Cracking the Reaction Pathway for Efficient HMF Electrooxidation: Strong Built‐In Electric Field and Multimetal Synergistic Effects

Abstract The 5‐hydroxymethylfurfural electro‐oxidation reaction (HMFOR), as an efficient biomass conversion method, has drawn significant attention due to its product 2,5‐furandicarboxylic acid (FDCA) being environmentally benign and producible under mild conditions. Nevertheless, the competing oxidation between aldehyde and hydroxymethyl groups in HMF molecules leads to uncontrolled reaction pathways and diminished FDCA selectivity. To overcome these challenges, this study develops a novel high‐entropy heterojunction catalyst—CuS@NiFeZrWCe‐LDH. The exceptional HMFOR performance stems from the synergistic effects of multimetallic components that intensify the built‐in electric field, enabling efficient charge transfer while preserving high oxidation states of metal active sites. The inherent electronic heterogeneity of multimetallic sites selectively adsorbs HMFOR intermediates, while the enhanced built‐in electric field promotes directional activation of the aldehyde group (─CHO) in HMF, effectively reducing C─H bond dissociation energy and precisely steering the reaction pathway toward HMFCA intermediate formation. The CuS@NiFeZrWCe‐LDH catalyst ultimately achieves 98.04% HMF conversion, 95.60% FDCA yield, and 97.34% Faradaic efficiency, collectively demonstrating outstanding catalytic performance. This work provides new insights for advancing biomass oxidation technologies.