Rational Design of Mixed Matrix Membranes Modulated by Trisilver Complex for Efficient Propylene/Propane Separation

The application of membrane-based separation processes for propylene/propane (C₃ H₆ /C₃ H₈ ) is extremely promising and attractive as it is poised to reduce the high operation cost of the established low temperature distillation process, but major challenges remain in achieving high gas selectivity/permeability and long-term membrane stability. Herein, a C₃ H₆ facilitated transport membrane using trisilver pyrazolate (Ag₃ pz₃ ) as a carrier filler is reported, which is uniformly dispersed in a polymer of intrinsic microporosity (PIM-1) matrix at the molecular level (≈15 nm), verified by several analytical techniques, including 3D-reconstructed focused ion beam scanning electron microscropy (FIB-SEM) tomography. The π-acidic Ag₃ pz₃ combines preferentially with π-basic C₃ H₆ , which is confirmed by density functional theory calculations showing that the silver ions in Ag₃ pz₃ form a reversible π complex with C₃ H₆ , endowing the membranes with superior C₃ H₆ affinity. The resulting membranes exhibit superior stability, C₃ H₆ /C₃ H₈ selectivity as high as ≈200 and excellent C₃ H₆ permeability of 306 Barrer, surpassing the upper bound selectivity/permeability performance line of polymeric membranes. This work provides a conceptually new approach of using coordinatively unsaturated 0D complexes as fillers in mixed matrix membranes, which can accomplish olefin/alkane separation with high performance.