Leveraging Free Volume Manipulation to Improve the Membrane Separation Performance of Amine‐Functionalized PIM‐1
Gas‐separation polymer membranes display a characteristic permeability–selectivity trade‐off that has limited their industrial use. The most comprehensive approach to improving performance is to devise strategies that simultaneously increase fractional free volume, narrow free volume distribution, a...
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Veröffentlicht in: | Angewandte Chemie (International ed.) 2021-03, Vol.60 (12), p.6593-6599 |
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creator | Mizrahi Rodriguez, Katherine Lin, Sharon Wu, Albert X. Han, Gang Teesdale, Justin J. Doherty, Cara M. Smith, Zachary P. |
description | Gas‐separation polymer membranes display a characteristic permeability–selectivity trade‐off that has limited their industrial use. The most comprehensive approach to improving performance is to devise strategies that simultaneously increase fractional free volume, narrow free volume distribution, and enhance sorption selectivity, but generalizable methods for such approaches are exceedingly rare. Here, we present an in situ crosslinking and solid‐state deprotection method to access previously inaccessible sorption and diffusion characteristics in amine‐functionalized polymers of intrinsic microporosity. Free volume element (FVE) size can be increased while preserving a narrow FVE distribution, enabling below‐upper bound polymers to surpass the H2/N2, H2/CH4, and O2/N2 upper bounds and improving CO2‐based selectivities by 200 %. This approach can transform polymers into chemical analogues with improved performance, thereby overcoming traditional permeability–selectivity trade‐offs.
A protection/deprotection strategy was developed to enhance the separation performance of amine‐functionalized PIM‐1. Thermal deprotection yielded a synergistic boost in size‐sieving and CO2 diffusion, ultimately surpassing the H2/CH4, O2/N2 and H2/N2 upper bounds and boosting CO2 permeability by 200 %. |
doi_str_mv | 10.1002/anie.202012441 |
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A protection/deprotection strategy was developed to enhance the separation performance of amine‐functionalized PIM‐1. Thermal deprotection yielded a synergistic boost in size‐sieving and CO2 diffusion, ultimately surpassing the H2/CH4, O2/N2 and H2/N2 upper bounds and boosting CO2 permeability by 200 %.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202012441</identifier><identifier>PMID: 33278319</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>amines ; Carbon dioxide ; Crosslinking ; gas separations ; Industrial applications ; Membrane permeability ; Membrane separation ; Membranes ; Microporosity ; microporous materials ; Permeability ; Polymers ; Selectivity ; Separation ; solid-state functionalization ; Sorption ; Upper bounds</subject><ispartof>Angewandte Chemie (International ed.), 2021-03, Vol.60 (12), p.6593-6599</ispartof><rights>2020 Wiley‐VCH GmbH</rights><rights>2020 Wiley-VCH GmbH.</rights><rights>2021 Wiley‐VCH GmbH</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4771-34f5756cd6f1936dedf3f8b8e15a34980f9e63fc962c8474c5f080584abb3d33</citedby><cites>FETCH-LOGICAL-c4771-34f5756cd6f1936dedf3f8b8e15a34980f9e63fc962c8474c5f080584abb3d33</cites><orcidid>0000-0001-7566-482X ; 0000-0002-9630-5890 ; 0000-0001-8943-569X ; 0000-0003-4823-2831 ; 0000-0002-5366-3743 ; 0000-0003-3286-1035 ; 0000-0003-3407-2873 ; 0000000253663743 ; 000000018943569X ; 0000000332861035 ; 0000000334072873 ; 0000000348232831 ; 0000000296305890 ; 000000017566482X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.202012441$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202012441$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>230,314,780,784,885,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/33278319$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/1786195$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Mizrahi Rodriguez, Katherine</creatorcontrib><creatorcontrib>Lin, Sharon</creatorcontrib><creatorcontrib>Wu, Albert X.</creatorcontrib><creatorcontrib>Han, Gang</creatorcontrib><creatorcontrib>Teesdale, Justin J.</creatorcontrib><creatorcontrib>Doherty, Cara M.</creatorcontrib><creatorcontrib>Smith, Zachary P.</creatorcontrib><title>Leveraging Free Volume Manipulation to Improve the Membrane Separation Performance of Amine‐Functionalized PIM‐1</title><title>Angewandte Chemie (International ed.)</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Gas‐separation polymer membranes display a characteristic permeability–selectivity trade‐off that has limited their industrial use. The most comprehensive approach to improving performance is to devise strategies that simultaneously increase fractional free volume, narrow free volume distribution, and enhance sorption selectivity, but generalizable methods for such approaches are exceedingly rare. Here, we present an in situ crosslinking and solid‐state deprotection method to access previously inaccessible sorption and diffusion characteristics in amine‐functionalized polymers of intrinsic microporosity. Free volume element (FVE) size can be increased while preserving a narrow FVE distribution, enabling below‐upper bound polymers to surpass the H2/N2, H2/CH4, and O2/N2 upper bounds and improving CO2‐based selectivities by 200 %. This approach can transform polymers into chemical analogues with improved performance, thereby overcoming traditional permeability–selectivity trade‐offs.
A protection/deprotection strategy was developed to enhance the separation performance of amine‐functionalized PIM‐1. Thermal deprotection yielded a synergistic boost in size‐sieving and CO2 diffusion, ultimately surpassing the H2/CH4, O2/N2 and H2/N2 upper bounds and boosting CO2 permeability by 200 %.</description><subject>amines</subject><subject>Carbon dioxide</subject><subject>Crosslinking</subject><subject>gas separations</subject><subject>Industrial applications</subject><subject>Membrane permeability</subject><subject>Membrane separation</subject><subject>Membranes</subject><subject>Microporosity</subject><subject>microporous materials</subject><subject>Permeability</subject><subject>Polymers</subject><subject>Selectivity</subject><subject>Separation</subject><subject>solid-state functionalization</subject><subject>Sorption</subject><subject>Upper bounds</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNqF0U1rFDEYB_BBFFurV48S9OJl17xNXo5L6erCVgsWryGTedKmzEzWZKbSnvoR_Ix-kmaZtoIXTwl5fvnDn6eq3hK8JBjTT3YIsKSYYkI5J8-qQ1JTsmBSsuflzhlbSFWTg-pVzlfFK4XFy-qAMSoVI_qwGrdwDclehOECrRMA-hG7qQd0WoJ3U2fHEAc0RrTpdyleAxovywz6JtkB0HfY2TSTM0g-pt4ODlD0aNWHAf7c_V5Pg9vPbRduoUVnm9PySF5XL7ztMrx5OI-q8_XJ-fGXxfbb583xartwXMrSgvta1sK1whPNRAutZ141CkhtGdcKew2CeacFdYpL7mqPFa4Vt03DWsaOqvdzbMxjMNmFEdyli8MAbjREKkF0XdDHGZV-PyfIo-lDdtB1pWCcsqFcSEEYE7TQD__Qqzil0m2vtNRc01oVtZyVSzHnBN7sUuhtujEEm_3OzH5n5mln5cO7h9ip6aF94o9LKkDP4Ffo4OY_cWb1dXPyN_wedjukPw</recordid><startdate>20210315</startdate><enddate>20210315</enddate><creator>Mizrahi Rodriguez, Katherine</creator><creator>Lin, Sharon</creator><creator>Wu, Albert X.</creator><creator>Han, Gang</creator><creator>Teesdale, Justin J.</creator><creator>Doherty, Cara M.</creator><creator>Smith, Zachary P.</creator><general>Wiley Subscription Services, Inc</general><general>Wiley Blackwell (John Wiley & Sons)</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0001-7566-482X</orcidid><orcidid>https://orcid.org/0000-0002-9630-5890</orcidid><orcidid>https://orcid.org/0000-0001-8943-569X</orcidid><orcidid>https://orcid.org/0000-0003-4823-2831</orcidid><orcidid>https://orcid.org/0000-0002-5366-3743</orcidid><orcidid>https://orcid.org/0000-0003-3286-1035</orcidid><orcidid>https://orcid.org/0000-0003-3407-2873</orcidid><orcidid>https://orcid.org/0000000253663743</orcidid><orcidid>https://orcid.org/000000018943569X</orcidid><orcidid>https://orcid.org/0000000332861035</orcidid><orcidid>https://orcid.org/0000000334072873</orcidid><orcidid>https://orcid.org/0000000348232831</orcidid><orcidid>https://orcid.org/0000000296305890</orcidid><orcidid>https://orcid.org/000000017566482X</orcidid></search><sort><creationdate>20210315</creationdate><title>Leveraging Free Volume Manipulation to Improve the Membrane Separation Performance of Amine‐Functionalized PIM‐1</title><author>Mizrahi Rodriguez, Katherine ; Lin, Sharon ; Wu, Albert X. ; Han, Gang ; Teesdale, Justin J. ; Doherty, Cara M. ; Smith, Zachary P.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4771-34f5756cd6f1936dedf3f8b8e15a34980f9e63fc962c8474c5f080584abb3d33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>amines</topic><topic>Carbon dioxide</topic><topic>Crosslinking</topic><topic>gas separations</topic><topic>Industrial applications</topic><topic>Membrane permeability</topic><topic>Membrane separation</topic><topic>Membranes</topic><topic>Microporosity</topic><topic>microporous materials</topic><topic>Permeability</topic><topic>Polymers</topic><topic>Selectivity</topic><topic>Separation</topic><topic>solid-state functionalization</topic><topic>Sorption</topic><topic>Upper bounds</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mizrahi Rodriguez, Katherine</creatorcontrib><creatorcontrib>Lin, Sharon</creatorcontrib><creatorcontrib>Wu, Albert X.</creatorcontrib><creatorcontrib>Han, Gang</creatorcontrib><creatorcontrib>Teesdale, Justin J.</creatorcontrib><creatorcontrib>Doherty, Cara M.</creatorcontrib><creatorcontrib>Smith, Zachary P.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>OSTI.GOV</collection><jtitle>Angewandte Chemie (International ed.)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mizrahi Rodriguez, Katherine</au><au>Lin, Sharon</au><au>Wu, Albert X.</au><au>Han, Gang</au><au>Teesdale, Justin J.</au><au>Doherty, Cara M.</au><au>Smith, Zachary P.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Leveraging Free Volume Manipulation to Improve the Membrane Separation Performance of Amine‐Functionalized PIM‐1</atitle><jtitle>Angewandte Chemie (International ed.)</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2021-03-15</date><risdate>2021</risdate><volume>60</volume><issue>12</issue><spage>6593</spage><epage>6599</epage><pages>6593-6599</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Gas‐separation polymer membranes display a characteristic permeability–selectivity trade‐off that has limited their industrial use. The most comprehensive approach to improving performance is to devise strategies that simultaneously increase fractional free volume, narrow free volume distribution, and enhance sorption selectivity, but generalizable methods for such approaches are exceedingly rare. Here, we present an in situ crosslinking and solid‐state deprotection method to access previously inaccessible sorption and diffusion characteristics in amine‐functionalized polymers of intrinsic microporosity. Free volume element (FVE) size can be increased while preserving a narrow FVE distribution, enabling below‐upper bound polymers to surpass the H2/N2, H2/CH4, and O2/N2 upper bounds and improving CO2‐based selectivities by 200 %. This approach can transform polymers into chemical analogues with improved performance, thereby overcoming traditional permeability–selectivity trade‐offs.
A protection/deprotection strategy was developed to enhance the separation performance of amine‐functionalized PIM‐1. Thermal deprotection yielded a synergistic boost in size‐sieving and CO2 diffusion, ultimately surpassing the H2/CH4, O2/N2 and H2/N2 upper bounds and boosting CO2 permeability by 200 %.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>33278319</pmid><doi>10.1002/anie.202012441</doi><tpages>7</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0001-7566-482X</orcidid><orcidid>https://orcid.org/0000-0002-9630-5890</orcidid><orcidid>https://orcid.org/0000-0001-8943-569X</orcidid><orcidid>https://orcid.org/0000-0003-4823-2831</orcidid><orcidid>https://orcid.org/0000-0002-5366-3743</orcidid><orcidid>https://orcid.org/0000-0003-3286-1035</orcidid><orcidid>https://orcid.org/0000-0003-3407-2873</orcidid><orcidid>https://orcid.org/0000000253663743</orcidid><orcidid>https://orcid.org/000000018943569X</orcidid><orcidid>https://orcid.org/0000000332861035</orcidid><orcidid>https://orcid.org/0000000334072873</orcidid><orcidid>https://orcid.org/0000000348232831</orcidid><orcidid>https://orcid.org/0000000296305890</orcidid><orcidid>https://orcid.org/000000017566482X</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | amines Carbon dioxide Crosslinking gas separations Industrial applications Membrane permeability Membrane separation Membranes Microporosity microporous materials Permeability Polymers Selectivity Separation solid-state functionalization Sorption Upper bounds |
title | Leveraging Free Volume Manipulation to Improve the Membrane Separation Performance of Amine‐Functionalized PIM‐1 |
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