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Molecular Mobility of Tert-butyl Alcohol Confined in a Breathing MIL-53 (Al) Metal-Organic Framework. / Khudozhitkov, Alexander E.; Toktarev, Alexander V.; Arzumanov, Sergei S. и др.
в: ChemPhysChem, Том 21, № 17, 02.09.2020, стр. 1951-1956.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Molecular Mobility of Tert-butyl Alcohol Confined in a Breathing MIL-53 (Al) Metal-Organic Framework
AU - Khudozhitkov, Alexander E.
AU - Toktarev, Alexander V.
AU - Arzumanov, Sergei S.
AU - Gabrienko, Anton A.
AU - Kolokolov, Daniil I.
AU - Stepanov, Alexander G.
N1 - Publisher Copyright: © 2020 Wiley-VCH GmbH Copyright: Copyright 2020 Elsevier B.V., All rights reserved.
PY - 2020/9/2
Y1 - 2020/9/2
N2 - We present a detailed solid-state NMR characterization of the molecular dynamics of tert-butyl alcohol (TBA) confined inside breathing metal-organic framework (MOF) MIL-53(Al). 27Al MAS NMR has demonstrated that TBA adsorption induces the iX phase of MIL-53 material with partially shrunk channels. 2H solid-state NMR has shown that the adsorbed alcohol exhibits anisotropic rotations of the methyl groups around two (Formula presented.) axes and librations of the molecule as a whole about the axis passing through the TBA C−O bond. These librations are realized by two distinct ways: fast molecule orientation change during the translational jump diffusion along the channel with characteristic time τD of about 10−9 s at 300 K; slow local librations at a single coordination site, representing framework hydroxyl groups, with τl≈10−6 s at 300 K. Self-diffusion coefficient of the alcohol in the MOF has been estimated: D=3.4×10−10 m2 s−1 at 300 K. It has been inferred that both the framework flexibility and the interaction with framework hydroxyl groups define the dynamics of TBA confined in the channels of MIL-53 (Al).
AB - We present a detailed solid-state NMR characterization of the molecular dynamics of tert-butyl alcohol (TBA) confined inside breathing metal-organic framework (MOF) MIL-53(Al). 27Al MAS NMR has demonstrated that TBA adsorption induces the iX phase of MIL-53 material with partially shrunk channels. 2H solid-state NMR has shown that the adsorbed alcohol exhibits anisotropic rotations of the methyl groups around two (Formula presented.) axes and librations of the molecule as a whole about the axis passing through the TBA C−O bond. These librations are realized by two distinct ways: fast molecule orientation change during the translational jump diffusion along the channel with characteristic time τD of about 10−9 s at 300 K; slow local librations at a single coordination site, representing framework hydroxyl groups, with τl≈10−6 s at 300 K. Self-diffusion coefficient of the alcohol in the MOF has been estimated: D=3.4×10−10 m2 s−1 at 300 K. It has been inferred that both the framework flexibility and the interaction with framework hydroxyl groups define the dynamics of TBA confined in the channels of MIL-53 (Al).
KW - alcohols
KW - hydroxyl groups
KW - metal-organic frameworks
KW - molecular mobility
KW - solid-state NMR spectroscopy
KW - BENZENE
KW - XYLENE ISOMERS
KW - NEUTRON-SCATTERING
KW - COMBINATION
KW - ADSORPTION
KW - SPIN-LATTICE-RELAXATION
KW - TRANSPORT DIFFUSIVITY
KW - DYNAMICS
KW - H-2 NMR
KW - MIL-47(V)
UR - http://www.scopus.com/inward/record.url?scp=85089031040&partnerID=8YFLogxK
U2 - 10.1002/cphc.202000445
DO - 10.1002/cphc.202000445
M3 - Article
C2 - 32697428
AN - SCOPUS:85089031040
VL - 21
SP - 1951
EP - 1956
JO - ChemPhysChem
JF - ChemPhysChem
SN - 1439-4235
IS - 17
ER -
ID: 24954077