Boosting Nitrate‐to‐Ammonia Conversion over Copper‐Based Electrocatalysts by Facilitating Hydrogenation and Product Desorption

作者：Yunying Wang, Tong Bao, Liyan Chen, Chaoqi Zhang, Jing Wang, Yingying Zou, Yamin Xi, Zhijie Li, Chengzhong Yu, Chao Liu · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202509090 · 被引用次数：17 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Caching and Content Delivery、Advanced Photocatalysis Techniques

Abstract Electrocatalytic nitrate reduction reaction (NitRR) in neutral condition offers a sustainable route for ammonia (NH 3 ) production and water purification. For the most extensively investigated Cu‐based electrocatalysts that favor NO 3 − adsorption, insufficient hydrogenation capability and sluggish NH 3 desorption hinder the ultimate performance. Herein, we report Ca‐doped Cu 2 O co‐modified by oxalate (Ca─Cu 2 O─OA) as a novel and high‐performance NitRR electrocatalyst. Experimental and theoretical results demonstrate that the Ca dopant with strong hydration effect facilitates the hydrogenation steps of adsorbed NO 3 − on the adjacent Cu active sites. The hydrogen‐bonding interaction between OA and adsorbed NH 3 promotes the product desorption. Together with the strong NO 3 − adsorption capability and inhibited hydrogen evolution as a side reaction, excellent NitRR performance with a high Faraday efficiency (FE) of 97.49% and a high NH 3 yield of 15.02 mg h −1 cm −2 is achieved in neutral condition, outperforming most reported electrocatalysts. This work has provided new insights into the rational design of advanced NitRR electrocatalysts.