Computational analysis of a Mn-based electrocatalyst with primary amine substituents in the secondary coordination sphere for CO2 reduction
Date of Award
Chemistry (BA, BS)
Dr. Julien Panetier
Science and Mathematics
Carbon dioxide; Reduction (Chemistry); Manganese catalysts
The purpose of this research was to report the mechanism for the two-electron, two-proton conversion of CO 2 to CO and H 2 O using a manganese(I) electrocatalyst, Mn(L)(CO) 3 Br (where L = bipyridyl ligand with aryl-amine moieties installed at the 6 position of 2,2’-bipyridine), synthesized by the Jurss group, including any other competing reactions, such as the hydrogen evolution reaction (HER). The “protonation- first” and “reduction-first” pathways were considered for CO 2 RR. Density functional theory (DFT) calculations were performed to determine the redox potentials and Gibb’s free energies for each step in the mechanism for CO 2 RR and HER. Herein, we show that the “reduction-first” pathway is the most favorable in the production of CO, especially under high applied potential (i.e., high overpotential regime used experimentally). Additionally, this work confirms the selectivity of Mn(L)(CO) 3 Br for CO production over H 2 formation. Repeating these calculations with a larger basis set and focusing future research on additional functionalized ligands will be an improvement upon this work.
Urban, Erin, "Computational analysis of a Mn-based electrocatalyst with primary amine substituents in the secondary coordination sphere for CO2 reduction" (2022). Undergraduate Honors Theses. 13.