Identification of Possible Mechanistic Pathways during the Electrochemical Reduction of CO2: Results from Constant Potential DFT Calculations

摘要

We investigated the mechanistic pathways by which CO2 on copper surfaces is electrochemically reduced using periodic Kohn-Sham Density Functional Theory that includes the effects of the electrochemical potential, solvent, and electrolyte. Our analysis revealed that at low-applied potential, C-C bond formation occurs through a CO dimer; however, at high-applied potentials, C-C bond formation occurs through reaction of adsorbed CHO and CO. Additionally, our model allowed us to study proton transfer from water via the Heyrovsky mechanism, which we show to be an important pathway for CO2 reduction.