Investigating CO<sub>2</sub> electro-reduction mechanisms: DFT insight into earth-abundant Mn diimine catalysts for CO<sub>2</sub> conversions over hydrogen evolution reaction, feasibility, and selectivity considerations

doi:10.1007/s11705-024-2502-5

2024, Vol. 18

Issue (12) : 150 https://doi.org/10.1007/s11705-024-2502-5

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

Murugesan Panneerselvam^1,²(

), Marcelo Albuquerque^1,³, Iuri Soter Viana Segtovich², Frederico W. Tavares^2,⁴, Luciano T. Costa¹(

)

¹. MolMod-CS-Institute of Chemistry, Fluminense Federal University, Valonginho Campus, Centro, Niterói 24020-14, Rio de Janeiro, Brazil
². Chemical Engineering Program (PEQ/COPPE), Federal University of Rio de Janeiro (UFRJ), Moniz Aragão, Rio de Janeiro, 21941-594, RJ, Brazil
³. Institute of Physics, Fluminense Federal University, Praia Vermelha Campus, Gragoatá, Niterói, Rio de Janeiro, Brazil
⁴. Chemical and Biochemical Process Engineering, School of Chemistry, Federal University of Rio de Janeiro, Rio de Janeiro 21941, Brazil

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Abstract

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.

Keywords manganese carbonyl complex CO₂ reduction reaction hydrogen evolution reaction selectivity density functional theory studies

Corresponding Author(s): Murugesan Panneerselvam,Luciano T. Costa

Just Accepted Date: 05 July 2024 Issue Date: 23 September 2024

Cite this article:

Murugesan Panneerselvam,Marcelo Albuquerque,Iuri Soter Viana Segtovich, et al. Investigating CO₂ electro-reduction mechanisms: DFT insight into earth-abundant Mn diimine catalysts for CO₂ conversions over hydrogen evolution reaction, feasibility, and selectivity considerations[J]. Front. Chem. Sci. Eng., 2024, 18(12): 150.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2502-5
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I12/150

Tab.1 Comparison of computed reduction potentials (in V) with experimentally available data vs. NHE (–4.6 V) at three different functionals with LANL2DZ(6-31G(d)//TZVP in CH₃CN medium

Scheme1 The proposed reaction mechanism for the CO₂RR and HER by ¹Mn species is illustrated. The protonation-first pathway (PFP) is depicted in red, while the reduction-first pathway (RFP) is indicated in blue.

Fig.1 The optimized geometries, including the bond lengths (in ?), of all the specified species delineated in Scheme 1, are provided.

Fig.2 The frontier molecular orbital scheme for charge transfer mechanism from HOMO to the LUMO orbitals in ¹Mn species.

Fig.3 The reaction free energy (ΔG) profile for CO₂ fixation and protonation steps.

Fig.4 The reaction free energy (ΔG) profile for the CO₂RR originating from the active ⁷Mn species. The PFP is illustrated in red, whereas the RFP is depicted in blue.

Fig.5 The reaction free energy (ΔG) profile for the formation of HCOO^– by CO₂RR originating from the active ⁵Mn species through CO₂ addition and protonation steps.

Fig.6 The reaction free energy (ΔG) profile for the formation of Mn-hydride toward hydrogen (H₂) evolution originating from the active ⁵Mn species through the protonation steps involved and also the selected bond lengths and possible hydrogen bond interactions.

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