近日，中国科学院化学所韩布兴团队报道了工业相关电流下硝酸盐半还原制羟胺的界面水受抑。相关论文于2025年12月9日发表在《美国化学会志》上。

羟胺具有广泛的应用前景。将硝酸盐电催化半还原为羟胺是其可持续生产的一条重要途径。然而，由于电催化过程中活性物种的供需失衡仍是关键挑战，已报道的路径通常导致氢化不足或过度，造成羟胺选择性较差。研究组提出了一种界面水受抑策略，以实现硝酸盐高选择性电催化半还原为羟胺。通过碱金属阳离子调控对双电层进行设计，精确调控界面水的活化以抑制过量活性氢的生成，进而控制活性氢的供给。此外，拉伸应变的铋基催化剂促进了*NO中间体的形成，增加了活性氢的需求并抑制了过度还原生成氨。

该策略在酸性条件下、120 mA cm^-2电流密度处实现了羟胺93.9%的法拉第效率，并成功以克级规模合成了具有高氮选择性的工业相关肟类产物。值得注意的是，该研究在工业级电流密度（>100 mA cm^-2）下实现了迄今最高的羟胺法拉第效率。这项工作通过界面水受抑策略，为调控半还原路径提供了一种普适性方法，从而构建了电催化反应中关键活性物种的供需平衡。

附：英文原文

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

Author: 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

Issue&Volume: December 9, 2025

Abstract: Hydroxylamine (NH2OH) has a broad range of applications. Electrocatalytic semireduction of nitrate (NO3–) to NH2OH 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 NH2OH. Herein, we demonstrate an interfacial water (H2O) frustration strategy to achieve highly selective electrocatalytic semireduction of nitrate (NO3–) to hydroxylamine (NH2OH). By engineering the electric double layer (EDL) through alkali metal cation modulation, we precisely regulated the activation of interfacial H2O 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 NH3. It achieved a Faradaic efficiency (FE) of 93.9% for NH2OH 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 NH2OH FE under industrial-level current densities (>100 mA cm–2). This work provided a generalizable approach for steering semireduction pathways through interfacial H2O frustration, which constructs the supply–demand balance of essential active species involved in electrocatalytic reactions.

DOI: 10.1021/jacs.5c19205

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c19205