Regulating C–O bond cleavage in electrocatalytic furfural hydrodeoxygenation over Lewis acid‐promoted Cu catalysts

Electrocatalytic hydrodeoxygenation of furfural (FF) to 2‐methylfuran (2‐MF) offers a mild route for biomass upgrading, but its selectivity is challenged by furfuryl alcohol formation, hydrogen evolution, and catalyst deactivation. Here, a Lewis acid‐promoted Cu‐ZnO@Al 2 O 3 catalyst is developed to regulate the interfacial FF reduction pathway in acidic electrolyte. At −0.5 V vs. the reversible hydrogen electrode (RHE), the catalyst delivers 95% 2‐MF selectivity, 77% Faradaic efficiency (FE), and 67% FF conversion. Control experiments with different supports, Al 2 O 3 phases, and Sr‐modified catalysts reveal a strong Lewis acidity–selectivity relationship. In situ Raman/Fourier‐transform infrared (FTIR) spectroscopy and density functional theory (DFT) calculations show that Lewis acid sites enhance FF adsorption, polarize C=O, stabilize oxygenated intermediates, and lower the C–O cleavage barrier from 0.54 to 0.15 eV, enabling selective electrocatalytic biomass upgrading.