AbstractTo overcome the chemical inertness of CO2, one strategy consists of pre‐activating or destabilizing it, to lower the reduction barrier, by preparing a carbene‐CO2compound where the CO2is bent rather than linear. This pre‐activation has been studied in ionic liquids (IL) based on imidazolium as a cation with different anions under conditions of mild pressure, room temperature and UV/Vis light. This screening showed that only 1‐butyl‐3‐methyl‐imidazolium acetate (C1C4ImOAc) was capable of effectively pre‐activating CO2by chemical sorption to give a more reactive 1‐butyl‐3‐methyl‐imidazolium‐2‐carboxylate (C1C4ImCO2) species. A co‐solvent can be used to consume the photo‐generated holes in Pd/g‐C3N4as a sacrificial agent but also to provide the protons necessary to reduce CO2. In this study, the influence of several type of co‐solvents such as H2O, isopropanol (iPrOH), and 1‐(2‐hydroxyethyl)‐3‐methyl imidazolium bis(trifluoromethanesulfonyl)imide [C1C2(OH)ImNTf2], has been tested on the activation of CO2in C1C4ImOAc. We first defined the optimal molar ratio of co‐solvent to be used in order not to compromise CO2pre‐activation for subsequent application in CO2transformation. Photocatalytic reductions of CO2to CO on Pd/g‐C3N4by varying different parameters demonstrated that CO2pre‐activation in a mixture of C1C4ImOAc and isopropanol was the most efficient to consider a prospective strategy of CO2photoreduction in an IL medium.
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