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 |
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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 |
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Affiliations |
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Funding (2)
1 | Russian Foundation for Basic Research | 14-03-91333 |
2 | French University Institute |
Abstract:
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.
Cite:
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
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
Dates:
Submitted: | Feb 12, 2015 |
Accepted: | Mar 25, 2015 |
Published online: | Mar 30, 2015 |
Published print: | Apr 16, 2015 |
Identifiers:
Web of science: | WOS:000353249500030 |
Scopus: | 2-s2.0-84928041179 |
Elibrary: | 24023601 |
Chemical Abstracts: | 2015:552781 |
Chemical Abstracts (print): | 162:533005 |
OpenAlex: | W2326066359 |