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1. Gas Uptake and Thermodynamics in Porous Liquids Elucidated by 129Xe NMR

Author

Mailhiot, Sarah E., primary, Peuravaara, Petri, additional, Egleston, Benjamin D., additional, Kearsey, Rachel J., additional, Mareš, Jiří, additional, Komulainen, Sanna, additional, Selent, Anne, additional, Kantola, Anu M., additional, Cooper, Andrew I., additional, Vaara, Juha, additional, Greenaway, Rebecca L., additional, Lantto, Perttu, additional, and Telkki, Ville-Veikko, additional

Published
2024
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6. Gas Uptake and Thermodynamics in Porous Liquids Elucidated by 129 Xe NMR.

Author

Mailhiot SE, Peuravaara P, Egleston BD, Kearsey RJ, Mareš J, Komulainen S, Selent A, Kantola AM, Cooper AI, Vaara J, Greenaway RL, Lantto P, and Telkki VV

Abstract

We exploited 129 Xe NMR to investigate xenon gas uptake and dynamics in a porous liquid formed by dissolving porous organic cages in a cavity-excluded solvent. Quantitative 129 Xe 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 129 Xe in the cages, which is in good agreement with the value provided by first-principles modeling. T 2 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 129 Xe NMR analysis also enables determination of the free energy of confinement, and it shows that Xe binding is predominantly enthalpy-driven.

Published
2024
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