Tian Xiaoyu, Liu Jiaxiang, Zhao Pengcheng, Li Xianping, Li Zhuo, Sheng Wenchao
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai Institute of Pollution Control and Ecological Security, Shanghai, 200092, P.R. China.
Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, P.R. China.
ChemSusChem. 2025 Apr 14;18(8):e202402150. doi: 10.1002/cssc.202402150. Epub 2024 Dec 19.
One important target for anion exchange membrane fuel cells (AEMFCs) is to enable the application of anode non-precious metal hydrogen oxidation reaction (HOR) catalyst. Nickel presents a promising candidate for alkaline HOR; yet, its practical application is hampered by the intrinsically sluggish activity and poor stability. Herein, a series of Ni-based metals (NiMo, NiCo, NiW and Ni) are electrodeposited as model catalysts to systematically explore the alkaline HOR by considering the role of adsorbed hydroxyl (OH). Spectroscopic studies together with density functional theory calculations shed light on the beneficial effect of transition metal M (M=Mo, Co, W) alloying/doping on HOR by introducing the charge transfer from M to Ni and down shifting Ni 3d band center. The HOR specific activities on Ni-based catalysts reveal a volcano-type relationship with the hydrogen binding energy (HBE). The strongly adsorbed OH is proven to induce deactivation for Ni active sites, and the deactivation potential is OH binding energy (OHBE) dependent. This study adds new insight into the HOR mechanism and stability of Ni-based electrocatalysts, providing a new avenue for the rational design of highly efficient and robust alkaline HOR catalysts.
阴离子交换膜燃料电池（AEMFCs）的一个重要目标是实现阳极非贵金属氢氧化反应（HOR）催化剂的应用。镍是碱性氢氧化反应的一个有前景的候选材料；然而，其实际应用受到固有活性缓慢和稳定性差的阻碍。在此，通过考虑吸附羟基（OH）的作用，电沉积一系列镍基金属（NiMo、NiCo、NiW和Ni）作为模型催化剂，以系统地探索碱性氢氧化反应。光谱研究以及密度泛函理论计算通过引入从过渡金属M（M = Mo、Co、W）到镍的电荷转移以及降低镍3d能带中心，揭示了过渡金属M合金化/掺杂对氢氧化反应的有益影响。镍基催化剂上的氢氧化反应比活性与氢结合能（HBE）呈现火山型关系。已证明强吸附的OH会导致镍活性位点失活，且失活电位取决于OH结合能（OHBE）。本研究为镍基电催化剂的氢氧化反应机理和稳定性增添了新的见解，为合理设计高效且稳定的碱性氢氧化反应催化剂提供了新途径。
