High-Performance Carbon Molecular Sieve Membranes Derived from a PPA-Cross-linked Polyimide Precursor for Gas Separation.

Carbon molecular sieve (CMS) membranes have emerged as attractive gas membranes due to their tunable pore structure and consequently high gas separation performances. In particular, polyimides (PIs) have been considered as promising CMS precursors because of their tunable structure, superior gas separation performance, and excellent thermal and mechanical strength. In the present work, polyphosphoric acid (PPA) was employed as both cross-linker and porogen, it created pores within the PI polymeric matrix, while it also effectively acting as a cross-linker to regulate the ultramicropores of the CMS membranes, thus simultaneously improving both permeability and selectivity of the CMS membranes. By employing PI/PPA hybrid with PPA content of 5 wt % as a precursor, the obtained CMS membrane exhibited a CO and He permeability of 1378.3 Barrer and 1431.4 Barrer, respectively, which was an approximately 10-fold increase compared to the precursor membrane. Under optimized conditions, the CO/CH and He/CH selectivity of the obtained CMS membrane reached 81.5 and 89.9, respectively, which was 278% and 307% higher than that of the pristine PI membrane. In addition, the membrane exhibited good long-term stability during a one-week continuous test. This study clearly denoted PPA can be used for precisely tailoring the ultramicroporosity of CMS membranes.