There is great interest in developing and engineering processes that convert CO2 into more valuable products such as CO, formate, and CH3OH. Recently, several reports in the literature have implicated nitrogen-containing heterocycles as promoting the selective (photo-)electroreduction of CO2 into these products. Although theory and experiment have reached consensus regarding some aspects these processes, numerous questions remain, including the precise mechanistic pathway that fundamentally explains how heterocycles in these particular reaction conditions enable CO2 reduction. We discuss results from our first principles quantum chemistry calculations, focusing on individual reaction mechanisms involving substituted and non-substituted pyridinium, imidazolium, and their 1- and 2-electron reduced products with CO2. Calculated pKas, standard redox potentials, and kinetic barrier heights are used provide first principles insight into which chemical species would be present under in situ electrochemical conditions in solution and on metal electrodes.  From this work, we rationalize different mechanistic possibilities warranting further scrutiny.

Unraveling mechanistic aspects of heterocycle-promoted CO<sub>2</sub> electroreduction with quantum chemistry

248th National Meeting (2014)

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Unraveling mechanistic aspects of heterocycle-promoted CO2 electroreduction with quantum chemistry

Unraveling mechanistic aspects of heterocycle-promoted CO₂ electroreduction with quantum chemistry