A Bifunctional Ionic Liquid for Capture and Electrochemical Conversion of CO 2 to CO over Silver.

Electrochemical conversion of CO 2 requires selective catalysts and high solubility of CO 2 in the electrolyte to reduce the energy requirement and increase the current efficiency. In this study, the CO 2 reduction reaction (CO 2 RR) over Ag electrodes in acetonitrile-based electrolytes containing 0.1 M [EMIM][2-CNpyr] (1-ethyl-3-methylimidazolium 2-cyanopyrolide), a reactive ionic liquid (IL), is shown to selectively (>94%) convert CO 2 to CO with a stable current density (6 mA·cm -2 ) for at least 12 h. The linear sweep voltammetry experiments show the onset potential of CO 2 reduction in acetonitrile shifts positively by 240 mV when [EMIM][2-CNpyr] is added. This is attributed to the pre-activation of CO 2 through the carboxylate formation via the carbene intermediate of the [EMIM] + cation and the carbamate formation via binding to the nucleophilic [2-CNpyr] - anion. The analysis of the electrode-electrolyte interface by surface-enhanced Raman spectroscopy (SERS) confirms the catalytic role of the functionalized IL where the accumulation of the IL-CO 2 adduct between -1.7 and -2.3 V vs Ag/Ag + and the simultaneous CO formation are captured. This study reveals the electrode surface species and the role of the functionalized ions in lowering the energy requirement of CO 2 RR for the design of multifunctional electrolytes for the integrated capture and conversion.