Electrolyte effect for carbon dioxide reduction reaction on copper electrode interface: A DFT prediction

An insightful understanding of the interaction between the electrolyte and reaction intermediate and how promotion reaction occurs of electrolyte is challenging in the electrocatalysis reaction. Herein, theoretical calculations are used to investigate the reaction mechanism of CO2 reduction reaction to CO with different electrolytes at the Cu(111) surface. By analyzing the charge distribution of the chemisorbed CO2 (CO2δ−) formation process, we find that the charge transfer is from metal electrode transfer to CO2 and the hydrogen bond interaction between electrolytes and CO2δ− not only plays a key role in the stabilization of CO2δ− structure but also reduces the formation energy of *COOH. In addition, the characteristic vibration frequency of intermediates in different electrolyte solutions shows that H2O is a component of HCO3−, promoting CO2 adsorption and reduction. Our results provide essential insights into the role of electrolyte solutions in interface electrochemistry reactions and help understand the catalysis process at the molecular level.