Reaction Mechanism of the Selective Reduction of CO$_2$ to CO by a Tetraaza [Co$^\text{II}$N$_4$H]$^{2+}$ Complex in the Presence of Protons

TL;DR

This study uses density functional theory to elucidate the mechanism by which a cobalt tetraaza complex selectively reduces CO2 to CO, explaining its high selectivity and predicting experimental rate dependencies.

Contribution

The paper provides a detailed DFT-based mechanistic insight into CO2 reduction by a specific cobalt complex, highlighting the role of CO2 as a Lewis acid and predicting rate behavior.

Findings

The catalyst favors formation of [CoIIN4H]2+–CO2− after reduction.

Protonation leads to a pathway producing CO, not formic acid.

The rate of CO formation increases linearly with CO2 partial pressure.

Abstract

The tetraaza [Co$^\text{II}$N$_4$H]$^{2+}$ complex (\textbf{1}) is remarkable for its ability to selectively reduce CO$_2$ to CO with 45\% Faradaic efficiency and a CO to H$_2$ ratio of 3:2. We employ density functional theory (DFT) to determine the reasons behind the unusual catalytic properties of \textbf{1} and the most likely mechanism for CO$_2$ reduction. The selectivity for CO$_2$ over proton reduction is explained by analyzing the catalyst's affinity for the possible ligands present under typical reaction conditions: acetonitrile, water, CO$_2$, and bicarbonate. After reduction of the catalyst by two electrons, formation of [Co$^\text{I}$N$_4$H]$^{+}$-CO$_{2}^{-}$ is strongly favored. Based on thermodynamic and kinetic data, we establish that the only likely route for producing CO from here consists of a protonation step to yield [Co$^\text{I}$N$_4$H]$^{+}$-CO$_{2}$H, followed by reaction with CO$_2$ to form [Co$^\text{II}$N$_4$H]$^{2+}$-CO and bicarbonate. This conclusion corroborates the idea of a direct role of CO$_2$ as a Lewis acid to assist in {C-O} bond dissociation, a conjecture put forward by other authors to explain recent experimental observations. The pathway to formic acid is predicted to be forbidden by high activation barriers, in accordance with the products that are known to be generated by \textbf{1}. Calculated physical observables such as standard reduction potentials and the turnover frequency for our proposed catalytic cycle are in agreement with available experimental data reported in the literature. The mechanism also makes a prediction that may be experimentally verified: that the rate of CO formation should increase linearly with the partial pressure of CO$_2$.