Construction and High-efficiency Hydrogen Evolution Performance of Porous Layered Cobalt-vanadium Hydroxide/Nickel-copper Composite Catalyst

doi:10.15541/jim20260031

Abstract

Abstract:

Given the urgent demand for non-precious metal electrocatalysts in the hydrogen production field, developing efficient, stable, and low-cost hydrogen evolution electrode materials is a key challenge for achieving sustainable water electrolysis for hydrogen generation. Using nickel mesh (NM) as the substrate, a three-dimensional porous composite catalyst comprising cobalt-vanadium layered hydroxide and a nickel-copper alloy (CoV LDH/NiCu/NM) was fabricated via a combined approach of hydrogen bubble dynamic template electrodeposition and cyclic voltammetry. The resulting material features an open porous architecture constructed from intertwined nanodendrites and stacked circular nanosheets, with nickel-copper alloy and cobalt-vanadium hydroxide as the primary crystalline phases. This unique structure significantly enhances the specific surface area, yielding an electrochemical active surface area (ECSA) approximately 110 times that of the bare NM substrate, thereby providing abundant catalytic sites and efficient mass transfer pathways for water electrolysis. Benefiting from synergistic multi-component and structural effects, the CoV LDH/NiCu/NM electrode exhibits exceptional hydrogen evolution reaction (HER) performance in 1 mol·L^-1 KOH electrolyte. Specifically, it delivers low overpotentials of 28 and 108 mV at current densities of 10 and 100 mA·cm^-2, respectively, along with a Tafel slope of 47.1 mV·dec^-1, indicating favorable reaction kinetics. The catalyst also exhibits good oxygen evolution reaction (OER) activity and enables overall water splitting with the overpotential of 329 mV and cell voltage of 1.506 V at 10 mA·cm^-2, demonstrating its potential as a bifunctional electrode. Moreover, the catalyst demonstrates outstanding long-term durability, with negligible degradation in overpotential after 72 h of continuous operation at 100 mA·cm^-2. Structural and electrochemical analyses reveal that the superior catalytic activity is primarily attributable to the well-defined porous nanosheet architecture. This work presents a promising strategy for the design of high-performance, noble-metal-free electrocatalysts for hydrogen evolution.

Key words: nickel-copper alloy, cobalt-vanadium hydroxide, hydrogen evolution reaction, intrinsic activity, synergistic effect

CLC Number:

TQ151
O611

SUN Qiangqiang, JIANG Meina, WEI Yuhang, WANG Dan, ZHOU Ziwen, LI Chun, CAO Baoyue. Construction and High-efficiency Hydrogen Evolution Performance of Porous Layered Cobalt-vanadium Hydroxide/Nickel-copper Composite Catalyst[J]. Journal of Inorganic Materials, 2026, 41(10): 1396-1406.

Figures/Tables 15

Fig. 1 SEM images of (a-c) NiCu/NM and (d-f) the optimal CoV LDH/NiCu/NM; (g) TEM image of CoV LDH/NiCu/NM (g1, g2) Filtered inverse Fourier transform images

Fig. 2 (a) EDS spectrum, (b) elemental distribution mappings and (c) XRD patterns of CoV LDH/NiCu/NM

Fig. 3 (a) Ni2p, (b) Cu2p, (c) Co2p, (d) V2p and (e) O1s XPS spectra of CoV LDH/NiCu/NM and (f) Raman spectra of different samples

Fig. 4 (a) LSV curves and (b) Tafel plots of the tested electrodes towards HER; (c) Multicurrent-step curves, (d) LSV curves with inset showing SEM image after 2000 cycles and (e) chronopotential curves of CoV LDH/NiCu/NM Colorful figures are available on website

Fig. 5 (a) CV curves of CoV LDH/NiCu/NM towards HER; (b) Double-layer capacitance curves, (c) Nyquist plots and (d) LSV curves by ECSA normalization of different electrodes towards HER Colorful figures are available on website

Fig. 6 (a) LSV curves and (b) Tafel plots of the tested electrodes towards OER; (c) Cell voltage-current curves and (d) chronopotentiometric curves in the 72-hour stability test of CoV LDH/NiCu/NM for overall water splitting

Fig. S1 (a-d) LSV curves of CoV LDH/NiCu/NM with different preparation parameters; (e-j) SEM images, (i) HER polarization curves, and (j) overpotential histogram of CoV LDH/NiCu/NM obtained with different molar ratios of nickel to copper salts (a) Vanadium source; (b) Potential window; (c) Scan rate; (d) Deposition cycles

Table S1 HER overpotentials of CoV LDH/NiCu/NM with different preparation parameters

Overpotential	Vanadium source			Scan rate
Overpotential	NH₄VO₃	VOSO₄	NaVO₃	0.002 V·s^-1	0.005 V·s^-1	0.010 V·s^-1	0.015 V·s^-1	0.020 V·s^-1
η₁₀/mV	45	53	28	52	45	49	52	55
η₁₀₀/mV	161	166	123	175	152	169	165	176
Overpotential	Potential window				Deposition cycles
Overpotential	-1.2-0.2 V	-1.1-0.1 V	-1.2-0.1 V	-1.1-0.2 V	2 Q	4 Q	6 Q	8 Q
η₁₀/mV	33	41	26	30	45	38	27	26
η₁₀₀/mV	142	157	128	158	165	141	107	125

Fig. S2 Comparison of characteristic diffraction peaks of CoV LDH/NiCu/NM and NiCu/NM with standard phases (a) Ni(111) and Cu(111) crystal planes; (b) (100), (101), (003) and (111) crystal planes of Co(OH)2

Fig. S3 (a) Ni2p and (b) Cu2p XPS spectra of CoV LDH/NiCu/NM and NiCu/NM

Fig. S4 Overpotential comparison of different hydrogen evolution catalysts

Fig. S5 Comparison of ECSA and its increase multiples of different hydrogen evolution catalysts

Fig. S6 Comparison of Rct of different hydrogen evolution catalysts

Fig. S7 Overpotential comparison of different oxygen evolution catalysts

Table S2 Overpotential comparisons of CoV LDH/NiCu/NM with reported non-noble-metal HER catalysts[S1-S10]

Material	Overpotential	Tafel slope	Ref.
CoV LDH/NiCu/NM	28 mV/-10 mA·cm⁻²108 mV/-100 mA·cm⁻²	47.1 mV·dec^-1	This work
NS-Fe-B	214 mV/-10 mA·cm⁻²	129 mV·dec^-1	[S1]
NiCu NPs	273 mV/-10 mA·cm⁻²	-	[S2]
Cu-Fe	153 mV/-10 mA·cm⁻²	36 mV·dec^-1	[S3]
HM	210 mV/-10 mA·cm⁻²	78 mV·dec^-1	[S4]
MoS₂@HEP	71 mV/-10 mA·cm⁻²	58 mV·dec^-1	[S5]
Co₄S₃-MnS-MoS₂@CC	88 mV/-10 mA·cm⁻²	64.10 mV·dec^-1	[S6]
Co₉S₈/MnS/MoS₂/NF	85 mV/-10 mA·cm⁻²	76.9 mV·dec^-1	[S7]
CoS₂₋_xSe_x	143 mV/-10 mA·cm⁻²	69.8 mV·dec^-1	[S8]
MnS-MoS₂/LA-Mo	176 mV/-10 mA·cm⁻²	42.9 mV·dec^-1	[S9]
Fe/Co-600	179 mV/-10 mA·cm⁻²	67.8 mV·dec^-1	[S10]

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