Ultraselective Carbon Molecular Sieve Membranes with Tailored Synergistic Sorption Selective Properties

Membrane‐based separations can reduce the energy consumption and the CO2 footprint of large‐scale fluid separations, which are traditionally practiced by energy‐intensive thermally driven processes. Here, a new type of membrane structure based on nanoporous carbon is reported, which, according to this study, is best referred to as carbon/carbon mixed‐matrix (CCMM) membranes. The CCMM membranes are formed by high‐temperature (up to 900 °C) pyrolysis of polyimide precursor hollow‐fiber membranes. Unprecedentedly high permselectivities are seen in CCMM membranes for CO2/CH4, N2/CH4, He/CH4, and H2/CH4 separations. Analysis of permeation data suggests that the ultrahigh selectivities result from substantially increased sorption selectivities, which is hypothetically owing to the formation of ultraselective micropores that selectively exclude the bulkier CH4 molecules. With tunable sorption selectivities, the CCMM membranes outperform flexible polymer membranes and traditional rigid molecular‐sieve membranes. The capability to increase sorption selectivities is a powerful tool to leverage diffusion selectivities, and has opened the door to many challenging and economically important fluid separations that require ultrafine differentiation of closely sized molecules.