Local Environment Determined Reactant Adsorption Configuration for Enhanced Electrocatalytic Acetone Hydrogenation to Propane

We demonstrate a widely applicable method to alter the adsorption configuration of multi-carbon containing reactants by no catalyst engineering but simply adjusting the local reaction environment of the catalyst surface. Using electrocatalytic acetone to propane hydrogenation (APH) as a model reaction and common commercial Pt/Pt-based materials as catalysts, we found local H+ concentration can significantly influence the adsorption mode of acetone reactant, for example, in vertical or flat mode, and target product selectivity. Electrocatalytic measurement combined with in situ spectroscopic characterizations reveals that the vertically adsorbed acetone is favorable for propane production while the flatly adsorbed mode suppresses the reaction. DFT calculations indicate that the H coverage on catalyst surface plays a decisive role in the adsorption configuration of acetone. The increased local acidity can facilitate the adsorption configuration of acetone from flat to vertical mode and suppress the competing hydrogen evaluation reaction, which consequently enhances the APH selectivity.