Electrocatalysts based on rhenium have proven to be highly selective for the reduction of carbon dioxide (CO2) to carbon monoxide (CO) while maintaining relatively low overpotentials and high turnover frequencies. Based on the conventional Lehn-type rhenium complex, the Nippe group has recently synthesized a new rhenium electrocatalyst, {Re[bpyMe(ImMe)](CO)3Cl}+, which features a charged imidazolium group in the secondary coordination sphere. The addition of the imidazolium group has shown to increase selectivity of carbon dioxide reduction over formation of hydrogen while reducing energetic cost in the presence of water. Here we proposed a catalytic mechanism for CO2 to CO in the presence of {Re[bpyMe(ImMe)](CO)3Cl}+ using computational methods. Our electronic structure calculations show that the imidazolium group plays a crucial role during catalysis by: (i) interacting with the substrate; and (ii) being involved during the protonation step.

Computational study for the mechanism of CO2 reduction using imidazolium-functionalized Rhenium electrocatalysts

255th National Meeting (2018)

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