多孔片层钴钒氢氧化物/镍铜复合催化剂的构筑及其高效产氢性能

doi:10.15541/jim20260031

无机材料学报 ›› 2026, Vol. 41 ›› Issue (10): 1396-1406.DOI: 10.15541/jim20260031

多孔片层钴钒氢氧化物/镍铜复合催化剂的构筑及其高效产氢性能

孙强强(), 姜美娜, 魏宇航, 王丹, 周子雯, 李春, 曹宝月()

商洛学院化学工程与现代材料学院, 陕西省尾矿资源综合利用重点实验室/商洛市石墨烯技术与应用研究中心, 商洛 726000

收稿日期:2026-01-19 修回日期:2026-03-09 出版日期:2026-10-20 网络出版日期:2026-04-16
通讯作者: 曹宝月, 教授. E-mail: 231052@slxy.edu.cn
作者简介:孙强强(1985-), 男, 博士, 副教授. E-mail:sqq3c118@slxy.edu.cn.
基金资助:
陕西省青年创新团队科学研究计划(23JP039);商洛市科技发展计划(2023-G-0007);大学生创新创业训练计划(S202311396002);大学生创新创业训练计划(S202511396011);陕西省秦岭矿产资源综合开发利用概念验证中心(2025CG-GNYZ2-08);教育科技人才体制机制一体改革试点项目(2025KJ-JKRC-34)

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

SUN Qiangqiang(), JIANG Meina, WEI Yuhang, WANG Dan, ZHOU Ziwen, LI Chun, CAO Baoyue()

Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Research Centre of Grapheme Technology and Application, School of Chemical Engineering and Modern Materials, Shangluo University, Shangluo 726000, China

Received:2026-01-19 Revised:2026-03-09 Published:2026-10-20 Online:2026-04-16
Contact: CAO Baoyue, professor. E-mail: 231052@slxy.edu.cn
About author:SUN Qiangqiang (1985-), male, PhD, associate professor. E-mail: sqq3c118@slxy.edu.cn
Supported by:
Shaanxi Provincial Youth Innovation Team Scientific Research Program(23JP039);Shangluo City Science and Technology Development Plan Project(2023-G-0007);College Student Innovation and Entrepreneurship Training Program(S202311396002);College Student Innovation and Entrepreneurship Training Program(S202511396011);Shaanxi Provincial Qinling Mineral Resources Comprehensive Development and Utilization Concept Verification Center(2025CG-GNYZ2-08);Pilot Project for the Integrated Reform of Education, Science and Technology Talent Systems and Mechanisms(2025KJ-JKRC-34)

摘要/Abstract

摘要：

鉴于目前非贵金属电催化剂在产氢领域的迫切需求, 开发高效、稳定且廉价的析氢电极材料是实现可持续电解水制氢的关键挑战。本研究以镍网(NM)为基底, 结合氢气泡模板法与循环伏安电沉积技术, 制备了具有多孔圆形纳米片层结构的钴钒氢氧化物/镍铜复合催化剂(CoV LDH/NiCu/NM)。该催化剂由镍铜合金和钴钒氢氧化物主晶相构成, 形成纳米枝晶与圆形纳米片交织堆叠的三维开放多孔结构, 使电化学活性面积提升至基底的110倍, 极大增加了活性位点并促进了传质过程。多种组分与结构的协同效应使CoV LDH/NiCu/NM在1 mol·L^-1 KOH电解液中表现出类铂的析氢性能, 当电流密度为10和100 mA·cm^-2时, 析氢过电位分别仅为28和108 mV; 塔菲尔(Tafel)斜率为47.1 mV·dec^-1, 显示出良好的反应动力学特征。在析氧反应及全水分解中也表现出良好活性(10 mA·cm^-2时过电位及分解槽压分别为329 mV和1.506 V), 展现出潜在的双功能应用价值。此外, 该催化剂还表现出卓越的长效稳定性与耐久性, 在100 mA·cm^-2下连续电解72 h后活性无明显衰减。结构-性能分析表明, 其优异的催化活性主要源于独特的多孔纳米片层结构。本研究为设计高效、稳定的非贵金属析氢电极提供了新思路。

关键词: 镍铜合金, 镍钒氢氧化物, 析氢反应, 本征活性, 协同效应

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

中图分类号:

TQ151
O611

孙强强, 姜美娜, 魏宇航, 王丹, 周子雯, 李春, 曹宝月. 多孔片层钴钒氢氧化物/镍铜复合催化剂的构筑及其高效产氢性能[J]. 无机材料学报, 2026, 41(10): 1396-1406.

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.

图/表 15

图1 (a~c) NiCu/NM和(d~f)优选CoV LDH/NiCu/NM的SEM照片; (g) CoV LDH/NiCu/NM的TEM照片

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

图2 CoV LDH/NiCu/NM的(a) EDS谱图、(b)元素分布图及(c) XRD谱图

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

图3 CoV LDH/NiCu/NM的(a) Ni2p、(b) Cu2p、(c) Co2p、(d) V2p、(e) O1s XPS谱图及不同样品的(f) Raman谱图

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

图4 不同测试电极的HER (a)极化曲线及(b) Tafel曲线; CoV LDH/NiCu/NM的HER (c)多电流阶跃曲线、(d) LSV曲线(插图为循环2000次后的SEM照片)及(e)计时电位曲线

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

图5 (a) CoV LDH/NiCu/NM电极的HER CV曲线; 不同电极的HER (b)充电双电层库仑曲线、(c) Nyquist曲线和(d) ECSA归一化后的LSV曲线

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

图6 不同测试电极的OER (a)极化曲线及(b) Tafel曲线; CoV LDH/NiCu/NM在全水分解中的(c)槽压电流曲线及(d) 72 h稳定性测试的计时电位曲线

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

图S1 (a~d)不同制备参数的CoV LDH/NiCu/NM的极化曲线; (e~j)不同镍铜盐摩尔比所得CoV LDH/NiCu/NM的SEM照片、(i) HER极化曲线及(j)过电位柱状图

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

表S1 不同制备参数所得CoV LDH/NiCu/NM的析氢过电位

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

图S2 CoV LDH/NiCu/NM、NiCu/NM与标准卡片特征衍射峰的对比

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

图S3 CoV LDH/NiCu/NM与NiCu/NM的(a) Ni2p和(b) Cu2p XPS谱图

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

图S4 不同析氢催化剂的过电位对比

Fig. S4 Overpotential comparison of different hydrogen evolution catalysts

图S5 不同析氢催化剂的ECSA及其递增倍数对比

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

图S6 不同析氢催化剂的电荷转移电阻(Rct)对比

Fig. S6 Comparison of Rct of different hydrogen evolution catalysts

图S7 不同析氧催化剂的过电位对比

Fig. S7 Overpotential comparison of different oxygen evolution catalysts

表S2 CoV LDH/NiCu/NM与文献报道的非贵金属催化剂析氢过电位的对比[S1-S10]

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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多孔片层钴钒氢氧化物/镍铜复合催化剂的构筑及其高效产氢性能

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

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