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This work presents an in\u2010situ synthesis strategy for polymer\u2010zeolitic\u2010imidazolate frameworks (polyZIF), utilizing polymer\u2010metal\u2010ligand coordination bonds combined with structural directing agents to produce crystalline microporous frameworks. With an accessible BET surface area of 261 m\n                    <jats:sup>2<\/jats:sup>\n                    g\n                    <jats:sup>\u22121<\/jats:sup>\n                    and a permanent porosity of ca. 4.42\u00a0\u00c5, polyZIF membrane demonstrates butadiene permeance (\u223c332 GPU) and the selectivity over\n                    <jats:italic>n<\/jats:italic>\n                    \u2010butene,\n                    <jats:italic>n<\/jats:italic>\n                    \u2010butane, iso\u2010butene, and iso\u2010butane (17.2, 28.1, 21.5, and 34.8) under mixed gas conditions, respectively. Demonstrating practical scalability, the improved dispersibility and reduced interfacial defects in polyZIF facilitates fabrication of large\u2010area defect\u2010free membranes (up to 80 cm\n                    <jats:sup>2<\/jats:sup>\n                    ) while maintaining robust C4 separation performance. This advancement not only establishes a novel preparation for constructing polyZIF membranes with C4 hydrocarbon molecular\u2010sieving capability but also provides critical insights into industrial application of ZIF\u2010based polymer membranes.\n                  <\/jats:p>","DOI":"10.1002\/anie.202506117","type":"journal-article","created":{"date-parts":[[2025,4,24]],"date-time":"2025-04-24T02:45:15Z","timestamp":1745462715000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Tailored Polymer\u2010Zeolite Imidazolate Framework Membranes for Aperture\u2010Matched C4 Hydrocarbon Separation"],"prefix":"10.1002","volume":"64","author":[{"given":"Ning","family":"Li","sequence":"first","affiliation":[{"name":"State Key Laboratory of Advanced Separation Membrane Materials Tiangong University  Tianjin 300387 China"},{"name":"School of Materials Science and Engineering Tiangong University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chao","family":"Ma","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Separation Membrane Materials Tiangong University  Tianjin 300387 China"},{"name":"School of Materials Science and Engineering Tiangong University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jingli","family":"Zhang","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Nankai University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lin","family":"Xu","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Nankai University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sa","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Nankai University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ziyue","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Separation Membrane Materials Tiangong University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Si","family":"Zhang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Separation Membrane Materials Tiangong University  Tianjin 300387 China"},{"name":"School of Chemical Engineering Tiangong University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiandong","family":"Pang","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering Nankai University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jingwei","family":"Hou","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering The University of Queensland  St Lucia QLD 4072 Australia"},{"name":"ARC Centre of Excellence for Green Electrochemical Transformation of Carbon Dioxide  Brisbane 4072 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhihua","family":"Qiao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Separation Membrane Materials Tiangong University  Tianjin 300387 China"},{"name":"School of Chemical Engineering Tiangong University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chongli","family":"Zhong","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Separation Membrane Materials Tiangong University  Tianjin 300387 China"},{"name":"School of Chemical Engineering Tiangong University  Tianjin 300387 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,5,2]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201607676"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/smll.202307990"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cej.2024.158302"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aam7232"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c06585"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202302564"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.abn8418"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.adq5577"},{"key":"e_1_2_7_9_1","author":"Peng X. 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