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Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation
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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
Journal of Materials Chemistry A, Volume: 13, Issue: 23, Pages: 17865 - 17876
Swansea University Authors:
Caterina Bezzu , 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...
| Published in: | Journal of Materials Chemistry A |
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| ISSN: | 2050-7488 2050-7496 |
| Published: |
Royal Society of Chemistry (RSC)
2025
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| Online Access: |
Check full text
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| URI: | https://cronfa.swan.ac.uk/Record/cronfa69524 |
| 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. 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. |
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| College: |
Faculty of Science and Engineering |
| Funders: |
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. |
| Issue: |
23 |
| Start Page: |
17865 |
| End Page: |
17876 |