Introduction In Chapter 3, we investigated the role of imidazolium cation in enhancing the performance of CO2 reduction in non-aqueous media by highlighting the coordination of the C2-proton to the adsorbed CO2, facilitating electron transfer and the first reduction step. It was also demonstrated that the 1,3-dimethyl imidazolium cation (MM) showed close to the best performance among cations studied. Several studies have investigated the performance of electrodes other than Au under nonaqueous conditions. For instance, Vera et al.47 achieved a high Faradaic efficiency (FE) of up to 90% for oxalic acid formation during CO2 reduction on a lead electrode in various nonaqueous solvents. Meanwhile, Sacci et al.102 attempted to improve the performance of CO2 reduction using CuSn alloys in a mixture of acetonitrile (MeCN) and butyl-methyl imidazolium cation but reported a low FE for CO formation (below 40%), likely due to difficulties in controlling the water content. In situ spectro-electrochemical studies by Koper et al.21 investigated CO formation on a Cu electrode in MeCN, but the concomitant reduction of water at various overpotentials may have affected the results. Additionally, the analysis did not permit the determination of FEs, limiting the ability to draw conclusions about the reaction efficiency. To overcome the current limitations and advance our understanding of CO2 reduction in nonaqueous media, here electrochemical experiments involving different transition metals besides gold are considered, in a carefully controlled acetonitrile solution containing 1,3-dimethyl imidazolium (MM) cation as co-catalyst. By examining the catalytic activity of transition metals and utilizing density functional theory (DFT) calculations, insights will be provided into the rate-determining steps and mechanism involved in CO2 reduction in non-aqueous media. Finally, we compare the observed volcano trend in non-aqueous and aqueous conditions, and
RkJQdWJsaXNoZXIy MTk4NDMw