Summary In this chapter, it is first demonstrated that the combination of imidazolium cations with anhydrous media (dry acetonitrile) leads to unprecedently low overpotential for CO2 conversion over conventional electrodes (such as Au foil) with 100% Faradaic efficiency for CO production. Modification of N1 and N3 functionality of imidazolium cation shows a direct correlation between the performance for CO2 reduction in anhydrous media and C2-H acidity of the cation. Based on NMR analyses, DFT calculations, and isotopic labeling study, showing an inverse kinetic isotope effect, it is demonstrated that the mechanism involves a concerted coupled proton-electron transfer with a partial proton transfer to the electrode-adsorbed CO2 intermediate.
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