Electrochemically Tunable Proton-Coupled Electron Transfer in Pd-Catalyzed Benzaldehyde Hydrogenation.

Acid functionalization of a carbon support allows to enhance the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol proportional to the concentration of Brønsted-acid sites. In contrast, the hydrogenation rate is not affected when H2 is used as a reduction equivalent. The different responses to the catalyst properties are shown to be caused by differences in the hydrogenation mechanism between the electrochemical and the H2 -induced hydrogenation pathways. The enhancement of electrocatalytic reduction is realized by the participation of support-generated hydronium ions in the proximity of the metal particles.