Probing the Dynamics of CO2 and CH4 within the Porous Zirconium Terephthalate UiO-66(Zr): A Synergic Combination of Neutron Scattering Measurements and Molecular Simulations | Sciact - CRIS-system of Boreskov Institute of Catalysis

Probing the Dynamics of CO2 and CH4 within the Porous Zirconium Terephthalate UiO-66(Zr): A Synergic Combination of Neutron Scattering Measurements and Molecular Simulations Full article

Journal

Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765

Output data

Year: 2011, Volume: 17, Number: 32, Pages: 8882-8889 Pages count : 8 DOI: 10.1002/chem.201003596

Tags

diffusion, metal-organic frameworks, molecular dynamics, neutron diffraction

Authors

Yang Qingyuan ^1,4 , Jobic Herve ² , Salles Fabrice ¹ , Kolokolov Daniil ^2,5 , Guillerm Vincent ³ , Serre Christian ³ , Maurin Guillaume ¹

Affiliations

1	Institut Charles Gerhardt Montpellier (UMR 5253) Universite Montpellier II, CNRS, ENSCM, Place E. Bataillon, 34095 Montpellier CEDEX 05 (France)
2	Institut de Recherches sur la Catalyse et l’Environnement de Lyon, Universite de Lyon, CNRS, 2. Av. A. Einstein, 69626 Villeurbanne (France)
3	Institut Lavoisier, UMR CNRS 8180, Universite de Versailles, 78035 Versailles (France)
4	Department of Chemical Engineering, Beijing University of Chemical Technology, Beijing (P. R. China)
5	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090 (Russia)

Funding (1)

European Commission

228862 FP7-NMP-2008-LARGE-2 MACADEMIA

Quasi-elastic neutron scattering (QENS) measurements combined with molecular dynamics (MD) simulations were conducted to deeply understand the concentration dependence of the self- and transport diffusivities of CH4 and CO2, respectively, in the humidity-resistant metal–organic framework UiO-66(Zr). The QENS measurements show that the self-diffusivity profile for CH4 exhibits a maximum, while the transport diffusivity for CO2 increases continuously at the loadings explored in this study. Our MD simulations can reproduce fairly well both the magnitude and the concentration dependence of each measured diffusivity. The flexibility of the framework implemented by deriving a new forcefield for UiO-66(Zr) has a significant impact on the diffusivity of the two species. Methane diffuses faster than CO2 over a broad range of loading, and this is in contrast to zeolites with narrow windows, for which opposite trends were observed. Further analysis of the MD trajectories indicates that the global microscopic diffusion mechanism involves a combination of intracage motions and jump sequences between tetrahedral and octahedral cages.

Yang Q. , Jobic H. , Salles F. , Kolokolov D. , Guillerm V. , Serre C. , Maurin G.
Probing the Dynamics of CO2 and CH4 within the Porous Zirconium Terephthalate UiO-66(Zr): A Synergic Combination of Neutron Scattering Measurements and Molecular Simulations
Chemistry - A European Journal. 2011. V.17. N32. P.8882-8889. DOI: 10.1002/chem.201003596 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Dec 13, 2010
Accepted:	Jun 28, 2011
Published online:	Jun 28, 2011
Published print:	Aug 1, 2011

Web of science:	WOS:000294704700017
Scopus:	2-s2.0-79960417076
Elibrary:	17002411
Chemical Abstracts:	2011:809195
Chemical Abstracts (print):	155:417886
OpenAlex:	W2138953685

DB	Citing
Web of science	134
Scopus	142
Elibrary	136
OpenAlex	147