Summary This thesis has delved into the realm of non-aqueous solvents, specifically focusing on the synergy between imidazolium cations and dry acetonitrile for electrochemical reduction of CO2. The initial phase of this work involved the establishment of a universal protocol for conducting electrochemical CO2 reduction experiments under strictly anhydrous conditions (Chapter 2). It became evident that the presence of other metals, whether in the form of counter electrodes or reference electrodes, could significantly impact the experimental outcomes. To mitigate potential artifacts in potential recording, a refined protocol was developed, ensuring the integrity of the obtained results. In Chapter 3, the integration of 0.5 mol% of 1,3-dimethyl imidazolium NTf2 (MM NTf2) into acetonitrile was revealed to substantially enhance the reaction kinetics of CO2 reduction on Au electrodes, as evidenced through comparison with alternative cations such as ammonium types and alkali metals. Notably, among the 1,3-dialkyl imidazolium cations studied, MM exhibited superior performance, allowing for the lowest overpotential required for CO2 reduction at the same current density. Through a combination of DFT calculations, observations of the inverse kinetic isotope effect, and electrochemical studies, a pivotal role of C2-hydrogenated imidazolium cations in promoting reaction kinetics was uncovered. This mechanism revolves around hydrogen bonding donation to the Au-adsorbed CO2 molecule, thereby facilitating the initial electron transfer. Intriguingly, this phenomenon shares resemblances with low-barrier hydrogen bonds observed in enzyme catalysis.. Building on the foundation established in Chapter 3, new avenues for exploration emerged, focusing on the refinement of imidazolium cation performance through modifications in their electronic properties (Chapter 4). C4,C5-substituted imidazolium cations were synthesized to investigate their potential in enhancing CO2 reduction efficiency. However, this endeavor
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