Orthogonal Design of Competing Deprotonation Process in Cation‐Mediated Ni(OH) ₂ for Achieving Industrial Level Biomass Electrooxidation

ABSTRACT The electrooxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) has attracted great attention in biomass value‐added conversion. However, the central challenge for achieving industrial‐level scalable biomass upgrading is that the catalysts’ inherent preference for activating O─H bond in the competitive oxygen evolution reaction (OER) over the strong C─H bond in organic molecules. Herein, we designed a Cu‐substituted Ni(OH) ₂ catalyst with orthogonal activity by precise valence engineering, selectively activating the aldehyde C─H in HMF oxidation while remaining inert toward the O─H cleavage in OER. Mechanistic studies and in situ characterizations confirm that the incorporation of Cu creates a unique local environment that fine‐tunes the deprotonation kinetics in two competing reactions, thereby improving selectivity and activity. This specific orthogonal design delivers outstanding performance, achieving an industrial‐scale current density of 1 A cm ⁻² at 1.55 V vs. RHE with a high Faraday efficiency for FDCA of 99.5%, which is comparable to the best catalysts reported to date. More importantly, the catalyst is continuously stable over 15 cycles. This work provides a new strategy for designing advanced electrocatalysts to achieve selective biomass conversion under industrial‐scale conditions.