See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/323124958

Tuning Electronic Structure of NiFe Layered Double Hydroxides with

Vanadium Doping toward High Efficient Electrocatalytic Water Oxidation

Article  in  Advanced Energy Materials · February 2018

DOI: 10.1002/aenm.201703341

CITATIONS READS

296 1,532

7 authors, including:

Pengsong Li Yaping Li
Yale University Beijing University of Chemical Technology
28 PUBLICATIONS   1,196 CITATIONS    69 PUBLICATIONS   3,845 CITATIONS   

SEE PROFILE SEE PROFILE

Guoxin Zhang Wen Liu

Shandong University of Science and Technology Yale University
79 PUBLICATIONS   4,199 CITATIONS    93 PUBLICATIONS   7,189 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

intercalation and catalysis View project

Transition metal Dichalcogenide View project

All content following this page was uploaded by Pengsong Li on 15 May 2018.

The user has requested enhancement of the downloaded file.

Communication
Water Oxidation
Tuning Electronic Structure of NiFe Layered Double
Hydroxides with Vanadium Doping toward High Efficient
Electrocatalytic Water Oxidation
Pengsong Li, Xinxuan Duan, Yun Kuang, Yaping Li, Guoxin Zhang, Wen Liu,*
and Xiaoming Sun*
Binary NiFe layer double hydroxide (LDH) serves as a benchmark non-noble
metal electrocatalyst for the oxygen evolution reaction, however, it still needs
a relatively high overpotential to achieve the threshold current density. Herein
the catalyst’s electronic structure is tuned by doping vanadium ions into the
NiFe LDHs laminate forming ternary NiFeV LDHs to reduce the onset poten-
tial, achieving unprecedentedly efficient electrocatalysis for water oxidation.
Only 1.42 V (vs reversible hydrogen electrode (RHE), ≈195 mV overpotential)
is required to achieve catalytic current density of 20 mA cm−2 with a small
Tafel slope of 42 mV dec−1 in 1 m KOH solution, which manifests the best of
NiFe-based catalysts reported till now. Electrochemical analysis and density
functional theory +U simulation indicate that the high catalytic activity of NiFeV
LDHs mainly attributes to the vanadium doping which can modify the elec-
tronic structure and narrow the bandgap thereby bring enhanced conductivity,
facile electron transfer, and abundant active sites.
Water splitting driving by renewable energy sources has drawn
much more attention for sustainable hydrogen production,
owing to the limited reserve of fossil fuels and increasing
concern on environmental pollution.[1] Oxygen evolution reac-
tion (OER) is a half-reaction for water splitting, which actually
plays a central role in controlling the energy efficiency of H2
production, featuring with complexity and sluggish kinetics.[2]
Driving OER with advanced electrocatalyst is highly desired
P. S. Li, X. X. Duan, Dr. Y. Kuang, Dr. Y. P. Li, Dr. W. Liu,
Prof. X. M. Sun
State Key Laboratory of Chemical Resource Engineering
College of Energy
Beijing Advanced Innovation Center for Soft Matter Science
and Engineering
Beijing University of Chemical Technology
Beijing 100029, China
E-mail: wenliu@mail.buct.edu.cn; sunxm@mail.buct.edu.cn
Dr. Y. Kuang
Department of Chemistry
Stanford University
Stanford, CA 94305, USA
Dr. G. X. Zhang
College of Electrical Engineering and Automation
Shandong University of Science and Technology
Tsingtao 266590, China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201703341.
DOI: 10.1002/aenm.201703341
Adv. Energy Mater. 2018, 1703341 1703341  (1 of 8)
www.advenergymat.de
but still limited to noble metal, such as
iridium (Ir) and ruthenium (Ru).[3] The
high cost of noble metal and scarcity in
resources have hindered their wide appli-
cation as the catalytic electrode for H2 pro-
duction. Therefore it is urgent to obtain
high performance OER catalysts based on
the earth-abundant elements other than
the noble metal-based catalysts (IrO2 and
RuO2).[4] The layered double hydroxides
(LDHs),[5] also known as hydrotalcite-like
clays, is a typical non-noble-metal-based
material that composed of layers of divalent
and trivalent metal cations coordinated
to hydroxide anions with guest anions
(typically CO32−) intercalated between the
layers.[6] The highly tunable structures,
such as layer numbers, metal species,
interlayer spacing, and more importantly,
the specific cation arrangements in the hydroxide layers, make
LDHs-based materials as promising OER catalysts to replace
the state-of-the-art noble metal based catalysts.[7]
The NiFe LDHs is nowadays known as one of the most active
OER catalysts with a low overpotential and high electrolysis
current.[8] However, it is still suffering from poor electronic con-
ductivity that hindering its further improvement and practical
application.[9] Recently, tremendous efforts have been devoted to
enhance the electrocatalytic activity, such as, exfoliation to fabri-
cate a single layer structure,[10] integrating the LDHs nanosheets
to form array on a conductive substrate,[11] loading noble metal
on the surface,[12] modification the interlayer anion to change
the electronic structure,[13] sulfurization,[14] defect engineering
to increase the active site,[15] topotactic reduction to metallic
nanosheets,[16] and doping.[17] It is already known that Fe in
NiFe LDHs is the key aspect for the high OER catalytic perfor-
mance,[18] so we can modify the chemical environment of Fe
by incorporating other valence variable transition metals (such
as Co[17a] and Mn[17b]) into NiFe LDHs laminate to enhance the
catalyst activity. Vanadium is an earth-abundant element and its
activity for electrochemical water oxidation has been explored as
active sites in NiV LDHs.[19] However, as a typical transition metal
with a series of valence states, the electron interaction and syner-
getic effect between V and other metals in the laminate of LDHs
have never been touched. On the other hand, the integrating of
nanosheets materials can enhance the intrinsic activity of OER
by providing electron transfer pathways from electron-conductive
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advenergymat.de

Figure 1.  A) The schematic diagram of NiFeV LDHs structure. B, C) SEM images of as-prepared NiFe LDHs and NiFeV LDHs nanosheets array. D) TEM
image of typical NiFeV LDHs nanosheets, the inset of (D) shows the thickness with obvious laminates. E) SAED patterns of NiFeV LDHs nanosheets
marked in (D), evidencing NiFeV LDHs had a good crystallinity. F) EDX patterns and corresponding element ratio of NiFeV LDHs.

substrate accelerating the OER kinetics.[20] Hence, it would be
worthwhile to explore the NiFeV LDHs nanosheets array elec-
trode as a promising OER electrocatalyst in energy research area.
Herein, for the first time, we synthesized vanadium doped
NiFe LDHs nanosheets array on nickel foam (denoted as NiFeV
LDHs) via a one-step hydrothermal method for OER electroca-
talysis. By the incorporation of vanadium into the NiFe LDHs
laminate, the NiFeV LDHs with a layered structure (as shown in
Figure 1A) showed an excellent OER catalytic performance. The
electrochemical results demonstrated that only a very low over-
potential (195 mV) was required for achieving the current density
of 20 mA cm−2, and afforded a small Tafel slope of 42 mV dec−1,
which was better than the NiFe LDHs and commercial RuO2/C
catalysts. The vanadium doping can narrow the bandgap of NiFe
LDHs, enhance the electric conductivity of the active material,
and promote OER activity, which is revealed by detailed electro-
chemical analysis and density functional theory (DFT)+U simu-
lation. The electronic structure engineering strategy developed
here by doping transition metal with high valence states can be
extended to other metal oxides or hydroxides to explore more
advanced OER electrocatalyst.
The vanadium doping NiFe LDHs nanosheets array were
directly grown on nickel foam from metal salt precursors in water
solution with the addition of urea via a one-step hydrothermal
method under optimized temperature and time. The NiFe LDHs
were synthesized by the similar route without vanadium salt
addition. After hydrothermal reaction, a brown film was coated
on the surface of nickel foam (Figure S1, Supporting Informa-
tion), indicating the successful growth of LDHs. The NiFeV
LDHs array had a darker color than the NiFe LDHs. The scanning
electron microscopy (SEM) images of the NiFe LDHs (Figure 1B)
and NiFeV LDHs (Figure 1C) both show 3D open porous struc-
ture with interconnected nanosheets growing vertically on the Ni
foam substrate. The NiFeV LDHs were very similar to NiFe LDHs
in morphology with a lateral size of several hundred nanometers.
As shown in Figure 1D, the 2D morphology of NiFeV LDHs
could be revealed again by the transmission electron microscopy
(TEM), which is peeled off from the surface of nickel foam by
the assistance of ultrasonication. The high-resolution TEM image
(inset of Figure 1D) revealed the thickness of ≈4.8 nm, corre-
sponding to 6–7 edge sharing octahedral MO6 layers. Figure 1E
showed the selected area electron diffraction (SAED) patterns of
NiFeV LDHs nanosheets marked in Figure 1D, which revealed
the NiFeV LDHs had a well hexagonal crystal phase and the dif-
fraction rings indexed the (100) and (110) lattices, which was
consistent with the X-ray diffraction (XRD) pattern (Figure 2A,
black line). The atomic ratios of transition metals in the as-
synthesized samples were determined by energy dispersive
X-ray (EDX) spectrometry analysis (Figure 1F), which revealed
that the Ni:Fe:V ratio (6.04:0.83:1) was close to the ratio of the
starting materials (6:1:1). High angle annular dark field imaging-
scanning transmission electron microscopy (HAADF-STEM)

Adv. Energy Mater. 2018, 1703341 1703341  (2 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 2.  A) XRD patterns of as-prepared NiFe LDHs and NiFeV LDHs nanosheets array. The high-resolution XPS of B) Ni and C) Fe in the NiFe LDHs
and NiFeV LDHs nanosheets array. D) The XPS spectra of V in the NiFeV LDHs nanosheets array.
observation and elemental mapping were utilized to confirm
the elemental distributions of the NiFeV LDHs structure. As
shown in Figure S2 (Supporting Information), a typical NiFeV
LDHs nanosheet was revealed that the vanadium element was
uniformly distributed with the iron and nickel element in LDHs
structure, and no local aggregation of vanadium can be observed.
The XRD patterns were employed to verify the crystal struc-
ture and composition of LDHs. The red line in Figure 2A illus-
trated the XRD patterns of the NiFe LDHs nanoarrays samples
(JCPDF: 40–0125, the clear reflections of (003), (006), (012),
(015), (110) and (113) were observed) following hydrothermal
synthesis on the Ni foam substrate (the peaks marked “#” stand
for the Ni foam). The XRD data of the NiFeV LDHs (black line)
showed a series of Bragg reflections in good agreement with the
well-known NiFe LDHs, indicating that the vanadium doping
did not change the layered structure. Vanadium ion could be
easily coprecipitated into the laminate of LDHs because it had
the six-coordination structure matching well with the crystal
structure of hydrotalcite.
In order to investigate the influence of vanadium element
on the surface chemical states and composition of NiFeV LDHs
nanosheets, X-ray photoelectron spectroscopy (XPS) was carried
out. The NiFe LDHs nanosheets served as the reference, and the
obtained results were shown in Figure 2B–D. The profile surveys
of the NiFe LDHs and NiFeV LDHs were provided in Figure S3
(Supporting Information). For NiFeV LDHs (black line, Figure S3,
Supporting Information), the spectrum clearly exhibits the ele-
ment signals of Ni, Fe, V, O and C, which were consistent with
the EDX results in Figure 1F. The high-resolution Ni 2p spectra
Adv. Energy Mater. 2018, 1703341 1703341  (3 of 8)
www.advenergymat.de
(Figure 2B) showed two peaks with binding energies at 856.4
and 874.1 eV correspond to the Ni2+ 2p3/2 and Ni2+ 2p1/2, respec-
tively, which was in good agreement with a previous report.[21]
The Fe 2p signal was composed of two peaks (Figure 2C)
belonging to Fe 2p1/2 and Fe 2p3/2 binding energies of the Fe
oxidation state (Fe3+).[22] Compared the valence states of Ni and
Fe between the NiFe LDHs and NiFeV LDHs, we could find
that there was no difference between the nickel element while
the binding energy of iron had some decrease from 713.1 to
712.4 eV after doping, indicating the chemical environment of
iron ion was modified by doping vanadium into the laminate.
The high-resolution V 2p spectrum was also decomposed into
V 2p3/2 and V 2p1/2 due to the spin-orbit splitting that separated
by ≈7.7 eV. Three components could be distinguished at 515.6 eV
(in magenta), 517.2 eV (in dark cyan), and 519.2 eV (in blue) and
were in good agreement with respectively V3+, V4+, and V5+.[23]
This result indicated that V3+ was partially oxidized by oxygen
to V4+ and V5+ during the synthesis.
In order to evaluate the oxygen-evolving performance of
the LDHs, electrochemical measurements were conducted on
the catalysts with an area of 1 cm2. Linear sweep voltammetry
(LSV) was recorded in an O2-saturated 1 m KOH solution using
a standard three-electrode system in which a platinum elec-
trode as the counter electrode, a saturated calomel electrode as
the reference electrode, and our catalyst electrode as the work
electrode, respectively. The NiFeV LDHs were directly applied
as the working electrode. For comparison, we measured the
electrocatalytic activity of RuO2/C, NiFe LDHs, NiV LDHs,
and Ni(OH)2. Figure 3A showed the LSV polarization curves
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advenergymat.de

Figure 3.  A) Polarization curves of the non-noble metal catalysts (NiFeV LDHs, NiFe LDHs, Ni(OH)2 and NiV LDHs) and the commercial RuO2/C
catalyst. B) The overpotential comparison of NiFeV LDHs, NiFe LDHs, and NiV LDHs at the current density of 20 mA cm−2 and 100 mA cm−2. C) The
corresponding Tafel plots of the three catalysts. D) The EIS curves of NiFe LDHs, NiV LDHs, and NiFeV LDHs. E) The Cdl calculations of NiFeV LDHs
and NiFe LDHs. F) The potentiostatic stability test under a certain potential (at 1.48 V vs RHE), the corresponding current density of NiFeV LDHs is
stable for over 18 h (the current density maintain 98%), demonstrating unprecedented high stability.

of OER on the catalytic electrodes. The NiFeV LDHs exhibited
a remarkable catalytic activity toward OER, which had a lower
onset potential than the commercial RuO2, NiV LDHs and even
NiFe LDHs. The reverse scan of CV curve from positive to nega-
tive potential (Figure S4, Supporting Information) revealed that
NiFeV LDHs only needed overpotential of 192 mV to achieve
the current density of 10 mA cm−2. To further highlight the
superiority of the NiFeV LDHs, the overpotentials at current
densities of 20 and 100 mA cm−2 were compared in Figure 3B.
The NiFeV LDHs, NiFe LDHs, and NiV LDHs needed overpo-
tential of 195, 249, and 330 mV to achieve the current density
of 20 mA cm−2, and 233, 280, and 390 mV to obtain current
of 100 mA cm−2, respectively, indicating that the NiFeV LDHs
catalyst had a very high energy efficiency for catalyzing OER
process. At the same time, we also explored the influence of
different metal ratios on the electrocatalytic water oxidation per-
formance (Figure S5, Supporting Information). From Figure S5
(Supporting Information), we could draw a conclusion that the
NiFeV LDHs exhibited the best OER performance when the metal
ratio (Ni2+:Fe3+:V3+) was 6:1:1. As we all know, when the ratio of
divalent to trivalent metal ion was 3:1 in hydrotalcite structure,
the trivalent metal ion was atomic dispersion in the laminate of
LDHs,[7c] which was beneficial to promote the electrocatalysis.
After part of the iron sties replaced by vanadium atoms, the
chemical environment of the iron ion was further optimized,
thereby enhancing the intrinsic activity. The Tafel slopes of
the NiFeV LDHs, NiFe LDHs, and NiV LDHs were shown in
Figure 3C. The Tafel slope of 42 mV dec−1 for NiFeV LDHs
was lower than 49 mV dec−1 for NiFe LDHs and 72 mV dec−1
for NiV LDHs, in the meantime, the NiFeV LDHs exhibited
a higher turnover frequency (TOF) value (0.04 s−1, Figure S6,
Supporting Information) at 1.48 V versus RHE, implying the
favorable OER kinetics for NiFeV LDHs. The electrochemical
active surface area (ECSA) was in proportion to the electro-
chemical double layer capacitance (Cdl). Therefore, Cdl was
calculated to estimate the ECSA by measuring the cyclic vol-
tammetry curves in the proper potential range without redox
processes (Figure S7, Supporting Information). The NiFeV
LDHs had much larger Cdl (6483 uF cm−2) than the NiFe LDHs
(3775 uF cm−2), suggesting more electrochemical active sites
of the NiFeV LDHs. Furthermore, electrochemical impedance
spectroscopy (EIS) analysis is performed to study the interfacial
properties of the electrocatalysts electrodes. From Figure 3D,
the electron-transfer resistance of NiFeV LHDs was much
lower than that of NiFe LDHs, which might be another reason
for the enhanced electrocatalytic performance. Long-term sta-
bility was a crucial criterion to evaluate the performance of the
catalysts. When operating the OER at the constant potential
of 1.48 V versus RHE, corresponding stable current densities
were observed on the NiFeV LDHs and NiFe LDHs electrodes
in 1 m KOH. The initial current density (about 187 mA cm−2) of
NiFeV LDHs was with slight attenuation (≈2%) after 18 h of
testing, and that of the NiFe LDHs maintaining only 89% of the
initial value (about 22 mA cm−2) as shown in Figure 3F,
revealing the NiFeV LDHs were much more stable than NiFe
LDHs under OER conditions. Moreover, the nearly unchanged
morphology of NiFeV LDHs after long-term stability test further
demonstrates the robustness of the array electrode (Figure S10,
Supporting Information). The EDX spectrometry of NiFeV
LDHs electrode (Figure S11, Supporting Information) revealed

Adv. Energy Mater. 2018, 1703341 1703341  (4 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advenergymat.de

Figure 4.  Proposed 4e-mechanism of oxygen evolution reaction on A) NiFe LDHs and B) NiFeV LDHs for DFT+U calculation. The Fe ion (*) in the
(100) crystal plane was the active site. G stands for the reaction Gibbs free energy. C) Gibbs free energy diagram for the four steps of OER on NiFe
LDHs (black line) and NiFeV LDHs (red line). The top was the brief 4e-mechanism of OER. The green box step was the determining step and η was
stand for overpotential. The lower activation Gibbs free energy of NiFeV LDHs predicts more favorable OER kinetics. D) Total density of states (TDOS)
curves of NiFeV LDHs and NiFe LDHs, the narrower bandgap of NiFeV LDHs indicates a more conductive structure.

that the Ni:Fe:V ratio was 75.76:11.59:12.65, which was similar to the stable structure of LDHs. In the same time, the high-
to the value of 76.72:10.58:12.70 before OER test, indicating resolution XPS profile of V after long term stability test was also
that vanadium was not etched out in 1.0 m KOH solution due illustrated in Figure S12 (Supporting Information). The V4+ and

Adv. Energy Mater. 2018, 1703341 1703341  (5 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
V5+ ions still existed on the NiFeV LDHs surface, which once
again proved that the vanadium was very stable in the LDHs
structure and hard to dissolve in 1 m KOH solution. All the
results demonstrate that the NiFeV LDHs have superior OER
activity as well as outstanding stability. Table S1 (Supporting
Information) compared the activity of NiFeV LDHs with recently
reported state-of-the-art LDHs catalysts. The NiFeV LDHs
showed superior catalytic performance than other reported
LDHs,[24] also ranking one of the most active non-noble metal-
based electrocatalyst in KOH, to the best of our knowledge.
The electrochemical performance revealed that the vana-
dium doping into the laminate of NiFe LDHs could enhance
the electrocatalytic activity for OER. To search the reasonable
analysis, we performed DFT+U computations to calculate the
Gibbs free energy of coordinate elementary steps and overpo-
tential for OER based on the following 4e-mechanism proposed
by Norskov for water oxidation
*
+H2 O →* OH + (H+ + e − ) ∆GI (I)
*
OH →* O + (H+ + e − ) ∆GII (II)
*
O + H2 O →* OOH + (H+ + e − ) ∆GIII (III)
*
OOH →* +O2 + (H+ + e − ) ∆GIV (IV)
where * stands for the active sites in catalysts, the ∆GI, ∆GII,
∆GIII, and ∆GIV stand for the reaction Gibbs free energies.
The overpotential η is defined in Equation (5)
η = max( ∆GI, ∆GII, ∆GIII, ∆GIV ) − 1.23eV (1)
The Fe ion played an important role in NiFe LDHs for OER
catalysis, and there were plenty of Fe ions with unsaturated coor-
dination in the edge of layered double hydroxides nanosheets, so
the Fe ion in the (100) crystal plane was selected as the active site
of both NiFeV LDHs and NiFe LDHs for DFT+U computations.
The corresponding LDHs structures were shown in Figure S13
(Supporting Information). Half of the iron ions in NiFe LDHs
structure were substituted by vanadium for the NiFeV LDHs.
Proposed 4e-mechanism of oxygen evolution reaction of NiFe
LDHs and NiFeV LDHs was presented in Figure 4A,B. The opti-
mized structures of the intermediates in the Gibbs free energy
landscape were shown in Figure 4C and Table S2 (Supporting
Information). The intermediate *OH, *O, and *OOH bound to
the active site through oxygen with a single bond in correspond-
ence with the above-mentioned 4e-mechanism. The largest
Gibbs free energy difference (Step II) was the rate determining
step, as shown in Figure 4B, which was the same for these
two catalysts. The Gibbs free energy difference value of NiFe
LDHs (∆GII = 1.89 eV) was larger than that of the NiFeV LDHs
(∆GII = 1.64 eV). In other words, the NiFeV LDHs need a lower
overpotential to drive water oxidation. For comparison, the V ion
in the (100) crystal plane was selected as the active site of NiFeV
LDHs for DFT+U computations. The Gibbs free-energy diagram
was shown in the Figure S14 (Supporting Information), similarly,
the step II was the determining step, while the Gibbs free energy
Adv. Energy Mater. 2018, 1703341 1703341  (6 of 8)
www.advenergymat.de
difference value (GII = 2.4 eV) was very higher than that of NiFe
LDHs, which indicated that the vanadium was not the active
site in NiFeV LDHs catalyst for OER, and the doping of vana-
dium could enhance the catalytic activity of Fe sites by electronic
interaction between Fe and V atoms in the laminate. To further
understand the doping effect in depth, the electronic structures
of NiFe LDHs and NiFeV LDHs were also calculated by DFT+U
method. As shown in the total densities of states (TDOSs,
Figure 4D) and the projected densities of sates (Figure S15,
Supporting Information), the bandgap between the valence and
conduction bands of NiFe LDH was about 1.56 eV, while a nar-
rower bandgap was observed after doping with vanadium ele-
ment, indicating a more conductive electronic structure. The
vanadium doping into the NiFe LDHs, which mainly changed
the conduction band sate of LDHs, could narrow the bandgap
thereby improving the electric conductivity of the active mate-
rial. In addition, the sheet resistance of the NiFe LDHs was
measured to be (2.4 ± 0.3) × 103 Ω sq−1, while that of NiFeV
LDHs was (1.3 ± 0.2) × 103 Ω sq−1, directly evidencing the
higher conductivity of NiFeV LDHs (Table S3, Supporting Infor-
mation). Therefore, the theory and experiment were in a great
agreement that the OER kinetics on the electrode could be facili-
tated by vanadium doping to improve the electric conductivity
along with the significantly enhanced intrinsic electrocatalytic
activity.
In summary, the vanadium doping NiFe LDHs nanosheets
array on the nickel foam (NiFeV LDHs) was fabricated using
a simple one-step hydrothermal method and evaluated as an
efficient electrocatalyst for OER. The NiFeV LDHs nanosheets
array showed an outstanding OER activity with a low Tafel
slope of 42 mV dec−1 and only a small overpotential of 195 mV
to drive current of 20 mA cm−2 in 1.0 m KOH solution, mani-
festing one of the best non-noble metal electrocatalyst for water
oxidation. The vanadium doping in the laminate of the layered
structure played an important role in boosting the OER catalytic
performance, which modulated the electronic structure and
thereby enhancing the electric conductivity, ensuring plentiful
catalytic sites on the electrode surface, and favoring fast electron
transfer, as revealed by the detailed electrochemical analysis
and DFT+U calculation. The facile fabrication process and out-
standing catalytic activity, together with the robust durable nature
of NiFeV LDHs, promise its practical application in the electro-
chemical water oxidation devices. In addition, this work may
open up opportunities in engineering the electronic structure
of LDHs to design more innovative electrocatalysts for H2 gas
production.
Experimental Section
Chemicals: Fe(NO3)3·9H2O, Ni(NO3)2·6H2O, VCl3, urea(CO(NH2)2),
KOH, HCl (≈37 wt%), Ni foam, water, and hexamethylenetetramine
(HMT) were purchased from China National Pharmaceutical Industry
Corporation Ltd. All the reagents were of analytical grade and used as
received without further purification.
Synthesis of NiFeV LDHs Nanosheets Array: Ni(NO3)2·6H2O (2.4 mmol),
Fe(NO3)3·9H2O (0.4 mmol), VCl3 (0.4 mmol), and CO(NH2)2 (5 mmol)
were dissolved in 35 mL of distilled water and stirred to form a clear
solution. Nickel foam (about 3 cm × 4 cm) was carefully cleaned with
concentrated HCl solution (37 wt%) in an ultrasound bath for 5 min in
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
order to remove the surface NiO layer, and then cleaned by deionized
water and absolute ethanol for 3 min each time. The above solution and
Nickel foam were then transferred to a 40 mL Teflon-lined stainless-steel
autoclave, which was sealed and maintained at 120 °C for 12 h, and then
cooled to room temperature naturally. A brown thin film on the metal
substrate was formed, then the products were subsequently rinsed
with deionized water/ethanol for three times with the assistance of
ultrasonication, and dried at 80 °C for 6 h. Loading amount (2.8 mg cm−2)
on the surface of the Ni foam was calculated by combining the inductively
coupled plasma optical emission spectrometry (ICP), EDX spectrometry,
and the general formula [M1−xIIMxIII(OH)2]z+(An−)z/n·2H2O (MII:
divalent metals, MIII: trivalent metals, An−: the interlayer anion).[10a]
The NiV LDHs nanosheets array was synthesized by the same
method without Fe(NO3)3·9H2O, and the amount of VCl3 was replaced
by 0.8 mmol.
The NiFe LDHs Nanosheets Array Was Synthesized Following the Previous
Report[11] with Some Modification: In a typical procedure, Ni(NO3)2·6H2O
(0.75 mmol), Fe(NO3)3·9H2O (0.25 mmol), and CO(NH2)2 (5 mmol)
were dissolved in 36 mL of distilled water and stirred to form a clear
solution. Nickel foam was carefully cleaned. The aqueous solution and
the Ni foam were transferred to a 40 mL Teflon-lined stainless-steel
autoclave, which was sealed, maintained at 120 °C for 12 h, and then
allowed to cool to room temperature naturally. The post-treatment was
the same as NiFeV LDHs.
The Ni(OH)2 Nanosheets Array were Synthesized Following the Previous
Reports[25] without Any Change: In a typical procedure, Ni(NO3)2·6H2O
(1.45 g) and HMT (1.40 g) were dissolved in 35–38 mL distilled water
and stirred to form a clear solution. The aqueous solution and the Ni
foam were transferred to a 40 mL Teflon-lined stainless-steel autoclave,
which was sealed, maintained at 100 °C for 10 h, and then allowed to
cool to room temperature within 15 min using cooling water. The thin
film on the metal substrate was rinsed several times with distilled water
and ethanol with the assistance of ultrasonication, and dried at 80 °C
for 6 h.
Materials Characterization: The size and morphology of the samples
were characterized using a field-emission SEM (JEOL JSM6335)
operating at 20 kV. High-resolution transmission electron microscopy
measurements were carried out using a JEOL JEM 2100 system operating
at 200 kV. X-ray powder diffraction patterns were recorded on an X-ray
diffractometer (Rigaku D/max 2500) with Cu Kα radiation (40 kV,
30 mA, λ = 1.5418 Å) at a scan rate of 10° min−1 in the 2θ range
from 8° to 80°. X-ray photoelectron spectra were carried out by using
a model of ESCALAB 250 and LabRAMAramis. The measurement of
sheet resistance was performed using the four points probe method in
sheet resistance measurement system (RTS-8). Elemental ratio of LDHs
catalysts was also investigated by inductively coupled plasma optical
emission spectrometry (ICP-MS; Thermo X Series 2).
Electrochemical Measurements: The electrochemical measurements
were carried out at room temperature in a three-electrode glass
cell connected to an electrochemical workstation (CHI 660e, CH,
Shanghai.). The nanosheets array on the metal substrate (1 cm × 1 cm)
was used as a working electrode. A platinum electrode and a saturated
calomel electrode (SCE) were used as counter and reference electrode,
respectively. Freshly prepared 1 m KOH aqueous solution was used as
the electrolyte, which was saturated by oxygen bubbles before and during
the OER experiments. Polarization curves were obtained using LSV with
a scan rate of 1 mV s−1. All polarization curves were corrected for the
Ohmic drops tested by impedance spectroscopy. The EIS was obtained
in 1 m KOH solution by applying an AC voltage of 5 mV amplitude at
open circuit potential with frequency from 100 kHz to 0.1 Hz. When
the long-term stability performance was tested, the Hg/HgO electrode
was used as the reference electrode for avoiding the instability of SCE
in alkaline solution working long hours. The TOF value was calculated
by the following equation: TOF = j·S/4F·n, where j is the current density
(mA cm−2) at different overpotential, S represents the surface area of
as-prepared electrode, the number 4 means a four-electron oxygen
evolution reaction, F is the Faraday’s constant (96485.3 C mol−1), and
n represents the moles of metal atoms on the electrode which can be
Adv. Energy Mater. 2018, 1703341 1703341  (7 of 8)
www.advenergymat.de
calculated by the loading weight and the molecular weight of the LDHs
catalyst.
Theoretical Calculation: All DFT calculations were carried out
by Vienna ab Initio Simulation Package. The projector augmented
wave pseudopotentials method was used for describing electron-ion
interactions. The Perdew–Burke–Ernzerh exchange correlation functional
with the on-site Coulomb Repulsion U term was used. The value of
U is 4.3 for Fe, 3.8 for Ni, and 3.4 for V. These U values are selected
according to the literature.[19,26] All the atom positions in the bulk LDHs
were optimized by the conjugate-gradient optimization procedure. The
Brillouin zone integrations were performed using a 3 × 3 × 3 Monkhorst-
Pack grid for the bulk. A spin-polarized approach was adopted. The
k-point sampling consists of 5 × 5 × 1 Monkhorst-Pack points for all
slab models. A vacuum of at least 16 Å was adopted along z-axis. During
structure optimization, all energies change criterion was set to 10−4 eV,
the atoms were relaxed until the force acting on each atom was less than
0.05 eV Å−1, the plane wave cutoff was set to 400 eV.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors sincerely appreciate the helpful discussion with Prof. Lei
Jiang. This work was financially supported by the National Natural
Science Foundation of China (NSFC), the National Key Research and
Development Project (Grant No. 2016YFF0204402), the Program for
Changjiang Scholars and Innovative Research Team in the University
(Grant No. IRT1205), the Fundamental Research Funds for the Central
Universities, the Long-Term Subsidy Mechanism from the Ministry of
Finance and the Ministry of Education of PRC.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
electronic structure, layered double hydroxides, vanadium doping, water
oxidation
Received: November 27, 2017
Revised: December 24, 2017
Published online:
[1] a) J. Luo, J.-H. Im, M. T. Mayer, M. Schreier, M. K. Nazeeruddin,
N.-G. Park, S. D. Tilley, H. J. Fan, M. Grätzel, Science 2014, 345,
1593; b) X. Jia, Y. Zhao, G. Chen, L. Shang, R. Shi, X. Kang,
G. I. N. Waterhouse, L.-Z. Wu, C.-H. Tung, T. Zhang, Adv. Energy
Mater. 2016, 6, 1502585; c) H. Schäfer, S. Sadaf, L. Walder,
K. Kuepper, S. Dinklage, J. Wollschläger, L. Schneider, M. Steinhart,
J. Hardege, D. Daum, Energy Environ. Sci. 2015, 8, 2685; d) Y. Zheng,
Y. Jiao, S. Z. Qiao, Adv. Mater. 2015, 27, 5372; e) H. Zhu, J. Zhang,
R. Yanzhang, M. Du, Q. Wang, G. Gao, J. Wu, G. Wu, M. Zhang,
B. Liu, J. Yao, X. Zhang, Adv. Mater. 2015, 27, 4752; f) S. Cobo,
J. Heidkamp, P. A. Jacques, J. Fize, V. Fourmond, L. Guetaz,
B. Jousselme, V. Ivanova, H. Dau, S. Palacin, Nat. Mater. 2012, 11,
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
802; g) H. Wang, H. W. Lee, Y. Deng, Z. Lu, P. C. Hsu, Y. Liu, D. Lin,
Y. Cui, Nat. Commun. 2015, 6, 7261; h) Y. Jin, H. Wang, J. Li, X. Yue,
Y. Han, P. K. Shen, Y. Cui, Adv. Mater. 2016, 28, 3785.
[2] a) M. W. Kanan, D. G. Nocera, Science 2008, 321, 1072; b) Y. Li, H. Dai,
Chem. Soc. Rev. 2014, 43, 5257; c) M. Bajdich, M. García-Mota,
A. Vojvodic, J. K. Nørskov, A. T. Bell, J. Am. Chem. Soc. 2013, 135,
13521; d) M. B. Stevens, L. J. Enman, A. S. Batchellor, M. R. Cosby,
A. E. Vise, C. D. M. Trang, S. W. Boettcher, Chem. Mater. 2017,
29, 120.
[3] a) N. Danilovic, R. Subbaraman, K. C. Chang, S. H. Chang,
Y. Kang, J. Snyder, A. P. Paulikas, D. Strmcnik, Y. T. Kim, D. Myers,
Angew. Chem., Int. Ed. 2014, 53, 14016; b) P. Lettenmeier,
L. Wang, U. Golla-Schindler, P. Gazdzicki, N. A. Cañas, M. Handl,
R. Hiesgen, S. S. Hosseiny, A. S. Gago, K. A. Friedrich, Angew.
Chem., Int. Ed. 2016, 55, 742.
[4] a) Y. Jiao, Y. Zheng, M. Jaroniec, S. Z. Qiao, Chem. Soc. Rev. 2015,
44, 2060; b) Y. Lee, J. Suntivich, K. J. May, E. E. Perry, Y. Shao-Horn,
J. Phys. Chem. Lett. 2012, 3, 399.
[5] D. G. Evans, X. Duan, Chem. Commun. 2006, 5, 485.
[6] Q. Wang, D. O’Hare, Chem. Rev. 2012, 112, 4124.
[7] a) X. Guo, F. Zhang, D. G. Evans, X. Duan, Chem. Commun.
2010, 46, 5197; b) B. Sels, D. D. Vos, M. Buntinx, F. Pierard,
K. D. Mesmaeker, P. Jacobs, Nature 1999, 400, 855; c) P. J. Sideris,
U. G. Nielsen, Z. Gan, C. P. Grey, Science 2008, 321, 113;
d) G. Fan, F. Li, D. G. Evans, X. Duan, Chem. Soc. Rev. 2014, 43, 7040;
e) G. R. Williams, D. O’Hare, J. Mater. Chem. 2006, 30, 3065.
[8] M. Gong, Y. Li, H. Wang, Y. Liang, J. Z. Wu, J. Zhou, J. Wang,
T. Regier, F. Wei, H. Dai, J. Am. Chem. Soc. 2013, 135, 8452.
[9] M. Gong, H. Dai, Nano Res. 2015, 8, 23.
[10] a) F. Song, X. Hu, Nat. Commun. 2014, 5, 4477; b) R. Liu, Y. Wang,
D. Liu, Y. Zou, S. Wang, Adv. Mater. 2017, 29, 1701546.
[11] Z. Lu, W. Xu, W. Zhu, Q. Yang, X. Lei, J. Liu, Y. Li, X. Sun, X. Duan,
Chem. Commun. 2014, 50, 6479.
[12] a) W. Zhu, L. Liu, Z. Yue, W. Zhang, X. Yue, J. Wang, S. Yu, L. Wang,
J. Wang, ACS Appl. Mater. Interfaces 2017, 9, 19807; b) S. Anantharaj,
K. Karthick, M. Venkatesh, T. V. S. V. Simha, A. S. Salunke, L. Ma,
H. Liang, S. Kundu, Nano Energy 2017, 39, 30.
[13] a) B. M. Hunter, W. Hieringer, J. R. Winkler, H. B. Gray,
A. M. Müller, Energy Environ. Sci. 2016, 9, 1734; b) D. Zhou, Z. Cai,
Y. Bi, W. Tian, M. Luo, Q. Zhang, Q. Zhang, Q. Xie, J. Wang, Y. Li,
Y. Kuang, X. Duan, M. Bajdich, S. Siahrostami, X. Sun, Nano Res.
2017, https://doi.org/10.1007/s12274-017-1750-9.
[14] N. Yang, C. Tang, K. Wang, G. Du, A. M. Asiri, X. Sun, Nano Res.
2016, 9, 3346.
[15] a) H. Liu, Y. Wang, X. Lu, Y. Hu, G. Zhu, R. Chen, L. Ma, H. Zhu,
Z. Tie, J. Liu, Nano Energy 2017, 35, 350; b) P. Zhou, Y. Wang,
Adv. Energy Mater. 2018, 1703341 1703341  (8 of 8)
View publication stats
www.advenergymat.de
C. Xie, C. Chen, H. Liu, R. Chen, J. Huo, S. Wang, Chem. Commun.
2017, 53, 11778; c) Y. Wang, Y. Zhang, Z. Liu, C. Xie, S. Feng, D. Liu,
M. Shao, S. Wang, Angew. Chem., Int. Ed. 2017, 56, 5867.
[16] P. Li, Q. Xie, L. Zheng, G. Feng, Y. Li, Z. Cai, Y. Bi, Y. Li, Y. Kuang,
X. Sun, X. Duan, Nano Res. 2017, 10, 2988.
[17] a) L. Qian, Z. Lu, T. Xu, X. Wu, Y. Tian, Y. Li, Z. Huo, X. Sun,
X. Duan, Adv. Energy Mater. 2015, 5, 1500245; b) Z. Lu, L. Qian,
Y. Tian, Y. Li, X. Sun, X. Duan, Chem. Commun. 2016, 52, 908;
c) K. Fan, Y. Ji, H. Zou, J. Zhang, B. Zhu, H. Chen, Q. Daniel, Y. Luo,
J. Yu, L. Sun, Angew. Chem., Int. Ed. 2017, 56, 3289.
[18] a) L. Trotochaud, S. L. Young, J. K. Ranney, S. W. Boettcher,
J. Am. Chem. Soc. 2014, 136, 6744; b) D. Friebel, M. W. Louie,
M. Bajdich, K. E. Sanwald, Y. Cai, A. M. Wise, M.-J. Cheng,
D. Sokaras, T.-C. Weng, R. Alonso-Mori, R. C. Davis, J. R. Bargar,
J. K. Nørskov, A. Nilsson, A. T. Bell, J. Am. Chem. Soc. 2015, 137,
1305; c) M. W. Louie, A. T. Bell, J. Am. Chem. Soc. 2013, 135,
12329.
[19] K. Fan, H. Chen, Y. Ji, H. Huang, P. M. Claesson, Q. Daniel,
B. Philippe, H. Rensmo, F. Li, Y. Luo, Nat. Commun. 2016, 7,
11981.
[20] a) J. X. Feng, H. Xu, Y. T. Dong, S. H. Ye, Y. X. Tong, G. R. Li, Angew.
Chem., Int. Ed. 2016, 128, 3758; b) M. Ledendecker, G. Clavel,
M. Antonietti, M. Shalom, Adv. Funct. Mater. 2015, 25, 393;
c) S. Chen, J. Duan, P. Bian, Y. Tang, R. Zheng, S.-Z. Qiao, Adv.
Energy Mater. 2015, 5, 1500936; d) X. Lu, C. Zhao, Nat. Commun.
2015, 6, 6616.
[21] M. Gong, W. Zhou, M. C. Tsai, J. Zhou, M. Guan, M. C. Lin,
B. Zhang, Y. Hu, D. Y. Wang, J. Yang, Nat. Commun. 2014, 5, 4695.
[22] a) J. Wang, X. Ma, F. Qu, A. M. Asiri, X. Sun, Inorg. Chem. 2017,
56, 1041; b) Z. Ye, T. Li, G. Ma, Y. Dong, X. Zhou, Adv. Funct. Mater.
2017, 27, 1704083.
[23] a) G. Silversmit, D. Depla, H. Poelman, G. B. Marin, R. D. Gryse,
J. Electron Spectrosc. Relat. Phenom. 2004, 135, 167; b) Y. Yu, P. Li,
X. Wang, W. Gao, Z. Shen, Y. Zhu, S. Yang, W. Song, K. Ding,
Nanoscale 2016, 8, 10731.
[24] a) Y. Jia, L. Zhang, G. Gao, H. Chen, B. Wang, J. Zhou, M. T. Soo,
M. Hong, X. Yan, G. Qian, J. Zou, A. Du, X. Yao, Adv. Mater. 2017,
29, 1700017; b) X. Long, J. Li, S. Xiao, K. Yan, Z. Wang, H. Chen,
S. Yang, Angew. Chem., Int. Ed. 2014, 126, 7714; c) Z. Li, M. Shao,
H. An, Z. Wang, S. Xu, M. Wei, D. G. Evans, X. Duan, Chem. Sci.
2015, 6, 6624.
[25] Z. Lu, Z. Chang, W. Zhu, X. Sun, Chem. Commun. 2011, 47, 9651.
[26] a) Y. Bi, Z. Cai, D. Zhou, Y. Tian, Q. Zhang, Q. Zhang, Y. Kuang,
Y. Li, X. Sun, X. Duan, J. Catal. 2018, 358, 100; b) M. Luo, Z. Cai,
C. Wang, Y. Bi, L. Qian, Y. Hao, L. Li, Y. Kuang, Y. Li, X. Lei, Z. Huo,
W. Liu, H. Wang, X. Sun, X. Duan, Nano Res. 2017, 10, 1732.
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim