Bioinspired Catalyst/Electrolyte Interfacial Hydrogen-Bond Network Engineering toward Proton Transfer Acceleration...

The electrocatalytic oxidation of biomass-derived alcohol offers a sustainable route to valuable chemicals, yet it is often impeded by sluggish proton-coupled electron transfer (PCET) kinetics, which limit both activity and long-term stability. Inspired by enzymatic proton relays, we herein propose a ligand-induced interfacial engineering strategy to reconstruct hydrogen-bond networks within the electrical double layer of Co(OH)₂. Using terephthalic acid (TPA) as a bioinspired ligand, we successfully accelerate proton transfer kinetics while simultaneously facilitating lattice-hydroxyl activation for efficient proton deintercalation. The resulting interface-modified catalyst delivers exceptional glycerol electrooxidation performance toward formate, achieving 95% selectivity, an industrial-grade current density above 800 mA cm^-2 at 1.6 V, and an outstanding stability exceeding 2600 h. Integrated mechanistic studies combining in situ spectroscopy, theoretical calculations, and molecular dynamics simulations elucidate the dual role of TPA in promoting proton deintercalation and reconstructing interfacial hydrogen-bond networks to enhance PCET kinetics. A membrane-electrode-assembly electrolyzer integrating this catalyst operates with efficiency at 1.29 V (10 mA cm^-2) and enables the kilogram-scale production of potassium diformate in the laboratory, demonstrating its practical potential for sustainable biomass valorization. This work provides a rational and generalizable approach to design high-performance electrocatalysts through bioinspired interfacial hydrogen-bond engineering.