Research Article

ISSN 1998-0124 CN 11-5974/O4

2020, 13(9): 2407–2412 https://doi.org/10.1007/s12274-020-2865-y

Interfacial engineering of Ni/V2O3 for hydrogen evolution reaction

Yang Chen1,§, Yuan Rao1,§, Rongzhi Wang1, Yanan Yu1, Qiulin Li2, Shujuan Bao2, Maowen Xu2, Qin Yue1,
Yanning Zhang1 (), and Yijin Kang1 ()
1
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China
2
Key Laboratory of Luminescent and Real-Time Analytical Chemistry, Ministry of Education, Institute for Clean Energy and Advanced
Materials, Faculty of Materials and Energy, Southwest University, Chongqing 400715, China
§
Yang Chen and Yuan Rao contributed equally to this work.

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
Received: 7 April 2020 / Revised: 4 May 2020 / Accepted: 8 May 2020

ABSTRACT
Electrocatalytic water splitting offers a sustainable route for hydrogen production, enabling the clean and renewable alternative
energy system of hydrogen economy. The scarcity and high-cost of platinum-group-metal (PGM) materials urge the exploration of
high-performance non-PGM electrocatalysts. Herein, a unique hierarchical structure of Ni/V2O3 with extraordinary electrocatalytic
performance (e.g., overpotentials as low as 22 mV at 20 mA·cm–2 and 94 mV at 100 mA·cm–2) toward hydrogen evolution reaction
in alkaline electrolyte (1 M KOH) is reported. The investigation on the hierarchical Ni/V2O3 with a bimodal size-distribution also offers
insight of interfacial engineering that only proper Ni/V2O3 interface can effectively improve H2O adsorption, H2O dissociation as
well as H adsorption, for an efficient hydrogen production.

KEYWORDS
hydrogen evolution reaction, hierarchical materials, interface, electrocatalysis, vanadium oxide

1 Introduction [10, 11]. Other progresses have also been made, such as
improving the alkaline HER performances by introducing possible
The depleting fossil fuels and their associated environmental synergistic effect on nickel-vanadium oxides interfaces [12, 13].
issues urge the exploration of alternative energy system, As interfacial interactions such as charge transfer and synergistic
preferably renewable energies. For its high energy density and effect on the constructed interfaces are essential for interface
ideally zero CO2 emission, hydrogen is one promising clean engineering [14, 15], however, an in-depth understanding of the
energy carrier and the hydrogen economy is considered as synergistic effect in nickel-vanadium oxides interfaces is still
one of the most promising alternative energy systems [1]. missing. Moreover, as the structure-property relationship plays
Electrocatalytic water splitting in which H2 is produced via a vital role in catalytic processes [16–20], HER electrocatalysts
hydrogen evolution reaction (HER) is the key component to may be further improved by precisely tailored nanostructures
shape the future of sustainable hydrogen economy [2]. Despite to enable beneficial properties.
acidic electrolytes offer fast kinetics for HER, most catalyst Herein, we report a unique nanostructure of Ni nanoparticles
materials suffer from acid corrosion and unmatched conditions with bimodal size distribution (1.4 ± 0.3 and 17.1 ± 4.6 nm)
related to oxygen evolution reaction (OER) on the anode, embedded in hierarchically assembled porous vanadium(III)
impeding the industrial application of water-splitting in the oxide flakes (denoted as Ni/V2O3 thereafter). The hierarchical
acidic system [3]. Particularly, the future of water electrolysis may structures with exposed active Ni/V2O3 interface render an
depend on non-Pt-group-metal (non-PGM) electrocatalysts excellent HER performance in alkaline solution with over-
due to the cost and scarcity of PGM materials [4]. Therefore, potential as low as 22 and 94 mV for a current density of 20
developing high-efficiency and cost-effective HER electrocatalysts and 100 mA·cm–2, respectively, and a prominent durability at a
operated in the alkaline condition is highly desirable yet high current density of 100 mA·cm–2 for at least 20 h. The bimodal
challenging due to the sluggish kinetics. size-distribution of the samples also offers an opportunity to
In general, electrocatalytic materials are expected to have both closely look at the role of different types of Ni/V2O3 interfaces
optimal hydrogen adsorption and water dissociation to achieve in the HER process. With the help of density functional theory
a desirable alkaline HER performance [5, 6]. Transition metals, (DFT) calculations, it is found that only proper Ni/V2O3 interface
such as Ni, are usually efficient in hydrogen adsorption while can effectively improve H2O adsorption, H2O dissociation as
transition metal (hydro)oxides are good at cleaving HO–H well as H adsorption.
bond in H2O [5–7]. Additionally, as recent findings revealed
that Ni-based electrocatalysts may be desirable for HER [8, 9], 2 Experimental
vanadium and its derivatives with abundant vacant d orbitals
and/or strong electron-electron interaction may further ele- 2.1 Synthesis of hierarchical Ni/V2O3 heterostructure
ctronically modify Ni atoms for an improved HER performance Typically, nickel foams (NF) with a dimension of 3 cm × 2 cm

Address correspondence to Yanning Zhang, yanningz@uestc.edu.cn; Yijin Kang, kangyijin@uestc.edu.cn

2408 Nano Res. 2020, 13(9): 2407–2412

were cleaned by ultra-sonication in acetone, 3 M hydrochloric slab were able to relax.

acid solution, and ethanol, respectively, and after that a piece of All of the calculations were performed using the Vienna
pretreated NF was immersed into the homogeneous mixture Ab initio simulation package (VASP) [23] and the projector
of 1 mmol NiCl2·6H2O, 1 mmol NH4VO3 and 30 mL ultrapure augmented wave (PAW) method [24]. The generalized gradient
water that is contained in a 50 mL Teflon-lined stainless approximation (GGA) [25] functional with the Perdew-Burke-
autoclave. Subsequently, the autoclave was sealed and maintained Emzerhof formulation was used to describe the exchange
at 160 °C for 6 h. After the hydrothermal reaction, the product correlation interaction among electrons. Calculations were
was rinsed with ultrapure water and ethanol, and then dried carried out using an energy cutoff of 500 eV for the plane
to obtain the initial precursor of NiVO3/NiO-1. Next, the wave expansion, the Brillouin zone was sampled with the
NiVO3/NiO-1 was annealed at 400 °C for 2 h under N2 Monkhorst-Pack scheme [26] and 3 × 3 × 1 k-point mesh.
atmosphere to prepare a stabilized precursor of NiVO3/NiO-2. To Between slabs, both a semi-empirical van der Waals (vdW) [27]
obtain the hierarchical Ni/V2O3 heterostructure, NiVO3/NiO-2 correction (optB86b-vdW) for dispersion interactions and a
was reduced in a tube furnace at 500 °C under forming gas vacuum gap of 10 Å in the z-direction were considered. Likewise,
(H2/Ar = 5/95) for 2 h. For comparison, Ni/V2O3 materials the values of total energy convergence and force convergence
with various input Ni/V ratios were also prepared by the same are 10–6 eV and 0.01 eV·Å–1, respectively. The spin-polarization
method. Electrocatalyst of Ni/V2O3-1 was produced by directly was considered and served in the calculations when necessary.
reducing NiVO3/NiO-1 in forming gas (i.e., without the 400 °C The CI-NEB [28] was employed to determine the transition
2 h annealing process). states for water dissociation on the constructed surfaces. To
be specific, we first deposited a H2O molecule on the catalyst
2.2 Characterizations surface and allowed it to relax to the most stable site. After
The crystalline structure was characterized by X-ray diffrac- that, we started with multiple initial configurations and
tometer (XRD, Rigaku Ultima IV) using Cu Kα (λ = 1.5418 Å) selected the one with minimum energy. Then, we found the
radiation. The electron microscopy analysis was done on scanning corresponding potential final locations of H+ and OH− on the
electron microscope (FEI Inspect F50) and transmission electron surface and allowed each of these configurations to relax.
microscope (JEM-2100). X-ray photoelectron spectroscopy Finally, we performed climbing image nudge elastic band
(XPS) measurements were recorded on ESCALab 250Xi using calculations on the most stable final H+OH configuration
monochromic Al Kα radiation. Inductively coupled plasma with the most stable initial H2O configuration.
mass spectrometry (ICP-MS) analysis was conducted on Agilent The charge density difference (ρdiff) on the V2O3 surface
7700. The specific surface areas (Barrett-Joyner-Halenda (BJH) before and after the deposition of Ni was calculated by Eq. (1)
method) and pore size distribution curves were obtained from ρdiff = ρ(Ni/V2O3) − ρ(V2O3) − ρ(Ni) (1)
Nitrogen adsorption-desorption isotherms measured by ASAP
In Eq. (1), ρ(Ni/V2O3), ρ(V2O3) and ρ(Ni) are the charge
2020 Plus Physisorption at 77 K.
density of Ni/V2O3, V2O3 and Ni, respectively.
2.3 Electrochemical measurements The hydrogen adsorption free energy ΔGH* is determined as
ΔGH* = ΔEH* + ΔEZPE − TΔS, where ΔEH* represents the hydrogen
The electrochemical measurements for HER and OER were adsorption energy, ΔEZPE is the difference in zero point energy
performed on a CHI 660E electrochemical workstation (CH between the adsorbed H and H in the gas phase H2 molecule,
Instruments) at room temperature using a conventional three- and ΔS is the entropy difference between adsorbed H and
electrode system. The synthesized self-supported electrocatalysts H2(g). Considering that the negligible vibrational entropy
(1 cm × 1 cm) were directly used as the working electrode. of H* and TS(H2) is 0.40 eV for H2 at 298 K and 1 atm, the
Hg/HgO, and graphite rod were used as the reference and the corresponding TΔS was determined as −0.20 eV. The hydrogen
counter electrode, respectively. 1 M KOH aqueous solution adsorption energy is calculated as: ΔEH* = E(M+H) − E(M)
was used as electrolyte. Polarization curves were recorded by − 1/2E(H2), where E(M+H), E(M) and E(H2) represent the total
linear sweep voltammetry (LSV) with iR-compensation. Overall energy of a slab with one adsorbed H atom on the surface,
water splitting activity was tested in a two-electrode electrolysis the total energy of the slab, and the energy of a H2 molecule,
device without iR-compensation, using Ni/V2O3 as both cathode respectively [29].
and anode electrocatalysts. Hg/HgO reference electrode is
calibrated against a reversible hydrogen electrode (RHE). All
potentials are reported in reference to that vs. RHE. Electro- 3 Results and discussion
chemical impedance spectroscopy (EIS) measurements were The hierarchical Ni/V2O3 nanostructure is prepared through a
investigated from 100 kHz to 0.01 Hz at −0.1V, with an alternating hydrothermal treatment followed by annealing and thermal
current (AC) voltage amplitude of 5 mV. Electrochemical reduction. In brief, a flower-like Ni-V precursor of NiVO3
surface area (ECSA) were estimated from the electrochemical (Figs. S1 and S2 in the ESM) is first grown on a NF through a
double-layer capacitance (Cdl) values, characterized by cyclic hydrothermal treatment of an aqueous solution that has
voltammetry (CV) scans. Long-term stability was tested by the dissolved NiCl2·6H2O and NH4VO3, and is subsequently annealed
chronoamperometry. in N2 to stabilize former precursor and to release the extra
strain in the materials (Fig. 1 and Fig. S3 in the ESM), and
2.4 Computational calculations then thermal reduced in H2/Ar (v/v = 5/95) atmosphere to
To simulate the bimodal system of Ni particles supported on transform the thermodynamically stabilized precursor into
V2O3, we used a Ni cluster with 4 atoms [21] adsorbed on a Ni/V2O3 hybrids. The crystalline structure and surface compo-
V2O3 (104) slab (denoted as Nic/V2O3, Fig. S23 in the Electronic sition of the resulting materials are studied by XRD and XPS
Supplementary Material (ESM)) and a Ni nanorod structure characterizations. As shown in Fig. 1(h), the distinctive peaks of
[22] with a height of 3-atomic layers and a width of 3-atoms the as-obtained Ni/V2O3 heterostructures can be well assigned
covalent bonded on a V2O3 (104) slab (denoted as Nir/V2O3, to cubic Ni (PDF# 04-0850) with the lattice constant of a =
Fig. S24 in the ESM). All Ni atoms were allowed to relax along 3.5238 Å, and hexagonal V2O3 (PDF# 34-0187) with the lattice
the z-direction, while only the three topmost layers of V2O3 constants of a = b = 4.954 Å and c =14.0083 Å. Compared with

| www.editorialmanager.com/nare/default.asp
Nano Res. 2020, 13(9): 2407–2412 2409

mobility than V2O3, driving the phase segregation. It’s similar to

the structural evolution of Ni1−xVxO2 [38] and Co2V2O7·xH2O
[39] after been reduced in NH3 atmosphere. The voids formation
is also known as Kirkendall effect [40, 41]. The bimodal size
distribution of Ni particles may be ascribed to the Ostwald
ripening.
The electrocatalytic HER performance of the hierarchical
Ni/V2O3 heterostructure is evaluated in 1 M KOH with a
conventional three-electrode system. Ni/V2O3 materials with
various Ni/V ratios are investigated to determine the optimal
Ni/V ratio for HER. As the obtained alkaline HER activities
are plotted against Ni-content, a reverse volcano-shape plot is
observed with the peak at Ni:V = 1:1 (Fig. S8 and Table S3 in
the ESM). The ICP-MS analysis (Table S1 in the ESM) reveals
a Ni:V ratio (a.t.) of 1:0.96 in Ni/V2O3, which is close to the
Ni:V ratio of 1:1 in the starting materials (i.e., NiCl2·6H2O
and NH4VO3). Thereafter, the Ni/V2O3 refers to the material
synthesized at a starting Ni/V ratio of 1:1. As shown in Figs. 2(a)
and 2(b) and Fig. S9(a) in the ESM, Ni/V2O3 exhibits a low
Figure 1 (a)–(c) SEM images, (d) and (e) TEM images (inset: SAED overpotential (η) of only 22 and 94 mV to achieve a current
pattern), (f) HRTEM image, (g) elemental map and (h) XRD pattern of density of 20 mA·cm−2 (η20) and 100 mA·cm−2 (η100), respectively,
Ni/V2O3. (i) Histogram for size distribution of Ni particles in Ni/V2O3. significantly outperforming NF (η20 = 282 mV, η100 = 356 mV),
Pt mesh (η20 = 77 mV, η100 = 150 mV) and precursors at the
precursor, XPS (Fig. S4 in the ESM) confirms new signals of same geometric surface area of 1 cm2. EIS measurements are
metallic nickel [7, 30] (Ni0 2p1/2: 870.5 eV; 2p3/2: 853.2 eV) and performed at −0.1 V (vs. RHE) to learn the kinetic impedances
tri-valance vanadium [31, 32] (V3+ 2p1/2: 522.9 eV; 2p3/2: 515.2 eV) of all samples. The obtained Nyquist plots indicate that charge
as well as an obviously reduced lattice oxygen [30, 33–36] (OL: transfer resistance (Rct) of Ni/V2O3 is as low as 1.0 Ω, that is
530.5 eV) in Ni/V2O3. These results evince the successful distinctly lower than that of NF, Pt mesh, percursors and other
conversion of precursor into hierarchical Ni/V2O3 materials by control samples (Fig. 2(c), Figs. S8(b) and S9(b) and Table S3
thermal reduction. in the ESM), indicating a rapid Faradaic process for Ni/V2O3.
To analyze the heterostructure of Ni/V2O3, scanning electron The durability testing of Ni/V2O3 are performed at a constant
microscopy (SEM) and transmission electron microscopy potential over 20 h, where j = ~ 100 mA·cm−2. As shown in Fig. 2(d),
(TEM) are performed. As shown in SEM images (Figs. 1(a)– the hierarchical Ni/V2O3 electrocatalysts retain 99.4% of their
1(c)), the resultant Ni/V2O3 materials well retain the hierar- initial HER activity. In addition, Ni/V2O3 also exhibits consi-
chical structure of precursor (Fig. S1 in the ESM) in which derable OER activity in 1 M KOH with an overpotential of 431 mV
nanosheets are assembled into microflowers, and the large at 100 mA·cm−2, making it suitable as a bifunctional electro-
area elemental mapping enabled by SEM indicates that elements catalyst for overall alkaline water splitting (Fig. S22 in the
of Ni, V and O are homogenously distributed throughout ESM). As a control sample, Ni/V2O3-1 is synthesized by directly
the hierarchical assembly (Fig. S3 in the ESM). The high reducing hydrothermal products (NiVO3/NiO-1) in H2/Ar (i.e.,
magnification SEM image (Fig. 1(c)), TEM images (Figs. 1(d) without the annealing). As revealed by XRD, XPS, SEM and
and 1(e) and Fig. S5(a) in the ESM) and energy dispersive TEM characterizations (Figs. S10–S14 in the ESM), Ni/V2O3-1
spectroscopy (EDS) elemental maps (Fig. S6 in the ESM) show possesses the same crystalline structure to Ni/V2O3, however,
that the segregated Ni nanoparticles and abundant pores slight signals of V2+ and substantial amount of Ni agglomerates
are well dispersed on the V2O3 nanosheets. As revealed by are observed in Ni/V2O3-1, for the absence of annealing process
N2 adsorption−desorption isotherm and the BJH pore-size in which Ni and V atoms can be stabilized. Electro-chemical
distribution analysis (Fig. S7 in the ESM), the self-supported
Ni/V2O3 electrocatalyst possesses a Brunauer–Emmett–Teller
(BET) surface area of 18.9 m2·g–1 with an average pore size of
8.3 nm. In the high resolution TEM (HRTEM) images (Fig. 1(f)
and Figs. S5(b)–S5(d) in the ESM), much smaller Ni nano-
particles other than those shown in Figs. 1(d) and 1(e) are
identified and therefore the size of Ni nanoparticles are clearly in
a bimodal distribution (Fig. 1(i)): the segregated Ni nanoparticles
(larger one) have an average size of 17.1 ± 4.6 nm and the
embedded Ni nanoparticles (smaller one) have an average size
of 1.4 ± 0.3 nm. The EDS element mapping images (Fig. S6 in
the ESM) also confirm the bimodal size distribution of Ni
particles in the hierarchical Ni/V2O3 heterostructure.
The formation of porous structure and hierarchical
heterostructure are originated from the different mobility and
reduction potential of Ni and V in NiVO3. Upon the thermal
reduction in H2/Ar, since the Ni has much lower surface
energy than V [37], the Ni atoms tend to diffuse outward and Figure 2 (a) Polarization curves, (b) overpotentials at the current density
result in break of Ni–O–V network. On the other hand, due to of 20 and 100 mA·cm−2 (i.e., η20 and η100) and (c) Nyquist plots (inset:
the different reduction potential, Ni is easier to be reduced zoom-in plots) of NF, Pt mesh and Ni/V2O3 at −0.1 V. (d) Chronoamperometry
than V, subsequently the metallic Ni atoms have much higher testing of Ni/V2O3.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

2410 Nano Res. 2020, 13(9): 2407–2412

measurements indicate that the sample of Ni/V2O3-1 has

similar ECSA, Rs and Rct to that of Ni/V2O3 (Figs. S9(b) and
S15 in the ESM), while Ni/V2O3-1 significantly underperforms
Ni/V2O3 in both HER activity (Fig. S9(a) in the ESM) and
durability (Fig. S16 in the ESM). The porous architecture of
Ni/V2O3 not only offers a large surface area to enable more
active sites and to optimize the mass transfer but also facilitates
the hydrogen bubbles to leave the surface of electrocatalysts
[42–44]. The interfacial synergy between Ni and V2O3 may
also greatly benefit the HER [12, 13].
In order to verify the possible synergetic effect on Ni/V2O3
interface, commercial Ni powder, V2O3 powder and their
mixtures are drop casted onto the carbon cloth (CC) with the
same loading to that of Ni/V2O3 hierarchical catalysts (Fig. S17
in the ESM). Such control experiment reveals an inert HER
activity of V2O3 and a moderate activity of Ni. The Ni-V2O3
sample created by mechanical mixing shows better activity
than the inert V2O3, but is not necessarily more active than Ni,
indicating that the improved HER activity on hierarchical
Ni/V2O3 must be from the nano-scale or atomic level
interaction of Ni and V2O3 species. Additionally, the improved
HER performance on the V2O3 decorated NF further evinces Figure 3 (a) DFT calculations of initial state (IS), transition state (TS)
the synergistic effect on the Ni/V2O3 interface. and final state (FS) for water dissociation, and H adsorption on Ni (111),
The structural and chemical characterizations indicate that V2O3(104), Nic/V2O3 and Nir/V2O3. (b) Reaction energy diagram of water
the composition and structure of the hierarchical Ni/V2O3 remain dissociation. (c) Hydrogen adsorption free energy.
almost unchanged after the durability test (Figs. S18–S20 in
the ESM), except that the small Ni particles of 1.4 nm are V2O3. The formation of Ni/V2O3 interfaces significantly decreases
disappeared (Figs. S19(c) and S19(d) in the ESM). To prove of ΔGH* value, namely, improve the HER performance. In
the presence of the small Ni nanoparticles in the initial HER particular, for the constructed Nir/V2O3 interface, the calculated
measurement, TEM images are taken on the electrocatalyst ΔGH* is only 0.02 eV (Fig. 3(c)), a value that is even lower than
operated in the durability test for 0.2 h and clearly show that that of Pt (ΔGH* = −0.09 eV). Considering a relatively high
small Ni particles indeed participated the initial HER process energy barrier of 0.89 eV for the water dissociation on Pt
(Fig. S21 in the ESM). The fact that the HER activity remains surface [51, 52], the theoretical calculation also offers an
the same regardless the presence of the small Ni nanoparticles explanation for the fact that Ni/V2O3 outperform Pt in alkaline
seems contradicting the conclusion above that the Ni/V2O3 HER. Water molecules have a tendency to be absorbed on the
interface matters in HER, because the small sized particles on V2O3 surface with the O atom on V sites adjacent to the Ni
the support materials usually help offering large amount of active nanorods and one H atom orienting toward Ni (denoted as HNi).
interfaces [45, 46]. Therefore, in order to better understand After the dissociation, the generated HNi prefers to stay the
how the Ni/V2O3 interface functions in HER, we employ the nearest Ni atoms and proceeds for further hydrogen generation.
tool of DFT to look at the role of different types of Ni/V2O3 Therefore, alkaline HER processes are significantly facilitated
interfaces. by the synergistic effect of Ni and V atoms near the Nir/V2O3
To gain insight into the enhanced alkaline HER activity interface through the intermediate HNi atom, as depicted in
and possible synergistic effect on the hierarchical Ni/V2O3, the Fig. S30 in the ESM.
key reaction steps in alkaline HER are studied using DFT Detailed electronic analyses are performed to study how Ni
calculations on the stable facet of Ni(111), V2O3(104), and the and V2O3 catalyze the HER and the influence of the interface
interface of Ni/V2O3 (Fig. 3(a), Figs. S23 and S24 in the ESM). on HER. The density of states (DOS) of Ni (111), V2O3 (104),
Here, the Ni cluster [21] and Ni nanorod [22] are built on a Nic/V2O3 and Nir/V2O3 are shown in Fig. 4(a) and Fig. S31 in
V2O3(104) slab (denote as Nic/V2O3 and Nir/V2O3, respectively) the ESM. The density of occupied states near to the Fermi
to simulate the smaller and larger Ni particles in Ni/V2O3 energy (the highlighted region in Fig. 4(a)) follow the order
systems. Whether or not the hydrogen binding energy is the of Nir/V2O3 > Nic/V2O3 > V2O3. The increased integral area of
sole-descriptor in the alkaline HER [47, 48], here both the
water dissociation and hydrogen adsorption are considered
(Figs. S25–S30 in the ESM). As a rate determining step for the
alkaline HER [49], the free energy diagram of water dissociation
in Fig. 3(b) shows that the energy barrier in breaking H–OH
bond is 2.25 eV for V2O3. Nic/V2O3 interface exhibits a
corresponding energy barrier of 1.08 eV, a value that is slightly
higher than pure Ni and Pt surface. Strikingly, a small barrier
of 0.74 eV is obtained on the Nir/V2O3 interface, implying the
preferred water dissociation on Nir/V2O3.
The adsorption free energy of hydrogen atom, ΔGH*, is then
calculated to evaluate the HER performance on electrocatalysts [1, Figure 4 (a) Total density of states of V2O3, Nic/V2O3, and Nir/V2O3. (b)
50]. As shown in Fig. 3(c), besides the high energy barrier of Electron density difference (isosurface level: 0.008 e·Å−3) of Nir/V2O3. The
water dissociation on V2O3(104), its ΔGH* value is as large as yellow and cyan contours represent the electron accumulation and depletion,
1.02 eV, clearly indicating the sluggish alkaline HER activity on respectively.

| www.editorialmanager.com/nare/default.asp
Nano Res. 2020, 13(9): 2407–2412 2411

this peak in Nir/V2O3, which are mainly from the contribution P.; Wang, Y. Y.; Zeng, M.; Zhong, J.; Li, Y. G. Mo2C nanoparticles
of Ni-d states since the partial density of states (PDOS) curve dispersed on hierarchical carbon microflowers for efficient electro-
of V atoms are almost unchanged (Fig. S31(d) in the ESM), catalytic hydrogen evolution. ACS Nano 2016, 10, 11337–11343.
implies the enhanced electrical conductivity in Nir/V2O3 [5] Subbaraman, R.; Tripkovic, D.; Chang, K. C.; Strmcnik, D.;
Paulikas, A. P.; Hirunsit, P.; Chan, M.; Greeley, J.; Stamenkovic, V.;
[53, 54]. Therefore, the affiliation of Ni-nanorod could greatly
Markovic, N. M. Trends in activity for the water electrolyser reactions
improve the alkaline HER performance of V2O3 compare to on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nat. Mater. 2012,
that of Ni-cluster. The electron density difference of Nir/V2O3 in 11, 550–557.
Fig. 4(b) shows obvious electron accumulation on the interface [6] Subbaraman, R.; Tripkovic, D.; Strmcnik, D.; Chang, K. C.;
between Ni and V2O3, which enables a fast electron transfer Uchimura, M.; Paulikas, A. P.; Stamenkovic, V.; Markovic, N. M.
for electrochemical reactions and further contributes to an Enhancing hydrogen evolution activity in water splitting by tailoring
expedited alkaline HER rate. Li+-Ni(OH)2-Pt interfaces. Science 2011, 334, 1256–1260.
[7] Weng, Z.; Liu, W.; Yin, L. C.; Fang, R. P.; Li, M.; Altman, E. I.;
Fan, Q.; Li, F.; Cheng, H. M.; Wang, H. L. Metal/oxide interface
4 Conclusions nanostructures generated by surface segregation for electrocatalysis.
In summary, a hierarchical Ni/V2O3 heterostructure is pro- Nano Lett. 2015, 15, 7704–7710.
duced by a hydrothermal-annealing-reduction treatment. The [8] Gong, M.; Wang, D. Y.; Chen, C. C.; Hwang, B. J.; Dai, H. J. A mini
review on nickel-based electrocatalysts for alkaline hydrogen evolution
obtained robust heterostructure of Ni/V2O3 exhibits excellent
reaction. Nano Res. 2016, 9, 28–46.
HER activity and durability in alkaline electrolyte, which are [9] Zeng, M.; Li, Y. G. Recent advances in heterogeneous electrocatalysts
demonstrated by a low overpotential of 94 mV at 100 mA·cm−2 for the hydrogen evolution reaction. J. Mater. Chem. A 2015, 3,
and a stable operation at a high current density of ~ 100 mA·cm−2 14942–14962.
for at least 20 h. The experimental investigations and DFT [10] Chen, Z. Y.; Song, Y.; Cai, J. Y.; Zheng, X. S.; Han, D. D.; Wu, Y. S.;
calculations indicate that only the proper Ni/V2O3 interface is Zang, Y. P.; Niu, S. W.; Liu, Y.; Zhu, J. F. et al. Tailoring the d-band
preferred for an outstanding HER kinetics. The enhanced centers enables Co4N nanosheets to be highly active for hydrogen
HER on the selected Ni/V2O3 interface can be explained as evolution catalysis. Angew. Chem., Int. Ed. 2018, 57, 5076–5080.
following: 1) H2O and H tend to absorb onto V-sites and [11] Qu, Y. J.; Yang, M. Y.; Chai, J. W.; Tang, Z.; Shao, M. M.; Kwok, C. T.;
Ni-sites close to the Ni/V2O3 interface, facilitating the synergistic Yang, M.; Wang, Z. Y.; Chua, D.; Wang, S. J. et al. Facile synthesis
of vanadium-doped Ni3S2 nanowire arrays as active electrocatalyst
effect on the interface; 2) the interface is concentrated with
for hydrogen evolution reaction. ACS Appl. Mater. Interfaces 2017,
charges that enable a fast electron transfer, accelerating 9, 5959–5967.
electrochemical reaction rates; 3) the charge flow optimizes [12] Ming, M.; Ma, Y. L.; Zhang, Y.; Huang, L. B.; Zhao, L.; Chen, Y. Y.;
the hydrogen adsorption ability of Ni. The energy barriers for Zhang, X.; Fan, G. Y.; Hu, J. S. 3D nanoporous Ni/V2O3 hybrid nanoplate
water dissociation and H adsorption on Ni/V2O3 are as low as assemblies for highly efficient electrochemical hydrogen evolution.
0.74 and 0.02 eV, respectively, that is close to the optimal J. Mater. Chem. A 2018, 6, 21452–21457.
values for alkaline HER. This work demonstrates that the [13] Ji, D.; Peng, L. S.; Shen, J. J.; Deng, M. M.; Mao, Z. X.; Tan, L. Q.;
interface engineering is an effective strategy to design high- Wang, M. J.; Xiang, R.; Wang, J.; Shah, S. S. A. Inert V2O3 oxide
performance electrocatalysts, and offers a low-cost, abundant, promotes the electrocatalytic activity of Ni metal for alkaline hydrogen
non-PGM electrocatalyst toward alkaline HER, advancing the evolution. Chem. Commun. 2019, 55, 3290–3293.
[14] Wu, C. H.; Liu, C.; Su, D.; Xin, H. L.; Fang, H. T.; Eren, B.; Zhang, S.;
development of hydrogen economy.
Murray, C. B.; Salmeron, M. B. Bimetallic synergy in cobalt–palladium
nanocatalysts for CO oxidation. Nat. Catal. 2019, 2, 78–85.
Acknowledgements [15] Liu, C.; Ma, Z.; Cui, M. Y.; Zhang, Z. Y.; Zhang, X.; Su, D.; Murray,
C. B.; Wang, J. X.; Zhang, S. Favorable core/shell interface within
The work is supported by the National Natural Science Co2P/Pt nanorods for oxygen reduction electrocatalysis. Nano Lett.
Foundation of China (Nos. 11874005, 21701153, 51601030 2018, 18, 7870–7875.
and 21773023). [16] Kang, Y. J.; Yang, P. D.; Markovic, N. M.; Stamenkovic, V. R. Shaping
electrocatalysis through tailored nanomaterials. Nano Today 2016,
Electronic Supplementary Material: Supplementary material 11, 587–600.
(XRD patterns, SEM images and corresponding EDS maps, [17] Chen, C.; Kang, Y. J.; Huo, Z. Y.; Zhu, Z. W.; Huang, W. Y.; Xin, H. L.;
XPS spectra, TEM images and corresponding EDS maps, N2 Snyder, J. D.; Li, D. G.; Herron, J. A.; Mavrikakis, M. et al. Highly
adsorption-desorption isotherms, LSV scans, Nyquist plots, crystalline multimetallic nanoframes with three-dimensional
electrocatalytic surfaces. Science 2014, 343, 1339–1343.
CV scans, i–t tests, calculation models and corresponding free
[18] Li, Y. G.; Wang, H. L.; Xie, L. M.; Liang, Y. Y.; Hong, G. S.; Dai, H.
energy for various substeps, DOS patterns, tables of ICP-MS,
J. MoS2 nanoparticles grown on graphene: An advanced catalyst
and comparison table of HER activity data with various Ni/V for the hydrogen evolution reaction. J. Am. Chem. Soc. 2011, 133,
ratios) is available in the online version of this article at 7296–9.
https://doi.org/10.1007/s12274-020-2865-y. [19] Liao, H. B.; Fisher, A.; Xu, Z. J. Surface segregation in bimetallic
nanoparticles: A critical issue in electrocatalyst engineering. Small
References 2015, 11, 3221–3246.
[20] Wang, Y. Q.; Zou, Y. Q.; Tao, L.; Wang, Y. Y.; Huang, G.; Du, S. Q.;
[1] Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; Norskov, Wang, S. Y. Rational design of three-phase interfaces for electrocatalysis.
J. K.; Jaramillo, T. F. Combining theory and experiment in electrocatalysis: Nano Res. 2019, 12, 2055–2066.
Insights into materials design. Science 2017, 355, eaad4998. [21] Xu, H.; Chu, W.; Sun, W. J.; Jiang, C. F.; Liu, Z. Q. DFT studies of
[2] Wang, J.; Xu, F.; Jin, H. Y.; Chen, Y. Q.; Wang, Y. Non-noble metal- Ni cluster on graphene surface: Effect of CO2 activation. RSC Adv.
based carbon composites in hydrogen evolution reaction: Fundamentals 2016, 6, 96545–96553.
to applications. Adv. Mater. 2017, 29, 1605838. [22] Green, I. X.; Tang, W. J.; Neurock, M.; Yates, J. T. Jr. Spectroscopic
[3] Wang, L.; Zhu, Y. H.; Zeng, Z. H.; Lin, C.; Giroux, M.; Jiang, L.; observation of dual catalytic sites during oxidation of CO on a
Han, Y.; Greeley, J.; Wang, C.; Jin, J. Platinum-nickel hydroxide Au/TiO2 catalyst. Science 2011, 333, 736–739.
nanocomposites for electrocatalytic reduction of water. Nano Energy [23] Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio
2017, 31, 456–461. total-energy calculations using a plane-wave basis set. Phys. Rev. B
[4] Huang, Y.; Gong, Q. F.; Song, X. N.; Feng, K.; Nie, K. Q.; Zhao, F. 1996, 54, 11169–11186.

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

2412 Nano Res. 2020, 13(9): 2407–2412

[24] Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector Sequential galvanic exchange and Kirkendall growth at room temperature.
augmented-wave method. Phys. Rev. B 1999, 59(3), 1758–1775. Science 2011, 334, 1377–1380.
[25] Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient [42] Sun, T. T.; Zhao, S.; Chen, W. X.; Zhai, D.; Dong, J. C.; Wang, Y.;
approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868. Zhang, S. L.; Han, A. J.; Gu, L.; Yu, R. et al. Single-atomic cobalt
[26] Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone sites embedded in hierarchically ordered porous nitrogen-doped
integrations. Phys. Rev. B 1976, 13, 5188–5192. carbon as a superior bifunctional electrocatalyst. Proc. Natl. Acad.
[27] Klimeš, J.; Bowler, D. R.; Michaelides, A. Van der Waals density Sci. USA 2018, 115, 12692–12697.
functionals applied to solids. Phys. Rev. B 2011, 83, 195131. [43] Liao, L.; Wang, S. N.; Xiao, J. J.; Bian, X. J.; Zhang, Y. H.; Scanlon,
[28] Henkelman, G.; Uberuaga, B. P.; Jónsson, H. A climbing image M. D.; Hu, X. L.; Tang, Y.; Liu, B. H.; Girault, H. H. A nanoporous
nudged elastic band method for finding saddle points and minimum molybdenum carbide nanowire as an electrocatalyst for hydrogen
energy paths. J. Chem. Phys. 2000, 113, 9901–9904. evolution reaction. Energy Environ. Sci. 2014, 7, 387–392.
[29] Yu, J. Y.; Zhou, W. J.; Xiong, T. L.; Wang, A. L.; Chen, S. W.; Chu, B. L. [44] Wang, S. Y.; Zhang, L.; Li, X.; Li, C. L.; Zhang, R. J.; Zhang, Y. J.;
Enhanced electrocatalytic activity of Co@N-doped carbon nanotubes Zhu, H. W. Sponge-like nickel phosphide–carbon nanotube hybrid
by ultrasmall defect-rich TiO2 nanoparticles for hydrogen evolution electrodes for efficient hydrogen evolution over a wide pH range.
reaction. Nano Res. 2017, 10, 2599–2609. Nano Res. 2017, 10, 415–425.
[30] Yao, Q. L.; Lu, Z. H.; Yang, Y. W.; Chen, Y. Z.; Chen, X. S.; Jiang, H. L. [45] Cargnello, M.; Doan-Nguyen, V. V. T.; Gordon, T. R.; Diaz, R. E.;
Facile synthesis of graphene-supported Ni-CeOx nanocomposites as Stach, E. A.; Gorte, R. J.; Fornasiero, P.; Murray, C. B. Control of
highly efficient catalysts for hydrolytic dehydrogenation of ammonia metal nanocrystal size reveals metal-support interface role for ceria
borane. Nano Res. 2018, 11, 4412–4422. catalysts. Science 2013, 341, 771–773.
[31] Shi, H. H.; Liang, H. F.; Ming, F. W.; Wang, Z. C. Efficient overall [46] Kang, Y. J.; Ye, X. C.; Chen, J.; Qi, L.; Diaz, R. E.; Doan-Nguyen, V.;
water-splitting electrocatalysis using lepidocrocite VOOH hollow Xing, G. Z.; Kagan, C. R.; Li, J.; Gorte, R. J. et al. Engineering catalytic
nanospheres. Angew. Chem., Int. Ed. 2017, 56, 573–577. contacts and thermal stability: Gold/iron oxide binary nanocrystal
[32] Fan, K.; Chen, H.; Ji, Y. F.; Huang, H.; Claesson, P. M.; Daniel, Q.; superlattices for CO oxidation. J. Am. Chem. Soc. 2013, 135, 1499–1505.
Philippe, B.; Rensmo, H.; Li, F. S.; Luo, Y. et al. Nickel-vanadium [47] Zheng, J.; Sheng, W. C.; Zhuang, Z. B.; Xu, B. J.; Yan, Y. S.
monolayer double hydroxide for efficient electrochemical water Universal dependence of hydrogen oxidation and evolution reaction
oxidation. Nat. Commun. 2016, 7, 11981. activity of platinum-group metals on pH and hydrogen binding
[33] An, L.; Zhang, Z. Y.; Feng, J. R.; Lv, F.; Li, Y. X.; Wang, R.; Lu, M.; energy. Sci. Adv. 2016, 2, e1501602.
Gupta, R. B.; Xi, P. X.; Zhang, S. Heterostructure-promoted oxygen [48] Intikhab, S.; Rebollar, L.; Fu, X. B.; Yue, Q.; Li, Y. W.; Kang, Y. J.;
electrocatalysis enables rechargeable zinc–air battery with neutral Tang, M. H.; Snyder, J. D. Exploiting dynamic water structure and
aqueous electrolyte. J. Am. Chem. Soc. 2018, 140, 17624–17631. structural sensitivity for nanoscale electrocatalyst design. Nano Energy
[34] Ou, G.; Xu, Y. S.; Wen, B.; Lin, R.; Ge, B. H.; Tang, Y.; Liang, Y. W.; 2019, 64, 103963.
Yang, C.; Huang, K.; Zu, D. et al. Tuning defects in oxides at room [49] Danilovic, N.; Subbaraman, R.; Strmcnik, D.; Chang, K. C.; Paulikas,
temperature by lithium reduction. Nat. Commun. 2018, 9, 1302. A. P.; Stamenkovic, V. R.; Markovic, N. M. Enhancing the alkaline
[35] Bao, K. Y.; Mao, W. T.; Liu, G. Y.; Ye, L. Q.; Xie, H. Q.; Ji, S. F.; hydrogen evolution reaction activity through the bifunctionality of
Wang, D. S.; Chen, C.; Li, Y. D. Preparation and electrochemical Ni(OH)2/metal catalysts. Angew. Chem., Int. Ed. 2012, 51, 12495–
characterization of ultrathin WO3−x /C nanosheets as anode materials 12498.
in lithium ion batteries. Nano Res. 2017, 10, 1903–1911. [50] Lin, H. L.; Shi, Z. P.; He, S. N.; Yu, X.; Wang, S. N.; Gao, Q. S.;
[36] Wu, H.; Lu, X.; Zheng, G. F.; Ho, G. W. Topotactic engineering of Tang, Y. Heteronanowires of MoC-Mo2C as efficient electrocatalysts for
ultrathin 2D nonlayered nickel selenides for full water electrolysis. hydrogen evolution reaction. Chem. Sci. 2016, 7, 3399–3405.
Adv. Energy Mater. 2018, 8, 1702704. [51] Nørskov, J. K.; Bligaard, T.; Logadottir, A.; Kitchin, J. R.; Chen, J.
[37] Vitos, L.; Ruban, A. V.; Skriver, H. L.; Kollár, J. The surface energy G.; Pandelov, S.; Stimming, U. Trends in the exchange current for
of metals. Surf. Sci. 1998, 411, 186–202. hydrogen evolution. J. Electrochem. Soc. 2005, 152, J23–J26.
[38] Ji, C. C.; Bi, J. L.; Wang, S.; Zhang, X. J.; Yang, S. C. Ni nanoparticle [52] Wang, P. T.; Zhang, X.; Zhang, J.; Wan, S.; Guo, S. J.; Lu, G.; Yao, J.
doped porous VN nanoflakes assembled into hierarchical hollow L.; Huang, X. Q. Precise tuning in platinum-nickel/nickel sulfide interface
microspheres with a structural inheritance from the Ni1−xVxO2 nanowires for synergistic hydrogen evolution catalysis. Nat. Commun.
cathode material for high performance asymmetric supercapacitors. 2017, 8, 14580.
J. Mater. Chem. A 2016, 4, 2158–2168. [53] Chen, S. C.; Kang, Z. X.; Hu, X.; Zhang, X. D.; Wang, H.; Xie, J. F.;
[39] Xiao, Y. L.; Tian, C. G.; Tian, M.; Wu, A. P.; Yan, H. J.; Chen, C. F.; Zheng, X. S.; Yan, W. S.; Pan, B. C.; Xie, Y. Delocalized spin states
Wang, L.; Jiao, Y. Q.; Fu, H. G. Cobalt-vanadium bimetal-based in 2D atomic layers realizing enhanced electrocatalytic oxygen
nanoplates for efficient overall water splitting. Sci. China Mater. evolution. Adv. Mater. 2017, 29, 1701687.
2018, 61, 80–90. [54] Pan, Y.; Sun, K. A.; Lin, Y.; Cao, X.; Cheng, Y. S.; Liu, S. J.; Zeng,
[40] Yin, Y. D.; Rioux, R. M.; Erdonmez, C. K.; Hughes, S.; Somorjai, G. L. Y.; Cheong, W. C.; Zhao, D.; Wu, K. L. et al. Electronic structure and
A.; Paul Alivisatos, A. Formation of hollow nanocrystals through d-band center control engineering over M-doped CoP (M = Ni, Mn,
the nanoscale kirkendall effect. Science 2004, 304, 711–714. Fe) hollow polyhedron frames for boosting hydrogen production. Nano
[41] González, E.; Arbiol, J.; Puntes, V. F. Carving at the nanoscale: Energy 2019, 56, 411–419.

| www.editorialmanager.com/nare/default.asp