Directing the Electrochemical C─N Coupling Toward Efficient Amide Synthesis via Ammonia Activation‐Mediated Pathway

Abstract Electrochemically oxidative C─N coupling using alcohol and ammonia as feedstocks offers a sustainable alternative for the chemosynthesis of amide organonitrogens. The achievements of high activity and selectivity yet remains challenging via the conventional alcohol oxidation pathway. Here, we present an alternative ammonia‐activation mediated pathway to favor the electrochemical C─N coupling necessary. Spectroscopic and theoretical investigations untangle that this manipulated process begins with the oxidation of ammonia to endow active *NH 2 species, which then efficiently couple with alcohol species to form C─N bonds. This alternative C─N coupling pathway exhibits accelerated kinetics and, more importantly, bypasses the formation of aldehyde intermediate, thereby preventing unfavorable overoxidation. As a result, this pathway achieves a high Faradaic efficiency of 50.1% and a carbon selectivity of 87.6% for efficient formamide electrosynthesis over a NiCuRu‐based (oxy)hydroxide catalyst, with a productivity of 557.2 µmol cm −2 h −1 . Such electrosynthetic approach further exhibit the universality of waste biomass/plastics‐driven carbon feedstocks, achieving considerable Faradaic efficiencies of 32%–60%. Techno‐economic analysis confirms the potential profitability of using renewable electricity input, highlighting the significant advantages of green chemical manufacturing for sustainable development.