In this study, novel mixed matrix membranes (MMMs) with hollow zeolite imidazole frameworks (H_ZIF-8) were introduced with regard to CO2/CH4 gas separation. H_ZIF-8 nanoparticles (low density and large BET surface area) and amphiphilic PVC-g-POEM (poly(vinyl chloride)-g-poly(oxyethylene methacrylate)) graft copolymer showed good interfacial properties and uniform distribution, which resulted in improved gas permeation properties interacted with PVC-g-POEM by secondary bonding interactions. Two Tg values expressed the glassy PVC chains and the rubbery POEM chains, suggesting that the copolymer had a well-defined and microphase-separated structure. We observed that H_ZIF-8 interrupted the mobility of polymer chain, contributing to the increased Tg, was dispersed homogeneously in the coopolymer matrix without noticable aggregation.

Solvothermal surface coating was employed to form hetero-nanostructures consisting of a polystyrene (PS) core and ZIF-8 shell. Upon selective removal of the PS core, hollow zeolite imidazole frameworks (H_ZIF-8) with a particle size of 700 nm and surface area of 1528.5 m²/g were generated. Synthesis was confirmed by Field-emission scanning electron microscopy(FE-SEM), transmission electron microscopy(TEM), X-raydiffraction(XRD) and Brunauer-Emmett-Teller (BET) analysis. Free-standing mixed matrix membranes (MMMs) were prepared by dispersing H_ZIF-8 filler in poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) graft copolymer matrix. PVC-g-POEM worked well as a robust matrix to homogeneously disperse H_ZIF-8 with good interfacial contact due to the microphase-separated, amphiphilic properties of the hydrophobic glassy PVC main chains and the hydrophilic rubbery POEM side chains. Secondary bonding interactions were responsible for the good interfacial properties of the MMMs, as confirmed by Fourier-transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC), FE-SEM, and XRD analysis. MMMs exhibited significantly enhanced CO2permeabilityrelativetopure PVC-g-POEM membranes: an 8.9-fold increase in permeability from 70.0 to 623 Barrer (1 Barrer = 1 × 10–10cm³(STP)·cm/cm²·s·cmHg) with only a small decrease in CO2/CH4 selectivity from 13.7 to 11.2 at 35℃, as measured via the time-lag method.