6FDA-DAM:DABA Co-Polyimide Mixed Matrix Membranes with GO and ZIF-8 Mixtures for Effective CO₂/CH₄ Separation

This work presents the gas separation evaluation of 6FDA-DAM:DABA (3:1) co-polyimide and its enhanced mixed matrix membranes (MMMs) with graphene oxide (GO) and ZIF-8 (particle size of <40 nm). The 6FDA-copolyimide was obtained through two-stage poly-condensation polymerization, while the ZIF-8 nanoparticles were synthesized using the dry and wet method. The MMMs were preliminarily prepared with 1-4 wt.% GO and 5-15 wt.% ZIF-8 filler loading independently. Based on the best performing GO MMM, the study proceeded with making MMMs based on the mixtures of GO and ZIF-8 with a fixed 1 wt.% GO content (related to the polymer matrix) and varied ZIF-8 loadings. All the materials were characterized thoroughly using TGA, FTIR, XRD, and FESEM. The gas separation was measured with 50:50 vol.% CO₂:CH₄ binary mixture at 2 bar feed pressure and 25 °C. The pristine 6FDA-copolyimide showed CO₂ permeability (P_CO2) of 147 Barrer and CO₂/CH₄ selectivity (α_CO2/CH4) of 47.5. At the optimum GO loading (1 wt.%), the P_CO2 and α_CO2/CH4 were improved by 22% and 7%, respectively. A combination of GO (1 wt.%)/ZIF-8 fillers tremendously improves its P_CO2; by 990% for GO/ZIF-8 (5 wt.%) and 1.124% for GO/ZIF-8 (10 wt.%). Regrettably, the MMMs lost their selectivity by 16-55% due to the non-selective filler-polymer interfacial voids. However, the hybrid MMM performances still resided close to the 2019 upper bound and showed good performance stability when tested at different feed pressure conditions.