Extrinsically microporous polymer membranes derived from thermally cross-linked perfluorinated aryl-ether-free polymers for gas separation

Ju Ho Shin, Hyun Jung Yu, Jiyoon Jung, Heseong An, Jung Hoon Park, Albert S. Lee () and Jong Suk Lee ()
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Ju Ho Shin: Sogang University
Hyun Jung Yu: Sogang University
Jiyoon Jung: Korea Institute of Science and Technology
Heseong An: Sunchon National University
Jung Hoon Park: Dongguk University
Albert S. Lee: Korea Institute of Science and Technology
Jong Suk Lee: Sogang University

Nature Communications, 2025, vol. 16, issue 1, 1-12

Abstract: Abstract State-of-the-art membranes derived from polymers of intrinsic microporosity offer promising alternatives to energy-intensive, thermally driven separation techniques but often suffer from reduced performance under condensable gases or physical aging. Here, extrinsically microporous polymer membranes (EMPMs) are introduced as a distinct class of microporous membranes, fabricated from perfluorinated aryl-ether-free aromatic polymers via defluorination-induced thermal cross-linking. This process generates extrinsic micropores, increases intersegmental distances, and significantly enhances gas permeability. EMPMs exhibit a Brunauer-Emmett-Teller surface area of 552 m2 g−1 and demonstrate exceptional plasticization resistance under equimolar CO2/CH4 mixed gas at pressures up to 40 bar. CO2 permeability increases from 280 to 12,000 Barrer at 1 bar and 35 °C, while CO2/N2 selectivity reaches 46 at −20 °C, surpassing the 2019 polymeric upper bound. Furthermore, extrinsically microporous hollow fiber membranes prepared via dip-coating achieve a CO2 permeance of 2174 gas permeation units and CO2/N2 selectivity of 30 at −20 °C, highlighting their industrial relevance. This study establishes a scalable method for fabricating high-performance microporous polymeric membranes with exceptional stability for sustainable energy and environmental applications.

Date: 2025
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DOI: 10.1038/s41467-025-62372-y

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