Metal/Oxide Interface Enabling Selective Electrocatalytic Reduction of Oxime to Amine in Neutral Electrolyte

Electrochemical reduction of oximes promises a sustainable route for amine synthesis but is currently limited by the lack of mild electrolyte and low-cost catalyst systems. Here, we for the first time report selective electroreduction of a series of oximes to their corresponding amines in a pH-neutral aqueous electrolyte enabled by a Pb-PbO catalyst. Taking acetoxime as a model reactant, we find that the coexistence of Pb and PbO phases in the catalyst structure is essential for the high Faradaic efficiency and near-unity product selectivity for isopropylamine. Mechanistic studies reveal that the reduction starts with a rate-determining proton-coupled electron transfer step and proceeds through 2-propanimine as an intermediate. The same electrocatalyst also demonstrates high selectivity for other structurally diverse oxime reactants. These findings highlight the critical role of the metal/oxide interface in promoting selective and generalizable electrosynthesis of amines from oximes under mild conditions.