Highly Compatible Hydroxyl-Functionalized Microporous Polyimide-ZIF‑8 Mixed Matrix Membranes for Energy Efficient Propylene/Propane Separation

Mixed-matrix membranes composed of mechanically strong, solution-processable polymers and highly selective ultramicroporous fillers (pore size < 7 Å) are superior candidate membrane materials for various energy-intensive gas separation applications because of their structural tunability to achieve enhanced gas permeability and gas–pair selectivity. However, their industrial implementation has been severely hindered because inefficient compatibility of the polymer matrices and crystalline fillers results in poorly performing membranes with low filler capacity and interfacial defects. Herein, we report for the first time a unique strategy to fabricate highly propylene/propane selective mixed-matrix membranes (MMMs) composed of a hydroxyl-functionalized microporous polyimide (PIM-6FDA-OH) and an ultramicroporous, strongly size-sieving zeolitic imidazolate framework (ZIF-8). Excellent compatibility between PIM-6FDA-OH and ZIF-8 with selective filler loading up to 65 wt % resulted from N···O–H induced hydrogen bonding as evidenced by Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The newly developed MMMs demonstrated <i>unprecedented mixed-gas performance</i> for C₃H₆/C₃H₈ separation and outstanding plasticization resistance of up to at least 7 bar feed pressure. The reported fabrication concept is expected to be applicable to a wide variety of OH-functionalized polymers and alternative tailor-made imidazolate framework materials designed for MMMs to achieve optimal gas separation performance