Due to their high global warming potential (GWP), hydrofluorocarbons (HFCs) are included in various regulations as substances to be phased down. Gas separation membrane technology is expected to provide a better choice for refrigerant separation. In this study, a series of metal-organic frameworks (MOFs)/ polydimethylsiloxane (PDMS) mixed matrix membranes (MMMs) were prepared for the separation of the refrigerant blend R454A (GWP = 145), which consists of a near-zeotropic difluoromethane (R32, GWP = 675) and 2,3,3,3-tetrafluoropropene (R1234yf, GWP = 4). ZIF-71-NH2 was prepared for the first time by solvent-assisted ligand exchange (SALE), and then ZIF-71-NH2@ Ionic Liquid (IL) was prepared by embedding [C2mim][BF4] into the pores of ZIF-71-NH2 by capillary action method. The results showed that a hydrogen bonding network was established between the amino group and PDMS, which improved the interfacial compatibility, and reduced the pore size of ZIF-71, which contributed to an excellent gas separation performance of ZIF-71-NH2/PDMS MMMs. Restricting [C2mim][BF4] to the ZIF-71-NH2 pore can further reduce its pore size, and enhance R32/R1234yf separation performance due to the high selective solubility for R32 and R1234yf. The selectivity of 10wt.% ZIF-71-NH2/PDMS MMM is 25.6% over that of 10wt.% ZIF-71/PDMS MMM. The selectivity of ZIF-71-NH2@IL/PDMS MMM is 38.3% higher than that of ZIF-71-NH2/PDMS MMM. The ZIF-71-NH2/PDMS and ZIF-71-NH2@IL/PDMS MMMs exhibited the most excellent R32/R1234yf separation performance compared with the data currently published in the literature. Moreover, both designed MMMs demonstrated excellent resistance to ageing.
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