Understanding Electrochemical CO₂ Reduction on Ag(111): A Potential-Dependent Kinetics and Selectivity Study

Electrochemical carbon dioxide reduction (CO₂R) provides a sustainable pathway to mitigate greenhouse gas emissions while generating valuable chemical feedstocks. Achieving high selectivity and activity in CO₂R catalysts, however, requires a detailed understanding of the atomistic reaction mechanisms at electrochemical interfaces. In this work, we employ density functional theory (DFT), kinetic modeling, and potential-dependent analyses to investigate CO₂R pathways on Ag(111) surfaces. Our study identifies the most favorable reaction route for CO formation and rationalizes silver’s high selectivity toward this product at low overpotentials. Furthermore, we uncover that the rate-limiting step for methane and methanol production is the reduction of *CHO to *CHOH contrary to the commonly assumed *CO to *CHO step highlighting a shift in mechanistic understanding for C1 product formation. These insights advance the fundamental knowledge of CO₂R reaction networks and provide design principles for next-generation electrocatalysts with improved selectivity and efficiency.