高耐久性Ni-Cu-Mo催化剂的制备及其电解氨制氢性能

doi:10.15541/jim20250384

无机材料学报 ›› 2026, Vol. 41 ›› Issue (9): 1247-1254.DOI: 10.15541/jim20250384

高耐久性Ni-Cu-Mo催化剂的制备及其电解氨制氢性能

李智杰(), 王潇漾(), 穆晓江, 朱思靖, 苗蕾()

广西大学物理科学与工程技术学院, 南宁 530004

收稿日期:2025-09-30 修回日期:2026-02-14 出版日期:2026-09-20 网络出版日期:2026-03-18
通讯作者: 苗蕾, 教授. E-mail: miaolei@gxu.edu.cn;
王潇漾, 助理教授. E-mail: wangxy@gxu.edu.cn
作者简介:李智杰(2000-), 男, 硕士研究生. E-mail: 1974773095@qq.com
基金资助:
广西科技计划(AB25069268);广西科技计划(AA23062070)

Highly Durable Ni-Cu-Mo Catalyst: Preparation and Performance for Hydrogen Evolution through Ammonia Oxidation Reaction

LI Zhijie(), WANG Xiaoyang(), MU Xiaojiang, ZHU Sijing, MIAO Lei()

School of Physical Sciences and Engineering Technology, Guangxi University, Nanning 530004, China

Received:2025-09-30 Revised:2026-02-14 Published:2026-09-20 Online:2026-03-18
Contact: MIAO Lei, professor. E-mail:miaolei@gxu.edu.cn;WANG Xiaoyang, assistant professor. E-mail:wangxy@gxu.edu.cn
About author:LI Zhijie (2000-), male, Master candidate. E-mail: 1974773095@qq.com
Supported by:
Scientific Research and Technology Development Program of Guangxi(AB25069268);Scientific Research and Technology Development Program of Guangxi(AA23062070)

摘要/Abstract

摘要：

开发低成本、高活性及高稳定性的电化学氨氧化反应(Ammonia Oxidation Reaction, AOR)催化剂是提升氨电解制氢技术整体效率的关键。本研究通过简便的一步水热法, 以泡沫镍(Nickel Foam, NF)为基底和镍源, 原位构筑了Cu、Mo均匀负载且具有层次化纳米花蕊结构的Ni-Cu-Mo整体式催化剂, 并将其直接应用于氨水产氢。实验结果显示, Ni-Cu-Mo催化剂表现出卓越的电催化活性, 其起始电位仅为1.32 V (vs. RHE)@10 mA·cm^-2, 在1.5 V (vs. RHE)电位下可以持续运行64 h, 电流密度稳定维持在100 mA·cm^-2以上, 展现出极佳的工业应用潜力。性能增强机制解析表明: Mo掺杂调控形成的纳米花蕊形貌提供了丰富的活性位点暴露空间; 三维NF骨架不仅确保了高效的电荷传输, 还增强了电解过程中的机械与化学稳定性; Ni和Cu之间的电子效应显著加速了AOR反应动力学。本研究研制的新型自支撑Ni-Cu-Mo催化剂为高效氨氧化制氢提供了重要材料平台, 也为未来设计氨-氢混合零碳燃料相关的电催化体系提供了新思路。

关键词: 氨氧化, 电催化, 纳米复合材料, 氨-氢混合零碳燃料, 长期稳定性

Abstract:

Developing low-cost, highly active, and durable electrocatalysts for the ammonia oxidation reaction (AOR) is pivotal for enhancing the overall efficiency of ammonia-to-hydrogen conversion technologies. In this work, a monolithic Ni-Cu-Mo electrocatalyst featuring a hierarchical nanoflower architecture was in-situ constructed on a nickel foam (NF) substrate which was both the support and nickel source via a facile one-step hydrothermal method. The integrated electrode was directly applied to ammonia-to-hydrogen production. Experimental results demonstrate that the Ni-Cu-Mo catalyst exhibits exceptional electrocatalytic activity, achieving a low onset potential of 1.32 V (vs. RHE)@10 mA·cm^-2. Furthermore, it maintains a stable current density exceeding 100 mA·cm^-2 for 64 h of continuous operation at 1.5 V (vs. RHE), showcasing outstanding potential for industrial applications. Mechanistic insights reveal that the morphology of hierarchical nanoflower induced by Mo-doping provides ample exposure of active sites, while the three-dimensional NF scaffold ensures efficient charge transport and enhances mechanical and chemical stability during the electrolysis process. Simultaneously, the electronic interaction between Ni and Cu significantly accelerates the AOR reaction kinetics. This study presents a novel self-supported Ni-Cu-Mo electrocatalyst as a robust material platform for efficient ammonia-based hydrogen production and provides innovative strategies for designing electrocatalytic systems for ammonia-hydrogen blended zero-carbon fuels in the future.

Key words: ammonia oxidation, electrocatalysis, nanocomposite, ammonia-hydrogen blended zero-carbon fuel, long-term stability

中图分类号:

O643

李智杰, 王潇漾, 穆晓江, 朱思靖, 苗蕾. 高耐久性Ni-Cu-Mo催化剂的制备及其电解氨制氢性能[J]. 无机材料学报, 2026, 41(9): 1247-1254.

LI Zhijie, WANG Xiaoyang, MU Xiaojiang, ZHU Sijing, MIAO Lei. Highly Durable Ni-Cu-Mo Catalyst: Preparation and Performance for Hydrogen Evolution through Ammonia Oxidation Reaction[J]. Journal of Inorganic Materials, 2026, 41(9): 1247-1254.

图/表 16

图1 催化剂的制备流程示意图

Fig. 1 Schematic diagram of preparation processes of catalysts

图2 Ni-Cu-Mo、Ni-Mo、Ni-Cu的XRD图谱

Fig. 2 XRD patterns of Ni-Cu-Mo, Ni-Mo and Ni-Cu

图3 Ni-Cu-Mo催化剂的SEM照片

Fig. 3 SEM images of Ni-Cu-Mo catalyst

图4 Ni-Cu-Mo的(a, b) TEM照片及(c~f) EDS元素分布图

Fig. 4 (a, b) TEM images and (c-f) EDS elemental mappings of Ni-Cu-Mo

图5 Ni-Cu-Mo电极的XPS谱图

Fig. 5 XPS spectra of Ni-Cu-Mo electrode (a) Ni2p; (b) Cu2p; (c) Mo3d; (d) O1s

图6 (a)不同氨浓度下Ni-Cu-Mo电极的LSV曲线; Ni-Cu-Mo、Ni-Cu、Ni-Mo、NF的(b) CV曲线和(c) LSV曲线

Fig. 6 (a) LSV curves of Ni-Cu-Mo electrode at different ammonia concentrations; (b) CV curves and (c) LSV curves of Ni-Cu-Mo, Ni-Cu, Ni-Mo and NF Colorful figures are available on website

图7 (a) Ni-Cu-Mo、Ni-Cu、Ni-Mo、NF的Tafel斜率; Ni-Cu-Mo、Ni-Cu、Ni-Mo的(b) EIS谱图(插图为等效电路)和(c) Cdl图

Fig. 7 (a) Tafel slopes of Ni-Cu-Mo, Ni-Cu, Ni-Mo and NF; (b) EIS spectra with inset showing equivalent circuit and (c) Cdl results of Ni-Cu-Mo, Ni-Cu and Ni-Mo

图8 在(a, b) 1.5和(c, d) 1.6 V (vs. RHE)下Ni-Cu-Mo三电极系统产生的AOR气体的GC分析

Fig. 8 GC analysis of AOR gas collected by three-electrode system at (a, b) 1.5 and (c, d) 1.6 V (vs. RHE)

图9 (a) Ni-Cu-Mo的i-t曲线; (b)与文献报道催化剂的稳定性对比[15,25,39-47]

Fig. 9 (a) i-t curve of Ni-Cu-Mo; (b) Stability compared with reported catalysts[15,25,39-47]

图S1 Ni-Cu催化剂不同倍率的SEM照片

Fig. S1 SEM images of Ni-Cu catalysts at different magnifications

图S2 Ni-Mo催化剂不同倍率的SEM照片

Fig. S2 SEM images of Ni-Mo catalysts at different magnifications

图S3 (a) Ni-Cu-Mo、(b) Ni-Cu和(c) Ni-Mo在不同扫描速度下的CV曲线

Fig. S3 CV curves collected at different scanning speeds using (a) Ni-Cu-Mo, (b) Ni-Cu and (c) Ni-Mo

图S4 (a) Ni-Cu和(b) Ni-Mo的i-t曲线

Fig. S4 i-t curves of (a) Ni-Cu and (b) Ni-Mo

表S1 Ni-Cu-Mo、Ni-Cu催化剂64 h i-t测试前后元素价态比例变化

Table S1 Changes in the valence state ratios of Ni-Cu-Mo and Ni-Cu catalysts before and after 64 h i-t test

	Ni-Cu-Mo				Ni-Cu
	Cu(+2)	Cu(0)	Ni(+2)	Mo(+6)	Cu(+2)	Cu(0)	Ni(+2)	Mo(+6)
Before	28.38%	71.62%	100%	100%	21.05%	78.95%	100%	-
After	0	100%	100%	100%	82.85%	17.15%	100%	-

图S5 Ni-Cu-Mo催化剂64 h i-t测试后的XPS谱图

Fig. S5 XPS spectra of Ni-Cu-Mo catalyst after 64 h i-t test

图S6 Ni-Cu电极64 h i-t测试前后的XPS谱图

Fig. S6 XPS spectra of Ni-Cu electrode before and after 64 h i-t test (a, d) Ni2p; (b, e) Cu2p; (c, f) O1s

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高耐久性Ni-Cu-Mo催化剂的制备及其电解氨制氢性能

Highly Durable Ni-Cu-Mo Catalyst: Preparation and Performance for Hydrogen Evolution through Ammonia Oxidation Reaction

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