Theory-Guided Modification of Ionic Liquid on Cu2O Promotes Asymmetric C–C Coupling for CO2 Conversion

The electrocatalytic reduction of carbon dioxide (CO2RR) by copper oxide-based materials is conducive to the formation of high value-added products, but their activities and selectivities remain unsatisfactory. Organic ligand modification is a promising strategy to achieve a high CO2RR activity. Here, the modification of Cu2O with 1-butyl-3-methylimidazolium chloride (Bmim-Cu2O) enhanced the adsorption of reaction intermediates and improved the stability of the catalyst in the CO2RR, which displays a high Faradaic efficiency of ≈85% to C2+ products with a current density as large as ≈352.5 mA cm–2. In situ characterization reveals a stronger *CO signal with bridge configuration and a stronger *OCCHO signal over Bmim-Cu2O than unmodified Cu2O and can improve the stability during electrochemical CO2 reduction. Density functional theory calculations show that local molecular modulation can effectively regulate the electronic structure of Cu2O and enhance the adsorption of *CO and *CHO intermediates through the stabilization of a noncovalent interaction, which can greatly promote the asymmetric *CO–*CHO coupling in the electrochemical reaction process.