Probing the Guest-Mediated Structural Mobility in the UiO-66(Zr) Framework by 2H NMR Spectroscopy | Sciact - CRIS-system of Boreskov Institute of Catalysis

Probing the Guest-Mediated Structural Mobility in the UiO-66(Zr) Framework by 2H NMR Spectroscopy Full article

Journal

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

Output data

Year: 2017, Volume: 121, Number: 21, Pages: 11593-11600 Pages count : 8 DOI: 10.1021/acs.jpcc.7b03259

Tags

Anisotropy; Benzene; Chemical activation; Frequency estimation; Nuclear magnetic resonance spectroscopy

Authors

Khudozhitkov Alexander E. ^1,2 , Jobic Hervé ³ , Kolokolov Daniil I. ^1,2 , Freude Dieter ⁴ , Haase Jürgen ⁴ , Stepanov Alexander G. ^1,2

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
3	Institut de Recherches sur la Catalyse et l’Environnement de Lyon, CNRS, Universitéde Lyon, 2. Av. A. Einstein, 69626 Villeurbanne, France
4	Fakultat fur Physik und Geowissenschaften, Universitat Leipzig, Linne ̈ strasse 5, 04103 Leipzig, Germany

Funding (2)

1	German Research Foundation	HA 1893/16
2	Federal Agency for Scientific Organizations	0303-2016-0003

The solid-state 2H NMR technique (analysis of both the spectrum line shape and the spin–lattice relaxation) was used to probe both slow and fast dynamical modes of the phenylene fragments of terephthalate linkers of the UiO-66(Zr) framework affected by the presence of benzene guest in the pores of the material. Such approach allowed us to probe different motions within a broad range of time scale, 10–3–10–11 s. The internal dynamics in the UiO-66(Zr) framework is represented by torsional motions of the phenylene fragment of the linker including 2-site 180° flips (π-flips) of the plane of the phenylene ring and its restricted librations. In the presence of benzene loaded in the MOF pores the rate of π-flips decreases essentially and the activation barrier for this motion increases. The activation barrier has been found to increase almost in a linear fashion on benzene loading. Such observation is surprisingly unique among other MOFs with mobile linkers, like MIL-53(Al) or MOF-5. The fast librational motion occurs on a scale of ∼1010 Hz and shows no notable dependence on the guest loading. It has been established that anisotropy of T1 relaxation of the 2H NMR powder pattern of the phenylene fragments is especially sensitive to the librational motion when this motion is in a range of 107–1011 Hz. Within this range of libration frequencies, analysis of the anisotropic spin–lattice (T1) relaxation allows quantitative estimation of the rate of librational motion.

Khudozhitkov A.E. , Jobic H. , Kolokolov D.I. , Freude D. , Haase J. , Stepanov A.G.
Probing the Guest-Mediated Structural Mobility in the UiO-66(Zr) Framework by 2H NMR Spectroscopy
The Journal of Physical Chemistry C. 2017. V.121. N21. P.11593-11600. DOI: 10.1021/acs.jpcc.7b03259 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Apr 6, 2017
Accepted:	May 4, 2017
Published online:	May 16, 2017
Published print:	Jun 1, 2017

Web of science:	WOS:000402775200064
Scopus:	2-s2.0-85020689692
Elibrary:	29748712
Chemical Abstracts:	2017:713032
Chemical Abstracts (print):	166:525013
OpenAlex:	W2611402444

DB	Citing
Web of science	21
Scopus	21
Elibrary	18
OpenAlex	20