Thermodynamics of CO Adsorption on Electrodes and Its Implications for Selectivity Control in Electrochemical CO₂ Reduction

Electrocatalytic conversion of CO2 into valuable multicarbon (C2+) products powered by renewable electricity is a promising strategy to close the carbon cycle. The thermodynamics of CO adsorption, e.g., the CO binding energy, has been proposed and employed as a descriptor in the catalyst design for the electrochemical CO2 reduction reaction (CO2RR). This perspective briefly summarizes existing strategies to measure the enthalpy and entropy of CO adsorption at electrochemical interfaces, analyzes the mechanistic information extracted from the thermodynamics of CO adsorption on catalyst surfaces, and discusses the factors beyond CO adsorption that affect the performance of the CO2RR performance.