Synergistic Integration of Intermediate Adsorption and Hydrogen Supply to Boost Nitrate Electroreduction to Ammonia Performance via Anchoring Nickel on Monolithic Copper Nanocone Arrays

Electrocatalytic nitrate reduction to ammonia (NRA) is a sustainable approach for wastewater remediation and value‐added ammonia synthesis. The development of high‐performance electrocatalysts is crucial for practical implementation. Herein, we reported a rationally designed nickel‐anchored monolithic copper nanocone array (Ni/Cu‐NCAs) as an efficient NRA catalyst. The catalyst demonstrated outstanding NRA performance, achieving 96% nitrate conversion, 96.3% ammonium (NH 4 + )selectivity, 95.4% NH 4 + Faradaic Efficiency, and a high NH 4 + yield rate of 0.272 mmol·h −1 ·cm −2 . Combined experimental characterizations and density functional theory (DFT) calculations confirmed that the introduced Ni species modulated the d ‐band center of Cu sites to optimize the adsorption of key reaction intermediates, while simultaneously providing abundant active hydrogen (*H) for subsequent hydrogenation steps. The synergistic effect significantly accelerated reaction kinetics and promoted selective ammonia formation. This work developed a high‐efficiency monolithic Cu‐based NRA electrocatalyst, and shed new light on the bimetallic synergistic mechanism for nitrate electroreduction.