Diffusion of Benzene in the Breathing Metal–Organic Framework MIL-53(Cr): A Joint Experimental–Computational Investigation | Sciact - CRIS-system of Boreskov Institute of Catalysis

Diffusion of Benzene in the Breathing Metal–Organic Framework MIL-53(Cr): A Joint Experimental–Computational Investigation Full article

Journal

The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455

Output data

Year: 2015, Volume: 119, Number: 15, Pages: 8217-8225 Pages count : 9 DOI: 10.1021/acs.jpcc.5b01465

Tags

Activation energy; Computational chemistry; Metal-Organic Frameworks; Molecular dynamics; Neutron scattering; Organometallics; Rotational flow

Authors

Kolokolov D.I. ^1,6 , Jobic H. ² , Rives S. ^2,3 , Yot P.G. ³ , Ollivier J. ⁴ , Trens P. ⁵ , Stepanov A.G. ^1,6 , Maurin G. ³

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Institut de Recherches sur la Catalyse et l’Environnement de Lyon, CNRS, Universitéde Lyon, 2. Av. A. Einstein, 69626 Villeurbanne, France
3	Institut Charles Gerhardt Montpellier, UMR 5253 UM CNRS ENSCM, UniversitéMontpellier, Place E. Bataillon, Montpellier cedex 05, 34095, France
4	Institut Laue Langevin, BP 156, 38042 Grenoble, France
5	Institut Charles Gerhardt Montpellier, UMR 5253 CNRS UM ENSCM UM1, Ecole Nationale Superieure de Chimie Montpellier, 8 ́rue de l’Ecole Normale, cedex 05, 34296, France
6	Novosibirsk State University, Faculty of Natural Sciences, Department of Physical Chemistry, Pirogova Street 2, Novosibirsk 630090, Russia

Funding (2)

1	Russian Foundation for Basic Research	14-03-91333
2	French University Institute

A combination of experimental (quasi-elastic neutron scattering and 2H NMR) and computational (molecular dynamics) tools was used to uncover the molecular mobility of benzene trapped inside the flexible channel-type MIL-53 (Cr3+) MOF. This material was shown to undergo a contraction of the structure upon benzene adsorption with the formation of a narrow pore phase with a smaller aperture. This confinement was found to strongly influence the dynamics of the guest: benzene diffuses in a region centered in the middle of the pore by a 1D-jump translational mechanism along the tunnel ruled by the presence of the μ2-OH groups present at the MOF pore wall. This translational diffusion is combined with a fast uniaxial rotational motion around the C6-axis. Any other rotational motion that involves the tumbling of the phenyl rings about the channel axis is much less probable due to a high activation energy barrier (49 kJ mol–1). In this way benzene can be pictured as a rotating disc that diffuses rapidly through the central part of the channel by short jumps between neighboring low energy basins located in the vicinity of the μ2-OH groups of the MIL-53 channels.

Kolokolov D.I. , Jobic H. , Rives S. , Yot P.G. , Ollivier J. , Trens P. , Stepanov A.G. , Maurin G.
Diffusion of Benzene in the Breathing Metal–Organic Framework MIL-53(Cr): A Joint Experimental–Computational Investigation
The Journal of Physical Chemistry C. 2015. V.119. N15. P.8217-8225. DOI: 10.1021/acs.jpcc.5b01465 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Feb 12, 2015
Accepted:	Mar 25, 2015
Published online:	Mar 30, 2015
Published print:	Apr 16, 2015

Web of science:	WOS:000353249500030
Scopus:	2-s2.0-84928041179
Elibrary:	24023601
Chemical Abstracts:	2015:552781
Chemical Abstracts (print):	162:533005
OpenAlex:	W2326066359

DB	Citing
Web of science	40
Scopus	40
Elibrary	37
OpenAlex	38