Electrochemical Hydrogenation of Furfural in Aqueous Acetic Acid Media with Enhanced 2-Methylfuran Selectivity Using CuPd Bimetallic Catalysts.

Herein, we report a series of CuPd catalysts for electrochemical hydrogenation (ECH) of furfural to 2-methylfuran (MF or FurCH 3 where Fur=furyl) in aqueous 0.1 M acetic acid (pH 2.9). The highest faradaic efficiency (FE) for MF reached 75 % at -0.58 V vs. reversible hydrogen electrode with an average partial current density of 4.5 mA cm -2 . In situ surface-enhanced Raman spectroscopic and kinetic isotopic experiments suggested that electrogenerated adsorbed hydrogen (H ads ) was involved in the reaction and incorporation of Pd enhanced the surface coverage of H ads and optimized the adsorption pattern of furfural, leading to a higher FE for MF. Density functional theory calculations revealed that Pd incorporation reduced the energy barrier for the hydrogenation of FurCH 2 * to FurCH 3 *. Our study demonstrates that catalyst surface structure/composition plays a crucial role in determining the selectivity in ECH and provides a new strategy for designing advanced catalysts for ECH of bio-derived oxygenates.