Mesoporous Anti‐Perovskite CuNi 3 N for Sustainable Formate Electrosynthesis from Complete Electrooxidation of Biomass Glucose

Electrocatalytic glucose oxidation reaction (GLUOR) offers a sustainable route to realize efficient biomass upcycling and synthesize highly valuable chemicals under ambient conditions. Despite great potentials, main challenges remain to simultaneously hold high yield rate and Faradaic efficiency (FE). In this study, mesoporous anti‐perovskite CuNi 3 N (m‐CuNi 3 N) is reported as a novel high‐performance electrocatalyst to enable complete GLUOR for sustainable formate electrosynthesis. In comparison to counterpart electrocatalysts, m‐CuNi 3 N delivers remarkable electrocatalytic performance for formate electrosynthesis, with a superior formate FE of 92.5% and an impressive formate yield rate of 1.93 mmol h −1 cm −2 as well as excellent cycling stability of reaching 210 h at 1.65 V (vs. the reversible hydrogen electrode). Multiple experiments and density functional theory calculations reveal that m‐CuNi 3 N follows an indirect GLUOR mechanism, in which Cu‐induced charge redistribution of Ni leads to rapid accumulation of Ni(III)‐OOH and high nucleophilic activity of Ni 3+ ‐O‐(OH) ads intermediate. These features, combined with enhanced glucose adsorption ability, synergistically promote the oxidation cleavage of C─C bonds and thus maximize selective formate electrosynthesis. More impressively, this route is electrocatalytically available for upcycling of the most common macromolecular biomass of starch wastes into valuable potassium formate, highlighting high economic feasibility and market potential in industry.