Cation Vacancy‐Modulated NiOOH for Electro‐Oxidative Alcohol Dehydrogenation and Amide Synthesis Coupled With Hydrogen Evolution

Utilizing thermodynamically favorable biomass conversion to replace oxygen evolution reactions (OER) can achieve efficient H 2 production under low energy consumption. However, this strategy has seldom been studied in the electrosynthesis of C–N oxidative coupling reactions (COR), mainly due to the challenge of simultaneously achieving efficient oxidation and coupling reaction. Herein, an electrochemical etching strategy was employed to prepare a V + ‐NiOOH catalyst rich in cation vacancies (V + ), which succeeded in the electrosynthesis of benzamide from benzyl alcohol (BA) and NH 3 at 1.50 V versus RHE, with 86% selectivity and 100% conversion. Synchrotron radiation analysis confirmed that the presence of V + promoted the generation of high‐valent Ni 4+ (t 2g 6 e g 0 ) species and activated the lattice oxygen in Ni 4+ ‐O lat ‐Ni 3+ . Related in situ characterization and theoretical calculations explained the significant role of Ni 4+ ‐O lat ‐O∙ in catalyzing the oxidation of O–H and C–H bonds, and the dynamic reconstruction between Ni 3+ and Ni 4+ inhibited the poisoning effect of NH 3 on the catalyst. Notably, by coupling with cathodic H 2 production, an amide yield of 0.81 mmol h −1 was achieved under 200 mA, and the H 2 production energy consumption was reduced by 24.1%. It provides important guidance for promoting green and efficient utilization of resources and energy.