Adsorption and Diffusion of H2 in the MOF Type Systems MIL-47(V) and MIL-53(Cr): A Combination of Microcalorimetry and QENS Experiments with Molecular Simulations | Sciact - CRIS-system of Boreskov Institute of Catalysis

Adsorption and Diffusion of H2 in the MOF Type Systems MIL-47(V) and MIL-53(Cr): A Combination of Microcalorimetry and QENS Experiments with Molecular Simulations Full article

Journal

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

Output data

Year: 2009, Volume: 113, Number: 18, Pages: 7802-7812 Pages count : 11 DOI: 10.1021/jp811190g

Tags

METAL-ORGANIC FRAMEWORK; ELASTIC NEUTRON-SCATTERING; WALLED CARBON NANOTUBES; HYDROGEN ADSORPTION; GAS-ADSORPTION; LIGHT GASES; STORAGE; DYNAMICS; TRANSPORT; SITES

Authors

Salles Fabrice ¹ , Kolokolov Daniil I. ² , Jobic Herve ² , Maurin Guillaume ¹ , Llewellyn Philip L. ³ , Devic Thomas ⁴ , Serre Christian ⁴ , Ferey Gerard ⁴

Affiliations

1	Institut Charles Gerhardt Montpellier, UMR CNRS 5253, UM2, ENSCM, Place E. Bataillon, 34095 Montpellier Cedex 05, France
2	Université Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de Recherches sur la Catalyse et l’Environnement de LYON, 2. Av. A. Einstein, F-69626 Villeurbanne, France
3	Laboratoire Chimie Provence, Universités d’Aix-Marseille I,II et III-CNRS, UMR 6264, Centre de Saint Jérôme, 13397 Marseille, France
4	Institut Lavoisier, UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 78035 Versailles Cedex, France

Quasi-elastic neutron scattering measurements are combined with molecular dynamics simulations to determine the self-diffusivity (Ds) profile of hydrogen in the metal organic framework materials MIL-47(V) and MIL-53(Cr) (MIL, Materials Institut Lavoisier) as a function of loading. Experimentally, a sudden increase in Ds for H2 at low loading (≤1 H2/unit cell) was observed with values at least two orders of magnitude higher than in zeolites. This unusual behavior has been denoted as “super-mobility”. Here, two different force fields available in the literature to represent the H2/H2 and H2/MOF framework interactions have been considered to capture such experimental findings via molecular dynamics simulations. We have shown that (i) a similar magnitude of the energetic contribution for the H2/H2 and H2/MOF framework interactions and (ii) a smoothness of the potential energy surfaces are required in order to match the supermobility of H2 at low loading. The diffusion mechanism at the microscopic scale was successfully simulated in both materials and described in terms of the chemical features of the MIL framework, i.e., the presence or absence of the μ2 hydroxyl group. It appears that a one-dimensional (1D) diffusion along the z axis and purely random three-dimensional (3D) diffusion processes are observed for MIL-53(Cr) and MIL-47(V), respectively. The adsorption properties were then simulated using the different force fields initially fitted to the diffusion results and compared to manometry measurements. Finally, the comparison of diffusion and adsorption results for the different force fields leads us to choose the best compromise to describe both dynamic and thermodynamic properties.

Salles F. , Kolokolov D.I. , Jobic H. , Maurin G. , Llewellyn P.L. , Devic T. , Serre C. , Ferey G.
Adsorption and Diffusion of H2 in the MOF Type Systems MIL-47(V) and MIL-53(Cr): A Combination of Microcalorimetry and QENS Experiments with Molecular Simulations
The Journal of Physical Chemistry C. 2009. V.113. N18. P.7802-7812. DOI: 10.1021/jp811190g WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Dec 18, 2008
Accepted:	Feb 28, 2009
Published online:	Apr 3, 2009
Published print:	May 7, 2009

Web of science:	WOS:000265687600050
Scopus:	2-s2.0-65549083150
Elibrary:	19489721
Chemical Abstracts:	2009:405650
Chemical Abstracts (print):	150:481533
OpenAlex:	W2092448491

DB	Citing
Web of science	85
Scopus	84
Elibrary	55
OpenAlex	91