Investigating CO2 electro-reduction mechanisms: DFT insight into earth-abundant Mn diimine catalysts for CO2 conversions over hydrogen evolution reaction, feasibility, and selectivity considerations

This study investigates the detailed mechanism of CO₂ conversion to CO using the manganese(I) diimine electrocatalyst [Mn(pyrox)(CO)₃Br], synthesized by Christoph Steinlechner and coworkers. Employing density functional theory calculations, we thoroughly explore the electrocatalytic pathway of CO₂ reduction alongside the competing hydrogen evolution reaction. Our analysis reveals the significant role of diimine nitrogen coordination in enhancing the electron density of the Mn center, thereby favoring both CO₂ reduction and hydrogen evolution reaction thermodynamically. Furthermore, we observe that triethanolamine (TEOA) stabilizes transition states, aiding in CO₂ fixation and reduction. The critical steps influencing the reaction rate involve breaking the MnC(O)–OH bond during CO₂ reduction and cleaving the MnH–H–TEOA bond in the hydrogen evolution reaction. We explain the preference for CO₂ conversion to CO over H₂ evolution due to the higher energy barrier in forming the Mn-H₂ species during H₂ production. Our findings suggest the potential for tuning the electron density of the Mn center to enhance reactivity and selectivity in CO₂ reduction. Additionally, we analyze potential competing reactions, focusing on electrocatalytic processes for CO₂ reduction and evaluating “protonation-first” and “reduction-first” pathways through density functional theory calculations of redox potentials and Gibbs free energies. This analysis indicates the predominance of the “reduction-first” pathway in CO production, especially under high applied potential conditions. Moreover, our research highlights the selectivity of [Mn(pyrox)(CO)₃Br] toward CO production over HCOO⁻ and H₂ formation, proposing avenues for future research to expand upon these findings by using larger basis sets and exploring additional functionalized ligands.