Research Article

Cite This: ACS Catal. 2018, 8, 11342−11351 pubs.acs.org/acscatalysis

Interfacial Interaction between FeOOH and Ni−Fe LDH to Modulate

the Local Electronic Structure for Enhanced OER Electrocatalysis
Jiande Chen,† Feng Zheng,‡ Shao-Jian Zhang,† Adrian Fisher,‡ Yao Zhou,*,† Zeyu Wang,∥ Yuyang Li,§
Bin-Bin Xu,§ Jun-Tao Li,*,† and Shi-Gang Sun†,§
†
College of Energy, Xiamen University, Xiamen 361005, China
‡
Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge CB30AS, United Kingdom
§
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
∥
Pen-tung Sah Institute of Micro-Nano Science and Technology, Xiamen University, Xiamen 361005, China
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*
S Supporting Information

ABSTRACT: Toward the pursuit of high-performance Ni2+/Co2+/Fe3+-

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relevant oxygen evolution reaction (OER) electrocatalysts, the modulation

of local electronic structure of the active metal sites provides the
fundamental motif, which could be achieved either through direct
modifications of local chemical environment or interfacial interaction with
a second metal substrate which possesses high electronegativity (typically
noble metal Au). Herein, we report that the local electronic structure of Ni−
Fe layered double hydroxide (LDH) could be favorably modulated through
strong interfacial interactions with FeOOH nanoparticles (NPs). The
biphasic and multiscale composites FeOOH/LDH demonstrated an
increasingly pronounced synergy effect for OER catalysis when the average
size of FeOOH NPs decreases from 18.0 to 2.0 nm. Particularly, the
composite with average size of FeOOH NPs of 2.0 nm exhibited an
overpotential of 174 mV at 10 mA cm−2 and a tafel slope of 27 mV dec−1 in
1.0 M KOH, outmatching all the noble and non-noble OER catalysts reported so far; it also operates smoothly in various
stability tests. A mechanistic study based on XANES and EXAFS analysis, d.c. voltammetry and large amplitude Fourier
Transformed a.c. voltammetry proved the presence of high-oxidation-state Fe(3+δ)+sites with relatively short Fe(3+δ)+−O bond
from the highly unsaturated ultrafine FeOOH NPs which could reform the local electronic structure and favorably manipulate
the electronic oxidation and thus electrocatalytic behaviors of the Ni2+ species in the Ni−Fe LDH, hence leading to the easy
formation, excellent OER activity, and extraordinary structural and catalytic stability. Our work puts an emphasis on the role of
the solid−solid interfacial chemistry between a Ni−Fe LDH and a non-noble-metal component in engineering the local
electronic structure of the active metal sites, which successfully pushed forward the catalytic activity of the well-studied Ni−Fe
LDH far beyond its current limit in OER catalysis and opened up an avenue for rational design of OER electrocatalysts.
KEYWORDS: FeOOH nanoparticles, Ni−Fe LDH, local electronic structure, interfacial interaction, OER electrocatalysis

1. INTRODUCTION compounds, are even more attractive. Among them, Ni−Fe

Water splitting which employs electricity converted from solar
energy represents a promising approach to clean hydrogen
energy.1−3 Its half reaction, oxygen evolution reaction (OER),
is the rate-determining step due to its sluggish kinetics.4,5 Over
the past decade, various nanostructured solid compounds of
Fe, Co, and Ni have been explored as the most promising OER
catalysts.6−9 Their oxyhydroxides, i.e., MOOH (M = Fe, Co,
Ni), are particularly interesting.10,11 MOOH nanocrystals with
one to three dimensions were synthesized and explored with
remarkable OER catalytic activity in the past three years;12−14
and mechanistic studies suggested that the oxidation of
divalent Co2+ or Ni2+ into CoOOH or NiOOH species
provided the genuine active sites for the OER process.11
Compared with those single-metal catalysts, the relevant
bimetal catalysts, specifically the Ni−Fe or Co−Fe solid
layered double hydroxides (LDH) represent the most
promising candidates. Ever since its intrinsically excellent
catalytic activity for OER was first identified in 2013,15
numerous efforts including the integration with conductive
carbonaceous materials,16 or structure engineering such as
exfoliation or chemical composition optimizations have been
attempted to further bring down its overpotential in OER
electrocatalysis.17,18 In spite of these enormous efforts,
however, so far the overpotential for a current density of 10
mA cm−2 in 1.0 M KOH for most OER catalysts remains
higher than 200 mV.19
Received: August 31, 2018
Revised: October 21, 2018
Published: October 23, 2018

© 2018 American Chemical Society 11342 DOI: 10.1021/acscatal.8b03489

ACS Catal. 2018, 8, 11342−11351
ACS Catalysis
To pursue high-performance OER electrocatalysts, the
modulation of the local electronic structure of Co2+ or Ni2+
provides the essential motif. Toward this end, direct
modifications of the local chemical compositions render an
intuitively effective strategy. Typically, the Fe3+ species, when
coexisting with Ni2+ or Co2+ in a bimetal catalysts, could
reallocate the electronic density and even rearrange their
coordination structure via partial charge transfer,20 which
appears to facilitate the oxidation of Ni2+ or Co2+ and enhance
their OER catalytic activity. It was also reported that only the
surface Fe species adsorbed at the edge/defect sites (that is,
not those in the bulk) of the Ni2+-based phase are effective for
promotion of the catalytic performance of Ni2+.21 Additionally,
the local electronic structure of Ni2+ in the Ni−Fe LDH could
also be favorably adjusted by replacing part of the Ni2+ sites
with divalently charged Fe2+ species.18
In parallel to the chemical composition modification,
interfacing the Ni2+- or Co2+-based catalysts with a second
phase with relatively strong electronegativity were also proved
supportive for OER catalysis. This strategy so far has been
witnessed with great success for the noble metal Au which
possess the highest electronegativity. Thin film or layers of
Co3O4,22 NiOOH,23 Ni(OH)2/Co(OH)224 or MnOx25 when
supported on an Au substrate demonstrated profoundly
enhanced OER activities. In such biphasic composites, there
exists a partial electron transfer from the Co2+ or Ni2+ species
across the solid−solid interface to the more-electronegative Au
substrate, which favors the generation of Ni3+/4+ or Co3+/4+
centers and thus supports the OER process. Solid−solid
interfaces at mesocale between the Ni2+- or Co2+-based
catalysts and non-noble metal compounds via a core−shell
configuration were also attempted, although with limited
improvement in the OER catalytic activity.26,27
Herein, for the first time we report that FeOOH
nanoparticles (NPs) could profoundly boost the OER catalytic
performance of the Ni−Fe LDH via strong interfacial
interaction. Specifically, FeOOH/LDH nanocomposites
where numerous FeOOH NPs with average size from 2.0 to
18.0 nm were stably anchored on the thin nanopetals of the
hierarchically structured Ni−Fe LDH flowers were synthesized
via either a one-pot (Scheme 1a) or a stepwise hydrothermal
method (Scheme 1b). More importantly, we demonstrated the
presence of high-oxidative-state Fe(3+δ)+ species in the FeOOH
NPs which interact with the Ni−Fe LDH and modulate the
local electronic structure of its Ni2+ species through the
formation of oxygen bridges such as Fe(3+δ)+−O−Ni2+ with
relatively short bond length (Scheme 1c). Such interfacial
interaction was found to promote the oxidation of Ni2+ in the
Ni−Fe LDH and reedit their electrochemical catalytic
behaviors favorably. The FeOOH/LDH composites exhibited
a strong catalytic synergy effect on OER electrocatalysis, and
this effect was found increasingly pronounced when the
FeOOH NPs decrease from 18.0 to 2.0 nm. Impressively, the
FeOOH2 nm/LDH with FeOOH of 2.0 nm displayed an
overpotential of 174 mV at 10 mA cm−2 in 1.0 M KOH,
representing the most active OER electrocatalysts so far as we
know.
2. EXPERIMENTAL SECTION
2.1. Chemicals and Materials. Nickel(II) chloride
hexahydrate (AR, ≥ 98%), iron(II) chloride tetrahydrate
(AR, ≥ 98%), urea (AR, ≥ 99%), ammonium fluoride (AR, ≥
96%) and KOH (AR, ≥ 85%) were from Sinopharm Chemical
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Scheme 1. (a) One-Pot Synthesis where (1) the
Intermediate LDH Flower Is Formed in the Early Stage, on
Which Later FeOOH NPs are Deposited to Form (2) the
FeOOH2 nm/LDH Composite; (b) The Stepwise Synthesis
where (3) the Preformed LDH is Used As a Support for
Preferential Deposition of FeOOH NPs with Various
Average Sizes to Give (4) the FeOOH/LDH; and (c)
Schematic Depiction of the Interfacial Interaction via the
Formation of Oxygen Bridges (e.g., Fe(3+δ)+−O−Ni2+) with
Relative Short Bond Length between the FeOOH NPs with
Ni−Fe LDH
Reagent Co., Ltd. Perfluorosulfonic acid-PTEE copolymer
(Nafion solution, 5 wt %) was from Alfa Aesar. Stainless steel
nanoparticles (SNPs, 316L, which consist of 62−72 wt % Fe,
16−18 wt % Cr, 10−14 wt % Ni and 2−3 wt % Mo) were
purchased from Naiou Nanotechnology Co., Ltd. (Shanghai,
China). Deionized water was collected through the Millipore
purified water system. All the reagents were used as-received
without further purification.
2.2. One-Pot Synthesis of FeOOH2 nm/LDH. NiCl2·
6H2O (119 mg), urea (600 mg) and NH4F (110 mg) were
well dissolved in 60.0 mL of deionized water. Toward the
mixture, the SNPs (100 mg) which were washed with
deionized water and ethanol and then dried in vacuum was
added. The suspension was sonicated and mechanically stirred
for 10 min, which then was hydrothermally treated at 120 °C
for 15 h in a Teflon-lined stainless steel autoclave (whose
volume was 80 mL, similarly thereafter). After cooling down to
room temperature, a magnet (2 × 2 × 2 cm3) was placed and
kept static in the mixture for 5 min. Afterward, those adsorbed
on the magnet were removed from the mixture; and those left
in the solution, after being separated through centrifugation,
was redispersed in water. The above operation was repeated
three times to give the FeOOH2 nm/LDH composite which
was dried in vacuum at 60 °C for 10 h.
2.3. Synthesis of the Intermediate Sample LDH-6h.
The operation and conditions for formation of LDH-6h was
the same as that of the FeOOH2 nm/LDH composite, except
that the hydrothermal reaction time was 6 h for the LDH-6h
whereas it was 15 h for the FeOOH2 nm/LDH composite.
DOI: 10.1021/acscatal.8b03489
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2.4. Synthesis of LDH-s. NiCl2·6H2O (119 mg), FeCl2·
4H2O (22 mg), urea (600 mg), and NH4F (110 mg) were well
dissolved in 60.0 mL of deionized water. The solution was then
heated at 120 °C for 15 h in a Teflon-lined stainless steel
autoclave. After cooling down to room temperature, the
product LDH-s were washed with water for three times and
dried at 60 °C for 10 h.
2.5. Stepwise Synthesis of FeOOHxnm/LDH. FeCl2·
4H2O (1.0−6.0 mg) and urea (20 mg) were dissolved in 60.0
mL deionized water, into which 50.0 mg of the aforementioned
LDH-s was dispersed by magnetic stirring for 10 min. The
mixture was heated at 120 °C for 6 h in a Teflon-lined stainless
steel autoclave. After cooling down to room temperature, the
products were washed with water for three times and dried at
60 °C for 10 h. Note that for synthesis of FeOOH18 nm/LDH
and FeOOH10 nm/LDH, a dosage of 6.0 mg and 3.0 mg FeCl2·
4H2O was applied in each synthesis, respectively, and other
parameters were kept the same.
2.6. Characterizations. The as-synthesized samples were
examined by powder X-ray diffraction (PXRD, Rigaku Ultima
IV, radiation source Cu Ka) at a 2θ range of 10° to 90° with
scan speed 5° min−1. The morphology was observed on field
emission scanning electron microscope (FESEM, Hitachi S-
4800 and Zeiss Supra 55), Transmission electron microscopy
(TEM, JEOL JEM-2100) and high-resolution TEM (HRTEM,
Tecnai F30). Raman spectrum (XploRA, HORIBA) was
obtained to understand the structure information. The X-ray
photoelectron spectroscopy (XPS, PHI 5000 VB III) was used
to explore the constitution of the samples and the binding
energies reported are referenced to C 1s at 284.5 eV. The X-ray
absorption near edge structure (XANES) and extended X-ray
absorption fine structure (EXAFS) were performed in the
transmission mode at the beamline (BL14W1) at the Shanghai
Synchrotron Radiation Facility (SSRF). X-ray Absorption
spectrum (XAS) data were calibrated, normalized, and
analyzed by Athena software. The reference spectra of Fe2O3
and NiO was used to estimate the Fe and Ni chemical state.
2.7. Electrochemical Measurements. For direct current
(d.c.) electrochemical measurements, a three-electrode setup
was employed, including a Hg/HgO electrode as the reference
electrode, a graphite electrode as the counter electrode, and a
glassy carbon disk electrode (GCE, 5 mm in diameter) as the
working electrode. The catalyst ink was prepared by dispersing
5 mg catalyst and 2 mg acetylene black powder in 1.0 mL
solution which consists of 0.50 mL deionized water, 0.47 mL
ethanol and 30 μL 5% Nafion solution by ultrasonication for
30 min. Then 10 μL of the ink was drop-casted on the polished
GCE and dried at room temperature overnight. Potentials were
referenced to a reversible hydrogen electrode (RHE): EvsRHE =
EvsHg/HgO + 0.098 + 0.059 × pH. The overpotential (η) was
calculated according to the following equation: η = EvsRHE
−1.23 V. All the samples were activated by repetitive cyclic
voltammetry (CV) scans at the potential range 1.0 V - 1.8 V vs
RHE. Linear sweep voltammetry (LSV) was recorded in an
O2-saturated 1.0 M KOH solution at a scan rate of 10 mV s−1.
All the data presented were corrected for 80% iR loss. The
steady state currents from the controlled-potential electrolysis
using the multipotential step technique were used to acquire
the Tafel slope of the FeOOH2 nm/LDH within the potential
range from 1.30 to 1.52 V (vs RHE). Note that the cell was
purified with O2 for 1 h before the measurement, and the time
required to reach a steady state was 10 min. The samples were
subjected to repetitive CV scans at a scan rate of 300 mV s−1
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and chronopotentiometry measurement for catalytic stability
test.
Faraday efficiency (FE) was estimated by gas chromatograph
in a modified two-compartment electrochemical cell, in which
the cap was clamped to the anode chamber with a seal. A piece
of Nafion membrane was used as the separator. Oxygen in the
air (21%) was collected used as a contrast signal (p1). The 1.0
M KOH solution was purged with He gas. Then a constant
current (0.1 A) was applied for water splitting prior to the GC
measurement. The He gas delivered into the anode chamber at
a rate of 20 mL min−1 and then vented into the GC to obtain
the signal of the as-generated O2 (p2). The O2 concentration
(c) was calculated from the GC peak areas (S) according to the
equation c = 21% × Sp2/Sp1. On this basis, the Faraday
efficiency is acquired from the equation FE = 4c × V × F/(Vm
× I × t) where V denotes the volume of the collected gas, Vm
the gas molar volume constant, F the Faraday’s constant, I the
applied constant current, and t the time.
Large amplitude Fourier Transformed (F.T) alternating
current (a.c.) voltammetric measurements were conducted via
a homemade potentiostat with a standard three electrode
configuration. A GCE (3 mm diameter) deposited with 4 μL of
the aforementioned catalyst ink and dried overnight was
adopted as the working electrode. A platinum electrode was
used as the counter electrode with a silver/silver chloride (Ag/
AgCl) provided the reference electrode. All a.c. voltammetric
measurements were conducted in 1.0 M fresh KOH solution
with scan rate = 13.04 mV s−1 and frequency = 5 Hz, providing
a sufficient kinetic sensitivity because of the slow rates of the
probed electron-transfer processes and enough a.c. current in
higher order harmonics.28 The amplitude ΔE = 0.1 V was
applied, so a sufficient level of nonlinearity is provided to allow
detection of higher order harmonics without significant ohmic
losses and broadening.29 Fourier transform technique was
adopted to convert the time domain raw data into the
frequency domain power spectrum. Then a series of current
data was generated through the usage of an inverse FT
algorithm as a function of time for the power spectrum. Note
that the raw data was not compensated for its iR loss.
3. RESULT AND DISCUSSION
3.1. One-Pot Synthesis of FeOOH2 nm/LDH Compo-
site. Ni−Fe LDH or MOOH (M = Fe, Co, or Ni)
nanocrystals with one to three dimensions have been
synthesized and exploited separately as oxygen evolution
reaction (OER) electrocatalysts over the past several years.
Nevertheless, the composite of these two so far was rarely
reported. In this work, as depicted in Scheme 1, we first
demonstrated one-pot synthesis of the biphasic and multiscale
composite FeOOH2 nm/LDH which has average size of 2.0 nm.
And inspired by the mechanistic study of such a one-pot
process, an efficient stepwise method was further established
leading to the formation of FeOOHxnm/LDH nanocomposites
with controllable average size of FeOOH NPs.
Shown in Scheme 1a, the one-pot synthesis of FeOOH2 nm/
LDH involved the usage of stainless steel nanoparticles (SNPs,
diameter 60 nm, Figure S1a of the Supporting Information, SI)
as a Fe source, which was hydrothermally treated with mixture
of NiCl2, urea and NH4F for 15 h. The as-obtained composites
assume a microflower-like morphology with numerous radially
arranged and slightly wrinkled Ni−Fe LDH nanosheets ca. 10
nm in thickness; their overall size range from 1.5 to 2.0 μm in
diameter (Figure 1a−c, Figure S2). EDS analysis (Figure S3a)
DOI: 10.1021/acscatal.8b03489
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Figure 1. (a, b) SEM, (c−f) TEM and (g) HRTEM images of the
FeOOH2 nm/LDH, inset in (g) is the FFT pattern of a FeOOH NP.
(h) Size distribution of FeOOH NPs.
and elemental mapping (Figure S4) validated the homoge-
neous distribution of Ni, Fe, O, C, and F within the sample,
suggesting the coexistence of CO32− and F−as the intercalating
anions in the LDH nanosheets (CO32−: F− = 4.4:1, Table S1).
Under higher TEM magnifications, numerous ultrafine
FeOOH NPs were spotted which are immobilized homoge-
neously on the LDH thin nanosheets with slightly higher TEM
image contrast (indicated by the red arrows in Figure 1e,f and
Figure S5b). Such ultrafine FeOOH NPs have an average size
of 2.0 nm. HRTEM observation revealed that their lattice
fringes are distinctively oriented from those of the LDH
nanosheets; and based on the relevant FFT patterns (inset in
Figure 1g), two interplanar spacings were identified as 0.20 and
0.44 nm, corresponding to (120) and (010) planes of the
FeOOH crystal, respectively (Figures 1g and S5c,d).
Accordingly, XRD pattern of such FeOOH2 nm/LDH was
shown in Figure 2a. Well-defined peaks at 11.3°, 22.7°, 33.5°,
34.4°, 38.7°, 46.0°, 60.0°, and 61.2° are assigned to the planes
of (003), (006), (101), (012), (015), (018), (110), and (113)
of the Ni−Fe LDH, respectively, confirming the formation of
LDH crystals for the sample. No signals of FeOOH NPs could
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Figure 2. (a) XRD patterns of the samples; XPS spectra of (b) Ni 2p,
(c) Fe 3p, (d) O 1s, and (e) Cr 2p of FeOOH2 nm/LDH. (f) Raman
spectra of the samples.
be identified in the XRD pattern, due to their small size
(average size 2.0 nm, Figures 1e,f and S5). The weak bands at
19.2° and 52.2° imply the presence of some Ni(OH)2
impurity. The peaks at 43.6°, 44.6°, 50.8°, and 64.9° originate
from the residual SNPs (Figure S1a).
The chemical compositions of such FeOOH2 nm/LDH were
further verified by XPS analyses. The full spectrum of XPS
analyses reaffirms the presence of Ni, Fe, O, F, and C elements
(Figure S9a). The deconvolution of Ni 2p3/2 spectrum yields
two components, one at 853.1 eV with a satellite at 858.6 eV
for metallic Ni in the residual SNPs, and the other at 856.3 eV
with a satellite peak at 861.8 eV which is ascribed to Ni2+ in the
Ni−Fe LDH (Figure 2b).30 As the Fe 2p3/2 spectrum overlaps
with Ni LMM Auger peaks (Figure S9b), the Fe 3p spectrum
was acquired centered at ca. 56.4 eV which belongs to
trivalently charged Fe3+ species (Figure 2c).31,32 The O 1s
spectrum consists of three peaks occurring at 529.9 eV for Fe−
O in FeOOH, 531.4 and 532.1 eV for oxygen species in M−
OH (M = Ni, Fe) and CO32− in the Ni−Fe LDH as the
intercalating anion, respectively (Figure 2d). The Cr 2p
spectrum shows little dissolution of Cr element from the
precursor SNPs into the sample (Figure 2e).
The formation of such LDH-supported FeOOH NPs was
further verified by Raman spectroscopy. In Figure 2f, the two
bands centered at ca. 446 and 530 cm−1 are associated with
Ni−O vibration in NiO6 octahedron in the Ni−Fe LDH.33
Importantly, FeOOH2 nm/LDH composite displays two addi-
tional characteristic bands at ca. 571 and 660 cm−1, confirming
the formation of FeOOH NPs.34 Note that the band of
FeOOH at 571 cm−1 overlaps partially with the Ni−O band of
the Ni−Fe LDH at 530 cm−1, which together appear as a much
broader band than that of the pure LDH.35
3.2. Stepwise Synthesis of FeOOHxnm/LDH (x = 10, 18
nm) Composites. A mechanistic study on the formation of
DOI: 10.1021/acscatal.8b03489
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the above biphasic multiscale Fe2 nm/LDH nanocomposite was

further conducted, which led to a stepwise synthesis of the
FeOOHxnm/LDH with controllable average size of FeOOH
NPs. To study the formation mechanism of the FeOOH2 nm/
LDH (which was sampled at 15 h), the intermediate was
sampled at the reaction time of 6 h (named LDH-6h), which
are only Ni−Fe LDH flowers (that is, no FeOOH NPs) as
revealed by SEM (Figure S6) and XRD analysis (Figure 2a),
HRTEM observation (Figure S7a,b) and its Raman spectrum
(Figure 2f). Such a result suggests that, in the one-pot
synthesis of FeOOH2 nm/LDH, the Ni−Fe LDH flowers
occurred in the early stage, subsequently the ultrafine
FeOOH NPs were formed on the LDH nanopetals via an
on-site manner (Scheme 1a). Consistently, the molar fraction
of Fe in FeOOH2 nm/LDH is almost two times that in LDH-6h
(Table S1).
In the early stage of such a one-pot synthesis, with a slightly
alkaline pH value from urea hydrolysis at 120 °C, Fe3+ cations
would be slowly released from the corrosion of SNPs (Figure
S5a). The occurrence of the intermediate LDH-6h suggests
that Fe3+ cations released in the early stage would all
precipitate as Ni−Fe LDH (i.e., no formation of FeOOH)
before all the Ni2+ in the solution are consumed. Such a
speculation could be supported by the formation of LDH-s, a
second control sample prepared by replacing solid SNPs with
FeCl2 to react with Ni2+. TEM observation (Figure S7c,d),
XRD analysis (Figure 2a), and Raman spectrum (Figure 2f)
confirmed that only large LDH flowers with similar Ni:Fe
atomic ratio as the FeOOH2 nm/LDH were formed in this Figure 3. TEM images and size distributions of FeOOH NPs of
LDH-s. And the LDH flowers in this sample have much larger (a,b,c,e) FeOOH18 nm/LDH and (d,f) FeOOH10 nm/LDH composites
and thicker petals due to its much higher instantaneous Fe3+ synthesized through the stepwise method. Inset in (c) is a HRTEM
image of a FeOOH NP.
concentration.
Evolving into the later stage, with all Ni2+ precursor
precipitated as Ni−Fe LDH flowers, we speculate that Fe3+ interfacial interactions between the FeOOH NPs and the
cations continuously released from the etched SNPs are Ni−Fe LDH nanosheets. More importantly, the occurrence of
expected to deposit preferentially on the LDH flower as such strong interfacial interactions was also found capable of
FeOOH NPs via heterogeneous nucleation (Scheme 1a). Note reediting local electronic structure and also OER catalytic
that the low instantaneous Fe3+ concentration well controls the property of the Ni−Fe LDH, as further addressed in following
precipitation kinetics and accounts for the ultrafine size of sections.
FeOOH (i.e., 2 nm). With enormous surface polar groups or 3.3. Size-Dependent Synergy Effect on OER Electro-
defects, the Ni−Fe LDH nanosheets would induce or favor the catalysis by FeOOHxnm/LDH Composite. The as-prepared
formation of FeOOH, e.g., through hydrogen bonding or electrocatalysts including LDH-6h, LDH-s, FeOOH2 nm/LDH,
oxygen bridge bonding.21 To verify such a hypothesis, depicted FeOOH10 nm/LDH, and FeOOH18 nm/LDH were evaluated for
in Scheme 1b, the aforementioned LDH-s (which are oxygen evolution reaction (OER) in 1.0 M KOH. After
preformed pure Ni−Fe LDH flowers, Figure S7c,d) was activated by repeated cyclic voltammogram scans (CVs, Figure
subjected to a second round of hydrothermal treatment with S10a), the polarization curves were obtained at 10 mV s−1 to
small doses of FeCl2 and urea. Interestingly, numerous reduce the capacitive current, from which the overpotential (η)
FeOOH NPs appeared on the Ni−Fe LDH flowers (Figures at 10 mA cm−2, an important criterion to evaluate the OER
3 and S8), and their average sizes could be controlled by activity, were extracted. Shown in Figure 4a and Table S1, the
modulating the relevant deposition kinetics (e.g., usage of FeOOH2 nm/LDH demonstrated η of 174 mV, compared to
SNPs as iron source, manipulation of FeCl2 concentration). 203 mV by FeOOH10 nm/LDH, 216 mV by FeOOH18 nm/
Herein two more samples were prepared via such a stepwise LDH, 266 mV by LDH-6h, and 267 mV by LDH-s, all of
method, FeOOH18 nm/LDH and FeOOH10 nm/LDH, with which are much lower than those of the SNPs, or the carbon
average size of FeOOH NPs as 18.0 and 10.0 nm, respectively. black or Ni(OH)2 nanocrystals (Figure S10b). The caculation
XRD analysis of FeOOH18 nm/LDH displays two weak peaks at of the Faraday efficiency revealed an value up to 98.5% for the
16.8° and 35.1°, corresponding to (200) and (211) planes of FeOOH2 nm/LDH composite, confirming that the current was
FeOOH NPs (Figure 2a). attributed to water splitting (Figure S15). The relevant Tafel
On this basis, we demonstrate that FeOOHxnm/LDH plots reveal a Tafel slope as small as 27 mV dec−1 for
composites with the average size of FeOOH NPs controllable FeOOH2 nm/LDH, 46 mV dec−1 for FeOOH18 nm/LDH, 71
from 2.0 to 18.0 nm could be straightforwardly synthesized mV dec−1 for the LDH-6h and 73 mV dec−1 for the LDH-s,
through either a one-pot or a stepwise method. The robust respectively. The Tafel slope for the FeOOH2 nm/LDH was
formation of such FeOOHxnm/LDH composites for the first further evaluated using the steady-state polarization currents
time suggests strong intrinsic affinity and pronounced measured with the multipotential step techniques (Figure
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Figure 4. (a) LSV curves and (b) Tafel plots of various samples. (c)
Comparison of the OER overpotential at 10 mA cm−2 with reported
non-noble catalysts. (d) Comparison of overpotentials. (e) Linear
plots of cathodic charging currents versus the scan rate. (f)
Galvanostatic polarization curves of FeOOH2 nm/LDH, insert in (f)
is LSV curves of FeOOH2 nm/LDH before and after 1000 CV cycles.
(g) SEM and (h) TEM images FeOOH2 nm/LDH after 1000 CV
cycles.
S16). The as-obtained Tafel slope of FeOOH2 nm/LDH is 35
mV dec−1, very close to the result acquired based on the
relevant LSV curve (Figure 4b). Actually, LDH-6h and LDH-s
demonstrated similar performances as those LDH-based
electrocatalysts reported elsewhere, and the three FeOOH/
LDH composites are superior to most existing OER electro-
catalysts (Figure 4c and Table S2). Particularly, the
FeOOH2 nm/LDH outperformed the state-of-the-art OER
catalysts reported so far.
Moreover, the η for FeOOH2 nm/LDH is 92 mV lower than
that of LDH-6h, and η for FeOOH 10 nm /LDH and
FeOOH18 nm/LDH are lower than that of LDH-s by 64 mV
and 51 mV, respectively. Note that the inherent OER catalytic
activity of FeOOH NPs is not even comparable to the bare
LDH. For instance, when loaded on inactive AlOOH
nanosheets, the η of the as-formed FeOOH/AlOOH was
larger than 400 mV (Figure S11). Therefore, an evident
synergy effect on OER electrocatalysis could be inferred
between the Ni−Fe LDH and FeOOH NPs which are well
interfaced with each other.21 And such a synergy effect was
dependent on the size of the FeOOH NPs, as η for the
nanocomposites decreases monodirectionally when the
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FeOOH NPs decreased from 18.0 to 10.0 nm and then to
2.0 nm (Figure 4c,d).
Owing to the strong interaction between the well interfaced
FeOOH NPs and Ni−Fe LDH nanosheets, the FeOOH/LDH
composite also exhibited excellent OER catalytic and structural
stability. As displayed in Figure 4f, there was little degradation
in its catalytic activity after the FeOOH2 nm/LDH being
subjected to 1000 CV cycles in 1.0 M KOH. It also operated
smoothly at 10 mA cm−2 for at least 25 h; moreover, after
working at a constant current density as high as 50 mA cm−2
for more than 15 h, the overpotential only increased slightly
(Figure 4f), which might be caused by leakage of the
conductive carbon according to the electrochemical impedance
analysis (Figure S10c). Consistently, the structural stability of
the composites was further confirmed by XRD, SEM, TEM,
and XPS characterizations of the spent catalyst. The relevant
XRD spectrum mainly revealed the signals of Ni−Fe LDH
(Figure S17). Both the Ni−Fe LDH flowers and the ultrafine
FeOOH NPs barely changed in size after the 1000 CV cycles
(Figures 4g,h and S12). And XPS analysis displayed that a part
of the Ni became trivalently charged, owing to the emergence
of NiOOH, while little change was observed in the Fe(III)
species (Figure S17). The strong interfacial interactions
between the FeOOH NPs and Ni−Fe LDH nanosheets
function effectively to prevent the aggregation of the active
FeOOH NPs and maintain their ultrafine size throughout the
electrolysis (Figures 4g,h and S12), leading to their excellent
structural and catalytic stability.
3.4. Interfacial Interactions between FeOOH NPs and
Ni−Fe LDH. The underlying mechanism for the superior
activity and the size-dependent synergy catalytic effect of such
FeOOHxnm/LDH composites was attempted. The difference in
the electrochemical active surface area (ECSA) among these
catalysts were evaluated and was excluded to be a potential
reason, though larger population of active sites is always
expected for nanocrystals with smaller sizes. In this regard,
specifically, the electrochemical double-layer capacitance (Cdl)
at the solid−liquid interface were obtained using the equation i
= vCdl where i denotes the cathodic charging current in CVs
obtained with different scan rates v in a non-Faradaic region
(Figures 4e and S13).36 The Cdl were obtained as 0.188 mF,
0.164 mF, and 0.110 mF for FeOOH2 nm/LDH, LDH-s, and
FeOOH18 nm /LDH, respectively. Then the ECSA was
estimated from the equation ECSA = Cdl/Cs where Cs is the
specific capacitance (0.04 mF cm−2). The FeOOH2 nm/LDH
yielded an ECSA of 4.71 cm−2. Nevertheless, the other control
samples exhibited similar ECSA (3.72 cm−2 for LDH-6h and
2.75 cm−2 for FeOOH18 nm/LDH, respectively). Such similar
ECSA for all of the samples (Figures 4e and S13, Table S1) in
return indicates the intrinsic extraordinary catalytic activity of
the active sites in the FeOOHxnm/LDH composites, especially
in the FeOOH2 nm/LDH. Additionally, the role of the
difference in the Fe content among these catalysts was also
excluded by simply relating their molar ratio of Fe to Ni with
their corresponding OER performances (Table S1), although
the Fe content in LDH was previously proven to affect the
OER performance.10,37 The intercalation of anionic types in
the LDH might also play a role in their performance
sometimes. However, herein the contribution of the intercalat-
ing F− anion could be ignored, considering that all the F−
species would eventually be replaced by carbonate anions
when the catalyst was immersed in a strong base (i.e., 1.0 M
KOH electrolyte).38
DOI: 10.1021/acscatal.8b03489
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ACS Catalysis Research Article

Recently, it was revealed that only surface Fe3+ (most likely

those adsorbed at the edge or defects) are responsible for the
enhanced OER catalytic activity of Ni2+.21 In ourbipha-
sic FeOOH/LDH nanocomposite, synthesized in hydrothemal
conditions and closely interfaced with each other, interfacial
oxygen bridges such as Fe−O−Ni (Scheme 1c) are expected
to occur extensively between the FeOOH NPs and the Ni−Fe
LDH nanosheets, especially for the case with ultrafine FeOOH
NPs which have large ratio of highly unsaturated surface atoms.
Such Fe−O−Ni couples on the interface, just like the
aforementioned Fe3+ species adsorbed at the edges or defects
of Ni(II)-based catalysts,21 shall be able to promote the
oxidation of NiII in the Ni−Fe LDH, generating the synergy
catalytic effect between the two. And with decreasing sizes of
FeOOH NPs, the ratio of surface atoms and degree of
unsaturation increases, leading to stronger interfacial inter-
action between the FeOOH and the Ni−Fe LDH and hence
more pronounced synergy catalytic affect toward OER
electrocatalysis.
The occurrence of the above interfacial interaction between
the FeOOH NPs and the Ni−Fe LDH was directly proven by
their characteristic local electronic structures. Toward this end,
the FeOOH2 nm/LDH and the bare LDH-6h were further
analyzed by XAS. As displayed in Figure 5a, the XANES
spectrum of the Fe K-edge for the two samples were compared
to that of the standard Fe2O3 reference to understand the
oxidative state of Fe species. Interestingly, the XANES
spectrum of Fe K-edge for the LDH-6h agrees well with that
of the Fe2O3 reference, whereas that of FeOOH2 nm/LDH
exhibits a blue shift compared to the reference (Figure 5a,
inset). That is, the Fe element in the FeOOH2 nm/LDH exists
as Fe(3+δ)+ species, which assumes an average valence higher
than the trivalently charged Fe3+ in the bare Ni−Fe LDH
flowers of the LDH-6h. It is widely recognized that surface Figure 5. (a) XANES spectra of the Fe K-edge, and the inset is the
oxygen atoms (especially those at the edge and/or corner) are enlarged absorption edge. (b) The k3-weighted Fourier-transformed
unsaturatedly coordinated and therefore bind with foreign EXAFS R-space patterns. (c) The first cycle of CV scan and (d) the
atoms more tightly.39 Hence the highly oxidative Fe(3+δ)+ relevant cathodic peaks. (e) Total ac plus dc current versus time data
species in the FeOOH2 nm/LDH composites originate from and the corresponding (f) first, (g) second, and (h) third harmonic
the ultrafine FeOOH2 nm NPs owing to its large population of components of a.c. voltammograms.
unsaturated surface atoms. Consistently, for the Ni K-edge, the
XANES spectrum of FeOOH2 nm/LDH demonstrates the bond in the FeOOH2 nm/LDH is consistent with its higher
occurrence of Ni(3+δ)+ with oxidation state slightly larger than oxidation-state-sensitive energy of the main absorption thresh-
the divalently charged Ni2+ in the NiO reference (Figure S14), old in the XANES spectra (Figure 5a).41 The presence of such
whereas those in the LDH-6h are typical Ni2+ species which is short Fe(3+δ)+−O bond on the interface formed between
in accordance with previous reports.40 Such a result clearly FeOOH NPs and the Ni−Fe LDH is expected to interact with
proved the role of the Fe(3+δ)+ species in FeOOH NPs in Ni2+ with stronger strength and contribute to the high OER
reforming the local electronic structure of Ni2+ in the Ni−Fe catalytic performance.
LDH via interfacial interaction, as depicted in Scheme 1c. The changes in the local electronic structure of Ni2+
To further clarify the local coordination environment, imparted evident influences on their electrochemical oxidation
especially the Fe local structure, the k3 weighted extended X- and catalytic behavior, as revealed by both direct current (d.c.)
ray absorption fine structure (EXAFS) spectra were extracted and alternating current (a.c.) voltammetric measurement. The
from the relevant Fe K-edge signal (Figure 5b). The first cycle of the CV scans (from the forward to the reverse) of
FeOOH2 nm/LDH and the LDH-6h exhibited similar R-space the FeOOHxnm/LDH and the bare Ni−Fe LDH microflowers
curves with two major peaks, one at the shorter radial distance (i.e., LDH-s and LDH-6h) were analyzed. Shown in Figure 5c,
corresponding to the nearest Fe−O and a second peak at the unexpectedly, regardless of their differentiated OER perform-
longer radial distance contributed by the coordination shells of ance demonstrated in Figure 4a, all of these samples displayed
Fe−M. These peaks and the absence of major peaks at higher almost identical onset potential at ca. 1.5 V in the forward scan
radial distances indicate the local electronic structure of Fe (vs RHE). Nevertheless, in the subsequent reverse scan, the
species in FeOOH2 nm/LDH mainly assume octahedrally performances of these catalysts become clearly differentiated
coordinated MO6 units.21,40 Moreover, compared with those from each other, suggesting the occurrence of a dramatic
in the LDH-6h, the Fe−O bond in the FeOOH2 nm/LDH activation effect in the forward scan. The potential difference
exhibits evidently shorter radial distance, as depicted in Figure (Δη) at the current density of 10 mA cm−2 between the
5b and also in Scheme 1c. Such a contraction in the Fe−O forward scan and the reverse one was thus evaluated.
11348 DOI: 10.1021/acscatal.8b03489
ACS Catal. 2018, 8, 11342−11351
ACS Catalysis
Specifically, the FeOOH2 nm/LDH exhibited the largest Δη of
61 mV, compared to 50 mV for the FeOOH18 nm/LDH, 31 mV
for LDH-s and 23 mV for LDH-6h. Clearly, the presence of the
numerous interfacial FeOOH NPs facilitates the activation of
the Ni−Fe LDH; and the smaller the FeOOH NPs are, the
more effective they would contribute to the activation. This
renders direct evidence to the aforementioned interfacial
interaction between the FeOOH and the Ni−Fe LDH.
The comparison of the resulting cathodic band for Ni3+/Ni4+
reduction in the reverse scan is also revealing. Demonstrated in
Figure 5d, compared with those bare Ni−Fe LDH micro-
flowers (i.e., LDH-s and LDH-6h), the cathodic peaks for the
FeOOHxnm/LDH composites cover much larger areas and shift
evidently to more positive potentials, especially for the
FeOOH2 nm/LDH with FeOOH NPs of only 2 nm in size.
Such different electrochemical reduction behaviors of Ni3+/
Ni4+ species clearly proved that the occurrence of a partial-
charge-transfer activation effect on the Ni2+ sites exerted by the
interfacial Fe(3+δ)+ sites. It has been well documented that
noble metal such as gold, owing to their high electronegativity,
could enhance the OER catalytic activity of cobalt or nickel
oxides or hydroxides through solid−solid interfacial inter-
action. 22 In our FeOOH/LDH composite, owing to
Fe(3+δ)+species with high oxidative valence and relatively
short bond from the FeOOH NPs, the oxidation of the
adjacent Ni2+ species in the Ni−Fe LDH into Ni3+/Ni4+ would
be promoted, which was believed to provide genuine active
sites for OER.
As the anodic bands in the forward scan of the above d.c.-
based CV cycles for all the samples were generally too weak for
analysis (Figure S10d), herein, these samples were further
analyzed by higher order harmonic data derived from large
amplitude Fourier Transformed (FT) a.c. voltammetry which
resembles the use of vary fast scan rates in d.c. studies but with
a major attribute of having little capacitance background
current (Figure 5c).42 According to previous FT a.c.
voltammetry studies on CoOx, MnOx and NiOx, their OER
catalysis experiences two major processes, processes I and II.
Process I is associated with the redox transformation of the
metal sites which is believed not directly involved in water
oxidation catalysis; process II is coupled to the rate-limiting
chemical step and its kinetics governs the water oxidation.28
The first, second and third harmonics derived from the a.c.
voltammograms for our FeOOH2 nm/LDH composite and bare
Ni−Fe LDH confirmed the presence of these two processes,
which however occurred at potentials significantly more
negative than those given by the NiOx film or our control
sample Ni(OH)2 (Figure 5f−h).28 Compared in Figure 5h, in
the third harmonic component which has maximum kinetic
sensitivity, the relevant peaks for process I of FeOOH2 nm/
LDH, though occurring at identical potential as that of the bare
LDH-s, exhibited evidently higher current magnitude,
suggesting faster electron transfer kinetics for the redox
transformation of Ni2+ (and/or Fe3+) in the FeOOH2 nm/
LDH composite. The voltage position of the process II, which
relates closely to the water oxidation kinetics,28 is also clearly
differentiated among different samples. Compared with the
LDH-s, the two relevant peaks for process II for the
FeOOH2 nm/LDH take place evidently at lower potential,
reverifying its advantageous catalytic kinetics. Such compara-
tive a.c. voltammetry results directly reaffirmed the favorable
role of the interfacial oxygen bridges such as Fe(3+δ)+−O−Ni in
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Research Article
regulating the electrooxidation behaviors and enhancing the
catalytic activity of Ni2+ in the FeOOH/LDH composite.
4. CONCLUSIONS
In summary, FeOOH/LDH nanocomposites with average size
of FeOOH NPs tunable from 2.0 to 18.0 nm were prepared
flexibly for the first time; more importantly, with the assistance
of analytic techniques including XANES, EXAFS, d.c.
voltammetry and large amplitude Fourier Transformed a.c.
voltammetry, we also proved that, owing to the strong solid−
solid interfacial interactions between the Ni−Fe LDH
nanosheets and numerous FeOOH NPs, the oxidation of
Ni2+ in the Ni−Fe LDH could be promoted effectively by the
highly oxidative interfacial Fe(3+δ)+ species from the unsatu-
rated FeOOH NPs, leading to evidently enhanced OER
electrocatalytic activity compared with the bare Ni−Fe LDH.
Such a synergy catalytic effect was also found dependent on the
size of the FeOOH NPs, which becomes increasingly
pronounced with decreasing average size of FeOOH NPs.
Specifically, the FeOOH2 nm/LDH with FeOOH NPs of 2.0
nm outperformed all of the noble or non-noble OER
electrocatalysts reported so far, giving an overpotential of
174 mV at 10 mA cm−2 and a small Tafel slope of 27 mV dec−1
in 1.0 M KOH; it also displayed excellent structural and
catalytic durability. With extraordinary OER catalytic activity,
excellent stability, ease of preparation, and low cost, such
FeOOH/LDH composite is expected to be a superior OER
electrocatalyst for efficient water oxidation. Our FeOOH/LDH
composites represent the first example to favorably manipulate
the local electronic structure of active metal sites through
strong solid−solid interfacial interaction with a non-noble
metal component in the pursuit of highly efficient OER
electrocatalysts.
■
ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.8b03489.
TEM image, EDX analysis, Tables, SEM images, and
OER activity of control samples (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: zhouy@xmu.edu.cn.
*E-mail: jtli@xmu.edu.cn.
ORCID
Yao Zhou: 0000-0003-4021-6597
Jun-Tao Li: 0000-0002-9650-6385
Shi-Gang Sun: 0000-0003-2327-4090
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The National Key Research and Development Program of
China (No. 2017YFA0206500), the National Natural Science
Foundation of China (No. 21703182, 21621091), the
Fundamental Research Funds for the Central Universities
(No. 20720180080), and the Education and Scientific
Research Project for Young and Middle-aged Scholars of
FuJian Province (No. JAT170016) were acknowledged. XAS
DOI: 10.1021/acscatal.8b03489
ACS Catal. 2018, 8, 11342−11351
ACS Catalysis
measurements were performed at the beamline (BL14W1) at
the Shanghai Synchrotron Radiation Facility (SSRF).
■
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11351 DOI: 10.1021/acscatal.8b03489

ACS Catal. 2018, 8, 11342−11351