Enhancing the propylene/propane separation performances of ZIF-8 membranes by post-synthetic surface polymerization

Zeolitic-imidazole framework-8 (ZIF-8) membranes have shown exceptional propylene/propane separation performances. Their commercial applications have, however, been impeded by several challenges. One such challenge is the difficulty of managing microstructural defects (i.e., grain boundary defects) in a consistent manner, leading to poor membrane performances and ultimately to a reproducibility issue. Herein, we introduce a new effective strategy to seal the microstructural defects of polycrystalline ZIF-8 membranes using post-synthetic surface polymerization which consists of two steps: (1) introduction of initiator ligands on the membrane surface by post-synthetic ligand exchange and (2) in situ polymerization of poly(methyl methacrylate) (PMMA) via atom transfer radical polymerization. The ZIF-8 membranes were fully covered with ultra-thin PMMA layers of sub-10 nm thickness, increasing the propylene/propane separation factor from ∼60 to ∼106 with unexpectedly increased propylene permeance, effectively improving the membrane reproducibility. The enhanced separation properties of the PMMA-coated ZIF-8 membranes were attributed to the ultra-thin PMMA layers as well as to the possible facilitated propylene transport by Cu ions in the PMMA layers.