Vacancy‐Rich Ni(OH)2 Drives the Electrooxidation of Amino C−N Bonds to Nitrile C≡N Bonds

Abstract Electrochemical synthesis based on electrons as reagents provides a broad prospect for commodity chemical manufacturing. A direct one‐step route for the electrooxidation of amino C−N bonds to nitrile C≡N bonds offers an alternative pathway for nitrile production. However, this route has not been fully explored with respect to either the chemical bond reforming process or the performance optimization. Proposed here is a model of vacancy‐rich Ni(OH) 2 atomic layers for studying the performance relationship with respect to structure. Theoretical calculations show the vacancy‐induced local electropositive sites chemisorb the N atom with a lone pair of electrons and then attack the corresponding N(sp 3 )−H, thus accelerating amino C−N bond activation for dehydrogenation directly into the C≡N bond. Vacancy‐rich nanosheets exhibit up to 96.5 % propionitrile selectivity at a moderate potential of 1.38 V. These findings can lead to a new pathway for facilitating catalytic reactions in the chemicals industry.