(202b) Modulating the Active Sites of Metal?Nitrogen?Doped Carbon Catalysts By Orbital Coupling for Highly Active and Selective CO2 Electrochemical Reduction

The electrochemical CO₂ reduction reaction (CO₂RR) is a potential strategy for converting waste CO₂ into a valuable chemical and closing the CO₂ cycle. We propose a computational screening route for highly active and selective metal-nitrogen-doped carbon (M-N-C) catalysts, followed by their experimental validations. This screening approach leads to a more reasonable electrocatalyst design as well as insights into the relationship between experimental and theoretical investigations. In addition, we extended our study of catalysts with dual atom centers beyond a single M-N-C. The neighboring iron dual-sites anchored on nitrogen-doped carbon matrix (Fe₂-N-C) outperform their single atomic counterparts in terms of CO Faradaic efficiency over wider potential ranges along with turnover frequency and durability. The orbital coupling between the iron dual-sites modifies the energy gap between antibonding and bonding states in CO binding, hence decreasing CO binding energy and promoting activity. This research presents new insights into the structure–performance relationship on CO₂RR electrocatalysts at the atomic scale and extends the application of dual-atom electrocatalysts for heterogeneous electrocatalysis and beyond.