Anomaly in the Chain Length Dependence of n-Alkane Diffusion in ZIF-4 Metal-Organic Frameworks

Hwang, Seungtaik; Gopalan, Arun; Hovestadt, Maximilian; Piepenbreier, Frank; Chmelik, Christian; Hartmann, Martin; Snurr, Randall; Kärger, Jörg

doi:10.3390/molecules23030668

Title: Anomaly in the Chain Length Dependence of n-Alkane Diffusion in ZIF-4 Metal-Organic Frameworks

Journal Article · Thu Mar 15 00:00:00 EDT 2018 · Molecules

DOI:https://doi.org/10.3390/molecules23030668· OSTI ID:1474411

Hwang, Seungtaik ^[1]; Gopalan, Arun ^[2]; Hovestadt, Maximilian ^[3]; Piepenbreier, Frank ^[3]; Chmelik, Christian ^[1]; Hartmann, Martin ^[3];

^[2]; Kärger, Jörg ^[1]

Univ. Leipzig, Leipzig (Germany). Faculty of Physics and Earth Sciences
Northwestern Univ., Evanston, IL (United States). Dept. of Chemical and Biological Engineering
Friedrich-Alexander-Univ. Erlangen-Nürnberg, Erlangen (Germany). Erlangen Catalysis Resource Center

Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here in this paper, we present such data, obtained by monitoring the chain length dependence of the uptake of n-alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n-butane was observed, followed by an increase for n-pentane, and another decrease for n-hexane. This observation was confirmed by uptake measurements with n-butane/n-pentane mixtures, which yield faster uptake of n-pentane. Further evidence is provided by the observation of overshooting effects, i.e. by transient n-pentane concentrations exceeding the (eventually attained) equilibrium value. Accompanying grand canonical Monte Carlo simulations reveal, for the larger n-alkanes, significant differences between the adsorbed and gas phase molecular configurations, indicating strong confinement effects within ZIF-4, which, with increasing chain length, may be expected to give rise to configurational shifts facilitating molecular propagation at particular chain lengths.

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Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; German Science Foundation (DFG); Alexander von Humboldt Foundation

Grant/Contract Number:: SC0008688; HA 1893/17-1; KA 953/35-1; FG02-17ER16362

OSTI ID:: 1474411

Journal Information:: Molecules, Vol. 23, Issue 3; ISSN 1420-3049

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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Diffusion processes in a poly-crystalline zeolitic material: A molecular dynamics study Thomas, Angela Mary; Subramanian, Yashonath The Journal of Chemical Physics, Vol. 149, Issue 6 https://doi.org/10.1063/1.5037146	journal	August 2018

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Title: Anomaly in the Chain Length Dependence of n-Alkane Diffusion in ZIF-4 Metal-Organic Frameworks

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