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

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 Fe₁Bi single-atom alloy (Fe₁Bi SAA) featuring Fe-Bi atomic interfaces that collaborate for the one-pot electrosynthesis of cyclohexanone oxime. The Fe₁Bi 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.