Pillared Carbon Membranes Derived from Cardo Polymers

Carbon molecular sieve membranes (CMSMs) were prepared by carbonizing the high free volume polyimide BTDA-BAF that is obtained from the reaction of benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA) and 9,9-bis(4-aminophenyl) fluorene (BAF). The bulky cardo groups prevented a tight packing and rotation of the chains that leads to high permeabilities of their CMSMs. The incorporation of metal-organic polyhedra 18 (MOP-18, a copper-based MOP) in the BTDA-BAF polymer before pyrolysis at 550 °C prevented the collapse of the pores and the aging of the CMSMs. It was found that upon decomposition of MOP-18, a distribution of copper nanoparticles minimized the collapse of the graphitic sheets that formed the micropores and mesopores in the CMSM. The pillared CMSMs displayed CO₂ and CH₄ permeabilities of 12,729 and 659 Barrer, respectively, with a CO₂/CH₄ selectivity of 19.3 after 3 weeks of aging. The permselectivity properties of these membranes was determined to be at the 2019 Robeson upper bound. In contrast, the CMSMs from pure BTDA-BAF aged three times faster than the CMSMs from MOP-18/BTDA-BAF and exhibited lower CO₂ and CH₄ permeabilities of 5337 and 573 Barrer, respectively, with a CO₂/CH₄ selectivity of 9.3. The non-pillared CMSMs performed below the upper bound.