Enhancing Ether Hydrogenolysis via Support Surface Proton Adsorption and Transfer Using Off-Field Electrocatalysis

The efficient and selective electrocatalytic hydrogenolysis of C–O bonds is highly desired for producing chemicals and fuels from biomass. Although protons are known to play a critical role in C–O activation, the effect of catalyst supports on proton transfer remains insufficiently understood. Herein, using the Eu 2+ /Eu 3+ redox mediator and Pd/TiO 2 as the catalyst, we achieved >99% conversion and selectivity in the hydrogenolysis of benzyl phenyl ether, exhibiting 7-fold activity of Pd/C under a dilute acidic environment. We demonstrate that, compared to carbon supports, TiO 2 facilitates proton transfer to Pd active sites, creating a localized high proton concentration. More importantly, protonation of the ether linkage (C–O–C) reduces the electron transfer energy barrier for hydrogenolysis, thereby enhancing the Faradaic efficiency. These findings offer valuable insights for designing electrocatalysts for efficient C–O bond cleavage and establish a practical platform for electrocatalytic biomass valorization.