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

Huang, Ju; Zhu, Jianqiu; Liu, Bowen; Dai, Chencheng; Chen, Zhimin; Wu, Hao; Li, Gang; Du, Shichao et al. · Nat Commun · 2026

basic_science · Level V

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Abstract

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-Cu<sub>3</sub>N) featuring dual-nitrogen active sites. The catalyst achieves >99% DHMF selectivity and >98% Faradaic efficiency, with a production rate of 63.4 mmol cm<sup>-2</sup> h<sup>-1</sup> at 500 mA cm<sup>-2</sup> 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.