www.acsaem.

org Article

CoMoP/NiFe-Layered Double-Hydroxide Hierarchical Nanosheet

Arrays Standing on Ni Foam for Efficient Overall Water Splitting
Wanshan Mai, Qian Cui, Ziqiong Zhang, Kaikai Zhang, Guoqiang Li, Lihong Tian, and Wei Hu*
Cite This: ACS Appl. Energy Mater. 2020, 3, 8075−8085 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
Downloaded via NATL UNIV OF SCIENCES & TECHNOLOGY on July 21, 2025 at 11:50:26 (UTC).
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: For efficient water splitting and replacement of expensive Pt or Ir

with the earth-abundant materials, we have designed a heterostructure based on
the two-dimensional (2D) bimetallic phosphide and layered double hydroxide
(LDH) to construct the electrode assembly (i.e., CoxMo1P/NiFe-LDH) and
observed its catalytic activities for hydrogen evolution reaction (HER), oxygen
evolution reaction (OER), and overall water splitting. The optimized
Co5.0Mo1P/NiFe-LDH hybrid obtained via the hydrothermal−phosphating−
electrodeposition process consists of hierarchical nanosheet arrays including
some silky and ultrathin NiFe-LDH nanosheets and numerous tiny and cross-
linking Co5.0Mo1P nanoplates. Electrochemical tests display that Ni foam
(NF)/Co5.0Mo1P/NiFe-LDH not only exhibits outstanding performance
toward both HER and OER with an HER overpotential (η at 10 mA/cm2)
of 98.9 mV and an OER overpotential (at 50 mA/cm2) of 225 mV
outperforming NF/Co5.0Mo1P and NF/CoP but also presents superb stability
in 1.0 M KOH. Moreover, it affords a cell voltage for water splitting of 1.68 V at 50 mA/cm2 with an excellent durability for more
than 27 h. The abundant and intensive exposure of active sites provided by 2D porous and hierarchical nanosheet arrays and a strong
electronic coupling and fast electronic transmission between various interfaces would explain the improved performance. In addition,
the anchor effect between Co/Mo phosphides and NiFe-LDHs prevents corrosion of electrolyte solution and slows down the
dissolution of the P element. This efficient and highly stable bifunctional electrode can serve as a practical electrode for
electrochemical energy storage and conversion.
KEYWORDS: Ni foam, water splitting, hydrogen evolution reaction, oxygen evolution reaction, transition-metal phosphides,
layered double hydroxides

1. INTRODUCTION row transition-metal compounds (TMCs), such as Co-, Ni-,

As one of the clean energy storage and conversion Fe-, and Mo-based catalysts classified according to the
technologies, water electrolysis which can transform electrical chemical elements because of their high theoretical activities,
energy generated from the solar, wind, and other intermittent rich reserves, and low cost. Their oxides,8,9 phosphides
energies to chemical energy has a great potential to be (TMPs),10−12 sulfides,13,14 selenides,15 and alloys16 demon-
industrialized large scale.1,2 However, this process is still strate high HER/OER efficiency with some even surpassing
hampered by catalytic materials which are mainly precious the activity of noble metal benchmarks. Furthermore,
metals, such as Pt-based catalysts for hydrogen evolution constructing composites of these TMCs and heteroatom-
reaction (HER),3,4 and Ir- or Ru-based materials for oxygen doped C materials, such as Cu-MOF/GO,17 CoP/NC
evolution reaction (OER);5 therefore, the restrictions from nanopolyhedrons,18 Co−N−C,11 and CoP@porous NC,19
price and reserves are obvious. For tackling these challenges of and so forth, can also achieve the purpose for catalyzing
energy shortage and environmental degradation, the explora- both HER and OER. Obviously, in addition to the chemical
tion of cost-effective, easily available, highly efficient, and composition, the porous structures, suitable structure defects,
durable electrocatalysts to achieve the overall water splitting charge transfer capability, and synergistic effect between
(OWS) including two-half reactions, that is, HER and OER is
a feasible and promising strategy.6,7 Received: June 30, 2020
State-of-the-art research efforts for pursuing bifunctional Accepted: July 30, 2020
catalysts which can catalyze HER and OER simultaneously in Published: July 30, 2020
the same electrolyte mainly focus on their preparation, overall
catalytic activity and stability, and improvement strategies for
performance. Highly concerned materials are mainly the first-

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsaem.0c01538

8075 ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials www.acsaem.org Article

Figure 1. Schematic diagram of the preparation of CoxMo1P/NiFe-LDH on the NF substrate.

Figure 2. XRD patterns of the bare NF, NF/NiFe-LDH, NF/CoP, NF/Co5.0Mo1P, and NF/Co5.0Mo1P/NiFe-LDH (a), FESEM images of one-
step generated NF/Co5.0Mo1P (b,c) and two-step prepared NF/Co5.0Mo1P/NiFe-LDH (d,e), and SEM elemental mapping of NF/Co5.0Mo1P (f)
and NF/Co5.0Mo1P/NiFe-LDH (g).

components have exerted a strong influence on the electro- nanochains on NF can firmly anchor the subsequently grown
chemical activity and so became important considerations in NiFe-LDH. Further, MoP@Ni3P/NF nanosheets have given a
material designs. lower HER overpotential (η@10 mA/cm2 = 45 mV) and OER
Considering the high mass transfer and conductivity overpotential (η@35 mA/cm2 = 331 mV).21 It has been noted
requirements on the catalyst layer during H2 or O2 gas release, that 2D nanosheets have denser and more exposed active
assembling catalyst materials and conductive substrate without centers than those of 0D and 1D materials, where the diffusion
extra binders became a more practical choice. Novel electrode of water molecules (reactants) and gas (products) release can
assemblies with unique spatial morphology and more active be accelerated and the reactive efficiency has been improved.
sites for application purpose are coming thick and fast. Nevertheless, it was well documented that the single LDHs
Commonly, various structure-wise, hierarchical 3D materials display wonderful OER activity but relatively weak HER
with hollows and mesopores have been built directly on performance,22,23 while TMPs show more excellent HER
conductive supports, such as carbon paper, Ni foam (NF), or activity than their OER behavior, which suffers from a high
Ti foil. Therefore, it is very scientific and practical to synthesize OER overpotential and poor stability because of the leaching
active materials with hierarchical 3D porous structures and of P.24,25 Therefore, 2D−2D heterostructure assembling
hollow interiors directly attaching to the conductive substrates transition-metal LDH nanosheets on the surface of TMPs
which not only ensure highly exposed surface area, favorable has become a primary choice in which the synergy and
conductivity, and fast charge transfer but also promote the interfacial properties are very attractive, but achieving the most
mass transfer and structural stability during electrolysis. For advantages of two substances and a desirable OWS capability is
examples, porous Ni nanochains@NiFe-layered double- worth considering.
hydroxide (LDH) nanosheets with core−shell structures Herein, we apply a 2D heterostructure to form a 3D porous
have illustrated extraordinary performance for OER (η@10 electrode assembly, in which NiFe-LDH nanosheet arrays have
mA/cm2 = 218 mV), HER (η@10 mA/cm2 = 92 mV), and been electrodeposited vertically on the surface of bimetallic
OWS (cell voltage@10 mA/cm2 = 1.53 V).20 In addition to TMPs nanoflowers, which is previously generated on the NF
the advantages of large surface area, abundant active sites, and substrate through the hydrothermal−phosphating process. The
rich mass transfer channels offered by the porous core−shell resulting 2D heterostructure exhibits extremely low HER and
structures, the structure stability owing to in situ-grown Ni OER overpotentials and an excellent stability. Particularly, it
8076 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials www.acsaem.org Article

affords the OWS cell voltage of 1.68 V at 50 mA/cm2 with an LDH).29,30 In addition, relative to the strong diffraction of the
outstanding durability more than 27 h, which exceeds Fe/ NF substrate, characteristic peaks for the NiFe-LDH are not
Ni3S2/NF (1.54 V at 10 mA/cm2),26 CoP@NF (1.62 V at 10 well defined because of the thin catalyst films covered on the
mA/cm2),27 and Co5Mo1.0O/NF/Co5Mo1.0P/NF device (1.68 NF and poor crystallization degree.
V at 10 mA/cm2).28 Morphology of the as-prepared NF/Co5.0Mo1P and NF/
Co5.0Mo1P/NiFe-LDH is obtained using scanning electron
2. EXPERIMENTAL SECTION microscopy (SEM). Bare NF has distinct three-dimensional
CoxMo1P/NiFe-LDH nanosheet arrays were built on the NF surface network structures with a smooth surface (Figure S3). After
through a facile two-step procedure modified from Shao’s work,22 hydrothermal−phosphating treatment, the glabrous Ni frames
including the hydrothermal−phosphating step and electrodeposition are fully covered by the as-synthesized Co5.0Mo1P nanoflakes
process (Figure 1). First, bimetallic TMPs arrays with different Co/ (Figures 2b,c and S4), which stand upright on the NF with a
Mo ratios grow on the surface of NF (NF/CoxMo1P) via a sheet thickness of about 25−50 nm and obvious spherical
hydrothermal−phosphating process. In a typical synthesis, an protrusions, and connect into porous structures. After
inorganic salt solution including required amount of Co(NO3)2· electrodeposition, it can be noted that the hierarchical
6H2O and Na2MoO4·2H2O and a cleaned NF (2 cm × 3 cm × 1.6 nanoarrays have formed on the Co5.0Mo1P nanoflakes (Figure
mm) were placed into a 30 mL Teflon-lined stainless-steel autoclave
and then hydrothermally reacted for 6 h at 150 °C. After cooling to
S5). There exist some silky NiFe-LDH nanosheets with a
room temperature, NF covered with a dark purple thin film was smoother surface and thinner thickness (∼9 nm) than that of
obtained by washing with DI water and ethanol and then drying in Co5.0Mo1P (Figure 2d,e) and some tiny and cross-linking
vacuum at 60 °C for 6 h. Then, a tube furnace with NaH2PO2 nanoflakes attached at the bottom of nanoflower petals
powders at upstream and a purple NF at downstream was calcined at (denoted by the yellow circles in Figure 2d). Such large-
450 °C for 2 h with a heating speed of 5 °C/min in nitrogen flow. scale porous structures and highly exposed surface areas have a
Finally, a black NF/CoxMo1P was obtained after cooling naturally. very beneficial effect on the catalytic process, including HER
Adjusting the feeding ratio between Co and Mo, various bimetallic and OER by improving the mass transfer and the utilization of
NF/TMP composites (i.e., NF/Co2.3Mo1P, NF/Co4.0Mo1P, NF/ active sites.22,30 SEM elemental mapping of NF/Co5.0Mo1P
Co5.0Mo1P, and NF/Co6.5Mo1P) and the single metallic Co- and Mo-
phosphides were also prepared on NF according to this protocol, that
(Figure 2f) reveals a uniform distribution of Co, Mo, and P on
is, NF/CoP and NF/MoP. the surface of NF. The mapping results of NF/Co5.0Mo1P/
Second, NiFe-LDH nanosheets were formed via a fast electro- NiFe-LDH samples (Figure 2g) show a homogeneous
deposition method in a three-electrode cell taking the as-prepared distribution of NiFe-LDH arrays on the first-generated NF/
NF/Co5.0Mo1P as the working electrode, graphite rod as the counter Co5.0Mo1P substrate.
electrode, and Ag/AgCl as the reference electrode. The electrolyte The nanoflake structures of Co5.0Mo1P grown on the NF
consisted of 1.5 M FeSO4·7H2O and 1.5 M Ni(NO3)2·6H2O. At a substrate are also displayed by transmission electron
potential (E) of −1.0 V versus Ag/AgCl, the electrodeposition was microscopy (TEM) images (Figure 3a) with the d-spacing of
executed for 50, 100, and 200 s, respectively. After withdrawing from
the electroplating pool and rinsing with water, NF/Co5.0Mo1P/NiFe-
LDH (t) (t represents electrodeposition time) electrodes were
prepared.
For comparison, NiFe-LDH was electrodeposited directly on the
NF substrate to form NF/NiFe-LDH assembly as a comparison
sample. IrO2 and Pt/C (20 wt % Pt) ink was dropped on NF (the
loading was 2.4 mg/cm2), respectively, to get the NF/IrO2 and NF-
supported Pt/C reference sample.

3. RESULTS AND DISCUSSION

3.1. Structure and Morphology Features of the
Electrode Materials. Crystal structure characteristics of
NF/Co5.0Mo1P/NiFe-LDH and NF/Co5.0Mo1P have been
obtained from X-ray diffraction (XRD), which have also been
compared with NF/CoP, NF/NiFe-LDH, and the NF
substrate (Figure 2a). Note that the diffraction peaks of NF/
CoP can be indexed to the (110), (111), (210), and (300)
planes of CoNiP (PDF#71-2336) and the (111), (200), and
(220) planes of the NF substrate, meaning that the metal Ni
on the surface of NF participates in the hydrothermal−
phosphating reaction.29 XRD patterns for the bimetallic NF/
CoxMo1P samples, such as the typical NF/Co5.0Mo1P, NF/ Figure 3. TEM and HRTEM images of NF/Co5.0Mo1P (a,b) and
Co6.5Mo1P, and NF/Co4.0Mo1P match well with the single NF/Co5.0Mo1P/NiFe-LDH (c,d).
metallic NF/CoP (Figure S1) except for a slight right shift
(Figure S2), indicating that the successful doping of Mo leads
to the lattice shrinkage.29 Further, NF/Co5.0Mo1P/NiFe-LDH 0.22 nm corresponding to CoNiP(111) plane (Figure 3b). The
obtained by electrodeposition taking NF/Co5.0Mo1P as a selected area electron diffraction (SAED) pattern (inset in
substrate shows that the imperceptible diffraction peaks at Figure 3b) also exhibits discrete spots indexed to the (111),
about 23 and 34° are indexed to the NiFe-LDH (006) and (201), and (300) planes and suggests the polycrystalline nature
(009) planes, respectively, consistent with the structure of of Co5.0Mo1P, consistent with the results observed by
NiFe-LDH directly deposited on the NF substrate (NF/NiFe- Strongin.31 It is found that the thinner electrodeposited
8077 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials www.acsaem.org Article

Figure 4. Full-scan XPS spectra of NF/Co5.0Mo1P/NiFe-LDH and NF/Co5.0Mo1P assemblies (a), and Co 2p (b), Mo 3d (c), P 2p (d), Ni 2p (e),
and Fe 2p (f) spectra for NF/Co5.0Mo1P, NF/NiFe-LDH, and NF/Co5.0Mo1P/NiFe-LDH.

NiFe-LDH nanosheets with a d-spacing of 0.26 nm Co5.0Mo1P/NiFe-LDH, meaning that the hybrid possesses a
corresponded to the LDH (012) plane (Figure 3c,d). stronger electrophilicity leading to the superior OER activity.41
X-ray photoelectron spectroscopy (XPS) investigations of The fine-scan P 2p region for both samples (Figure 4d)
NF/CoP, NF/Co 5.0 Mo 1 P, NF/NiFe-LDH, and NF/ consists of two pairs of peaks attributing to the metal−
Co5.0Mo1P/NiFe-LDH composites have been conducted for phosphides (M−P) at 129.6 eV and P−Ox species at 133.8−
further understanding the interaction between Co5.0Mo1P 133.5 eV which derive from the surface oxidation of samples
nanoflakes and NiFe-LDH nanosheets. Full-scan XPS spectra exposed to air.29,42,43 The high-resolution Ni 2p spectra of NF/
and energy-dispersive spectroscopy indicate that NF/ Co5.0Mo1P, NF/CoP, NF/NiFe-LDH, and NF/Co5.0Mo1P/
Co5.0Mo1P contains P, Co, Mo, and Ni elements, and NF/ NiFe-LDH can be decomposed into two parts, that is, the
Co5.0Mo1P/NiFe-LDH consists of Ni, Fe, P, Mo, and Co partially charged Niδ+ (here, δ is close to 0)44 and Ni2+/3+
elements (Figures 4a and S6). The high-resolution Co 2p XPS species accompanied by the satellite peaks (Figure 4e). In the
spectrum (Figure 4b) shows that for the NF/Co5.0Mo1P case of NF/Co5.0Mo1P, the Ni signal comes from the surface of
sample, two pairs of peaks at 776.8 eV/791.9 eV and 781.8 eV/ the phosphated NF substrates which has been also proved by
797.8 belong to Co0 (2p3/2/2p1/2) and Co2+ (2p3/2/2p1/2), XRD. The Ni2+/3+ peak at 856.7 eV arises from the surface
respectively, with the Co2+ satellite peaks at 785.4 and 802.6 oxidation of phosphides,45 and a clearly observed Ni 2p3/2 peak
eV,32−34 which are upshifted by ∼0.4 eV relative to the NF/ at 852.9 eV is ascribed to the Ni−P bonding,46 whose binding
CoP sample (776.4 eV/791.0 eV for Co0 and 781.6 eV/796.5 energy is slightly higher than that of metallic Ni (852.6 eV)
eV Co2+). It indicates that Mo doping modifies the electronic meaning the presence of partially charged Niδ+ species.
structures of Co centers resulting into a strong electronic Compared with NF/CoP, Ni 2p peaks of NF/Co5.0Mo1P
interaction between Co and Mo centers, which regulates the exhibit the same law of binding energy shift (positive shift)
adsorption energy of H and is beneficial to HER.35,36 When with Co 2p, indicating that there is a strong electronic
electrodepositing NiFe-LDH nanosheets on NF/Co5.0Mo1P, interaction between Co, Mo, and Ni.47 For NF/NiFe-LDH
both Co0 and Co2+ peaks shift negatively by 1.5 and 0.6 eV and NF/Co5.0Mo1P/NiFe-LDH samples, Ni2+/Ni3+ peaks
respectively, meaning the increasing electron density around became dominant, corresponding to Ni(OH)2/NiOOH
the Co sites. It has been confirmed that during HER, metals in species in LDH. After NiFe-LDH growing on NF/
the TMPs act as the main active centers and follow the similar Co5.0Mo1P, the main Ni2+/Ni3+ peak (855.8 eV) shifts to a
reactive mechanism with the metal complex catalysts, in which lower binding energy (∼0.9 eV) compared to that of NF/
metal-active sites with increased electron density facilitates the Co5.0Mo1P (856.7 eV), suggesting an electronic structure
adsorption of H atoms (the first step of HER) resulting in the change on forming the LDH structure.48 The Fe 2p region of
improved HER.37 The deconvolution Mo 3d XPS spectra for NF/NiFe-LDH has three pairs of peaks (Figure 4f); the first
NF/Co5.0Mo1P and NF/Co5.0Mo1P/NiFe-LDH samples all doublet (711.3 eV/724.5 eV) can be assigned to Fe2+ (2p3/2
contain four peaks (Figure 4c), where two peaks assign to and 2p1/2),49 the second doublet (713.9 eV/727.2 eV) comes
Mo4+ (3d5/2/3d3/2) and the other two belong to Mo6+ (3d5/2/ down to Fe3+ species in FeOOH,50,51 and the satellite peaks of
3d3/2) because of the surface oxidation of samples.38−40 Fe3+ form the last pair (718.8 eV/731.7 eV).50 When NiFe-
However, it is noted that the Mo4+ (3d5/2) and Mo6+ (3d5/2) LDH nanosheets are electrodeposited on Co5.0Mo1P, the peaks
positions of NF/Co5.0Mo1P/NiFe-LDH move to the left by 0.5 of Fe 2p, Co 2p, Mo 3d, Ni 2p, and P 2p are all negatively
and 0.7 eV, respectively, compared with NF/Co5.0Mo1P, shifted. This shift is because of the transfer of protons from Ni
consistent with the trend of Co sites which still benefits the or Fe cations in the LDH to the nanoflowers (Co5.0Mo1P),
H adsorption during HER. The Mo6+/Mo4+ molar ratio resulting in a strong electronic interaction between the
increases from 0.16:1 for NF/Co5.0Mo1P to 1.68:1 for NF/ nanoflowers (Co5.0Mo1P) and the nanosheets (NiFe-LDH)
8078 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials www.acsaem.org Article

Figure 5. (a) OER polarization curves at a scan rate of 5 mV/s, (b) overpotential comparison at 50 mA/cm2, (c) Tafel curves of NF/Co5.0Mo1P/
NiFe-LDH, NF/Co5.0Mo1P, NF, NF/NiFe-LDH and NF/IrO2 in 1.0 M KOH, (d) Cdl results of NF/Co5.0Mo1P/NiFe-LDH, NF/Co5.0Mo1P, NF,
NF/NiFe-LDH, (e) EIS measured at ηOER = 310 mV for the corresponding electrocatalysts, and (f) stability measured by CP toward OER at 50
mA/cm2 of NF/Co5.0Mo1P/NiFe-LDH, NF/Co5.0Mo1P, NF/CoP, and NF/NiFe-LDH.

in the electrode assembly (no binder required), thereby Note that for NF/CoP, the oxidation peak of Co species
possibly improving the catalytic activity of NF/Co5.0Mo1P/ locates at ∼1.39 V, while these anodic peaks for NF/CoxMo1P
NiFe-LDH, which had been demonstrated by other hybrid shift to the lower potential (∼1.37 V), revealing that the
systems.46 electronic structure of CoP has likely been altered by Mo
3.2. Electrochemical Performance of Materials. doping, which has been proved by the foregoing XPS results.
3.2.1. Oxygen Evolution Reaction. OER performance of the Mo-doping may lower the thermodynamic barrier of the
obtained NF/Co5.0Mo1P and NF/Co5.0Mo1P/NiFe-LDH proton-coupled electron transfer pre-equilibrium and boost the
assemblies has been assessed by linear sweep voltammetry O−O bond formation, thus reducing the OER activation
(LSV) in 1.0 M KOH medium and is illustrated in Figure 5 energy and resulting in performance improvement.53 In
along with NF, NF/NiFe-LDH, and NF/IrO2 for comparison. addition, the electrodeposition time (t = 50, 100, 200 s) for
The NF/Co5.0Mo1P/NiFe-LDH hierarchical nanosheet arrays preparing NF/Co5.0Mo1P/NiFe-LDH has also been accurately
produce a significantly higher OER current density (Figure 5a) regulated, and the NF/Co5.0Mo1P/NiFe-LDH (100 s) hybrid
and greatly reduced overpotential (η@50 mA/cm2 is 225 mV, affords significant higher OER current than those of other
Figure 5b) compared to other electrodes. OER activities hybrids [i.e., NF/Co 5.0 Mo 1 P/NiFe-LDH (50 s), NF/
increase in the order of NF < NF/Co5.0Mo1P < NF/IrO2 < Co5.0Mo1P/NiFe-LDH (200 s)] and the un-electrodeposited
NF/NiFe-LDH < NF/Co5.0Mo1P/NiFe-LDH. It is noted that one, NF/Co5.0Mo1P (Figure S8). It is obvious that the activity
OER performance on the hierarchical NF/Co5.0Mo1P/NiFe- is significantly improved by forming the NF/Co5.0Mo1P/NiFe-
LDH nanosheet hybrid exceeds any single component, that is, LDH composites, even exceeding the NF/IrO2 benchmark.
Co5.0Mo1P and NiFe-LDH, meaning the strong synergies However, the activity on NF/Co5.0Mo1P/NiFe-LDH (200 s)
between Co5.0Mo1P and NiFe-LDH. All electrodes have the does not exhibit the expected increase relative to that of NF/
obvious anodic peaks in 1.1−1.5 V potential window, which Co5.0Mo1P/NiFe-LDH (100 s) because of the blocked mass
might be associated with the oxidation of the transition metals transfer path result from the excessive LDH nanoflakes
(Ni or Co or Fe).52 In fact, the Co/Mo molar ratio of 5.0:1 is a electrodeposited on NF/Co5.0Mo1P, which matches well with
pre-optimized result via the molar ratio screening (Figure S7) Shao’s results.22 The optimized NF/Co5.0Mo1P/NiFe-LDH
that the electrode with the Co/Mo ratio of 5.0:1 obtains the assembly has the lowest Tafel slope (55 mV/dec) suggesting
maximum current density among all the tested NF/CoxMo1P. its fastest OER process (Figure 5c). The calculated turnover
8079 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials www.acsaem.org Article

Figure 6. (a) HER polarization curves at a potential scan rate of 5 mV/s, (b) corresponding potential comparison at −10 and −50 mA/cm2,
respectively, (c) Tafel curves, (d) Cdl results of NF/Co5.0Mo1P/NiFe-LDH, NF/Co5.0Mo1P, NF, NF/NiFe-LDH and NF-supported Pt/C, (e)
Nyquist plots at ηHER = 40 mV, and (f) stability measured by CP towards HER at −50 mA/cm2 on NF/Co5.0Mo1P/NiFe-LDH and NF/Co5.0Mo1P
in 1.0 M KOH.

frequency value at 1.45 V is ca. 4.2 s−1 obtained using a slope compared to other samples. The chronopotentiometry
reported method (Supporting Information).54 These parame- (CP) test (Figure 5f) shows that NF/Co5.0MoP and NF/
ters can be compared to recent results reported on many Co5.0MoP/NiFe-LDH are very stable for OER, and the
efficient OER catalysts (Table S1) and make the NF/ potentials required for maintaining a constant current density
Co5.0Mo1P/NiFe-LDH a high-class nonprecious OER catalyst. (50 mA/cm2) just increase slightly by 0.3% for NF/Co5.0Mo1P
Electrochemical active surface area (ECSA) of each catalyst and 0.2% for NF/Co5.0MoP/NiFe-LDH during the 24 h test
has been estimated from its double-layer capacitances (Cdl), period, which are better than that of the reported NiCoP/NF
which can be measured using a simple cyclic voltammetry (the potential at 10 mA/cm2 increased by 1.3%).56 It had been
method in a narrow potential window with no Faradic reported that the TMPs usually suffer from activity
processes (Figure S9).55 As shown in Figure 5d, Cdl decreases deterioration because of the easy dissolution of P leading to
in the order of NF/Co5.0Mo1P/NiFe-LDH (25.68 mF/cm2) > the destruction of P-based species which are efficient to OER
NF/Co5.0Mo1P (21.46 mF/cm2) > NF/NiFe-LDH (1.48 mF/ during the long-time electrolysis.57,58 Surprisingly, neither NF/
cm2) > NF (1.40 mF/cm2), suggesting that the previously Co5.0Mo1P, NF/NiFe-LDH, nor NF/Co5.0Mo1P/NiFe-LDH
generated Co5.0Mo1P nanoflakes on NF provide a huge open exhibits the activity degradation, which is much different from
surface resulting in the much larger ECSA in NF/Co5.0Mo1P/ the single-metal phosphide (NF/CoP), owing to the
NiFe-LDH hybrid relative to the NiFe-LDH directly formed synergistic effect between Co5.0Mo1P and NiFe-LDH.
on NF, which fully demonstrates the heterostructure 3.2.2. Hydrogen Evolution Reaction. HER performance of
advantages of 2D Co5.0Mo1P/NiFe-LDH. Electrochemical the as-prepared NF/Co 5.0 Mo 1 P, NF/NiFe-LDH, NF/
impedance spectroscopy (EIS) results obtained at the OER Co5.0Mo1P/NiFe-LDH assemblies has also been compared
overpotential of 310 mV (Figure 5e and Table S2) have via LSV in 1.0 M KOH medium taking NF and NF-supported
verified that NF/Co5.0Mo1P/NiFe-LDH has the lowest charge Pt/C (20 wt % Pt) as the reference electrodes. Figure 6a gives
transfer resistance (Rct) between the electrolyte and electro- the detailed polarization curves recorded on the above-
catalyst interface, where the Rct for NF/Co5.0Mo1P/NiFe- mentioned electrodes, demonstrating that the optimized NF/
LDH, NF/Co5.0Mo1P, NF/NeFe-LDH and NF is 0.16, 0.38, Co5.0Mo1P/NiFe-LDH electrode possesses much higher HER
0.24, and 1.63 Ω, respectively, suggesting a relative faster activity than those of NF/Co5.0Mo1P, NF/NiFe-LDH, and the
charge transfer kinetics on NF/Co5.0Mo1P/NiFe-LDH. The bare NF. Typically, to generate a HER current density of −10
higher ECSA and lower Rct for NF/Co5.0Mo1P/NiFe-LDH mA/cm2, NF/Co5.0Mo1P/NiFe-LDH just provides 98.9 mV
also contribute to its lower overpotential and smaller Tafel which is dramatically lower than the potentials needed on NF/
8080 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials www.acsaem.org Article

Figure 7. (a) OWS polarization curves of NF/Co5.0Mo1P/NiFe-LDH|NiFe-LDH/Co5.0Mo1P/NF, NF/Co5.0Mo1P/NiFe-LDH|Co5.0Mo1P/NF,

NF/Co5.0Mo1P|Co5.0Mo1P/NF, and NF|NF cells at 5 mV/s and (b) long-term stability tests carried out at constant current densities of 100 mA/
cm2. Inset is the digital photograph of the single-electrolyte cell with two electrodes.

Co5.0Mo1P (104.1 mV), NF (185.3 mV), and NF/NiFe-LDH synergy effect between Co5.0Mo1P and NiFe-LDH again. EIS
(201.2 mV) (Figure 6b), including other typical HER catalysts results (Figure 6e and Table S2) show that NF/Co5.0Mo1P/
(Table S3). The performance trend is similar in the case of NiFe-LDH has the smallest Rct for HER among the tested
taking the potential at −50 mA/cm2 as the evaluation standard. samples, suggesting a rapid and favorable kinetics on the NF/
Obviously, the gap between noble metal and nonprecious Co5.0Mo1P/NiFe-LDH heterostructure.59 The CP test at −50
metal catalysts has been narrowed by building a 2D composite mA/cm2 (Figure 6f) reveals that both the optimized NF/
structure of TMP and LDH. We have also inspected the Co/ Co5.0Mo1P/NiFe-LDH and NF/Co5.0Mo1P maintain their
Mo molar ratio- and electrodeposition time-dependent HER activity after 27 h of continuous test, which is superior to
activities for NF/CoxMo1P and NF/Co5.0Mo1P/NiFe-LDH that of the most reported electrocatalytic materials (usually
electrodes, respectively. The results show that the Co/Mo tested at −10 mA/cm2 and for less than 24 h). Above-
molar ratio of 5.0:1 is the best formula, which shows the lowest mentioned results illustrate that the NF/Co5.0Mo1P/NiFe-
E@−10 mA/cm2 among all the tested NF/CoxMo1P electro- LDH heterostructure can be applied as an excellent bifunc-
des (Figure S10). HER activity of these phosphides decreases tional electrocatalyst toward both OER and HER.
in the following order: Co5.0Mo1P > Co4.0Mo1P > Co6.5Mo1P > In addition, in the neutral electrolyte case (i.e., 1.0 M
Co2.3Mo1P > CoP > MoP. It is visible that the HER activity on phosphate-buffered saline), NF/Co5.0Mo1P/NiFe-LDH also
Co/Mo phosphides exceeds that of the single-metal−P (CoP has excellent HER and OER activities. Polarization curves in
or MoP), exhibiting a significant synergy effect between Co Figure S13a,c and Tafel plots in Figure S13b,d show that NF/
and Mo species. Actually, in the Co−Mo−P system, three
Co5.0Mo1P/NiFe-LDH has the lowest HER overpotential of
elements all have performed their respective functions.
147 mV and OER overpotential of 430 mV to get a current
Specifically, because of the electronegative P, the nearby
density of 10 mA/cm2 with the smallest Tafel slope among all
metal atoms (Co or Mo) are positively charged and have
strong adsorption capacity for the HER intermediates (e.g., the tested samples, indicating its faster kinetics for both OER
OH− and H2O). According to Strongin’s density functional and HER in the neutral electrolyte. EIS in Figure S14e shows
theory calculation results,31 the Gibbs adsorption free energies that Rct for HER (η = 40 mV) of NF/Co5.0Mo1P/NiFe-LDH,
for OH− and H2O (ΔGOH− and ΔGH2O) on CoP are much NF/Co5.0Mo1P, NF/NiFe-LDH, and NF is 0.2, 26.0, 2.4, and
32.0 Ω, respectively, and the corresponding Rct for OER (η =
higher than those on Co/Mo alloy but display the moderate 220 mV) in Figure S14f is 2.3, 66.2, 2.4, and 720.0 Ω. It verifies
values on Mo-doped CoP. P plays key roles for pushing the the enhanced charge transfer rate of NF/Co5.0Mo1P/NiFe-
Volmer step during the HER process. H-binding on CoP is too
LDH than that of other tested samples in neutral solution
strong resulting the catalytic active sites in always being
consistent with the results in KOH situation.
occupied; the Mo-doping will weaken the H-binding to
3.2.3. Overall Water Splitting. Taking NF/Co5.0Mo1P or
promote the evolution of H2 (Tafel step). Thus, this clever
NF/Co5.0Mo1P/NiFe-LDH as the HER cathode or OER
chemical interaction between each element leads to the
outstanding HER performance for the Co−Mo−P system. anode to construct the single-electrolyte cells, denoted as NF/
Meanwhile, HER performance on NF/Co5.0Mo1P/NiFe-LDH Co 5.0 Mo 1 P/NiFe-LDH|NiFe-LDH/Co 5.0 Mo 1 P/NF, NF/
electrodes prepared by electrodepositing for different times Co5.0Mo1P/NiFe-LDH|Co5.0Mo1P/NF, and NF/Co5.0Mo1P|
increases as the following order, 50 < 200 < 100 s (Figure Co5.0Mo1P/NF, respectively, we further evaluate their OWS
S11). Therefore, all testing results manifest that NF/ performance in 1.0 M KOH. During the test period, as the
Co5.0Mo1P/NiFe-LDH (100 s) has the best HER activity. applied voltage increases, hydrogen and oxygen gas bubbles
Interestingly, the decrease in the Tafel slope of the electrode from cathode and anode, respectively, become more and more
after electrodeposition (NF/Co5.0Mo1P/NiFe-LDH) indicates intense. As shown in Figure 7a, the cell voltage of NF/
a strong interaction between Co5.0Mo1P nanoflakes and NiFe- Co5.0Mo1P/NiFe-LDH|NiFe-LDH/Co5.0Mo1P/NF (1.68 V at
LDH nanosheets leading to reducing the charge transfer 50 mA/cm2 and 1.79 V at 100 mA/cm2) is significantly lower
resistance between different interfaces (Figure 6c). From than that of NF/Co5.0Mo1P/NiFe-LDH|Co5.0Mo1P/NF (1.71
Figures 6d and S12, it is found that the NF/Co5.0Mo1P/NiFe- V at 50 mA/cm2 and 1.82 V at 100 mA/cm2), NF/Co5.0Mo1P|
LDH hybrid has the highest Cdl (32.28 mF/cm2) than those of Co5.0Mo1P/NF (1.77 V at 50 mA/cm2 and 1.91 V at 100 mA/
others, suggesting that our hierarchical-structured NF/ cm2), and NF|NF (1.92 V at 50 mA/cm2). These parameters
Co5.0Mo1P/NiFe-LDH provides more open active sites are superior or comparable to the results on the recently
facilitating the electrocatalytic reaction, demonstrating a reported non-noble metal materials (Table S4). Moreover,
8081 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials www.acsaem.org Article

abovementioned electrolysers present very stable CP responses Mo4+/Mo6+ molar ratio of 0.22:1 (0.60:1 for the fresh sample),
upon a 27 h long-time test at 100 mA/cm2 (Figure 7b). while in case of the post-OER one, Mo6+ is dominant (Figure
For further insights into the stability of materials, the SEM 9c). No significant variation is seen from the P 2p spectrum for
images of NF/Co5.0Mo1P/NiFe-LDH and NF/Co5.0Mo1P the post-HER NF/Co5.0Mo1P/NiFe-LDH sample, but the M−
after 27 h OER have been compared which show that the P peaks in post-OER NF/Co5.0Mo1P/NiFe-LDH disappears,
simple 2D-structured Co5.0Mo1P nanoplates have collapsed or suggesting in the strong anodic condition during OER, and
stripped from NF frames partially (Figure 8a), while the TMPs have been oxidized to MOx or M−OOH (Figure 9d).
This phase transformation can be further confirmed by a
decrease in P atom % (Figure S14). The Ni 2p spectrum after a
long-time HER test is similar with the fresh one, but the δ
value for Niδ+ peaks in the post-OER sample is close to
1(Figure 9e). Both post-HER and post-OER samples have no
obvious changes in Fe 2p fine spectra (Figure 9f). In
comparison, changes in Co 2p3/2, Mo 3d, P 2p, and Ni 2p3/2
fine-scan spectra of NF/Co5.0Mo1P/NiFe-LDH after long-time
OER measurement are more notable, where the peaks at the
low binding energies (775.3 eV for Co 2p3/2, 230.4 eV for Mo
3d5/2, 129.6 eV for M−P, and 852.8 eV for Ni 2p3/2 of the fresh
surface) disappeared including the appearance of M−O after
the OER stability test, meaning the oxidation of the catalyst
surface and the phase transformation of TMPs to M−Ox or
M−OOH species, which are still considered active phases for
OER.55 Overall, the NF/Co5.0Mo1P/NiFe-LDH hybrid still
maintains the nanosheet architectures and main crystalline
phases attributing to the synergistic effect of the strong
interface interaction in the Co5.0Mo1P and NiFe-LDH
heterostructure.
The abovementioned results illustrate that the hierarchical
Co5.0Mo1P/NiFe-LDH nanosheets growing on NF have
outstanding OER and HER bifunctional activities and long-
term durability, which could be attributed to the following
advantages: (1) Mo-doping tunes the electronic structure
leading to optimizing the HER performance, (2) the
heterostructure of Co/Mo phosphide nanoflakes and NiFe-
LDH nanosheets provides highly exposed surface allowing the
efficient use of active sites, (3) the open and cross-linked
Figure 8. SEM images of NF/Co5.0Mo1P (a) and NF/Co5.0Mo1P/
channels perpendicular to the NF substrate are very beneficial
NiFe-LDH (b) as the OER anode after the 27 h stability test. TEM to gas release during HER and OER, (4) the strong synergy on
and HRTEM images of NF/Co5.0Mo1P/NiFe-LDH after long-time interfaces between Co/Mo phosphides and NiFe-LDH plays
HER (c,d and inset) and OER measurements (e,f and inset). an importance influence on bifunctional activity, (5) the direct
electrodeposition of LDH on Co/Mo phosphides and the
morphology of the NF/Co5.0Mo1P/NiFe-LDH heterostructure hydrothermal generation of Co/Mo phosphides on NF
is basically unchanged (Figure 8b). The NF/Co5.0Mo1P/NiFe- without any binders not only guarantee good mechanical
LDH assembly after long-time HER and OER tests is also adhesion but also electrical conductivity, and (6) NF has
characterized, respectively, by TEM and XPS. For the post- participated in catalytic reactions to a certain extent. This
HER and post-OER NF/Co5.0Mo1P/NiFe-LDH samples, the strategy of construction of the 2D heterostructure could be
main crystal structure and morphology basically remain the widely applied into the energy conversion-related devices.
same as seen before from the TEM, high-resolution (HR)
TEM, and SAED images in Figure 8c−f. However, some subtle 4. CONCLUSIONS
changes are observed by XPS analysis. It can be observed from In summary, we have successfully built a heterostructure
O 1s spectra (Figure 9a) that the molar ratio of M−OH/H− assembly based on the NF substrate, transition-metal
O−H for the post-HER NF/Co5.0Mo1P/NiFe-LDH sample is phosphide, and LDH, which are the hierarchical nanosheet
6.4:1 increasing from 3.9:1 of the fresh one, and the post-OER arrays including the thicker Co/Mo phosphide nanoflakes and
NF/Co5.0Mo1P/NiFe-LDH has M−O species besides M−OH the thinner NiFe-LDH nanosheets. The as-synthesized
and H−O−H species. It suggests that M−P species on the heterostructure possesses more excellent bifunctional perform-
surface of the catalyst converts to M−OH during HER and ance with overpotentials (η at 50 mA/cm2) of 173 mV for
M−O/MOOH during OER, which are still considered as the HER and 225 mV for OER compared to the simple NF/
typical catalytic phases for both reactions. The increased O Co5.0Mo1P nanostructure. The electrolyser taking NF/
content in NF/Co5.0Mo1P/NiFe-LDH after long-time HER/ Co5.0Mo1P/NiFe-LDH as the OER anode and HER cathode,
OER also confirms this phase transformation (Figure S14). Co respectively, exhibits the lowest cell voltage (1.68 V at 50 mA/
2p fine spectra display that peaks originally representing the cm2) for water splitting with respect to other water splitting
Co0 shift right in both cases (Figure 9b). The Mo 3d spectrum devices and the outstanding stability. The suitable 2D
for the post-HER NF/Co5.0Mo1P/NiFe-LDH sample has the heterostructure, the synergy between Co/Mo phosphide
8082 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials www.acsaem.org Article

Figure 9. XPS patterns of the NF/Co5.0Mo1P/NiFe-LDH electrode after long-time HER and OER tests. (a) O 1s, (b) Co 2p, (c) Mo 3d, (d) P 2p,
(e) Ni 2p, and (f) Fe 2p spectra for the post-HER and post-OER NF/Co5.0Mo1P/NiFe-LDH samples.

nanoflakes and NiFe-LDH nanosheets, the electronic regu- Kaikai Zhang − Hubei Collaborative Innovation Center for
lation coming from the Mo-doping, and the partially involved Advanced Organic Chemical Materials, Ministry-of-Education
Ni atoms on the NF substrate explain such excellent activity Key Laboratory for the Synthesis and Applications of Organic
and stability. This 2D heterostructure is expected to provide a Functional Molecules, Hubei University, Wuhan 430062,
new option for electrode design of energy-related devices. China

■
*
ASSOCIATED CONTENT
sı Supporting Information
Guoqiang Li − Hubei Collaborative Innovation Center for
Advanced Organic Chemical Materials, Ministry-of-Education
Key Laboratory for the Synthesis and Applications of Organic
The Supporting Information is available free of charge at Functional Molecules, Hubei University, Wuhan 430062,
https://pubs.acs.org/doi/10.1021/acsaem.0c01538. China
Details for physical and electrochemical character- Lihong Tian − Hubei Collaborative Innovation Center for
izations of NF/CoxMo1P and NF/Co5.0Mo1P/NiFe- Advanced Organic Chemical Materials, Ministry-of-Education
LDH (t) (PDF) Key Laboratory for the Synthesis and Applications of Organic

■
Functional Molecules, Hubei University, Wuhan 430062,
China
AUTHOR INFORMATION
Complete contact information is available at:
Corresponding Author
https://pubs.acs.org/10.1021/acsaem.0c01538
Wei Hu − Hubei Collaborative Innovation Center for Advanced
Organic Chemical Materials, Ministry-of-Education Key
Author Contributions
Laboratory for the Synthesis and Applications of Organic
Functional Molecules, Hubei University, Wuhan 430062, The manuscript was written through contributions of all
China; orcid.org/0000-0002-2812-537X; authors. All authors have given approval to the final version of
Email: [email protected], [email protected] the manuscript.
Authors Funding
Wanshan Mai − Hubei Collaborative Innovation Center for Author W.H. received funding from National Natural Science
Advanced Organic Chemical Materials, Ministry-of-Education Foundation of China (NSFC no. 21606075), and L.T. received
Key Laboratory for the Synthesis and Applications of Organic
Functional Molecules, Hubei University, Wuhan 430062, funding from National Natural Science Foundation of China
China (NSFC no. 51872081).
Qian Cui − Hubei Collaborative Innovation Center for Advanced Notes
Organic Chemical Materials, Ministry-of-Education Key
The authors declare no competing financial interest.

■
Laboratory for the Synthesis and Applications of Organic
Functional Molecules, Hubei University, Wuhan 430062,
China ACKNOWLEDGMENTS
Ziqiong Zhang − Hubei Collaborative Innovation Center for This work is supported by the National Natural Science
Advanced Organic Chemical Materials, Ministry-of-Education
Foundation of China (NSFC nos. 21606075 and 51872081).
Key Laboratory for the Synthesis and Applications of Organic
Functional Molecules, Hubei University, Wuhan 430062, The authors thank the Shiyanjia Lab for HRTEM observation
China (www.shiyanjia.com).
8083 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials

■
www.acsaem.org Article

REFERENCES cobalt-based metal−organic frameworks. Chem. Mater. 2015, 27,

7636−7642.
(1) Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; (19) Peng, Z.; Yu, Y.; Jiang, D.; Wu, Y.; Xia, B. Y.; Dong, Z. N-doped
Nørskov, J. K.; Jaramillo, T. F. Combining theory and experiment in carbon shell coated CoP nanocrystals encapsulated in porous N-
electrocatalysis: Insights into materials design. Science 2017, 355,
doped carbon substrate as efficient electrocatalyst of water splitting.
No. eaad4998.
Carbon 2019, 144, 464−471.
(2) Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.;
(20) Cai, Z.; Bu, X.; Wang, P.; Su, W.; Wei, R.; Ho, J. C.; Yang, J.;
Mi, Q.; Santori, E. A.; Lewis, N. S. Solar water splitting cells. Chem.
Wang, X. Simple and cost effective fabrication of 3D porous core−
Rev. 2010, 110, 6446−6473.
shell Ni nanochains@ NiFe layered double hydroxide nanosheet
(3) Zeng, X.; Shui, J.; Liu, X.; Liu, Q.; Li, Y.; Shang, J.; Zheng, L.;
bifunctional electrocatalysts for overall water splitting. J. Mater. Chem.
Yu, R. Single-Atom to Single-Atom Grafting of Pt1 onto FeN4 Center:
A 2019, 7, 21722−21729.
Pt1@FeNC Multifunctional Electrocatalyst with Significantly En-
(21) Wang, F.; Chen, J.; Qi, X.; Yang, H.; Jiang, H.; Deng, Y.; Liang,
hanced Properties. Adv. Energy Mater. 2018, 8, 1701345.
T. Increased nucleation sites in nickel foam for the synthesis of
(4) Li, Q.; Zou, X.; Ai, X.; Chen, H.; Sun, L.; Zou, X. Revealing
MoP@ Ni3P/NF nanosheets for bifunctional water splitting. Appl.
Activity Trends of Metal Diborides Toward pH-Universal Hydrogen
Surf. Sci. 2019, 481, 1403−1411.
Evolution Electrocatalysts with Pt-Like Activity. Adv. Energy Mater.
(22) Zhou, L.; Jiang, S.; Liu, Y.; Shao, M.; Wei, M.; Duan, X.
2019, 9, 1803369.
(5) Spöri, C.; Briois, P.; Nong, H. N.; Reier, T.; Billard, A.; Kühl, S.; Ultrathin CoNiP@ Layered Double Hydroxides Core−Shell Nano-
Teschner, D.; Strasser, P. Experimental Activity Descriptors for sheets Arrays for Largely Enhanced Overall Water Splitting. ACS Appl.
Iridium-based Catalysts for the Electrochemical Oxygen Evolution Energy Mater. 2018, 1, 623−631.
Reaction (OER). ACS Catal. 2019, 9, 6653−6663. (23) Zhang, C.; Zhao, J.; Zhou, L.; Li, Z.; Shao, M.; Wei, M. Layer-
(6) Gray, H. B. Powering the planet with solar fuel. Nat. Chem. by-layer assembly of exfoliated layered double hydroxide nanosheets
2009, 1, 7. for enhanced electrochemical oxidation of water. J. Mater. Chem. A
(7) Kim, J. H.; Lee, J. S. Solar Water Splitting: Elaborately Modified 2016, 4, 11516−11523.
BiVO4 Photoanodes for Solar Water Splitting. Adv. Mater. 2019, 31, (24) Cai, P.; Huang, J.; Chen, J.; Wen, Z. Oxygen-containing
1970146. amorphous cobalt sulfide porous nanocubes as high-activity electro-
(8) Liu, Z.; Tan, H.; Liu, D.; Liu, X.; Xin, J.; Xie, M.; Song, L.; Dai, catalysts for the oxygen evolution reaction in an alkaline/neutral
L.; Liu, H. Promotion of Overall Water Splitting Activity Over a Wide medium. Angew. Chem., Int. Ed. 2017, 56, 4858.
pH Range by Interfacial Electrical Effects of Metallic NiCo-nitrides (25) Zhang, R.; Wang, X.; Yu, S.; Wen, T.; Zhu, X.; Yang, F.; Sun,
Nanoparticle/NiCo2O4 Nanoflake/graphite Fibers. Adv. Sci. 2019, 6, X.; Wang, X.; Hu, W. Ternary NiCo2Px nanowires as pH-universal
1801829. electrocatalysts for highly efficient hydrogen evolution reaction. Adv.
(9) Zhuang, M.; Liu, Z.; Ding, Y.; Xu, G.-L.; Li, Y.; Tyagi, A.; Zhang, Mater. 2017, 29, 1605502.
X.; Sun, C.-J.; Ren, Y.; Ou, X.; Wong, H.; Cai, R.; Abidi, I. H.; Zhang, (26) Zhang, G.; Feng, Y.; Lu, W.; He, D.; Wang, C.; Li, Y.; Wang,
Q.; Xu, F.; Amine, K.; Luo, Z. Methacrylated gelatin-embedded X.; Cao, F. Enhanced catalysis of electrochemical overall water
fabrication of 3D graphene-supported Co3O4 nanoparticles for water splitting in alkaline media by Fe doping in Ni3S2 nanosheet arrays.
splitting. Nanoscale 2019, 11, 6866−6875. ACS Catal. 2018, 8, 5431−5441.
(10) Wang, S.; Zhang, L.; Li, X.; Li, C.; Zhang, R.; Zhang, Y.; Zhu, (27) Qiu, B.; Han, A.; Jiang, D.; Wang, T.; Du, P. Cobalt phosphide
H. Sponge-like nickel phosphide−carbon nanotube hybrid electrodes nanowire arrays on conductive substrate as an efficient bifunctional
for efficient hydrogen evolution over a wide pH range. Nano Res. catalyst for overall water splitting. ACS Sustainable Chem. Eng. 2018,
2017, 10, 415−425. 7, 2360−2369.
(11) Wang, J.; Cui, W.; Liu, Q.; Xing, Z.; Asiri, A. M.; Sun, X. Recent (28) Zhang, Y.; Shao, Q.; Long, S.; Huang, X. Cobalt-molybdenum
Progress in Cobalt-Based Heterogeneous Catalysts for Electro- nanosheet arrays as highly efficient and stable earth-abundant
chemical Water Splitting. Adv. Mater. 2016, 28, 215−230. electrocatalysts for overall water splitting. Nano Energy 2018, 45,
(12) Yang, N.; Tang, C.; Wang, K.; Du, G.; Asiri, A. M.; Sun, X. 448−455.
Iron-doped nickel disulfide nanoarray: A highly efficient and stable (29) Wang, J.; Chang, K.; Sun, Z.; Lee, J. H.; Tackett, B. M.; Zhang,
electrocatalyst for water splitting. Nano Res. 2016, 9, 3346−3354. C.; Chen, J. G.; Liu, C.-J. A Combined experimental and theoretical
(13) Qi, K.; Yu, S.; Wang, Q.; Zhang, W.; Fan, J.; Zheng, W.; Cui, X. study of the accelerated hydrogen evolution kinetics over wide pH
Decoration of the inert basal plane of defect-rich MoS2 with Pd atoms range on porous transition metal doped tungsten phosphide
for achieving Pt-similar HER activity. J. Mater. Chem. A 2016, 4, electrocatalysts. Appl. Catal., B 2019, 251, 162−167.
4025−4031. (30) Li, X.; Hao, X.; Wang, Z.; Abudula, A.; Guan, G. In-situ
(14) Zhu, Y.; Song, L.; Song, N.; Li, M.; Wang, C.; Lu, X. intercalation of NiFe LDH materials: An efficient approach to
Bifunctional and Efficient CoS2−C@ MoS2 Core−Shell Nano- improve electrocatalytic activity and stability for water splitting. J.
fiberElectrocatalyst for Water Splitting. ACS Sustainable Chem. Eng. Power Sources 2017, 347, 193−200.
2019, 7, 2899−2905. (31) Thenuwara, A. C.; Dheer, L.; Attanayake, N. H.; Yan, Q.;
(15) Liu, S.; Jiang, Y.; Yang, M.; Zhang, M.; Guo, Q.; Shen, W.; He, Waghmare, U. V.; Strongin, D. R. Co-Mo-P Based Electrocatalyst for
R.; Li, M. Highly conductive and metallic cobalt−nickel selenide Superior Reactivity in the Alkaline Hydrogen Evolution Reaction.
nanorods supported on Ni foam as an efficient electrocatalyst for ChemCatChem 2018, 10, 4832.
alkaline water splitting. Nanoscale 2019, 11, 7959−7966. (32) Liu, J.; Ji, Y.; Nai, J.; Niu, X.; Luo, Y.; Guo, L.; Yang, S.
(16) Lv, Y.; Batool, A.; Wei, Y.; Xin, Q.; Boddula, R.; Jan, S. U.; Ultrathin amorphous cobalt−vanadium hydr(oxy) oxide catalysts for
Akram, M. Z.; Tian, L.; Guo, B.; Gong, J. R. Homogeneously the oxygen evolution reaction. Energy Environ. Sci. 2018, 11, 1736−
Distributed NiFe Alloy Nanoparticles on 3D Carbon Fiber Network 1741.
as a Bifunctional Electrocatalyst for Overall Water Splitting. (33) Liang, Q.; Jin, H.; Wang, Z.; Xiong, Y.; Yuan, S.; Zeng, X.; He,
ChemElectroChem 2019, 6, 2497. D.; Mu, S. Metal-organic frameworks derived reverse-encapsulation
(17) Jahan, M.; Liu, Z.; Loh, K. P. Graphene oxide and copper- Co-NC@ Mo2C complex for efficient overall water splitting. Nano
centered metal organic framework composite as a tri-functional Energy 2019, 57, 746−752.
catalyst for HER, OER, and ORR. Adv. Funct. Mater. 2013, 23, 5363− (34) Zhang, K.; Mai, W.; Li, J.; Li, G.; Tian, L.; Hu, W. Bimetallic
5372. Co3.2Fe0.8N−Nitrogen−Carbon Nanocomposites for Simultaneous
(18) You, B.; Jiang, N.; Sheng, M.; Gul, S.; Yano, J.; Sun, Y. High- Electrocatalytic Oxygen Reduction, Oxygen Evolution, and Hydrogen
performance overall water splitting electrocatalysts derived from Evolution. ACS Appl. Nano Mater. 2019, 2, 5931−5941.

8084 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085
ACS Applied Energy Materials www.acsaem.org Article

(35) Guan, C.; Xiao, W.; Wu, H.; Liu, X.; Zang, W.; Zhang, H.; (51) Ma, Y.; Wang, Y.; Xie, D.; Gu, Y.; Zhang, H.; Wang, G.; Zhang,
Ding, J.; Feng, Y. P.; Pennycook, S. J.; Wang, J. Hollow Mo-doped Y.; Zhao, H.; Wong, P. K. NiFe-layered double hydroxide nanosheet
CoP nanoarrays for efficient overall water splitting. Nano Energy 2018, arrays supported on carbon cloth for highly sensitive detection of
48, 73−80. nitrite. ACS Appl. Mater. Interfaces 2018, 10, 6541−6551.
(36) Liu, X.; Wei, B.; Su, R.; Zhao, C.; Dai, D.; Ma, X.; Xu, L. Mo- (52) Sivanantham, A.; Ganesan, P.; Shanmugam, S. Hierarchical
Doped Cobalt Phosphide Nanosheets for Efficient Hydrogen NiCo2S4 nanowire arrays supported on Ni foam: an efficient and
Generation in an Alkaline Media. Energy Technol. 2019, 7, 1900021. durable bifunctional electrocatalyst for oxygen and hydrogen
(37) Xing, Z.; Liu, Q.; Asiri, A. M.; Sun, X. Closely Interconnected evolution reactions. Adv. Funct. Mater. 2016, 26, 4661−4672.
Network of Molybdenum Phosphide Nanoparticles: A Highly (53) Surendranath, Y.; Kanan, M. W.; Nocera, D. G. Mechanistic
Efficient Electrocatalyst for Generating Hydrogen from Water. Adv. studies of the oxygen evolution reaction by a cobalt-phosphate
Mater. 2014, 26, 5702−5707. catalyst at neutral pH. J. Am. Chem. Soc. 2010, 132, 16501−16509.
(38) Chu, H.; Zhang, D.; Jin, B.; Yang, M. Impact of morphology on (54) Niu, Y.; Li, W.; Wu, X.; Feng, B.; Yu, Y.; Hu, W.; Li, C. M.
the oxygen evolution reaction of 3D hollow Cobalt-Molybdenum Amorphous nickel sulfide nanosheets with embedded vanadium oxide
Nitride. Appl. Catal., B 2019, 255, 117744. nanocrystals on nickel foam for efficient electrochemical water
(39) Li, Y.; Xu, H.; Huang, H.; Wang, C.; Gao, L.; Ma, T. One- oxidation. J. Mater. Chem. A 2019, 7, 10534−10542.
dimensional MoO2−Co2Mo3O8@C nanorods: a novel and highly (55) Zhang, H.; Li, X.; Hähnel, A.; Naumann, V.; Lin, C.; Azimi, S.;
efficient oxygen evolution reaction catalyst derived from metal− Schweizer, S. L.; Maijenburg, A. W.; Wehrspohn, R. B. Bifunctional
organic framework composites. Chem. Commun. 2018, 54, 2739− heterostructure assembly of NiFe LDH nanosheets on NiCoP
2742. nanowires for highly efficient and stable overall water splitting. Adv.
(40) Chen, J.; Ge, Y.; Feng, Q.; Zhuang, P.; Chu, H.; Cao, Y.; Smith, Funct. Mater. 2018, 28, 1706847.
W. R.; Dong, P.; Ye, M.; Shen, J. Nesting Co3Mo Binary Alloy (56) Liang, H.; Gandi, A. N.; Anjum, D. H.; Wang, X.;
Nanoparticles onto Molybdenum Oxide Nanosheet Arrays for Schwingenschlögl, U.; Alshareef, H. N. Plasma-assisted synthesis of
Superior Hydrogen Evolution Reaction. ACS Appl. Mater. Interfaces NiCoP for efficient overall water splitting. Nano Lett. 2016, 16, 7718−
2019, 11, 9002−9010. 7725.
(41) Bao, J.; Wang, Z.; Xie, J.; Xu, L.; Lei, F.; Guan, M.; Huang, Y.; (57) Li, D.; Baydoun, H.; Kulikowski, B.; Brock, S. L. Boosting the
Zhao, Y.; Xia, J.; Li, H. The CoMo-LDH ultrathin nanosheet as a catalytic performance of iron phosphide nanorods for the oxygen
highly active and bifunctional electrocatalyst for overall water evolution reaction by incorporation of manganese. Chem. Mater.
splitting. Inorg. Chem. Front. 2018, 5, 2964−2970. 2017, 29, 3048−3054.
(42) Tang, C.; Gan, L.; Zhang, R.; Lu, W.; Jiang, X.; Asiri, A. M.; (58) Li, D.; Baydoun, H.; Verani, C. N.; Brock, S. L. Efficient water
Sun, X.; Wang, J.; Chen, L. Ternary FexCo1−xP Nanowire Array as a oxidation using CoMnP nanoparticles. J. Am. Chem. Soc. 2016, 138,
Robust Hydrogen Evolution Reaction Electrocatalyst with Pt-like 4006−4009.
Activity: Experimental and Theoretical Insight. Nano Lett. 2016, 16, (59) Zhou, Y.; Wang, Z.; Pan, Z.; Liu, L.; Xi, J.; Luo, X.; Shen, Y.
6617−6621. Exceptional Performance of Hierarchical Ni−Fe (hydr)oxide@NiCu
(43) Pei, Y.; Yang, Y.; Zhang, F.; Dong, P.; Baines, R.; Ge, Y.; Chu, Electrocatalysts for Water Splitting. Adv. Mater. 2019, 31, 1806769.
H.; Ajayan, P. M.; Shen, J.; Ye, M. Controlled electrodeposition
synthesis of Co−Ni−P film as a flexible and inexpensive electrode for
efficient overall water splitting. ACS Appl. Mater. Interfaces 2017, 9,
31887−31896.
(44) Liang, H.; Gandi, A. N.; Xia, C.; Hedhili, M. N.; Anjum, D. H.;
Schwingenschlögl, U.; Alshareef, H. N. Amorphous NiFe-OH/NiFeP
electrocatalyst fabricated at low temperature for water oxidation
applications. ACS Energy Lett. 2017, 2, 1035−1042.
(45) Infantes-Molina, A.; Cecilia, J. A.; Pawelec, B.; Fierro, J. L. G.;
Rodríguez-Castellón, E.; Jiménez-López, A. Ni2P and CoP catalysts
prepared from phosphite-type precursors for HDS−HDN competitive
reactions. Appl. Catal., A 2010, 390, 253−263.
(46) Ledendecker, M.; Krick Calderón, S.; Papp, C.; Steinrück, H.-
P.; Antonietti, M.; Shalom, M. The Synthesis of Nanostructured
Ni5P4 Films and their Use as a Non-Noble Bifunctional Electro-
catalyst for Full Water Splitting. Angew. Chem., Int. Ed. 2015, 54,
12361−12365.
(47) Gao, D.; Guo, J.; Cui, X.; Yang, L.; Yang, Y.; He, H.; Xiao, P.;
Zhang, Y. Three-dimensional dendritic structures of NiCoMo as
efficient electrocatalysts for the hydrogen evolution reaction. ACS
Appl. Mater. Interfaces 2017, 9, 22420−22431.
(48) Friebel, D.; Louie, M. W.; Bajdich, M.; Sanwald, K. E.; Cai, Y.;
Wise, A. M.; Cheng, M.-J.; Sokaras, D.; Weng, T.-C.; Alonso-Mori, R.;
Davis, R. C.; Bargar, J. R.; Nørskov, J. K.; Nilsson, A.; Bell, A. T.
Identification of highly active Fe sites in (Ni, Fe) OOH for
electrocatalytic water splitting. J. Am. Chem. Soc. 2015, 137, 1305−
1313.
(49) Liu, W.-J.; Dang, L.; Xu, Z.; Yu, H.-Q.; Jin, S.; Huber, G. W.
Electrochemical oxidation of 5-Hydroxymethylfurfural with NiFe
layered double hydroxide (LDH) nanosheet catalysts. ACS Catal.
2018, 8, 5533−5541.
(50) Shi, G.; Yu, C.; Fan, Z.; Li, J.; Yuan, M. Graphdiyne-supported
NiFe layered double hydroxide nanosheets as functional electro-
catalysts for oxygen evolution. ACS Appl. Mater. Interfaces 2019, 11,
2662−2669.

8085 https://dx.doi.org/10.1021/acsaem.0c01538
ACS Appl. Energy Mater. 2020, 3, 8075−8085