Selective C-C Coupling by Spatially Confined Dimeric Metal Centers

Abstract: Direct conversion of carbon dioxide (CO2) to high-energy fuels and high-value chemicals is a fascinating sustainable strategy. For most of the current electrocatalysts for CO2 reduction, however, multi-carbon products are inhibited by large overpotentials and low selectivity. For practical applications, there remains a big gap of knowledge in proper manipulation of the C-C coupling process. Herein, we exploit dispersed 3d transition metal dimers as spatially confined dual reaction centers for selective reduction of CO2 to liquid fuels. Various nitrogenated holey carbon monolayers are shown to be promising templates to stabilize these metal dimers and dictate their electronic structures, allowing precise control of the catalytic activity and product selectivity. By comprehensive first-principles calculations, we screen the suitable transition metal dimers that universally have high activity for ethanol (C2H5OH). Furthermore, remarkable selectivity for C2H5OH against other C1 and C2 products is found for Fe2 dimer anchored on C2N monolayer. The correlation between the activity and d band center of the supported metal dimer as well as the role of electronic coupling between the metal dimer and the carbon substrates are thoroughly elucidated.