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Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation

Carmen Rizzuto Orcid Logo, Francesca Nardelli Orcid Logo, Marcello Monteleone Orcid Logo, Lucia Calucci Orcid Logo, Caterina Bezzu Orcid Logo, Mariolino Carta, Elena Tocci Orcid Logo, Elisa Esposito Orcid Logo, Giorgio De Luca Orcid Logo, Bibiana Comesaña-Gándara Orcid Logo, Neil B. McKeown Orcid Logo, Bekir Sayginer Orcid Logo, Peter M. Budd Orcid Logo, Johannes C. Jansen Orcid Logo, Alessio Fuoco Orcid Logo

Journal of Materials Chemistry A, Volume: 13, Issue: 23, Pages: 17865 - 17876

Swansea University Authors: Caterina Bezzu Orcid Logo, Mariolino Carta

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DOI (Published version): 10.1039/d4ta08839e

Abstract

Previously, it has been reported that amine-PIM-1, a polymer of intrinsic microporosity obtained by reduction of nitrile groups of PIM-1 to primary amine groups, shows enhanced CO2 selectivity during mixed gas permeation studies with respect to single gas measurements for gas pairs involving CO2. Th...

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Published in: Journal of Materials Chemistry A
ISSN: 2050-7488 2050-7496
Published: Royal Society of Chemistry (RSC) 2025
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URI: https://cronfa.swan.ac.uk/Record/cronfa69524
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This distinct and potentially useful behaviour was ascribed to the affinity of CO2 for the polymer amine groups. Here, we demonstrate that enhanced selectivity originates from both CO2 physisorption and chemisorption. A combination of 13C and 15N solid-state NMR spectroscopic analyses of a CO2-loaded amine-PIM-1 membrane allowed the identification and quantitative determination of both chemisorbed and physisorbed species and the characterization of polymer-CO2 interactions. Experiments with 13C isotopically enriched CO2 unequivocally demonstrated the conversion of 20% of the NH2 groups into carbamic acids at 298 K and a CO2 pressure of 1 bar. Chemisorption was supported by the strong heat of CO2 adsorption for amine-PIM-1 that was estimated as 50 kJ mol&#x2212;1. 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spelling 2025-06-12T12:09:29.2911163 v2 69524 2025-05-16 Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation 0ae638b129bf53b1ba5162afa9374e08 0000-0001-6918-8281 Caterina Bezzu Caterina Bezzu true false 56aebf2bba457f395149bbecbfa6d3eb Mariolino Carta Mariolino Carta true false 2025-05-16 EAAS Previously, it has been reported that amine-PIM-1, a polymer of intrinsic microporosity obtained by reduction of nitrile groups of PIM-1 to primary amine groups, shows enhanced CO2 selectivity during mixed gas permeation studies with respect to single gas measurements for gas pairs involving CO2. This distinct and potentially useful behaviour was ascribed to the affinity of CO2 for the polymer amine groups. Here, we demonstrate that enhanced selectivity originates from both CO2 physisorption and chemisorption. A combination of 13C and 15N solid-state NMR spectroscopic analyses of a CO2-loaded amine-PIM-1 membrane allowed the identification and quantitative determination of both chemisorbed and physisorbed species and the characterization of polymer-CO2 interactions. Experiments with 13C isotopically enriched CO2 unequivocally demonstrated the conversion of 20% of the NH2 groups into carbamic acids at 298 K and a CO2 pressure of 1 bar. Chemisorption was supported by the strong heat of CO2 adsorption for amine-PIM-1 that was estimated as 50 kJ mol−1. Molecular dynamics simulations with models based on the experimentally determined polymer structure gave a detailed description of intra- and interchain hydrogen bond interactions in amine-PIM-1 after chemisorption, as well as of the effect of chemisorption on polymer porosity and physisorption. Journal Article Journal of Materials Chemistry A 13 23 17865 17876 Royal Society of Chemistry (RSC) 2050-7488 2050-7496 28 4 2025 2025-04-28 10.1039/d4ta08839e COLLEGE NANME Engineering and Applied Sciences School COLLEGE CODE EAAS Swansea University Another institution paid the OA fee The authors are gratefully acknowledging the Ministry for Universities and Research (MUR) of Italy for financial support under the program PRIN 2020 under the project “doMino” (2020P9KBKZ) and the Grants TED2021-131170A-I00 and CNS2022-135430 funded by MICIU/AEI/10.13039/501100011033 and by the European Union NextGenerationEU/PRTR. The research leading to these results has received funding from the European Union's Horizon Europe research and innovation programme under grant agreement No 101115488, project DAM4CO2 and by UK Research and Innovation (UKRI) under the UK government's Horizon Europe funding guarantee, grant numbers 10083164 and 10091537. 2025-06-12T12:09:29.2911163 2025-05-16T10:35:23.6587551 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Carmen Rizzuto 0000-0001-5125-3567 1 Francesca Nardelli 0000-0002-9793-1367 2 Marcello Monteleone 0000-0001-8339-062x 3 Lucia Calucci 0000-0002-3080-8807 4 Caterina Bezzu 0000-0001-6918-8281 5 Mariolino Carta 6 Elena Tocci 0000-0001-8731-2063 7 Elisa Esposito 0000-0001-8561-1510 8 Giorgio De Luca 0000-0003-2963-3381 9 Bibiana Comesaña-Gándara 0000-0002-6953-6837 10 Neil B. McKeown 0000-0002-6027-261x 11 Bekir Sayginer 0000-0002-3704-8628 12 Peter M. Budd 0000-0003-3606-1158 13 Johannes C. Jansen 0000-0003-4538-6851 14 Alessio Fuoco 0000-0002-8355-0141 15 69524__34291__a4df10303129477d8984cae5a97d6ee6.pdf 69524.VOR.pdf 2025-05-16T10:42:01.0091026 Output 2733554 application/pdf Version of Record true This Open Access Article is licensed under a Creative Commons Attribution 3.0 Unported Licence. true eng http://creativecommons.org/licenses/by/3.0/
title Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation
spellingShingle Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation
Caterina Bezzu
Mariolino Carta
title_short Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation
title_full Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation
title_fullStr Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation
title_full_unstemmed Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation
title_sort Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation
author_id_str_mv 0ae638b129bf53b1ba5162afa9374e08
56aebf2bba457f395149bbecbfa6d3eb
author_id_fullname_str_mv 0ae638b129bf53b1ba5162afa9374e08_***_Caterina Bezzu
56aebf2bba457f395149bbecbfa6d3eb_***_Mariolino Carta
author Caterina Bezzu
Mariolino Carta
author2 Carmen Rizzuto
Francesca Nardelli
Marcello Monteleone
Lucia Calucci
Caterina Bezzu
Mariolino Carta
Elena Tocci
Elisa Esposito
Giorgio De Luca
Bibiana Comesaña-Gándara
Neil B. McKeown
Bekir Sayginer
Peter M. Budd
Johannes C. Jansen
Alessio Fuoco
format Journal article
container_title Journal of Materials Chemistry A
container_volume 13
container_issue 23
container_start_page 17865
publishDate 2025
institution Swansea University
issn 2050-7488
2050-7496
doi_str_mv 10.1039/d4ta08839e
publisher Royal Society of Chemistry (RSC)
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 1
active_str 0
description Previously, it has been reported that amine-PIM-1, a polymer of intrinsic microporosity obtained by reduction of nitrile groups of PIM-1 to primary amine groups, shows enhanced CO2 selectivity during mixed gas permeation studies with respect to single gas measurements for gas pairs involving CO2. This distinct and potentially useful behaviour was ascribed to the affinity of CO2 for the polymer amine groups. Here, we demonstrate that enhanced selectivity originates from both CO2 physisorption and chemisorption. A combination of 13C and 15N solid-state NMR spectroscopic analyses of a CO2-loaded amine-PIM-1 membrane allowed the identification and quantitative determination of both chemisorbed and physisorbed species and the characterization of polymer-CO2 interactions. Experiments with 13C isotopically enriched CO2 unequivocally demonstrated the conversion of 20% of the NH2 groups into carbamic acids at 298 K and a CO2 pressure of 1 bar. Chemisorption was supported by the strong heat of CO2 adsorption for amine-PIM-1 that was estimated as 50 kJ mol−1. Molecular dynamics simulations with models based on the experimentally determined polymer structure gave a detailed description of intra- and interchain hydrogen bond interactions in amine-PIM-1 after chemisorption, as well as of the effect of chemisorption on polymer porosity and physisorption.
published_date 2025-04-28T05:29:52Z
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score 11.096295

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