1 x(OH)2.194 Furthermore, some recent reports have superaerophobicity of NiFe-LDH@Ni3N-NF can benefit the ion
shown that LDH nanoarrays can also be prepared without transport at the electrode/electrolyte interface as well as expose
using additional precursors; the metal foam itself can be used more active sites by accelerating bubble release. This work
as both a reactant and a substrate; for example, NiFe foam can highlighted the effectiveness of hierarchical structure in mod-
ulating the superwetting behaviour of the electrode and con-
tributing to its enhanced electrochemical performance.
The adhesion force measurement between bubbles and
electrode surfaces is another tool for studying the superwetting
behaviour of an electrode. The interaction force between the
gas bubbles and electrode interfaces can be assessed using a
high-sensitivity micro-electromechanical balance system. In
detail, a 2 mL gas bubble (the buoyancy can be roughly
neglected) was suspended on a metal ring in electrolyte, and
the force of this balance system was initially set to zero.
Subsequently, the electrode surfaces were brought into contact
with the gas bubble at a moving rate of 0.02 mms 1. The force
was increased gradually until it reached the maximum, and the
shape of the air bubble changed from spherical to elliptical.
Subsequently, when the electrode moved down further, the
Fig. 19 Preparation methods for LDH nanoarrays. (a) A schematic illus-
contact was reduced sharply to almost zero and the shape of
tration of the synthesis and morphology of NiMn-LDHs/CNTs. Step (I): the the air bubble changed back to spherical. The critical force to
surface modification of CNTs with functional groups (e.g., –OH, –CO, which the gas bubble was subjected can be regarded as the
–COO). Step (II): the grafting of NiMn-LDH nanosheets onto the CNTs by adhesive force between the electrode surface and the gas
an in situ growth method. Reproduced with permission.193 Copyright 2014
bubble. As shown in Fig. 20c, the bubble adhesion force on a
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) A schematic illustra-
tion of the electrodeposition route for preparing MFe-LDH (M = Co, Ni and
superaerophobic electrode was rather small, indicating that a
Li) nanoarrays. Reproduced with permission.194 Copyright 2015, The Royal superaerophobic electrode can benefit from bubble release and
Society of Chemistry. have a positive effect on the gas evolution reaction.200
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Fig. 20 Measurements of superaerophobic nanoarrays. (a) Digital images of hydrogen bubbles on blank nickel foam (NF) and Ni2P/NF, showing the
pinning and bouncing states of one bubble on the electrode. The schematic illustration below shows the adhesion behaviour of one H2 bubble on the
blank NF (left) and Ni2P/NF nanoarrays (right). The contact area is an ‘‘isolated zone’’ due to the bubble effect. Reproduced with permission.198 Copyright
2019, The American Chemical Society. (b) Static electrolyte droplet contact angles (blue) and air bubble contact angles under electrolyte (red) at the Ni
foam and NiFe LDH@Ni3N/NF. Reproduced with permission.199 Copyright 2020, The Royal Society of Chemistry. (c) Adhesive behaviour of a gas bubble
on a (Ni0.33Fe0.67)2P electrode; inset: the bubble contact angle (E1581 1.21) suggests a negligible interaction between the electrode and gas bubble.
Reproduced with permission.200 Copyright 2017, Wiley-VCH.
The advancing/receding contact angles (yA and yR) can be activity,204 in which the Ce doping increased the intrinsic activity
obtained by using a microbalance in a tensiometer,201 and of the nanocomposite and the hierarchical structure benefited
reflect the solid/gas wetting behaviour. Similar to the adhesion electrolyte contacting with edge sites on the LDHs. In addition,
force measurement device, the advancing/receding contact the hierarchical structure based on the interaction between the LDH
angles were used rather than the force between a bubble and nanosheets and carbon nanotubes exhibited superaerophobic
a solid surface. For aerophilic surfaces, their yR is o901. These properties, benefiting oxygen gas bubble release for enabling a
surfaces exhibited strong affinities, as indicated by the residual fast increase in the reaction rate (current) during the OER.
bubble in the pull-off experiments, whereas aerophobic surfaces The superaerophobic properties of LDH nanoarrays can be
were shown to have little affinity with bubbles, and their yR is 4901. further strengthened by using other materials. Xie et al. modified
NiFe-LDH nanoarrays with Cetyltrimethyl Ammonium Bromide
6.4 Application of superaerophobic nanoarrays of LDHs for (CTAB), on which the bubble adhesion force was as low as 1.03 mN,
the OER demonstrating an excellent superaerophobicity of the electrode. In
Due to the merits of superaerophobic nanoarrays for gas OER measurement, the NiFe-LDHs modified with CTAB illustrated
evolution reactions (OER, for example), LDH nanosheets were the smallest bubble released size, though their intrinsic activity
assembled on various substrates to prepare superaerophobic remained almost unchanged. Furthermore, metal oxide/hydroxide
electrodes for the OER. Metallic foams, carbon nanotubes, nanowires can also be used to construct superaerophobic OER
doped graphene oxides, carbon clothes and metal hydroxide electrodes. Sun et al. reported ultrathin NiFeCo-LDH nanosheets
nanowires that have high specific area, excellent electronic decorated on Co2(OH)2CO3 nanowires with merits that include a
conductivity and available anchoring sites for LDH nucleation highly exposed active area and an accelerated bubble release for
are commonly used as substrates for the preparation of super- oxygen evolution. Cu nanowires have also been used as substrates
aerophobic LDH nanoarrays. Xue et al. used a nonwoven for the preparation of LDH nanoarrays for the OER. The vertically
stainless-steel fabric (NWSSF) with varied interconnected pore aligned NiFe-LDH nanosheets provide open-channels for
channels as substrates to prepare NiFe-LDH nanoarrays.202 As effective gas release and OH penetration, resulting in high
reported in this work, LDHs grown on the NWSSF had the current densities of 10 and 100 mA cm 2 at overpotentials of
largest bubble contact angle compared with LDHs grown on NF 199 and 281 mV, respectively; which significantly surpass the
or ordinary SSF, further suggesting the lowest OER onset results obtained from pure NiFe-LDHs.205 Then researchers
potential and the fastest current density increase among the have tried to combine merits both in the site-tailoring and
three samples. Wu et al. decorated NiFe-LDHs on NiFe alloy via the construction of superaerophobic nanoarrays based on
an in situ method to improve the intrinsic activity for the LDHs together, to design an outstanding OER electrode. Cai
OER.203 The exposure of active sites could improve the interlayer et al. carried out a study using Fe2+ to substitute Ni2+ in LDH
electron and ion transfer in the FeNi-LDH/FeNi nanoarrays. This nanosheets, and simultaneously constructed NiFe2+Fe3+-LDH
in turn jointly contributed to the record low overpotential of 90 mV nanoarrays for the OER. The NiFe2+Fe3+-LDH arrays exhibited
for the OER onset and the smallest overpotential of 130 mV for the an impressive low OER overpotential of 195 mV at 10 mA cm 2,
OER at 10 mA cm 2 in alkaline electrolyte. A Ce-doped NiFe-LDH which is 54 mV lower than that on colloidal NiFe2+Fe3+-LDHs.
nanosheet/carbon nanotube hierarchical nanocomposite was This work combines both the advantages from the modulation
designed and prepared by Tang et al. for enhanced OER of intrinsic activity and the optimization of gas evolution
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behaviour, showing an outstanding performance of the OER on the ultrathin 2D single crystalline structure of the precursor of
the LDH arrays. Wang et al. further prepared LDH-based nanoar- CoFe-LDHs but showed different crystalline phases. The com-
rays coupled with MoS2, which exhibited remarkable superaer- parison between b2 and b4 confirmed the elimination of the
ophobicity for enhancing the OER efficiency; the intrinsic activity hydroxyl groups from the LDHs in the in situ topotactic process,
and fast bubble release of the composite jointly contribute to leading to the shrinkage of the lattice distance. With a slight
their excellent overall water splitting performance.206 oxidation in air, the surface of the metal alloy (CoFe alloy was
taken as an example) was converted to a Co/FeO interface,
6.5 Superaerophobic nanoarrays of LDH derivatives for the which exhibited an efficient OER catalytic activity, with only a
OER low overpotential of 250 mV required to reach a current density
A topotactic transition involves a structural change to a crystal- of 10 mA cm 2, as well as a small Tafel slope of 55 mV dec 1, as
line solid, which may include loss or gain of material; and the shown in Fig. 21c.
crystal lattice of the product phase shows one or more, crystal- In the meantime, some other similar procedures, including
lographically equivalent, orientational relationships with the sulfurization, phosphorisation, selenization and nitridation,
crystal lattice of the parent phase. have been carried out on LDHs to prepare highly efficient
The topotactic derivatives from LDH nanoarrays prepared OER catalysts, though these procedures are not exactly topo-
under mild conditions can potentially inherit the structural tactic conversions, because no hard evidence demonstrates that
and morphological characteristics of the LDHs,207,208 namely, the atomic arrangements of materials before and after reduction
the single atomic dispersion of high valence metal ions and procedures matched with their precursors. Nevertheless, a series of
nanosheet morphology. Besides, the degree of topotactic transition highly efficient OER catalysts have been developed by this means.
and controlled post-oxidation can largely decide and optimize the For instance, Du et al. prepared a hydroxide as a precursor and
electronic structure of metal sites in materials, providing excellent then converted the bimetallic hydroxide into bimetallic phosphide
opportunities for the design of efficient OER electrodes. The subsequently via a gas phase phosphorisation process.211 The high
assembly of topotactic derivatives as nanoarray electrodes for the temperature process did not significantly change the perpendi-
OER, involving catalytic electrode design at the materials level and cular nanoplate array structure. The as-prepared FeNiP nanoplate
architecture level, has also been studied widely. material exhibited a much higher OER activity than benchmark
The topotactic conversion from ultrathin metal hydroxides IrO2, and it required an overpotential B70 mV lower than that on
to metal was first studied by Kuang et al., where NiOH was NiFe-LDHs to reach a current density of 10 mA cm 2. Cao et al.
transformed into Ni metal nanosheets.209 Thereafter, the same prepared a free-standing electrocatalyst with a vertically oriented
conversion strategy was applied to convert LDHs to metal alloys.210 Fe-doped Ni3S2 nanosheet array grown on three-dimensional (3D)
The authors prepared single crystalline alloy nanosheets with Ni foam (Fe-Ni3S2/NF), which exhibited high activity and durability
highly tuneable metallic compositions (NiFe, CoFe, NiCo and for the OER.212 The nanoarray structure of the electrode can
NiCoFe) by topotactic reduction of LDHs as the precursors. The benefit the full exposure of the active sites to an electrolyte and
single-atomic dispersion of the minor metallic compositions the high accessibility of OH in the electrolyte to the electrode
(in that work, Fe) was confirmed by EXAFS as shown in Fig. 21a, surface. Furthermore, the discontinuous three-phase contact lines
in which only Co–Co and Co–Fe bonds but not Fe–Fe bonds (TPCL) can also lower the bubble adhesion force, leading to
were identified in CoFe alloys. The comparison between b1 with promoted OER performance on Fe–Ni3S2/NF; that is, a lower
b3 in Fig. 21b showed that the obtained CoFe alloy inherited overpotential (Z) is required for the OER to reach a given current
Fig. 21 Structure, morphology and electrochemical performance of CoFe alloy topotactically derived from CoFe-LDHs. (a) Normalized XANES spectra
of Co (left plots) and Fe (right plots) in CoFe alloy nanosheets, and the dispersion of Co and Fe atoms in the alloy (the illustration below). It should be
noted that the dashed line (Co foil reference) in the right plots is not the real spectrum but copied from the left plots, and is used only for the comparison
of different coordination states. (b) Electron diffraction patterns of a single layer region of CoFe-LDHs (b1) and CoFe alloy nanosheets (b2), and HRTEM
images of CoFe-LDH (b3) and CoFe alloy (b4) nanosheets; showing the lattice shrinkage on the basal plane of the nanosheets before and after in situ
reduction. (c) Voltammograms showing the OER onset potential and current density as functions of potential on five CoFe alloy nanosheets with different
oxidation degrees. Reproduced with permission.210 Copyright 2017, Springer.
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density in comparison with its counterparts. Specifically, the Z

values required for driving the OER to current densities at 10,
20, and 100 mA cm 2 on Fe 17.5%-Ni3S2/NF are 214, 222, and
249 mV, respectively, which are not only much smaller than the
corresponding Z values required on Ni3S2/NF (287, 306, and
363 mV) but also very much smaller than those of the benchmark
OER catalyst IrOx (347, 377, and 465 mV).
Hu et al. prepared bimetallic (FexNi1 x)2P nanoarrays as
OER catalysts in both alkaline and neutral electrolytes. The
synthetic process involved the growth of NiFe-LDHs on nickel

foam and a second-step of phosphorisation.213 The OER activity
was largely enhanced and could be attributed to both the Fe

doping and the phosphorisation process; which involved the
synergistic effect between Ni and Fe, as well as the hetero-
structure interface in the Fe–Ni phosphide derived core–shell
hybrids. The optimal composition yielded one of the highest
OER activities reported so far, with low overpotentials of
156 mV and 255 mV to drive current densities of 10 mA cm 2
and 500 mA cm 2, respectively. The performance also surpassed
those of precious catalysts (IrO2, RuO2) under alkaline conditions.
Wang et al. used NiFe-LDHs on nickel foam (NF) as the precursor
to prepare iron–nickel sulfide nanowalls on the NF. The edge-
exposed morphology of the iron–nickel sulfide nanowalls can
Fig. 22 LDHs and their derivatives as OER catalysts for seawater oxidation.
benefit the contact between electrolyte and electrodes for OH
(a) OER faradaic efficiency (see the left axis) and current density (see the right
penetration, presenting high OER activity with overpotentials of axis) achieved on NiFe LDHs supported on carbon, plotted as functions of
252 and 297 mV to achieve 100 and 500 mA cm 2, respectively; averaged measured potential during constant current potentiometric
which were much lower than those of control samples. A similar steps of 15 min each. The overpotential (Z) of approximately 480 mV,
morphology was observed in Ni- and Se-doped FeOOH, and the corresponding to the design criterion limit, is marked by a dotted vertical
line. Reproduced with permission.215 Copyright 2016, Wiley-VCH Verlag
synergy between Ni, Fe and Se contributed to greatly enhanced
GmbH & Co. KGaA, Weinheim. (b) LSV curves of Co-Fe LDHs/Ti and bare Ti
OER performance in terms of low overpotentials of 222, 261, and electrodes in seawater. Reproduced with permission.216 Copyright 2017,
279 mV at 10, 50, and 100 mA cm 2, which are 65, 73, and 85 mV Elsevier Ltd. (c) Schematic drawing of the fabrication process of a dual-
lower than those on FeOOH(Se)/NF without Ni. layer NiFe-LDH/NiSx-Ni foam (Ni3) anode for seawater splitting, including a
surface sulfurization step and an in situ electrodeposition of NiFe-LDHs.
(d) Durability tests (1000 h) recorded at a constant current density of
400 mA cm 2 of the seawater-splitting electrolyser using 1 M KOH + real
7. Feasibility of using LDHs as OER seawater at room temperature (R = 0.95 0.05 ohms), 1 M KOH + 1.5 M
catalysts for seawater splitting NaCl at room temperature (R = 0.8 0.05 ohms), and 6 M KOH electrolyte
at 80 1C (R = 0.55 0.05 ohms), respectively. Reproduced with
Industrial scale water electrolysis leads to a big concern about permission.217 Copyright 2019, the authors.
water supply since current electrolysis technology relies heavily
on pure water feeding. Considering the amount of seawater
that overweighs the amount of fresh water, electrocatalytic studied CoFe-LDHs as efficient anode catalysts for seawater
seawater splitting by electrolysis has a profound effect on the oxidation at near-neutral pH.216 As shown in Fig. 22b, the OER
development of hydrogen energy and economy.214 However, on the CoFe-LDHs required B530 mV overpotential to reach a
chloride ions exist in seawater as NaCl (B0.5 mol L 1), which benchmark current density of 10 mA cm 2, which was superior
brings selectivity (OER vs. chloride oxidation reaction, ClOR) to those on the majority of previously reported catalysts in
and electrode corrosion issues in the anodic reaction. neutral or near-neutral buffer solutions. It should be noted that
Strasser et al.215 employed NiFe-LDHs as anode catalysts in the 530 mV overpotential has exceeded the aforementioned
an alkaline seawater splitting configuration. Under alkaline 480 mV gap between the OER and ClOR, but the selectivity
conditions, ClOR gives hypochlorite with a standard potential towards the OER is still around 100%, possibly because of the
of 1.71 V (vs. RHE), which is 480 mV higher than that of OER. hydroxide structure of the LDHs that facilitates OH adsorption
Therefore, utilization of LDHs, highly active OER catalysts in for the OER instead of Cl adsorption for the ClOR. However, the
alkaline media, could avoid the competing chloride oxidation long-term stability study illustrated that the oxygen evolution
on the anode within the 480 mV overpotential gap. The faradaic current density was only maintained at around 86% of the
efficiency towards the OER with the molecular oxygen product original value after 8 hours during the chronoamperometry
was tested to be close to 100% under both fresh- and sea-water test, probably because of the instability of the LDHs when they
electrolyte conditions as shown in Fig. 22a. Chen and Yang also are working under near neutral conditions.
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The issue of Cl corrosion was well-addressed where sulfide Secondly, how to impartially compare the OER activity
was introduced besides the alkaline environment. Kuang et al. on LDHs? To compare the OER current density at a given
combined the merits of LDHs with superhydrophobic structure (over-)potential or to compare the (over-)potential required to
and a chloride repelling NiFe/NiSx–Ni foam anode structure drive the OER at a given current density? Which one is more
(referred to as Ni3 for brevity) for seawater splitting.217 Firstly, relevant to the fundamental study and/or applied research? In
the surface of the Ni foam was sulfurized with sulfur element in the literature, the current density of 10 mA cm 2 as a target has
toluene to prepare a NiSx layer, then an OER active NiFe hydroxide been used for a long time; however, this geometric activity can
was electrodeposited over it via the reduction of nitrate from a be influenced significantly by the catalyst loading, electrode
solution of Ni(NO3)2 and Fe(NO3)3 (Ni : Fe = 3 : 1), as shown in structure and electrochemical surface area, which in turn can lead
Fig. 22c. The NiSx evolved into a sulfate rich layer to protect the to confusion. The Tafel slope value can serve as an alternative to
anode from corrosion, while the LDH array served as a highly characterize the OER activity of LDHs, and the TOF, which takes
active OER catalyst. The seawater splitting performance was stable into account a number of parameters that include the current
for more than 1000 hours in alkaline seawater solution under density ( J ) at a given overpotential, the surface area of the electrode
conditions typically used in industry, requiring only 1.72 V (vs. (A), the Faraday constant (F), and the number of moles of metal on
RHE) to reach a current density of 400 mA cm 2 in 6 M KOH + the electrode (m), has received increasing attention.62 Although the
1.5 M NaCl at 80 1C as shown in Fig. 22d. In a real seawater TOF is not as direct as the overpotential value that is required to
electrolyser, continuous feeding of seawater leads to an increase in drive 10 mA cm 2 current density in comparing the OER activity, it
NaCl concentration until saturation. Therefore, chloride oxidation is more reliable and can be used for the comparison between
and corrosion issues becomes increasingly severe. In a very recent different types of catalysts/electrodes; therefore we strongly
report, seawater electrolysis in saturated NaCl was performed at recommend using the Tafel slope or TOF as a general index to
500 mA cm 2 for more than 100 h in 6 M NaOH when common- evaluate the OER activity of electrocatalysts. Furthermore, the
ion effects were introduced with an LDH derived phosphide as a characterization conditions, including the pH value, potential
bifunctional electrode,218 which led to stable triple production of scan rate in the voltammograms, selection of electrolyte, should
H2, O2 and NaCl. Therefore, after the selectivity and corrosion also be stated clearly or even unified.
issues mentioned above have been solved, we believe LDHs, and Thirdly, how to measure the electrochemical accessibility of
their derivatives, can be employed in alkaline electrolysers metal sites on LDHs? What would be a standard loading of
for seawater splitting in real applications after adopting appro- LDHs on electrodes? Traditionally, the electrochemical surface
priate engineering designs such as anti-corrosion electrolyte area (ECSA) calculated from capacitance has been widely used
storage systems, NaCl crystallization units, etc. to evaluate the electrochemical accessibility of electrocatalysts.
However, only catalyst materials with excellent electronic con-
ductivity are applicable for this method. The electron transport
8. Suggestions on the evaluation of is relatively sluggish due to the low conductivity of LDHs, which
OER performance makes using capacitance unsuitable for measuring the ECSA of
LDHs. It is worth mentioning that Boettcher proposed an
Despite the significant progress that has been made in recent years alternative approach, i.e., impedance spectroscopy method, to
in the synthesis and application of LDHs and their derivatives for measure the ECSA in spite of the low conductivity of LDHs.219
the OER, several critical issues still exist in the evaluation of OER Xu also reported several studies trying to come up with reliable
performance. Firstly, how to effectively determine the onset methods (surface redox reaction, double layer capacitance,
potential of the OER on LDHs? As observed in the OER polarisa- atomic force microscopy and BET method) capable of measuring
tion curves, the LDHs with two or more metals have redox the electrochemical accessibility.220,221 Furthermore, Simonov
potentials that often interfere or even overlap with the OER onset et al. studied the catalyst loading effect (from 0.004 mg cm 2 to
potentials. 0.40 mg cm 2) on the OER performance of NiFe-LDHs.222 The
Thus, it is difficult to distinguish the oxidation current that authors found that the high loading of catalysts did not always
arose from oxidation of low valent metal cations and that from correlate with a better performance, due to the aggregation of
the intrinsic OER. Some previous studies may unintendedly state catalysts on the electrode surface. If reliable activity comparisons
an extremely low onset potential (even close to 1.23 V vs. RHE) are to be achieved in this field, the standard measurement of ECSA
achieved; however, in fact, the so-called onset potential may be and loading of catalysts should be unified across the field.
due to the oxidation of Co2+ or Ni2+, which is noticeably different Finally, how to describe the surface chemistry of LDH
from the OER onset potential. Such great care is needed when derivatives? The latter include metal sulphides, selenides, and
quoting the onset potential of the OER. A practical suggestion is nitrides as electrocatalysts under OER working conditions.
to use the oxidation current increase in the back scan during the Although the topotactic derivatives of LDHs have already been
cyclic voltammogram measurements where no mixing oxidation intensively used as OER catalysts for water splitting, identifications
current would be produced, to confirm the OER onset potential. of the active sites, stable phases and interactions between the
Also, the starting point of the Tafel slope and the OER current outer shell and the inner core (specifically, electron transfer,
characterized by steady-state measurements are also considered lattice mismatch) of the derivatives under OER operational
as reliable methods. conditions are still very challenging. As pointed out by Jin,223
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metal chalcogenides, nitrides and phosphides were more likely to single site requires a minimum overpotential due to the scaling
be pre-catalysts rather than real functioning catalysts. The surface relationship as shown in Fig. 4. Therefore, a bold assumption
oxidation of metal sulphides/phosphides during the OER would be with the possibility of further enhancing the activity would be
inevitable, and it was the converted metal oxides/hydroxides that to break the scaling relationship during the OER. For example,
accounted for the OER activity, while the metal chalcogenides, Xiao et al. used calculations to prove that the active centre
nitrides and phosphides provided electron transfer channels. involving both Ni and Fe species in NiFe-LDHs showed superior
Hence, solid evidence is required before the recognition of metal OER activity over a single metal site. This indicates that the
sulphides, selenides, and nitrides as real OER active electro- overpotential required would be lower when the OER occurred
catalysts. Furthermore, a similar phenomenon may also be on multi-sites (stereoscopic configuration) involved at the
found in metal–organic-frameworks (MOFs) as OER active catalytic centre. Li et al. conducted a pioneering experimental
electrocatalysts. Although MOFs have shown excellent OER activity study, in which two-phase metal sulphide (LDH derivative)
and stability, the post-characterization studies have revealed that composites jointly contributed to a lower OER onset potential of
metal hydroxides were generated due to the ligand transformation 1.33 V (vs. RHE).224 This work, along with other LDH derivatives for
during the OER. The precise identification of the active phase the efficient OER, may serve as representatives proving that
during the OER is also crucial in designing efficient OER splitting the traditional four-step OER into more steps on multi-
electrocatalysts. sites can lower the energy barrier (i.e., overpotential required). By
combining various efforts on identification and tailoring of active
sites, including multi-active sites participating in the reaction,
9. Concluding remarks and there is promising potential to break the scaling relationship,
perspectives lower the reaction barriers and further improve the intrinsic
reactivity of LDHs and their derivatives for the OER. In addition,
2D layered double hydroxides (LDHs) have proven to be a new
combined with in situ characterization techniques, the well-
class of low-cost electrocatalysts for the OER of water splitting in
developed high-level computational chemistry approaches such
alkaline media, attributed to their unique structural characteristics
as molecular dynamics and density functional theory, together
including tuneable composition, single-atomic dispersion of high
with big data, artificial intelligence and machine learning, can also
valence metallic cations (two or even more species of high valent
be employed to design and screen new LDH based catalysts,
metallic cations can also be single atomically dispersed) and
achieving balance between the high intrinsic activities of multi-
exchangeable intercalated anions. The comprehensive studies
active sites and high stability under specific reaction conditions,
employing advanced experimental and theoretical techniques have
e.g., for large scale (sea)water splitting.
provided insights into the OER mechanisms, including identifi-
Secondly, how to maintain the chemical and mechanical
cation of active sites on LDHs at atomic and molecular levels. At
stability of LDHs at industry standards? This is equally important
the material level, enormous progress has been made in the
for the application of LDH-based catalysts in a water electrolyser.
compositional modulation, coordination environment tailoring,
From a chemical stability consideration, recent findings have
and topotactic conversion of LDHs to enhance their reactivity and
pointed out that anchoring noble metal can be helpful in main-
stability for the OER. At the electrode level, the combination of
taining the stability of transition metal cations in relatively low
nanoarray structures with LDHs has been performed to promote
valence states without significantly affecting the OER activity;165
mass transportation and gas product release from the electrode to
however, it would be even better if the stability of LDHs can be
meet the requirements of larger scale electrocatalytic water split-
maintained without using noble metal. In this regard, Markovic
ting for green hydrogen production.
pointed out that adding Fe3+ (0.1 mol L 1) into electrolyte can
To use LDHs and their derivatives as efficient OER catalysts
efficiently prevent the dissolution of active Fe3+ in transition
in an industrial scale water electrolyser, several other obstacles
metal (hydro)oxides.225 The Fe3+-containing electrolyte acted
or challenges cannot be overlooked, as shown in Fig. 23.
like Fe-buffer according to a dissolution–deposition dynamic
The first grand challenge is to break the scaling relationship
equilibrium theory. From a mechanical stability viewpoint, the
for improving the intrinsic reactivity of LDHs towards the OER.
in situ grown nanoarray electrode based on LDHs and their
Based on theoretical calculations, the OER occurring on a
derivatives is significantly superior over the corresponding
electrode prepared by the traditional spraying or dip-coating
method. The nanoarray electrode removes the binder and there
is a stronger interaction between the current collector and active
catalyst materials. The latter can protect the active materials
from falling off from the current collector, and the electro-
deposition method would be feasible for preparing large scale
nanoarray electrodes.
The third key challenge is to effectively embed LDHs onto
anion exchange membranes (AEMs), to prepare a stable nanoarray
Fig. 23 The conceptual sketch represents the perspectives of the future electrode-based membrane–electrode-assembly (MEA) for highly
development of LDHs for the OER. efficient large-scale electrochemical water splitting. Zhuang et al.
View Article Online
substrate, but the uniformity needs further confirmation when

the size of the electrode increases.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We acknowledge the helpful discussions with Prof. Hongjie Dai

(Stanford University), Dr. Weizheng Cai and Mr Junming Zhang
Fig. 24 Schematic illustration of the proposed ‘‘ideal’’ MEA (membrane– (Nanyang Technological University). This work was supported
electrode assembly) with both the anode and cathode having nanoarray by the National Natural Science Foundation of China (NSFC),
structures and being superaerophobic for efficient water splitting that the Royal Society and the Newton Fund through the Newton
includes the OER at the anode and the HER (hydrogen evolution reaction) Advanced Fellowship award (NAF\R1\191294), the UKRI/EPSRC
at the cathode.
(the PhD studentship to X. L. with Project Ref. 2120302 under
EP/R513180/1 and the PhD studentship to A. M. with Project
reported the combination of AEMs with Ni-Fe catalysts for pure Ref. 228419 under EP/S023909/1), the Program for Changjiang
water splitting,226 and Koshikawa et al. also reported the use of Scholars and Innovation Research Team in the University (No.
NiFe-LDHs as anodes on MEAs for water splitting.227 However, the IRT1205), the Fundamental Research Funds for the Central
MEA fabrication involved using carbon black as a diluent and Universities, the long-term subsidy mechanism from the Ministry
Nafion solution as the binder, which leads to additional resistance of Finance and the Ministry of Education of PRC, the start-up fund
in charge transport during the OER and overall water splitting. As from Beijing University of Chemical Technology (BUCTRC202025),
aforementioned, in situ decorating LDHs onto AEMs via electro- the fellowship of China Postdoctoral Science Foundation
static attractive force and nucleation can largely avoid the use of (2020M670107), and the Natural Science Foundation of Beijing,
binder and thus improve the mechanical stability of electrodes China (2214062).
compared with those prepared by simple spraying. However, the
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Layered double hydroxide-based electrocatalysts

for the oxygen evolution reaction: identification

50, 8790 and tailoring of active sites, and superaerophobic

Review Article Chem Soc Rev

Professor Xiaoming Sun joined the Professor Xue Duan, Academician