Sun Hongming, Yan Zhenhua, Tian Caiying, Li Cha, Feng Xin, Huang Rong, Lan Yinghui, Chen Jing, Li Cheng-Peng, Zhang Zhihong, Du Miao
College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, 300387, Tianjin, China.
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, 300071, Tianjin, China.
Nat Commun. 2022 Jul 5;13(1):3857. doi: 10.1038/s41467-022-31561-4.
The active-site density, intrinsic activity, and durability of Ni-based catalysts are critical to their application in industrial alkaline water electrolysis. This work develops a kind of promoters, the bixbyite-type lanthanide metal sesquioxides (LnO), which can be implanted into metallic Ni by selective high-temperature reduction to achieve highly efficient Ni/LnO hybrid electrocatalysts toward hydrogen evolution reaction. The screened Ni/YbO catalyst shows the low overpotential (20.0 mV at 10 mA cm), low Tafel slope (44.6 mV dec), and excellent long-term durability (360 h at 500 mA cm), significantly outperforming the metallic Ni and benchmark Pt/C catalysts. The remarkable hydrogen evolution activity and stability of Ni/YbO are attributed to that the YbO promoter with high oxophilicity and thermodynamic stability can greatly enlarge the active-site density, reduce the energy barrier of water dissociation, optimize the free energy of hydrogen adsorption, and avoid the oxidation corrosion of Ni.
镍基催化剂的活性位点密度、本征活性和耐久性对其在工业碱性水电解中的应用至关重要。这项工作开发了一种促进剂,即方铁锰矿型镧系金属倍半氧化物(LnO),它可以通过选择性高温还原植入金属镍中,以实现高效的Ni/LnO混合电催化剂用于析氢反应。筛选出的Ni/YbO催化剂表现出低过电位(10 mA cm时为20.0 mV)、低塔菲尔斜率(44.6 mV dec)和出色的长期耐久性(500 mA cm下360 h),显著优于金属镍和基准Pt/C催化剂。Ni/YbO卓越的析氢活性和稳定性归因于具有高亲氧性和热力学稳定性的YbO促进剂能够极大地增加活性位点密度、降低水离解的能量势垒、优化氢吸附的自由能并避免镍的氧化腐蚀。