Summary Electrochemical reduction of CO2 is extensively studied and trends in the activity of transition metals in aqueous electrolytes have been well established on the basis of differences in CO binding strength. This chapter shows a similar trend (volcano curve) for late-transition metals (Au, Ag, Zn, Cu, and Ni) in dry acetonitrile containing 1,3-dimethyl imidazolium cations, but with smaller performance factors between the late-transition metals and Au than previously determined in aqueous conditions. Moreover, all catalysts exhibit close to 100% selectivity to CO in non-aqueous process conditions. For metals providing a relatively low CO desorption energy in comparison to Au (Ag, Zn), adsorption of CO2 is proposed to be rate-determining, confirmed by DFT calculations. The high CO desorption energy calculated for Cu and Ni, likely limits the activity observed in reduction of CO2. The results of this study imply that metals unsuited for aqueous conditions, hold promise for cost-effective and practically feasible electrochemical conversion of CO2 to CO in imidazolium containing non-aqueous media. While this study finds that the selectivity remains unchanged under anhydrous MM-acetonitrile electrolyte conditions, it underscores the continued significance of the electronic properties of the catalysts in determining the overall rate of CO2 reduction
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