Understanding the role of imidazolium-based ionic liquids in the electrochemical CO 2 reduction reaction.

The development of efficient CO 2 capture and utilization technologies driven by renewable energy sources is mandatory to reduce the impact of climate change. Herein, seven imidazolium-based ionic liquids (ILs) with different anions and cations were tested as catholytes for the CO 2 electrocatalytic reduction to CO over Ag electrode. Relevant activity and stability, but different selectivities for CO 2 reduction or the side H 2 evolution were observed. Density functional theory results show that depending on the IL anions the CO 2 is captured or converted. Acetate anions (being strong Lewis bases) enhance CO 2 capture and H 2 evolution, while fluorinated anions (being weaker Lewis bases) favour the CO 2 electroreduction. Differently from the hydrolytically unstable 1-butyl-3-methylimidazolium tetrafluoroborate, 1-Butyl-3-Methylimidazolium Triflate was the most promising IL, showing the highest Faradaic efficiency to CO (>95%), and up to 8 h of stable operation at high current rates (-20 mA & -60 mA), which opens the way for a prospective process scale-up.