Synergistic Pd‐Au Catalyst for Selective Electrosynthesis of Dimethyl Carbonate in Conjunction with High‐Rate Redox System

This study reports ambient electrosynthesis of dimethyl carbonate with a palladium–gold catalyst. Material screening identifies a region of intermediate‐catalyst binding energy that facilitates interfacial electron and proton transfers for selective carbonylation, achieving a distinct maximum of 92% faradaic efficiency to dimethyl carbonate. Structural and electrochemical analyses suggest that the alloying of palladium and gold effectively modulates the CO* binding energy to the catalytic surface, in accord with subsequent computational studies. With an extended heterogeneous–homogeneous catalytic environment with a halide redox mediator, a remarkable partial current density of 52 mA cm−2 is observed for dimethyl carbonate for 100 h of continuous operation. One‐pot synthesis is used for a palladium–gold catalyst for the electrosynthesis of dimethyl carbonate. The alloying of the two noble metals modulates the CO* binding energy, maximizing the selectivity. The reaction can be accelerated to an industrially relevant partial current density of 52 mA cm−2 for dimethyl carbonate by employing a heterogeneous–homogeneous catalytic environment with a halide redox mediator.