Promoting Intermediate Stabilization and Coupling for Dimethyl Carbonate Electrosynthesis

The electrocatalytic coupling of methanol and CO to produce dimethyl carbonate (DMC) is an attractive strategy for converting C₁ resources into value-added products, while the controlled adsorption and coupling of two key intermediates, ^*CO and ^*OCH₃, have not been demonstrated yet. Herein, a heterointerface engineering strategy is developed to modulate intermediate adsorption and facilitate the C─O bond formation. By constructing a Pd and PdO heterostructure catalyst with abundant interfaces (designated as Pd/PdO-r), the Pd⁰ sites serve to stabilize ^*CO and the electrophilic Pd²⁺ sites can promote the ^*OCH₃ adsorption, thereby optimizing their spatial proximity and reactivity. In addition, the heterointerfaces allow to lower the coupling reaction barrier, enabling an efficient electrocatalytic pathway for the DMC synthesis. Consequently, the Pd/PdO-r heterostructure catalyst exhibited a high Faradaic efficiency of 86% with a DMC yield rate of 252 µmol h^-1 mg_cat ^-1 in flow cells. The work suggests an effective approach to design heterointerfaces for enhanced intermediate adsorption and coupling, thus promoting the formation of valuable multicarbon products from C₁ resources.