Kinetic Understanding of Catalytic Selectivity and Product Distribution of Electrochemical Carbon Dioxide Reduction Reaction

CO₂ can be electrochemically reduced to different products depending on the nature of catalysts. In this work, we report comprehensive kinetic studies on catalytic selectivity and product distribution of the CO₂ reduction reaction on various metal surfaces. The influences on reaction kinetics can be clearly analyzed from the variation of reaction driving force (binding energy difference) and reaction resistance (reorganization energy). Moreover, the CO₂RR product distributions are further affected by external factors such as electrode potential and solution pH. A potential-mediated mechanism is found to determine the competing two-electron reduction products of CO₂ that shifts from thermodynamics-controlled product formic acid at less negative electrode potentials to kinetic-controlled product CO at more negative electrode potentials. Based on detailed kinetic simulations, a three-parameter descriptor is applied to identify the catalytic selectivity of CO, formate, hydrocarbons/alcohols, as well as side product H₂. The present kinetic study not only well explains the catalytic selectivity and product distribution of experimental results but also provides a fast way for catalyst screening.