Cui Yuhuan, Sun Changning, He Yuexuan, Feng Zixuan, Ding Guopeng, Dai Qingqing, Wang Tonghui, Wang Zhili, Jiang Qing
College of Chemistry and Materials Science, Hebei University, Baoding 071002, China.
Key Laboratory of Automobile Materials, Ministry of Education, and School of Materials Science and Engineering, Jilin University, Changchun 130022, China.
Nano Lett. 2025 Jan 15;25(2):837-844. doi: 10.1021/acs.nanolett.4c05376. Epub 2025 Jan 1.
The electrochemical nitrate (NO) reduction reaction (NORR) offers a promising route for NO wastewater treatment and sustainable ammonia (NH) synthesis. However, the reaction still faces the challenges of unsatisfactory productivity and selectivity. Herein, we report a hierarchical nanoporous Ag,Ni-codoped Cu (np Ag,Ni-Cu) catalyst that exhibits a high NH Faradaic efficiency of 98.5% with an attractive NH yield rate of 41.1 mg h mg at -0.2 V vs RHE for the NORR. Density functional theory calculations and molecular dynamics simulations suggest that the excellent performance of np Ag,Ni-Cu results from a trimetallic synergistic effect and nanopore enrichment/confinement effect, in which the codoping of Ni and Ag into Cu can enhance NO adsorption, prevent *NO desorption, and suppress the hydrogen evolution reaction, while nanopores can promote NO accumulation on the internal surface of nanopores and confine the reaction intermediates within the nanopores for a deeper NO electroreduction.
电化学硝酸盐（NO）还原反应（NORR）为NO废水处理和可持续氨（NH₃）合成提供了一条很有前景的途径。然而，该反应仍面临生产率和选择性不尽人意的挑战。在此，我们报道了一种分级纳米多孔Ag、Ni共掺杂的Cu（np Ag,Ni-Cu）催化剂，在相对于可逆氢电极（RHE）为-0.2 V时，该催化剂对NORR表现出98.5%的高NH₃法拉第效率以及41.1 mg h⁻¹ mg⁻¹的诱人NH₃产率。密度泛函理论计算和分子动力学模拟表明，np Ag,Ni-Cu的优异性能源于三金属协同效应和纳米孔富集/限域效应，其中Ni和Ag共掺杂到Cu中可增强NO吸附、防止*NO解吸并抑制析氢反应，而纳米孔可促进NO在纳米孔内表面的积累，并将反应中间体限制在纳米孔内以实现更深层次的NO电还原。
