N-Heterocylic Carbene-Based Mn Electrocatalyst for Two-Electron CO2 Reduction over Proton Reduction

Kuber Singh Rawat, Arup Mahata, Indrani Choudhuri, Biswarup Pathak

Research output: Contribution to journalArticlepeer-review

24 Scopus citations

Abstract

A bifunctional, chelating N-heterocyclic carbene-pyridine (NHC-pyridine) containing Mn(I) complex [MnBr(NHC-pyridine)(CO)3] displays a strong selectivity for CO2 reduction over proton reduction. Interestingly, the two-electron reduction of this complex occurs at a single potential, as opposed to MnBr(bpy)(CO)3, which is reduced by two electrons in two separate one-electron reductions. Here, the Gibbs free energy barriers, reduction potentials, rate constants, and pKa values are predicted with theory to understand the one- vs two-electron reduction mechanism. The effects of weak and strong Brønsted acids [HCl, TFE (2,2,2-trifluoroethanol), PhOH, CH3OH, and H2O] are studied to gauge the preference for CO2 vs proton reduction; water is found to be an ideal proton donor that allows for strong CO2 selectivity.

Original languageEnglish (US)
Pages (from-to)8821-8831
Number of pages11
JournalJournal of Physical Chemistry C
Volume120
Issue number16
DOIs
StatePublished - Apr 28 2016

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