Bipyridine-based UiO-67 as novel filler in mixed-matrix membranes for CO2-selective gas separation

Bipyridine-based UiO-67 Metal-Organic Frameworks (MOFs) are for the first time successfully applied as filler material in Matrimid mixed-matrix membranes (MMMs). Extensive characterization of fillers (via XRD, NMR, SEM, ATR-FTIR, CO2 and N2 physisorption) and membranes (via XRD, SEM, ATR-FTIR, DSC, TGA and PALS) were performed to gain insight in the MMM separation behavior. Lewis basic sites in the MMMs function as CO2-carriers, doubling CO2/CH4 selectivity (from 38 for pristine Matrimid to 75 for the MMM with 10 wt% UiO-67-33), while the CO2 permeability was simultaneously improved from 16 Barrer (Matrimid) up till 26 Barrer for the MMM with 10 wt% UiO-67-33 (+63%). Gas permeation experiments suggested a facilitated transport mechanism to be responsible for these high mixed-gas selectivities. The concentration of the filler inside the membrane could be increased to 30 wt%, resulting in a permeability increase of 350% without losing selectivity compared to the Matrimid membrane. Use of N-heterocyclic ligands proved to be an interesting strategy and good alternative for functionalization of MOF surfaces to obtain improved membrane performance.