Reinforced Hydrogen-Bond Networks on Dehydrogenated Ni(OH) ₂ Surfaces Boost HMF Electrooxidation via Mediated Adsorption Configuration and Bond Polarization

The sluggish kinetics and high energy input of 5-hydroxymethylfurfural (HMF) electrooxidation hinder its practical application in biomass valorization. Here, we demonstrate that surface dehydrogenation of Ni(OH)2 dynamically enhances HMF electrooxidation activity by engineering reinforced hydrogen-bond microenvironments at the electrode/electrolyte interface. Combining DFT and AIMD simulations, we reveal that dehydrogenation exposes proton-accepting O sites, strengthening hydrogen-bond interactions with HMF and interfacial water. This stabilizes HMF via CH2OH-down adsorption configurations and polarizes C–H bonds, reducing the dissociation barrier of hydroxymethyl groups to 0.66 eV (vs 1.50 eV on pristine Ni(OH)2). Thermodynamic and kinetic analyses demonstrate that dehydrogenation shifts the dominant pathway to the 2,5-diformylfuran pathway. Our work provides atomic-scale insights into how surface chemistry regulates interfacial reaction dynamics, offering a design strategy for efficient electrocatalysts in biomass upgrading.