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 CH 2 OH-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.