In situ dual doping for constructing efficient CO2-to-methanol electrocatalysts

Methanol is a highly desirable product of CO₂ electroreduction due to its wide array of industrial applications. However, the development of CO₂-to-methanol electrocatalysts with high performance is still challenging. Here we report an operationally simple in situ dual doping strategy to construct efficient CO₂-to-methanol electrocatalysts. In particular, when using Ag,S-Cu₂O/Cu as electrocatalyst, the methanol Faradaic efficiency (FE) could reach 67.4% with a current density as high as 122.7 mA cm⁻² in an H-type cell using 1-butyl-3-methylimidazolium tetrafluoroborate/H₂O as the electrolyte, while the current density was below 50 mA cm⁻² when the FE was greater than 50% over the reported catalysts. Experimental and theoretical studies suggest that the anion S can effectively adjust the electronic structure and morphology of the catalysts in favor of the methanol pathway, whereas the cation Ag suppresses the hydrogen evolution reaction. Their synergistic interactions with host material enhance the selectivity and current density for methanol formation. This work opens a way for designing efficient catalysts for CO₂ electroreduction to methanol.