VI- Electrochemical data Figure S5.6 a depicts the linear sweep voltammetries (LSVs) of an iron (Fe) electrode under CO2 and He purging. We observe that the potential-current profiles under CO2 and He are remarkably similar, indicating that the Fe catalyst is almost inactive for CO2 reduction in the imidazolium-anhydrous MeCN electrolyte. This inactivity can be attributed to early catalyst poisoning by CO adsorption103 and the reduction of the imidazolium cation over the Fe catalyst, as evident from the potential-current profile under He purging. o provide a more comprehensive understanding of this behavior, the same LSV data are included for a Zn electrode in Figure S5.6 b. The figure clearly shows a considerable difference in the potentialcurrent profiles under CO2 and He purging, with a notably larger faradaic current under CO2 atmosphere, which indicates CO2 reduction activity. Figure S5.7 displays the LSV results for Au, Ni and Zn electrodes with MM-acetonitrile electrolyte under He purging Figure S5.5. Images of the reactor used for CO2 reduction with a Ni electrode are shown above. (a) shows the reactor after 90 minutes of electrolysis at -1 mA/cm2. and (b) shows it after 10 hours of electrolysis. In both images, the Ni surface appears clean and the solution is clear. The electrolyte used was 0.5 mol% MM NTf2 in anhydrous MeCN. a b
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