The efficient separation of gases has industrial, economic, and environmental importance. Here, we report the improvement in gas separation performance of a polyimide-based matrix (Matrimid^®5218) filled with a Cu-based metal organic framework [MOF, Cu₃(BTC)₂] with two different ionic liquids (ILs) confined within the pores. The chosen ILs are commonly used in gas solubilization, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF₄]) and 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][OTf]), and the incorporation of the [EMIM][BF₄]@Cu-BTC and [EMIM][OTf]@Cu-BTC composites in Matrimid^®5218 proved to be an efficient strategy to improve the permeability and selectivity toward CO₂/N₂ and CO₂/CH₄ mixtures.

Iongel-based CO₂ separation membranes were prepared by fast (< 1 min) UV-initiated polymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of different ionic liquids (ILs) with the [C₂mim]⁺ cation and anions such as [TFSI]⁻, [FSI]⁻, [C(CN)₃]⁻ and [B(CN)₄]⁻. The four ILs were completely miscible with the non-ionic PEGDA network. Transparent and free-standing iongels containing between 60 and 90 %wt of IL were obtained and characterized by diverse techniques (FTIR, TGA, DSC, DMTA, SEM, CO₂ solubility and pure gas permeability). The thermal and mechanical stability of the iongels, as well as CO₂ solubility, were found to be strictly dependent on the IL content and the anion’s nature. The TGA results indicated that the iongels mostly follow the thermal profile of the respective neat ILs. The DMTA analysis revealed that the iongels based on fluorinated anions have higher storage modulus than those of cyano-functionalized anions. Conversely, the PEGDA–C(CN)₃ iongels presented the highest CO₂ solubility values ranging from 72 to 80 mmol/g. Single CO₂ permeabilities of 583 ± 29 Barrer and ideal CO₂/N₂ selectivities of 66 ± 3 were obtained with the PEGDA–70 C(CN)₃ iongel membrane. This work demonstrates that the combination of PEGDA with high contents of the best performing ILs is a promising and simple strategy, opening up new possibilities in the design of high-performance iongel membranes for CO₂ separation.