{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,1]],"date-time":"2026-07-01T17:49:35Z","timestamp":1782928175580,"version":"3.54.5"},"reference-count":40,"publisher":"MDPI AG","issue":"13","license":[{"start":{"date-parts":[[2026,7,1]],"date-time":"2026-07-01T00:00:00Z","timestamp":1782864000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Spanish Research Agency","award":["PID2023-149594OB-C21"],"award-info":[{"award-number":["PID2023-149594OB-C21"]}]},{"name":"Spanish Research Agency","award":["PDC2025-165497-I00"],"award-info":[{"award-number":["PDC2025-165497-I00"]}]},{"name":"Alltogas","award":["PLEC2022-009349"],"award-info":[{"award-number":["PLEC2022-009349"]}]},{"DOI":"10.13039\/501100008431","name":"European Regional Development Fund","doi-asserted-by":"publisher","award":["CLU-2025-2-06, UIC 082"],"award-info":[{"award-number":["CLU-2025-2-06, UIC 082"]}],"id":[{"id":"10.13039\/501100008431","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>Mixed-matrix membranes (MMMs) incorporating porous organic fillers into high-performance polyimides were developed to investigate the influence of free volume and molecular architecture on gas transport. Four structurally rigid, intrinsically porous fillers (TFAP-Trp, Is-Trp, TFAP-TPB, and Is-TPB) were incorporated into a range of polymer matrices (P84\u00ae, Matrimid\u00ae, Pi-DAPOH, Pi-DAROH, Pi-HABAc, Pi-DAM, and PIM-1), enabling the development of a matrix-independent methodology for estimating intrinsic filler permeabilities for five gases (He, O2, N2, CH4, and CO2). This comprehensive multi-matrix, multi-gas study reveals a strong correlation between filler fractional free volume (FFV), BET surface area, and gas permeability, with isatin-based fillers exhibiting particularly high CO2 permeability. Filler incorporation generally resulted in substantial permeability enhancements (100\u2013350%) while maintaining selectivity, often with only minor losses or even favorable improvements in CO2\/CH4 and He\/CH4 separation performance. Several MMMs, particularly those based on Pi-DAPOH and Pi-DAROH polyimides, approached or exceeded the Robeson upper bound. Analysis of permeability as a function of gas kinetic diameter further elucidated clear structure\u2013property relationships, confirming that filler-induced disruption of polymer chain packing and the creation of additional transport pathways are the primary factors governing separation performance. Overall, these findings demonstrate that rationally designed porous organic fillers provide a robust and broadly applicable strategy for mitigating the permeability\u2013selectivity trade-off in polymer membranes and enhancing gas separation efficiency.<\/jats:p>","DOI":"10.3390\/polym18131645","type":"journal-article","created":{"date-parts":[[2026,7,1]],"date-time":"2026-07-01T16:50:33Z","timestamp":1782924633000},"page":"1645","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Linking Intrinsic Filler Properties to Gas Separation Performance in Polyimide-Based Mixed-Matrix Membranes"],"prefix":"10.3390","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3930-7451","authenticated-orcid":false,"given":"Alba","family":"Torres","sequence":"first","affiliation":[{"name":"Surface and Porous Materials (SMAP), Associated Research Unit to CSIC, Facultad de Ciencias, Universidad de Valladolid, Paseo Bel\u00e9n 7, 47011 Valladolid, Spain"},{"name":"Institute of Sustainable Processes (ISP), Universidad de Valladolid, Paseo Prado de la Magdalena 3-5, 47011 Valladolid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0799-8697","authenticated-orcid":false,"given":"Cenit","family":"Soto","sequence":"additional","affiliation":[{"name":"Surface and Porous Materials (SMAP), Associated Research Unit to CSIC, Facultad de Ciencias, Universidad de Valladolid, Paseo Bel\u00e9n 7, 47011 Valladolid, Spain"},{"name":"Institute of Sustainable Processes (ISP), Universidad de Valladolid, Paseo Prado de la Magdalena 3-5, 47011 Valladolid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1281-301X","authenticated-orcid":false,"given":"Javier","family":"Carmona","sequence":"additional","affiliation":[{"name":"Surface and Porous Materials (SMAP), Associated Research Unit to CSIC, Facultad de Ciencias, Universidad de Valladolid, Paseo Bel\u00e9n 7, 47011 Valladolid, Spain"},{"name":"Institute of Sustainable Processes (ISP), Universidad de Valladolid, Paseo Prado de la Magdalena 3-5, 47011 Valladolid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1207-6275","authenticated-orcid":false,"given":"Ra\u00fal","family":"Mu\u00f1oz","sequence":"additional","affiliation":[{"name":"Institute of Sustainable Processes (ISP), Universidad de Valladolid, Paseo Prado de la Magdalena 3-5, 47011 Valladolid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9886-9553","authenticated-orcid":false,"given":"Laura","family":"Palacio","sequence":"additional","affiliation":[{"name":"Surface and Porous Materials (SMAP), Associated Research Unit to CSIC, Facultad de Ciencias, Universidad de Valladolid, Paseo Bel\u00e9n 7, 47011 Valladolid, Spain"},{"name":"Institute of Sustainable Processes (ISP), Universidad de Valladolid, Paseo Prado de la Magdalena 3-5, 47011 Valladolid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8939-8518","authenticated-orcid":false,"given":"Pedro","family":"Pr\u00e1danos","sequence":"additional","affiliation":[{"name":"Surface and Porous Materials (SMAP), Associated Research Unit to CSIC, Facultad de Ciencias, Universidad de Valladolid, Paseo Bel\u00e9n 7, 47011 Valladolid, Spain"},{"name":"Institute of Sustainable Processes (ISP), Universidad de Valladolid, Paseo Prado de la Magdalena 3-5, 47011 Valladolid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9078-3990","authenticated-orcid":false,"given":"Alberto","family":"Tena","sequence":"additional","affiliation":[{"name":"Surface and Porous Materials (SMAP), Associated Research Unit to CSIC, Facultad de Ciencias, Universidad de Valladolid, Paseo Bel\u00e9n 7, 47011 Valladolid, Spain"},{"name":"Institute of Sustainable Processes (ISP), Universidad de Valladolid, Paseo Prado de la Magdalena 3-5, 47011 Valladolid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Antonio","family":"Hern\u00e1ndez","sequence":"additional","affiliation":[{"name":"Surface and Porous Materials (SMAP), Associated Research Unit to CSIC, Facultad de Ciencias, Universidad de Valladolid, Paseo Bel\u00e9n 7, 47011 Valladolid, Spain"},{"name":"Institute of Sustainable Processes (ISP), Universidad de Valladolid, Paseo Prado de la Magdalena 3-5, 47011 Valladolid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,7,1]]},"reference":[{"key":"ref_1","first-page":"100347","article-title":"Carbon Capture Science & Technology Mixed Matrix Membrane Formation with Porous Metal\u2014Organic Nanomaterials for CO2 Capture and Separation: A Critical Review","volume":"14","author":"Welton","year":"2025","journal-title":"Carbon Capture Sci. 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