Boosting the CO2/N2 selectivity of MMMs by vesicle shaped ZIF-8 with high amino content

Abstract

The amino functionalization of MOFs has been verified to be effective in improving the selective permeation of CO2. However, the introduction of amino groups into ZIF-8 by mixed ligands strategy is hard to achieve due to the high steric hindrance of benzene ring in 2-aminobenzimidazole ligand, resulting in insufficient content of amino groups. Therefore, in this work, polystyrene-acrylate (PSA) template is proposed to provide abundant adsorption and reaction sites for the rapid synthesis of NH2-ZIF-8 with high content of 2-aminobenzimidazole. Furthermore, the incomplete etching strategy is used to construct PSA modified hollow NH2-ZIF-8 nanospheres (PHNZ). Importantly, the thickness of PSA layer and the hollow size are adjusted by the etching time, as revealed by the SEM and TEM images. In this PHNZ, the modified PSA can provide good interface compatibility between PHNZ and Pebax matrix to enhance the CO2 selectivity, while the hollow structure can reduce the mass transfer resistance and improve the gas permeability. Moreover, the introduced amino groups can enhance the CO2 affinity of PHNZ and further improve the CO2/N2 selectivity of the PHNZ-based mixed matrix membranes (MMMs). Benefiting from the synergy of good interface compatibility and enhanced CO2 affinity from the amino groups, the PHNZ/Pebax MMMs present greatly improved CO2/N2 selectivity in contrast with pure Pebax and NH2-ZIF-8 based membranes. Besides, as the etching time increases, the PHNZ-2 and PHNZ-3 based MMMs present a higher CO2 permeability than that of NH2-ZIF-8 based MMM, revealing the significance of the hollow structure. The PHNZ-2/Pebax MMM with filler loading of 10 wt% expresses the best gas separation performance with the CO2 permeability of 121.9 Barrer and CO2/N2 selectivity of 96.6, respectively, showing an increase of 54.7 % and 98.0 % in contrast with pure Pebax membrane. Meanwhile, this CO2 separation performance is far beyond the Robeson upper bound in 2008 and close to the McKeown upper bound in 2019, demonstrating that the proposed PHNZ displays a promising and competitive potential in MMM based CO2 capture.