The ability to transform CO2 into various C1 building blocks in an efficient and sustainable manner, using highly tailored yet affordable catalysts is a highly desired goal for the chemical community. To achieve this, proton-coupled electrocatalytic reduction using renewable energy sources is the optimal course of action. First-row transition metal electrocatalysts designed with non-precious metals are the most attractive choice, however, they often underperform relative to their third row less-abundant counterparts. To address this issue, thoughtful ligand design with special attention paid toward stabilization of the rate-determining transition-state structure is a step in the right direction. In this work, we expand upon prior studies of the reference [fac-MnBr(bpy)(CO)3] electrocatalyst by introducing a cationic pyridinium moiety at the 6-position of the bpy ligand. In addition to providing a strong electron-withdrawing effect, the additional cationic charge introduces an electrostatic effect which can promote a lower catalyst overpotential. Furthermore, through-space stabilization of the charged metallo-carboxylate intermediate may also occur, increasing kinetic efficiency of the rate-determining step. A comprehensive evaluation of the [fac-Mn(6-pyridinium-bpy)(CO)3(CH3CN)]2+ complex will be here presented encompassing structural, electrochemical, electrocatalytic and computational characterization.

Investigation of the electrostatic effect for electrocatalytic CO2 reduction using the [fac-Mn(6-pyridinium-bpy)(CO)3(CH3CN)]2+ pre-catalyst

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.