Bioinspired Catalyst/Electrolyte Interfacial Hydrogen-Bond Network Engineering toward Proton Transfer Acceleration for Glycerol Electrooxidation

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 <i>in situ</i> 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.