Heteroepitaxial growth of ZIF-67 nanoparticles on the ZIF-L(Zn) nanosheets for fabrication of Pebax mixed matrix membranes with highly efficient CO2 separation

Abstract

ZIF-67 nanoparticles were grown on ZIF-L(Zn) nanosheets by in-situ heteroepitaxial method, resulting in ZIF-67@ZIF-L(Zn) as a charming two-dimensional (2D) nanocomposite for incorporation into the Pebax-1657 and improving its CO2/N2 separation performance. The fabricated nanofillers and membranes were analyzed by characterization tests (FTIR, XRD, FESEM, and EDAX-mapping) and gas separation experiments (effect of filler loading, filler type, feed pressure, and long-term stability). It was observed that the nanosheets were well dispersed in the matrix, and they had formed a proper interaction by creating hydrogen bonds at the interface; in addition, due to their crystalline nature, they increased the crystallinity of the MMMs. The results of the gas permeability test showed that these nanofillers, with their composite structure, had a synergistic effect on the gas solubility and screening and caused a significant improvement in the separation performance of MMMs. So that the best performance achieved with a CO2 permeability of 72.9 Barrer and a CO2/N2 selectivity of 102.9 at 10 bar for the MMM containing 2 wt% of ZIF-L(Zn)@ZIF-67, also exceeding Robeson's upper bound. Moreover, Mindex as a criterion for evaluation of the gas separation performance of MMMs in simultaneous improvement of the permeability and selectivity was proposed in this work. The Mindex values in the range of 0.5–1.5 were calculated for the MMM containing 2 wt% of ZIF-L(Zn)@ZIF-67 nanosheet which indicating a good quality for the gas separation performance. Furthermore, at equal filler loading (2 wt%), this membrane outperformed all MMMs containing other nanofillers (ZIF-67, ZIF-8, ZIF-L(Co), or ZIF-L(Zn)).