Gas Uptake and Thermodynamics in Porous Liquids Elucidated by 129Xe NMR
Mailhiot, Sarah E.; Peuravaara, Petri; Egleston, Benjamin D.; Kearsey, Rachel J.; Mareš, Jiří; Komulainen, Sanna; Selent, Anne; Kantola, Anu M.; Cooper, Andrew I.; Vaara, Juha; Greenaway, Rebecca L.; Lantto, Perttu; Telkki, Ville-Veikko (2024-05-09)
American chemical society
09.05.2024
Mailhiot, S. E., Peuravaara, P., Egleston, B. D., Kearsey, R. J., Mareš, J., Komulainen, S., Selent, A., Kantola, A. M., Cooper, A. I., Vaara, J., Greenaway, R. L., Lantto, P., & Telkki, V.-V. (2024). Gas uptake and thermodynamics in porous liquids elucidated by 129 xe nmr. The Journal of Physical Chemistry Letters, 15(20), 5323–5330. https://doi.org/10.1021/acs.jpclett.4c00223.
https://creativecommons.org/licenses/by/4.0/
© 2024 The Authors. Published by American Chemical Society. This article is licensed under CC-BY 4.0
https://creativecommons.org/licenses/by/4.0/
© 2024 The Authors. Published by American Chemical Society. This article is licensed under CC-BY 4.0
https://creativecommons.org/licenses/by/4.0/
Julkaisun pysyvä osoite on
https://urn.fi/URN:NBN:fi:oulu-202405143478
https://urn.fi/URN:NBN:fi:oulu-202405143478
Tiivistelmä
Abstract
We exploited 129Xe NMR to investigate xenon gas uptake and dynamics in a porous liquid formed by dissolving porous organic cages in a cavity-excluded solvent. Quantitative 129Xe NMR shows that when the amount of xenon added to the sample is lower than the amount of cages present (subsaturation), the porous liquid absorbs almost all xenon atoms from the gas phase, with 30% of the cages occupied with a Xe atom. A simple two-site exchange model enables an estimate of the chemical shift of 129Xe in the cages, which is in good agreement with the value provided by first-principles modeling. T2 relaxation times allow the determination of the exchange rate of Xe between the solvent and cage sites as well as the activation energies of the exchange. The 129Xe NMR analysis also enables determination of the free energy of confinement, and it shows that Xe binding is predominantly enthalpy-driven.
We exploited 129Xe NMR to investigate xenon gas uptake and dynamics in a porous liquid formed by dissolving porous organic cages in a cavity-excluded solvent. Quantitative 129Xe NMR shows that when the amount of xenon added to the sample is lower than the amount of cages present (subsaturation), the porous liquid absorbs almost all xenon atoms from the gas phase, with 30% of the cages occupied with a Xe atom. A simple two-site exchange model enables an estimate of the chemical shift of 129Xe in the cages, which is in good agreement with the value provided by first-principles modeling. T2 relaxation times allow the determination of the exchange rate of Xe between the solvent and cage sites as well as the activation energies of the exchange. The 129Xe NMR analysis also enables determination of the free energy of confinement, and it shows that Xe binding is predominantly enthalpy-driven.
Kokoelmat
- Avoin saatavuus [38618]
Ellei muuten mainita, aineiston lisenssi on https://creativecommons.org/licenses/by/4.0/