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

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 CO/N 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 CO permeability of 72.9 Barrer and a CO/N 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, M 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 M 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)).