Study of Xenon Mobility in the Two Forms of MIL-53(Al) Using Solid-State NMR Spectroscopy

Giovine, R, Volkringer, C, Springuel-Huet, MA, Nossov, A, Blanc, F ORCID: 0000-0001-9171-1454, Trébosc, J, Loiseau, T ORCID: 0000-0001-8175-3407, Amoureux, JP, Lafon, O and Pourpoint, F ORCID: 0000-0001-7537-7142 (2017) Study of Xenon Mobility in the Two Forms of MIL-53(Al) Using Solid-State NMR Spectroscopy Journal of Physical Chemistry C, 121 (35). pp. 19262-19268. ISSN 1932-7447, 1932-7455

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Abstract

The Al-based metal-organic framework (MOF) MIL-53(Al) exhibits a structural transition between a large-pore (lp) form and a narrow-pore (np) one. Such change is induced by temperature, external pressure, or the adsorption of guest molecules. ¹²⁹Xe solid-state NMR experiments under static and magic-angle spinning (MAS) conditions have been used to study the lp-np transition in MIL-53(Al) initially loaded with xenon gas under a pressure of 5 × 10⁴ Pa (at room temperature). The conversion of the lp form into the np one when the temperature decreases from 327 to 237 K and the reopening of the pores below 230 K are then observed. Furthermore, ¹H → ¹²⁹Xe cross-polarization under MAS (CPMAS) experiments demonstrate the possibility to observe the np phase at T ≤ 230 K, while the lp one is unseen because the xenon residence time is too short for successful cross-polarization transfer. Moreover, even for the np phase at 199 K, the xenon atoms still exhibit significant motion on time scale faster than a few milliseconds. We prove the exchange of Xe atoms between the lp and np forms at room temperature with the two-dimensional (2D) ¹²⁹Xe EXchange SpectroscopY (EXSY) NMR method. Using ¹²⁹Xe selective inversion recovery (SIR) experiments, the rate for this exchange has been measured at 43 ± 6 s^-1.

Item Type:	Article
Uncontrolled Keywords:	3402 Inorganic Chemistry, 34 Chemical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	14 Sep 2017 07:12
Last Modified:	01 Mar 2026 06:36
DOI:	10.1021/acs.jpcc.7b06006
Related Websites:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3009461
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