Shin Ju Ho, Yu Hyun Jung, Jung Jiyoon, An Heseong, Park Jung Hoon, Lee Albert S, Lee Jong Suk
Department of Chemical and Biomolecular Engineering, Sogang University, 35 Baekbeom-ro, Mapo-gu, Seoul, 04107, Republic of Korea.
Materials Architecturing Research Center, Korea Institute of Science and Technology, 5 Hwarang-ro 14-gil, Seongbuk-gu, Seoul, 02792, Republic of Korea.
Nat Commun. 2025 Aug 5;16(1):7143. doi: 10.1038/s41467-025-62372-y.
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 m g and demonstrate exceptional plasticization resistance under equimolar CO/CH mixed gas at pressures up to 40 bar. CO permeability increases from 280 to 12,000 Barrer at 1 bar and 35 °C, while CO/N selectivity reaches 46 at -20 °C, surpassing the 2019 polymeric upper bound. Furthermore, extrinsically microporous hollow fiber membranes prepared via dip-coating achieve a CO permeance of 2174 gas permeation units and CO/N 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.
源自固有微孔聚合物的先进膜为能源密集型热驱动分离技术提供了有前景的替代方案，但在可冷凝气体或物理老化条件下性能往往会下降。在此，外在微孔聚合物膜（EMPMs）作为一类独特的微孔膜被引入，它由无全氟芳基醚的芳香族聚合物通过脱氟诱导热交联制备而成。这一过程产生外在微孔，增加链段间距离，并显著提高气体渗透性。EMPMs的比表面积为552 m²/g，在高达40 bar的等摩尔CO/CH₄混合气体下表现出优异的抗增塑性能。在1 bar和35°C时，CO渗透率从280 Barrer增加到12000 Barrer，而在-20°C时，CO/CH₄选择性达到46，超过了2019年聚合物的上限。此外，通过浸涂制备的外在微孔中空纤维膜在-20°C时的CO渗透通量为2174气体渗透单位，CO/CH₄选择性为30，突出了它们的工业实用性。这项研究建立了一种可扩展的方法，用于制备具有卓越稳定性的高性能微孔聚合物膜，以用于可持续能源和环境应用。
