Amide-engineered copper nitride for shortcut-pathway-locked electroreduction of concentrated hydroxymethylfurfural

Achieving high selectivity in the electrocatalytic hydrogenation (ECH) of concentrated 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) remains a challenge due to competitive adsorption at high HMF concentrations, which limits active-site availability and suppresses *H generation. Regulating the balance between *H generation and HMF adsorption is therefore essential for maintaining selectivity under practical conditions. Here we show a surface amide-functionalized copper nitride catalyst (Ami-Cu3N) featuring dual-nitrogen active sites. The catalyst achieves >99% DHMF selectivity and >98% Faradaic efficiency, with a production rate of 63.4 mmol cm-2 h-1 at 500 mA cm-2 under concentrated HMF conditions. Mechanistic studies indicate that the combined roles of lattice nitrogen (promoting water dissociation) and amide nitrogen (modulating HMF adsorption) lower the energy barriers for both *H formation and HMF hydrogenation, facilitating high activity and selectivity. In addition, a coupled electrolysis system enables simultaneous production of value-added products at both electrodes. These findings provide design principles for electrocatalysts that enable selective biomass conversion at high reaction rates. Biomass electro-hydrogenation offers a sustainable route to value-added chemicals but suffers poor selectivity at high current densities. Here, the authors report an amide-functionalized Cu3N catalyst enabling near-quantitative HMF-to-DHMF conversion under industrially relevant conditions.