Inter‐Atomic Synergy on Single‐Atom Alloy Promotes Cyclohexanone Oxime Electrosynthesis

ABSTRACT The electrosynthesis of cyclohexanone oxime from cyclohexanone and nitrogenous feedstock driven by renewable electricity presents a sustainable alternative to energy‐intensive and hazardous industrial processes. However, achieving high activity and selectivity is challenged by the over‐reduction of key intermediates and the lack of effective sites for C─N coupling. Herein, we report a Fe ₁ Bi single‐atom alloy (Fe ₁ Bi SAA) featuring Fe‐Bi atomic interfaces that collaborate for the one‐pot electrosynthesis of cyclohexanone oxime. The Fe ₁ Bi SAA achieves a remarkable Faradaic efficiency of 70.9% and a yield rate of 0.94 mmol cm ⁻² h ⁻¹ for cyclohexanone oxime. Combined in situ electrochemical spectroscopic measurements and density functional theory calculations reveal an atomic‐scale synergistic mechanism: dispersed Fe sites adsorb and activate cyclohexanone, while adjacent Bi sites selectively reduce nitrite to the key hydroxylamine intermediate. The techno‐economic analysis based on flow electrolyzer operation confirms the potential economic viability of the electrosynthesis of cyclohexanone oxime. This work provides profound atomic‐level insight into cooperative catalysis for C─N coupling reactions toward the electrosynthesis of value‐added organonitrogen compounds.