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 (PCO2) of 147 Barrer and CO2/CH4 selectivity (αCO2/CH4) of 47.5. At the optimum GO loading (1 wt.%), the PCO2 and αCO2/CH4 were improved by 22% and 7%, respectively. A combination of GO (1 wt.%)/ZIF-8 fillers tremendously improves its PCO2; 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.

Department of Inorganic Chemistry University of Chemistry and Technology Prague Technická 5 166 28 Prague 6 Czech Republic

Department of Inorganic Technology University of Chemistry and Technology Prague Technická 5 166 28 Prague 6 Czech Republic

Department of Membrane Separation Processes Institute of Chemical Process Fundamentals of the CAS v v i Rozvojova 2 135 165 02 Prague 6 Czech Republic

Faculty of Process and Systems Engineering Otto von Guericke University Magdeburg Universitätsplatz 2 39106 Magdeburg Germany

Organic Materials Innovation Center Department of Chemistry University of Manchester Oxford Road Manchester M13 9PL UK

Tecnologico de Monterrey Campus Toluca Avenida Eduardo Monroy Cárdenas 2000 San Antonio Buenavista Toluca de Lerdo 50110 Mexico

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