Intramolecular electrostatic effects on reduction of CO2 to CO by iron porphyrin complexes: Insights from DFT calculations

Iron porphyrin (Por) complexes were found to be highly efficient molecular catalysts for electrocatalytic CO2 reduction and the catalytic performance can be modulated by the modification of ligands. Herein, density functional theory calculations were employed to investigate how the presence of second-sphere anionic carboxylate groups influences the CO2-to-CO conversion by Fe porphyrins. The kinetics and thermodynamics of individual chemical steps in the reaction cycle were systematically studied. Computations indicated that the catalytic active species is the ferrous complex with the two extra electrons being stored in the pi system of porphyrin and the rate-determining step is the CO2 binding. The synchronization of the Fe-to-CO2 and ligand-toFe electron transfers leads to the formation of FeIII(CO22-)(Por center dot-). The experimentally observed activity trend could be rationalized by the Bronsted-Evans-Polanyi principle. The electrostatic repulsive between the negatively charged hanging group and the CO2 moiety destabilizes the CO2 adduct and thereby raises the binding energy. Then, the two-step protonation occurs easily to give Fe(II)-CO. The further one-electron reduction triggers the dissociation of CO to regenerate of the formal Fe(I) porphyrin catalyst. The insights gained from this study may be helpful in designing efficient electrocatalysts for CO2 reduction.