Role of Filler Porosity and Filler/Polymer Interface Volume in Metal–Organic Framework/Polymer Mixed-Matrix Membranes for Gas Separation

Metal–organic frameworks (MOFs) and inorganic fillers are frequently incorporated into mixed-matrix membranes (MMMs) to overcome the traditional trade-off in permeability (P) and selectivity for pure organic polymer membranes. Therefore, it is of great interest to examine the influence of porous and nonporous fillers in MMMs with respect to the possible role of the polymer–filler interface, that is, the void volume. In this work, we compare the same MOF filler in a porous and nonporous state, so that artifacts from a different polymer–filler interface are excluded. MMMs with the porous MOF aluminum fumarate (Al-fum) and with a nonporous dimethyl sulfoxide solvent-filled aluminum fumarate (Al-fum­(DMSO)), both with Matrimid as polymer, were prepared. Filler contents ranged from 4 to 24 wt %. Gas separation performances of both MMMs were studied by mixed gas measurements using a binary mixture of CO2/CH4 with gas permeation following the theoretical prediction by the Maxwell model for both porous and nonporous dispersed phase (filler). MMMs with the porous Al-fum filler showed increased CO2 and CH4 permeability with a moderate rise in selectivity upon increasing filler fraction. The MMMs with the nonporous Al-fum­(DMSO) filler displayed a reduction in permeability while maintaining the selectivity of the neat polymer. A linear dependence of log P versus the reciprocal specific free fractional volume (sFFV) rules out a significant contribution from a void volume. The sFFV includes the free volume of the polymer and the MOF, but not the polymer–filler interface volume (so-called void volume). The sFFV for the MMM was calculated between 0.23 cm3/g for a 24 wt % Al-fum/Matrimid MMM and 0.12 cm3/g for a 24 wt % Al-fum­(DMSO)/Matrimid MMM. The negligible effect of an interface volume is supported by a good matching of theoretical and experimental density of the Al-fum and Al-fum/(DMSO) MMMs which gave a specific void volume below 0.02 cm3/g, often even below 0.01 cm3/g