Ultra-selective molecular-sieving gas separation membranes enabled by multi-covalent-crosslinking of microporous polymer blends.

Chen, Xiuling; Fan, Yanfang; Wu, Lei; Zhang, Linzhou; Guan, Dong; Ma, Canghai; Li, Nanwen · Nat Commun · 2021

basic_science · Level V

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Abstract

High-performance membranes exceeding the conventional permeability-selectivity upper bound are attractive for advanced gas separations. In the context microporous polymers have gained increasing attention owing to their exceptional permeability, which, however, demonstrate a moderate selectivity unfavorable for separating similarly sized gas mixtures. Here we report an approach to designing polymeric molecular sieve membranes via multi-covalent-crosslinking of blended bromomethyl polymer of intrinsic microporosity and Tröger's base, enabling simultaneously high permeability and selectivity. Ultra-selective gas separation is achieved via adjusting reaction temperature, reaction time and the oxygen concentration with occurrences of polymer chain scission, rearrangement and thermal oxidative crosslinking reaction. Upon a thermal treatment at 300 °C for 5 h, membranes exhibit an O<sub>2</sub>/N<sub>2</sub>, CO<sub>2</sub>/CH<sub>4</sub> and H<sub>2</sub>/CH<sub>4</sub> selectivity as high as 11.1, 154.5 and 813.6, respectively, transcending the state-of-art upper bounds. The design strategy represents a generalizable approach to creating molecular-sieving polymer membranes with enormous potentials for high-performance separation processes.