Mechanism and Selectivity of Electrochemical Reduction of CO₂ on Metalloporphyrin Catalysts from DFT Studies.

ABSTRACT: Electrochemical reduction of CO₂ to value-added chemicals has been hindered by poor product selectivity and competition from hydrogen evolution reactions. This study aims to unravel the origin of the product selectivity and competitive hydrogen evolution reaction on [MP]⁰ catalysts (M = Fe, Co, Rh and Ir; P is porphyrin ligand) by analyzing the mechanism of CO₂ reduction and H₂ formation based on the results of density functional theory calculations. Reduction of CO₂ to CO and HCOO^- proceeds via the formation of carboxylate adduct ([MP-COOH]⁰ and ([MP-COOH]^-) and metal-hydride [MP-H]^-, respectively. Competing proton reduction to gaseous hydrogen shares the [MP-H]^- intermediate. Our

SUBMITTER: Masood Z 

PROVIDER: S-EPMC9823635 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature