Probing the Hydrogen Equilibrium and Kinetics in Zeolite Iimidazolate Frameworks via Molecular Dynamics and Quasi-Elastic Neutron Scattering Experiments | Sciact - CRIS-system of Boreskov Institute of Catalysis

Probing the Hydrogen Equilibrium and Kinetics in Zeolite Iimidazolate Frameworks via Molecular Dynamics and Quasi-Elastic Neutron Scattering Experiments Full article

Journal

Journal of Chemical Physics
ISSN: 0021-9606 , E-ISSN: 1089-7690

Output data

Year: 2013, Volume: 138, Number: 3, Pages: 034706 Pages count : 10 DOI: 10.1063/1.4774375

Tags

Deuterium; Diffusion; Experiments; Hydrogen; Monte Carlo methods; Neutron scattering; Phase equilibria; Quantum theory; Sorption

Authors

Pantatosaki Evangelia ¹ , Jobic Hervé ² , Kolokolov Daniil I. ^2,3 , Karmakar Shilpi ⁴ , Biniwale Rajesh ¹ , Papadopoulos George K. ¹

Affiliations

1	School of Chemical Engineering, National Technical University of Athens, 9 Heroon Polytechniou Street, 157 80 Athens, Greece
2	Institut de Recherches sur la Catalyse et l’Environment de Lyon, Université Lyon1, CNRS, 2 avenue Albert Einstein, 69626 Villeurbanne, France
3	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
4	National Environmental Engineering Research Institute, Council of Scientific and Industrial Research, Environmental Materials Unit, Nehru Marg, Nagpur, Maharashtra 440020, India

Funding (1)

European Commission

233502 FP7-NMP-2008-EU-India-2 AMCOS

The problem of simulating processes involving equilibria and dynamics of guest sorbates within zeolitic imidazolate frameworks (ZIF) by means of molecular dynamics (MD) computer experiments is of growing importance because of the promising role of ZIFs as molecular "traps" for clean energy applications. A key issue for validating such an atomistic modeling attempt is the possibility of comparing the MD results, with real experiments being able to capture analogous space and time scales to the ones pertained to the computer experiments. In the present study, this prerequisite is fulfilled through the quasi-elastic neutron scattering technique (QENS) for measuring self-diffusivity, by elaborating the incoherent scattering signal of hydrogen nuclei. QENS and MD experiments were performed in parallel to probe the hydrogen motion, for the first time in ZIF members. The predicted and measured dynamics behaviors show considerable concentration variation of the hydrogen self-diffusion coefficient in the two topologically different ZIF pore networks of this study, the ZIF-3 and ZIF-8. Modeling options such as the flexibility of the entire matrix versus a rigid framework version, the mobility of the imidazolate ligand, and the inclusion of quantum mechanical effects in the potential functions were examined in detail for the sorption thermodynamics and kinetics of hydrogen and also of deuterium, by employing MD combined with Widom averaging towards studying phase equilibria. The latter methodology ensures a rigorous and efficient way for post-processing the dynamics trajectory, thereby avoiding stochastic moves via Monte Carlo simulation, over the large number of configurational degrees of freedom a nonrigid framework encompasses.

Pantatosaki E. , Jobic H. , Kolokolov D.I. , Karmakar S. , Biniwale R. , Papadopoulos G.K.
Probing the Hydrogen Equilibrium and Kinetics in Zeolite Iimidazolate Frameworks via Molecular Dynamics and Quasi-Elastic Neutron Scattering Experiments
Journal of Chemical Physics. 2013. V.138. N3. P.034706. DOI: 10.1063/1.4774375 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Oct 6, 2012
Accepted:	Dec 12, 2012
Published online:	Jan 17, 2013
Published print:	Jan 21, 2013

Web of science:	WOS:000313671700033
Scopus:	2-s2.0-84872818581
Elibrary:	20423201
Chemical Abstracts:	2013:97838
Chemical Abstracts (print):	158:254715
OpenAlex:	W2093770411

DB	Citing
Web of science	35
Scopus	35
Elibrary	35
OpenAlex	39