Computational insights into the catalytic role of the functional groups in Hydrogenation of CO2 with Manganese Complexes: A DFT study

Abstract

The replacement of noble metals in homogeneous catalysts for the current CO₂ hydrogenation reaction with 3d transition metals (Fe, Co, Ni and Mn), with lower costs, have attracted a great attention of many research groups to the interconversion of chemical and electrical energy, like CO₂ and H₂. Inspired by that motivation, catalysts containing transition metals need to be investigated and designed ideally based on the deep level of knowledge of the molecular structure, the chemical bonding between ligands and metals, and the state of electronic ergonomics related to this configuration. In this study, several Mn (I) complexes with monoophosphine ligands (PN ligands) were investigated in the hydrogenation reaction of CO₂. The results calculated by density functional theory show that the chemical bonding nature of the NH group and the functional groups associated with N can affect the structure, charge density and catalytic capacity which is a direct link to the CO₂ hydrogenation reaction mechanism. Finally, the results obtained from clarifying the role of N-H bonds in the design of the catalyst stabilize the anion format in the H₂ separation process. The calculation of density functional theory is performed using ORCA quantum calculation software.