Electrical‐Driven Directed‐Evolution of Copper Nanowires Catalysts for Efficient Nitrate Reduction to Ammonia

Abstract The electrocatalytic conversion of nitrate (NO 3 − ) to NH 3 (NO 3 RR) at ambient conditions offers a promising alternative to the Haber–Bosch process. The pivotal factors in optimizing the proficient conversion of NO 3 − into NH 3 include enhancing the adsorption capabilities of the intermediates on the catalyst surface and expediting the hydrogenation steps. Herein, the Cu/Cu 2 O/Pi NWs catalyst is designed based on the directed‐evolution strategy to achieve an efficient reduction of NO 3 ‾. Benefiting from the synergistic effect of the O V ‐enriched Cu 2 O phase developed during the directed‐evolution process and the pristine Cu phase, the catalyst exhibits improved adsorption performance for diverse NO 3 RR intermediates. Additionally, the phosphate group anchored on the catalyst's surface during the directed‐evolution process facilitates water electrolysis, thereby generating H ads on the catalyst surface and promoting the hydrogenation step of NO 3 RR. As a result, the Cu/Cu 2 O/Pi NWs catalyst shows an excellent FE for NH 3 (96.6%) and super‐high NH 3 yield rate of 1.2 mol h −1 g cat. −1 in 1 m KOH and 0.1 m KNO 3 solution at −0.5 V versus RHE. Moreover, the catalyst's stability is enhanced by the stabilizing influence of the phosphate group on the Cu 2 O phase. This work highlights the promise of a directed‐evolution approach in designing catalysts for NO 3 RR.