Breaking the Permeability-Selectivity Trade-Off: Advanced carbon molecular sieve membranes derived from thermally rearranged Mixed-Matrix membrane precursors

A crucial problem in membrane-based gas separation is to fabricate membranes with excellent permeability, selectivity, and stability. Here, a high-performance carbon molecular sieves membrane of TR-CMS/SSZ-13 was successfully produced by pyrolyzing a thermally rearranged (TR) mixed matrix membrane (MMM) that obtained from a copolyimide precursor (6FDA/ODA/6FAP(3:2)) and SSZ-13 zeolite as filler at 450 °C. The effect of SSZ-13 zeolite content and structures of precursors on the transport behavior of derived CMS membranes was thoroughly studied. After TR process, the as formed polybenzoxazole (PBO) chain resulted in an enhanced rigidity, higher fractional free volume (0.15 vs 0.17), and a significantly increased (1898 times) BET surface area. Further enhancing the treatment temperature to 650 °C, the formed TR-CMS membranes exhibited a huge improved BET surface area from 228.2 to 639.3 m2/g, delivering a remarkable gas separation performance with H2 permeability of 7089 Barrer and H2/CH4 selectivity of 136. When doping with SSZ-13 till 15 wt%, the TR-CMS/SSZ-13–15 % showed an even higher H2 (9726 Barrer) and CO2 permeability (6932 Barrer), as well as H2/CH4 (150 vs 136) and CO2/CH4 (107 vs 57) selectivity than the pure TR-CMS, which surpassed the newest 2019 Robeson Upper bound. This can associate with the strong interaction between the modified SSZ-13 and the polymer matrix that prevent the collapse of the aromatic strand during the pyrolysis process, thereby create more ultra-micropore volume and concentration. Conclusively, pyrolyzing TR-MMM precursor is an effective way to form high-performance membranes with good potential for CO2 separation and H2 purification.