Cr-based MOF/IL composites as fillers in mixed matrix membranes for CO2 separation

[Display omitted] •Bromide-based ILs, [PMIM][Br] and [BMIM][Br], were incorporated in MOF MIL-101(Cr).•MIL-101(Cr) and IL@MIL-101(Cr) composites gas adsorption performance was assessed.•MMMs with MIL-101(Cr) and the two IL@MIL-101(Cr) were developed and characterized.•The presence of IL in MIL-101(Cr) structure improved the MMMs mechanical properties.•IL@MOF composites can have an impact on the MMMs gas separation performance. New composite materials made of bromide-based ionic liquids (ILs) and metal–organic framework (MOF) MIL-101(Cr) were produced using two different ILs. The powdered composites [PMIM][Br]@MIL-101(Cr) and [BMIM][Br]@MIL-101(Cr) were rigorously characterized, and it was confirmed that both ILs were incorporated into the MOF structure. Single-component CO2 and N2 adsorption–desorption isotherms for the pristine MIL-101(Cr) and [BMIM][Br]@MIL-101(Cr), at 303 K and up to 10 bar, showed that the composite has lower gas adsorption capacity and selectivity when compared with the pristine MOF due to the IL incorporation. Mixed Matrix membranes (MMMs) were prepared by the solvent evaporation method, using Matrimid®5218 as the polymeric matrix, and MIL-101(Cr) and IL@MIL-101(Cr) composites as fillers with different loadings (10, 20 and 30 wt%). All prepared membranes were dense, except for the Matrimid®5218/[PMIM][Br]@MIL-101(Cr) ones, and their mechanical properties were improved by the presence of the IL in the composite fillers. Single-gas permeation experiments with CO2 and N2 were performed at 303 K for the Matrimid®5218/MIL-101(Cr) and Matrimid®5218/[BMIM][Br]@MIL-101(Cr) membranes, as the Matrimid®5218/[PMIM][Br]@MIL-101(Cr) showed voids. Independently of the filler percentage, the Matrimid®5218/MIL-101(Cr) membranes showed superior CO2 permeability than the Matrimid®5218/[BMIM][Br]@MIL-101(Cr) ones. In every case, the best CO2/N2 selectivity was achieved with a 20 wt% of filler loading, which indicates the existence of an optimum loading that yields the best membrane separation performance.