Interfacial Water Frustration for Nitrate Semireduction to Hydroxylamine at Industrial-Relevant Currents

作者：Shunhan Jia, Ruhan Wang, Weixiang Li, Chaofeng Zheng, Xinning Song, Hanle Liu, Libing Zhang, Limin Wu, Xingxing Tan, Xiaodong Ma, Baolong Qu, Rongjuan Feng, Qian Li, Qinglei Meng, Lihong Jing, Lei He, Xiaofu Sun, Buxing Han · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c19205 · 被引用次数：17 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Electrocatalysts for Energy Conversion、CO2 Reduction Techniques and Catalysts

Hydroxylamine (NH 2 OH) has a broad range of applications. Electrocatalytic semireduction of nitrate (NO 3 – ) to NH 2 OH is a promising pathway for its sustainable production. However, the reported route typically led to either insufficient or excessive hydrogenation because the mismatch between supply and demand of active species during electrocatalysis remains a critical challenge, resulting in poor selectivity to NH 2 OH. Herein, we demonstrate an interfacial water (H 2 O) frustration strategy to achieve highly selective electrocatalytic semireduction of nitrate (NO 3 – ) to hydroxylamine (NH 2 OH). By engineering the electric double layer (EDL) through alkali metal cation modulation, we precisely regulated the activation of interfacial H 2 O to inhibit excessive active hydrogen (*H) generation, thereby controlling the *H supply. In addition, tensile-strained bibased catalysts promoted *NO intermediate formation, enhancing *H demand and suppressing over-reduction to NH 3 . It achieved a Faradaic efficiency (FE) of 93.9% for NH 2 OH at 120 mA cm –2 under acidic conditions, which enabled the gram-scale synthesis of industrially relevant oximes with high nitrogen selectivity. Remarkably, this work achieved the highest NH 2 OH FE under industrial-level current densities (>100 mA cm –2 ). This work provided a generalizable approach for steering semireduction pathways through interfacial H 2 O frustration, which constructs the supply–demand balance of essential active species i...