Molecular Mobility of Tert-butyl Alcohol Confined in a Breathing MIL-53 (Al) Metal-Organic Framework

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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. et al.

In: ChemPhysChem, Vol. 21, No. 17, 02.09.2020, p. 1951-1956.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{64ccf0a9298b4dd884690233969a6c11,

title = "Molecular Mobility of Tert-butyl Alcohol Confined in a Breathing MIL-53 (Al) Metal-Organic Framework",

abstract = "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).",

keywords = "alcohols, hydroxyl groups, metal-organic frameworks, molecular mobility, solid-state NMR spectroscopy, BENZENE, XYLENE ISOMERS, NEUTRON-SCATTERING, COMBINATION, ADSORPTION, SPIN-LATTICE-RELAXATION, TRANSPORT DIFFUSIVITY, DYNAMICS, H-2 NMR, MIL-47(V)",

author = "Khudozhitkov, {Alexander E.} and Toktarev, {Alexander V.} and Arzumanov, {Sergei S.} and Gabrienko, {Anton A.} and Kolokolov, {Daniil I.} and Stepanov, {Alexander G.}",

year = "2020",

month = sep,

day = "2",

doi = "10.1002/cphc.202000445",

language = "English",

volume = "21",

pages = "1951--1956",

journal = "ChemPhysChem",

issn = "1439-4235",

publisher = "Wiley-Blackwell",

number = "17",

}

RIS

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.

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