Enhanced Nitrate-to-Ammonia Activity on Copper–Nickel Alloys via Tuning of Intermediate Adsorption

作者：Yuhang Wang, Aoni Xu, Ziyun Wang, Linsong Huang, Jun Li, Fengwang Li, Joshua Wicks, Mingchuan Luo, Dae‐Hyun Nam, Chih‐Shan Tan, Yu Ding, Jiawen Wu, Yanwei Lum, Cao‐Thang Dinh, David Sinton, Gengfeng Zheng, Edward H. Sargent · 发表于：Journal of the American Chemical Society · 年份：2020 · DOI：10.1021/jacs.9b13347 · 被引用次数：1390 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Caching and Content Delivery、Nanomaterials for catalytic reactions

Electrochemical conversion of nitrate (NO 3 – ) into ammonia (NH 3 ) recycles nitrogen and offers a route to the production of NH 3, which is more valuable than dinitrogen gas. However, today’s development of NO 3 – electroreduction remains hindered by the lack of a mechanistic picture of how catalyst structure may be tuned to enhance catalytic activity. Here we demonstrate enhanced NO 3 – reduction reaction (NO 3 – RR) performance on Cu 50 Ni 50 alloy catalysts, including a 0.12 V upshift in the half-wave potential and a 6-fold increase in activity compared to those obtained with pure Cu at 0 V vs reversible hydrogen electrode (RHE). Ni alloying enables tuning of the Cu d- band center and modulates the adsorption energies of intermediates such as *NO 3 –, *NO 2, and *NH 2 . Using density functional theory calculations, we identify a NO 3 – RR-to-NH 3 pathway and offer an adsorption energy–activity relationship for the CuNi alloy system. This correlation between catalyst electronic structure and NO 3 – RR activity offers a design platform for further development of NO 3 – RR catalysts.