The Nature of Carbon Dioxide in Bare Ionic Liquids

Ionic liquids (ILs) are among the most studied and promising materials for selective CO₂ capture and transformation. The high CO₂ sorption capacity associated with the possibility to activate this rather stable molecule through stabilization of ionic/radical species or covalent interactions either with the cation or anion has opened new avenues for CO₂ functionalization. However, recent reports have demonstrated that another simpler and plausible pathway is also involved in the sorption/activation of CO₂ by ILs associated with basic anions. Bare ILs or IL solutions contain almost invariable significant amounts of water and through interaction with CO₂ generate carbonates/bicarbonates rather than carbamic acids or amidates. In these cases, the IL acts as a base and not a nucleophile and yields buffer-like solutions that can be used to shift the equilibrium toward acid products in different CO₂ reutilization reactions. In this Minireview, the emergence of IL buffer-like solutions as a new reactivity paradigm in CO₂ capture and activation is described and analyzed critically, mainly through the evaluation of NMR data.