Nanoengineered ZIF fillers for mixed matrix membranes with enhanced CO2/CH4 selectivity

•Based on molecular simulations and predictive permeation models, amulti scale methodwas developed in order topredict CO2 and CH4 permeability and selectivity of mixed matrix membranes (MMMs) with ZIF fillers. The validity our computational approach was confirmed by actual permeability and selectivity experiments on ZIF-8 MMMs based on Pebax and 6FDA-DAM polymers.•With the aid of molecular simulations, CO2 and CH4 permeabilities were calculated for a large number of ZIF analogues, in which the building units (metal, linker and functional group) have been systematically modified.•MMMs with the aforementioned ZIF analogues as fillers, exhibitunprecedentedCO2/CH4separation performance.•The enhanced performance of these MMMs is attributed mainly to the smaller and/or less flexible pores of the modified ZIFs that enhance the kinetic-based separation of the smaller CO2 over the larger CH4.