Deciphering the Selectivity of the Electrochemical CO₂ Reduction to CO by a Cobalt Porphyrin Catalyst in Neutral Aqueous Solution: Insights from DFT Calculations.

ABSTRACT: Density functional theory (DFT) calculations were conducted to investigate the cobalt porphyrin-catalyzed electro-reduction of CO₂ to CO in an aqueous solution. The results suggest that Co^II -porphyrin (Co^II -L) undertakes a ligand-based reduction to generate the active species Co^II -L⋅^- , where the Co^II center antiferromagnetically interacts with the ligand radical anion. Co^II -L⋅^- then performs a nucleophilic attack on CO₂ , followed by protonation and a reduction to give Co^II -L-COOH. An intermolecular proton transfer leads to the heterolytic cleavage of the C-O bond, producing intermediate Co^II -L-CO. Subsequently, CO is released from Co^II -L-CO, and Co

SUBMITTER: Cao YC 

PROVIDER: S-EPMC9900731 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature