Molecular-Sieving Membrane by Partitioning the Channels in Ultrafiltration Membrane by In Situ Polymerization

Commercial ultrafiltration membranes have proliferated globally for water treatment. However, their pore sizes are too large to sieve gases. Conjugated microporous polymers (CMPs) feature well-developed microporosity yet are difficult to be fabricated into membranes. Herein, we report a strategy to prepare molecular-sieving membranes by partitioning the mesoscopic channels in water ultrafiltration membrane (PSU) into ultra-micropores by space-confined polymerization of multi-functionalized rigid building units. Nine CMP@PSU membranes were obtained, and their separation performance for H₂/CO₂, H₂/N₂, and H₂/CH₄ pairs surpass the Robeson upper bound and rival against the best of those reported membranes. Furthermore, highly crosslinked skeletons inside the channels result in the structural robustness and transfer into the excellent aging resistance of the CMP@PSU. This strategy may shed light on the design and fabrication of high-performance polymeric gas separation membranes.