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 C resources into value-added products, while the controlled adsorption and coupling of two key intermediates, CO and OCH, 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 Pd sites serve to stabilize CO and the electrophilic Pd sites can promote the OCH 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 mg 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 C resources.