金属镍铜负载钒氧化物的高效电解产氢性能

doi:10.15541/jim20220625

无机材料学报 ›› 2023, Vol. 38 ›› Issue (6): 647-655.DOI: 10.15541/jim20220625

金属镍铜负载钒氧化物的高效电解产氢性能

孙强强(), 陈子璇, 杨子玥, 王毅梦, 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:2022-10-24 修回日期:2022-12-25 出版日期:2022-12-28 网络出版日期:2022-12-28
通讯作者: 曹宝月, 副教授. 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:
陕西省科协青年人才托举计划项目(20200613);商洛学院科研发展平台专项(22KYZX01);大学生创新创业训练计划项目(S202211396016)

Amorphous Vanadium Oxide Loaded by Metallic Nickel-copper towards High-efficiency Electrocatalyzing Hydrogen Production

SUN Qiangqiang(), CHEN Zixuan, YANG Ziyue, WANG Yimeng, CAO Baoyue()

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

Received:2022-10-24 Revised:2022-12-25 Published:2022-12-28 Online:2022-12-28
Contact: CAO Baoyue, associate professor. E-mail: 231052@slxy.edu.cn
About author:SUN Qiangqiang (1985-), male, PhD, associate professor. E-mail: sqq3c118@slxy.edu.cn
Supported by:
The Youth Talent Support Program of Shaanxi University Science and Technology Association(20200613);Scientific Research Development Platform Special Project of Shangluo University(22KYZX01);National College Student Innovation and Entrepreneurship Training Program(S202211396016)

摘要/Abstract

摘要：

镍基电极材料是碱性电解水中最具工业应用前景的过渡金属催化剂, 而其缓慢的析氢反应动力学及低活失活问题仍亟待解决。本研究以泡沫镍(NF)为基底, 采用一步循环伏安法制备了主晶相为独立分相的多晶态金属镍铜合金、夹杂有少量非晶态V₂O₅相、具有三维多孔团簇结构的金属镍铜负载钒氧化物电催化剂(VO_x-NiCu/NF)。纳米颗粒、团簇交织形成的微米孔及泡沫镍的一级微孔共同构成了VO_x-NiCu/NF的三级多孔微纳结构, 使其电催化活性面积增加了28倍, 并在析氢反应中表现出优异的催化性能。在碱性介质中, 获得-10 mA·cm^-2的析氢电流密度, VO_x-NiCu/NF需要的过电势(η₁₀)仅为35 mV, 表现出类铂的催化活性, 具有优异的长效稳定性及强劲的耐用性。电极表面形成的多孔团簇结构, 显著增加了催化活性位点并为物质传递提供大量通道。镍铜合金及非晶态V₂O₅相, 在一定程度协同改善了材料的固有析氢活性。理想的组成及独特的结构特性提高了VO_x-NiCu/NF的催化性能, 其中结构优势对其最优效能起主导作用。动力学分析发现, VO_x-NiCu/NF在析氢过程遵循Volmer-Heyrovsky机理, 即表面活性氢原子的电化学脱附为电荷转移过程的决速步骤, 为后续深入研究催化机制奠定了基础。

关键词: 镍铜合金, 钒氧化物, 析氢反应, 团簇结构, 协同效应

Abstract:

Nickel-based electrocatalytic material is considered one of the cost-optimal transition metal catalysts in alkaline water electrolysis due to its accessible industrial-applicability. Nevertheless, slow hydrogen evolution kinetics and low activation are still the grand challenges. Herein, we report a three-dimentional porous cluster structure vanadium oxide implanting into nickel-copper alloy electrocatalyst with phase-separation metallic nickel and copper as the main crystal phase mixed up with amorphous vanadium oxide phase, which is fabricated in situ on nickel foam (NF) by one-step cyclic voltammetry. The tri-hierarchical porous micro-nano structure of VO_x-NiCu/NF was constructed by nanoparticles of whichmicropores were created by clusters. This nickel foam micropores endows the target catalyst with a 28-fold increased electrochemically active surface area (ECSA), comparable to Pt-like catalytic activity towards hydrogen evolution reaction (HER). Encouragingly, VO_x-NiCu/NF needs merely 35 mV (η₁₀) to drive -10 mA·cm^-2 towards HER in alkaline medium. In addition, the as-prepared VO_x-NiCu/NF exhibits excellent long-time stability and durability. These data suggest that the formation of cluster structure, piled by nanoparticles, creates a large number of surface micropores, which greatly enhance the active sites and provide abundant material transfer channels for HER. Formation of NiCu alloy and amorphous V₂O₅ phase synergically boost the intrinsic HER activity to a certain extent. Simultaneously, the ideal composition and unique structural characteristics of VO_x-NiCu/NF contribute to the superior catalytic performance with the structural advantage responsible for the predominant effect. On the basis of kinetic analysis, the HER at VO_x-NiCu/NF proceed via a Volmer-Heyrovsky mechanism, where chemical desorption of hydrogen adsorbed is regarded as the rate-limiting step. Therefore, this study lays a foundation for promotion electrocatalytic hydrogen production.

Key words: nickel-copper alloy, vanadium oxide, hydrogen evolution reaction, cluster structure, synergistic effect

中图分类号:

TQ151
O611

孙强强, 陈子璇, 杨子玥, 王毅梦, 曹宝月. 金属镍铜负载钒氧化物的高效电解产氢性能[J]. 无机材料学报, 2023, 38(6): 647-655.

SUN Qiangqiang, CHEN Zixuan, YANG Ziyue, WANG Yimeng, CAO Baoyue. Amorphous Vanadium Oxide Loaded by Metallic Nickel-copper towards High-efficiency Electrocatalyzing Hydrogen Production[J]. Journal of Inorganic Materials, 2023, 38(6): 647-655.

图/表 16

图1 (a)空白泡沫镍及(b~d)VOx-NiCu/NF在不同放大倍数下的SEM照片

Fig. 1 Different magnification SEM images of bare NF (a) and optimal VOx-NiCu/NF magnified by (b-d) 60000 times

图2 VOx-NiCu/NF的(a)EDX能谱图、(b)元素分布及(c)XRD谱图

Fig.2 (a) EDX, (b) element mappings and (c) XRD patterns of VOx-NiCu/NF

图3 VOx-NiCu/NF的(a)TEM照片(插图为选区电子衍射图样)及(b)HRTEM照片

Fig.3 (a) TEM image with insert showing corresponding SAED image and (b) HRTEM image of VOx-NiCu/NF

图4 VOx-NiCu/NF的(a)Ni2p, (b)Cu2p, (c)V2p和(d)O1s的XPS谱图

Fig. 4 (a) Ni2p, (b) Cu2p, (c) V2p, and (d) O1s XPS spectra of VOx-NiCu/NF

图5 VOx-NiCu/NF的(a)析氢极化曲线，(b)Tafel曲线及以(c)多电流阶跃法，(d)循环伏安法，(e)计时电位法测试的72 h催化稳定性结果

Fig. 5 (a) LSV curves and (b) Tafel plots of electrodes towards HER, (c, d) durability and stability tests of VOx-NiCu/NF towards the HER by (c) multicurrent-step, (d) CV curves before and after 5000 cycles with insert showing SEM image after 5000 cycles, and (e) chronopotentiometry of VOx-NiCu/NF for 72 h Colorful figures are available on website

表1 VOx-NiCu/NF与近期文献报道的析氢催化剂(1 mol·L-1 KOH溶液)性能

Table 1 HER activities of VOx-NiCu/NF with recently reported electrocatalysts in 1 mol·L-1 KOH alkaline solution

Material	Tafel slope/ (mV·dec^-1)	η₁₀/mV	Ref.
VO_x-NiCu/NF	36.9	35	This work
Co@N-CNT	94.0	44	[35]
FeCoNi-HNTAs	37.5	58	[36]
NiFeV/NF	62.0	125	[37]
Ni-Ce-Pr-Ho/NF	121.6	78	[38]
N/C/MoP	51.3	169	[39]
Co_xPy/Ni_xP_y-NPC	84.0	126	[40]
Ni/Mo₂C/NC	63.0	180	[41]
Ni-B/graphene	148	187	[42]
CoS₂/MoS₂/NC	80.0	215	[43]

图6 VOx-NiCu/NF的(a)循环伏安曲线，(b)双电容曲线，(c)交流阻抗谱图(插图为等效电路)及(d)归一化的LSV曲线

Fig. 6 (a) CV curves, (b) double-layer capacitance curves, (c) Nyquist plots with insert showing equivalent circuit and LSV curves by ECSA normalization of VOx-NiCu/NF towards HER Colorful figures are available on website

图S1 不同NaVO3浓度下VOx-NiCu/NF的(a)析氢极化曲线及(b)过电位

Fig. S1 (a) LSV curves and (b) overpotentials of VOx-NiCu/NF at different concentrations of NaVO3

图S2 不同扫速下VOx-NiCu/NF的(a)析氢极化曲线及(b)过电位

Fig. S2 (a) LSV curves and (b) overpotentials of VOx-NiCu/NF with different scan rates

图S3 不同沉积圈数所得VOx-NiCu/NF的(a)析氢极化曲线及(b)过电位

Fig. S3 (a) LSV curves and (b) overpotentials of VOx-NiCu/NF for different cycles of electrodeposition

图S4 不同电位窗口所得VOx-NiCu/NF的(a)析氢极化曲线及(b)过电位

Fig. S4 (a) LSV curves and (b) overpotentials of VOx-NiCu/NF for different potential scan ranges

图S5 不同电极的析氢过电位

Fig. S5 Overpotentials of different electrodes

图S6 5000圈CV测试前后VOx-NiCu/NF的物相及组成对比

Fig. S6 XRD patterns and compositions of VOx-NiCu/NF before and after 5000 cycles CV tests

图S7 (a)经过72 h长效稳定测试VOx-NiCu/NF的析氢活性及微观结构, (b)96 h的长时稳定性测试

Fig. S7 (a) Chemical activity and microstructure of VOx-NiCu/NF after a 72-h unintermittent running for HER, and (b) a 96-h unintermittent running for HER.

图S8 不同测试电极在析氢反应中的双电层电容和电催化活性面积

Fig. S8 ECSA and Cdl of different electrodes towards HER

图S9 不同电极在析氢过程的电荷转移电阻

Fig. S9 Charge transfer resistances (Rct) of different electrodes towards HER

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金属镍铜负载钒氧化物的高效电解产氢性能

Amorphous Vanadium Oxide Loaded by Metallic Nickel-copper towards High-efficiency Electrocatalyzing Hydrogen Production

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