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

Abstract 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.