Pulsed Electrosynthesis of Cyclohexanone Oxime From Nitrate and Cyclohexanol

Electrocatalytic C─N coupling offers a promising route for sustainable oxime synthesis, yet it suffers from mismatched reaction kinetics and mass transport limitations. Herein, we report a pulsed electrolysis strategy for cyclohexanone oxime (CHOX) synthesis from nitrate (NO 3 − ) and cyclohexanol (C 6 H 12 O). CuCe‐cMOF is designed and used as a model catalyst. Mechanistic investigations unravel that pulsed electrolysis synergizes with CuCe‐cMOF to enrich NO 3 − /C 6 H 12 O reactants and facilitate key * NH 2 OH/ * C 6 H 10 O intermediate formation and stabilization, thus offering a favorable microenvironment to enhance C─N coupling for CHOX synthesis. Under the optimum pulsed electrolysis conditions, we achieve the record‐high CHOX yield rate of 2.8 mmol cm −2 h −1 and Faradaic efficiency of 82.2%. Moreover, scaling up system to a 50 cm 2 electrolyzer leads to an output of 274.1 g CHOX/day with a minimum CHOX selling price of US$2.06 kg −1 , demonstrating a scalable and economically viable paradigm for industrial oxime synthesis.