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

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 ^[4]; Hartmann, Martin ^[3]; ^[2]; Kärger, Jörg ^[4]

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

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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: Alexander von Humboldt Foundation; German Science Foundation (DFG); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008688

OSTI ID:: 1474411

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

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Transport ofn-paraffins in zeolite T Magalhães, Fernão D.; Laurence, Robert L.; Conner, William Curtis AIChE Journal, Vol. 42, Issue 1 https://doi.org/10.1002/aic.690420108	journal	January 1996
Understanding the Window Effect in Zeolite Catalysis Dubbeldam, David; Calero, Sofía; Maesen, Theo L. M. Angewandte Chemie, Vol. 115, Issue 31 https://doi.org/10.1002/ange.200351110	journal	August 2003
Accelerated Diffusion of Long-Chain Alkanes between Nanosized Cavities Jobic, Hervé; Méthivier, Alain; Ehlers, Georg Angewandte Chemie International Edition, Vol. 43, Issue 3 https://doi.org/10.1002/anie.200352691	journal	January 2004
Extreme Flexibility in a Zeolitic Imidazolate Framework: Porous to Dense Phase Transition in Desolvated ZIF-4 Wharmby, Michael T.; Henke, Sebastian; Bennett, Thomas D. Angewandte Chemie International Edition, Vol. 54, Issue 22 https://doi.org/10.1002/anie.201410167	journal	April 2015
In-Depth Study of Mass Transfer in Nanoporous Materials by Micro-Imaging Hibbe, Florian; van Baten, Jasper M.; Krishna, Rajamani Chemie Ingenieur Technik, Vol. 83, Issue 12 https://doi.org/10.1002/cite.201100167	journal	October 2011
Scale-up of the Synthesis of Zeolitic Imidazolate Framework ZIF-4 Hovestadt, Maximilian; Vargas Schmitz, Jürgen; Weissenberger, Tobias Chemie Ingenieur Technik, Vol. 89, Issue 10 https://doi.org/10.1002/cite.201700105	journal	September 2017
Intracrystalline Transport Resistances in Nanoporous Zeolite X Feldhoff, Armin; Caro, Jürgen; Jobic, Hervé ChemPhysChem, Vol. 10, Issue 14 https://doi.org/10.1002/cphc.200900279	journal	October 2009
Transport Phenomena in Nanoporous Materials Kärger, Jörg ChemPhysChem, Vol. 16, Issue 1 https://doi.org/10.1002/cphc.201402340	journal	August 2014
Diffusion of normal paraffins in zeolite T Occurrence of window effect Gorring, R. Journal of Catalysis, Vol. 31, Issue 1 https://doi.org/10.1016/0021-9517(73)90265-0	journal	October 1973
The window effect in zeolitic diffusion Ruthven, Douglas M. Microporous and Mesoporous Materials, Vol. 96, Issue 1-3 https://doi.org/10.1016/j.micromeso.2006.07.005	journal	November 2006
Analysis of thermal effects in infrared and interference microscopy: n-Butane-5A and methanol–ferrierite systems Heinke, L.; Chmelik, C.; Kortunov, P. Microporous and Mesoporous Materials, Vol. 104, Issue 1-3 https://doi.org/10.1016/j.micromeso.2006.11.017	journal	August 2007
Algorithms and tools for high-throughput geometry-based analysis of crystalline porous materials Willems, Thomas F.; Rycroft, Chris H.; Kazi, Michaeel Microporous and Mesoporous Materials, Vol. 149, Issue 1 https://doi.org/10.1016/j.micromeso.2011.08.020	journal	February 2012
The predictive power of classical transition state theory revealed in diffusion studies with MOF ZIF-8 Chmelik, Christian; Kärger, Jörg Microporous and Mesoporous Materials, Vol. 225 https://doi.org/10.1016/j.micromeso.2015.11.051	journal	May 2016
Comparative QENS and PFG NMR diffusion studies of water in zeolite NaCaA Paoli, H.; Méthivier, A.; Jobic, H. Microporous and Mesoporous Materials, Vol. 55, Issue 2 https://doi.org/10.1016/s1387-1811(02)00399-2	journal	September 2002
Exploiting Framework Flexibility of a Metal–Organic Framework for Selective Adsorption of Styrene over Ethylbenzene Mukherjee, Soumya; Joarder, Biplab; Desai, Aamod V. Inorganic Chemistry, Vol. 54, Issue 9 https://doi.org/10.1021/acs.inorgchem.5b00206	journal	April 2015
Commensurate Adsorption of Hydrocarbons and Alcohols in Microporous Metal Organic Frameworks Wu, Haohan; Gong, Qihan; Olson, David H. Chemical Reviews, Vol. 112, Issue 2 https://doi.org/10.1021/cr200216x	journal	September 2011
DREIDING: a generic force field for molecular simulations Mayo, Stephen L.; Olafson, Barry D.; Goddard, William A. The Journal of Physical Chemistry, Vol. 94, Issue 26, p. 8897-8909 https://doi.org/10.1021/j100389a010	journal	December 1990
Diffusion Anomaly as a Function of Molecular Length of Linear Molecules: Levitation Effect Ghorai, Pradip Kr.; Yashonath, Subramanian; Demontis, Pierfranco Journal of the American Chemical Society, Vol. 125, Issue 23 https://doi.org/10.1021/ja028534i	journal	June 2003
On the Flexibility of Metal–Organic Frameworks Sarkisov, Lev; Martin, Richard L.; Haranczyk, Maciej Journal of the American Chemical Society, Vol. 136, Issue 6 https://doi.org/10.1021/ja411673b	journal	January 2014
Computer Simulation of Incommensurate Diffusion in Zeolites: Understanding Window Effects Dubbeldam, David; Smit, Berend The Journal of Physical Chemistry B, Vol. 107, Issue 44 https://doi.org/10.1021/jp035200m	journal	November 2003
Levitation Effect: Distinguishing Anomalous from Linear Regime of Guests Sorbed in Zeolites through the Decay of Intermediate Scattering Function and Wavevector Dependence of Self-Diffusivity Ghorai, Pradip Kr.; Yashonath, S. The Journal of Physical Chemistry B, Vol. 109, Issue 9 https://doi.org/10.1021/jp046121t	journal	March 2005
Molecular Cage Nestling in the Liquid-Phase Adsorption of n -Alkanes in 5A Zeolite Daems, Inge; Baron, Gino V.; Punnathanam, Sudeep The Journal of Physical Chemistry C, Vol. 111, Issue 5 https://doi.org/10.1021/jp0668145	journal	February 2007
Parallel Tempering Simulations of Liquid-Phase Adsorption of n -Alkane Mixtures in Zeolite LTA-5A Punnathanam, Sudeep; Denayer, Joeri F. M.; Daems, Inge The Journal of Physical Chemistry C, Vol. 115, Issue 3 https://doi.org/10.1021/jp110627g	journal	December 2010
Uncommon Synergy between Adsorption and Diffusion of Hexane Isomer Mixtures in MFI Zeolite Induced by Configurational Entropy Effects Titze, Tobias; Chmelik, Christian; Kärger, Jörg The Journal of Physical Chemistry C, Vol. 118, Issue 5 https://doi.org/10.1021/jp412526t	journal	January 2014
Molecular Dynamics Simulations of Alkanes in the Zeolite Silicalite: Evidence for Resonant Diffusion Effects Runnebaum, Ron C.; Maginn, Edward J. The Journal of Physical Chemistry B, Vol. 101, Issue 33 https://doi.org/10.1021/jp970774a	journal	August 1997
Transferable Potentials for Phase Equilibria. 1. United-Atom Description of n-Alkanes Martin, Marcus G.; Siepmann, J. Ilja https://doi.org/10.1021/jp972543+		March 1998
Resonant Diffusion of Normal Alkanes in Zeolites: Effect of the Zeolite Structure and Alkane Molecule Vibrations Tsekov, Roumen; Smirniotis, Panagiotis G. The Journal of Physical Chemistry B, Vol. 102, Issue 47 https://doi.org/10.1021/jp9819644	journal	November 1998
Uphill diffusion and overshooting in the adsorption of binary mixtures in nanoporous solids Lauerer, Alexander; Binder, Tomas; Chmelik, Christian Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8697	journal	July 2015
Microimaging of transient guest profiles to monitor mass transfer in nanoporous materials Kärger, Jörg; Binder, Tomas; Chmelik, Christian Nature Materials, Vol. 13, Issue 4 https://doi.org/10.1038/nmat3917	journal	March 2014
Diffusion in nanoporous materials: fundamental principles, insights and challenges Kärger, Jörg; Ruthven, Douglas M. New Journal of Chemistry, Vol. 40, Issue 5 https://doi.org/10.1039/c5nj02836a	journal	January 2016
Levitation effect in zeolites: Quasielastic neutron scattering and molecular dynamics study of pentane isomers in zeolite NaY Borah, Bhaskar J.; Jobic, H.; Yashonath, S. The Journal of Chemical Physics, Vol. 132, Issue 14 https://doi.org/10.1063/1.3367894	journal	April 2010
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks Park, K. S.; Ni, Z.; Cote, A. P. Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191 https://doi.org/10.1073/pnas.0602439103	journal	June 2006
A molecular simulation study of commensurate–incommensurate adsorption of n -alkanes in cobalt formate frameworks Krishna, R.; van Baten, J. M. Molecular Simulation, Vol. 35, Issue 12-13 https://doi.org/10.1080/08927020902744672	journal	October 2009
Computational structure characterisation tools in application to ordered and disordered porous materials Sarkisov, Lev; Harrison, Alex Molecular Simulation, Vol. 37, Issue 15 https://doi.org/10.1080/08927022.2011.592832	journal	December 2011
RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials Dubbeldam, David; Calero, Sofía; Ellis, Donald E. Molecular Simulation, Vol. 42, Issue 2 https://doi.org/10.1080/08927022.2015.1010082	journal	February 2015
Flexibility of zeolitic imidazolate framework structures studied by neutron total scattering and the reverse Monte Carlo method Beake, E. O. R.; Dove, M. T.; Phillips, A. E. Journal of Physics: Condensed Matter, Vol. 25, Issue 39 https://doi.org/10.1088/0953-8984/25/39/395403	journal	September 2013
Incommensurate Diffusion in Confined Systems Dubbeldam, D.; Calero, S.; Maesen, T. L. M. Physical Review Letters, Vol. 90, Issue 24 https://doi.org/10.1103/physrevlett.90.245901	journal	June 2003
Accelerated Diffusion of Long-Chain Alkanes between Nanosized Cavities Jobic, Hervé; Méthivier, Alain; Ehlers, Georg Angewandte Chemie, Vol. 116, Issue 3 https://doi.org/10.1002/ange.200352691	journal	January 2004
Understanding the Window Effect in Zeolite Catalysis Dubbeldam, David; Calero, Sofía; Maesen, Theo L. M. Angewandte Chemie International Edition, Vol. 42, Issue 31 https://doi.org/10.1002/anie.200351110	journal	August 2003
Diffusivities of n-Alkanes in 5A Zeolite Measured by Neutron Spin Echo, Pulsed-Field Gradient NMR, and Zero Length Column Techniques Jobic, Hervé; Kärger, Jörg; Krause, Cordula Adsorption, Vol. 11, Issue S1 https://doi.org/10.1007/s10450-005-5958-8	journal	July 2005
Diffusion of n-paraffins in offretite-erionite type zeolites Cavalcante, Célio L.; Eić, Mladen; Ruthven, Douglas M. Zeolites, Vol. 15, Issue 4 https://doi.org/10.1016/0144-2449(94)00061-V	journal	May 1995
The generalized Maxwell–Stefan model for diffusion in zeolites: Kapteijn, F.; Moulijn, J. A.; Krishna, R. Chemical Engineering Science, Vol. 55, Issue 15 https://doi.org/10.1016/S0009-2509(99)00564-3	journal	August 2000
Comparative QENS and PFG NMR diffusion studies of water in zeolite NaCaA Paoli, H.; Méthivier, A.; Jobic, H. Microporous and Mesoporous Materials, Vol. 55, Issue 2 https://doi.org/10.1016/S1387-1811(02)00399-2	journal	September 2002
Diffusion of pentane isomers in faujasite-type zeolites : NMR and molecular dynamics study Rajappa, Chitra; Krause, C.; Borah, B. J. Microporous and Mesoporous Materials, Vol. 171 https://doi.org/10.1016/j.micromeso.2012.12.036	journal	May 2013
Adsorptive Separation of Olefin/Paraffin Mixtures with ZIF-4 Hartmann, Martin; Böhme, Ulrike; Hovestadt, Maximilian Langmuir, Vol. 31, Issue 45 https://doi.org/10.1021/acs.langmuir.5b02907	journal	November 2015
Selective Adsorption of Water from Mixtures with 1-Alcohols by Exploitation of Molecular Packing Effects in CuBTC Gutiérrez-Sevillano, Juan José; Calero, Sofia; Krishna, Rajamani The Journal of Physical Chemistry C, Vol. 119, Issue 7 https://doi.org/10.1021/jp512853w	journal	February 2015
The first example of commensurate adsorption of atomic gas in a MOF and effective separation of xenon from other noble gases Wang, Hao; Yao, Kexin; Zhang, Zhijuan Chemical Science, Vol. 5, Issue 2, p. 620-624 https://doi.org/10.1039/C3SC52348A	journal	January 2014
Flexible metal–organic frameworks Schneemann, A.; Bon, V.; Schwedler, I. Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS00101J	journal	January 2014
Diffusion in nanoporous materials: fundamental principles, insights and challenges Kärger, Jörg; Ruthven, Douglas M. New Journal of Chemistry, Vol. 40, Issue 5 https://doi.org/10.1039/C5NJ02836A	journal	January 2016
Commensurate–incommensurate adsorption and diffusion in ordered crystalline microporous materials Krishna, Rajamani; van Baten, Jasper M. Physical Chemistry Chemical Physics, Vol. 19, Issue 31 https://doi.org/10.1039/C7CP04101B	journal	January 2017
Mass Transfer in a Nanoscale Material Enhanced by an Opposing Flux Chmelik, Christian; Bux, Helge; Caro, Jürgen Physical Review Letters, Vol. 104, Issue 8 https://doi.org/10.1103/PhysRevLett.104.085902	journal	February 2010
Incommensurate Diffusion in Confined Systems Dubbeldam, D.; Calero, S.; Maesen, T. L. M. Physical Review Letters, Vol. 90, Issue 24 https://doi.org/10.1103/PhysRevLett.90.245901	journal	June 2003

Cited By (2)

New insights into the breathing phenomenon in ZIF-4 Gandara-Loe, Jesus; Missyul, Alexander; Fauth, François Journal of Materials Chemistry A, Vol. 7, Issue 24 https://doi.org/10.1039/c8ta09713e	journal	January 2019
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

Similar Records

Molecular Simulations of the Chain Length Dependent Adsorption of C7‐C14 n‐Alkanes in ZIF‐8

Journal Article · Tue Aug 08 20:00:00 EDT 2023 · Chemie-Ingenieur-Technik · OSTI ID:2575872

Sorption and Transport of Vapors in ZIF-11: Adsorption, Diffusion, and Linker Flexibility

Journal Article · Mon Apr 29 20:00:00 EDT 2019 · Journal of Physical Chemistry. C · OSTI ID:1527278

Related Subjects

32 GCMC simulation
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ZIF-4
commensurate/incommensurate adsorption
n-alkanes
transport diffusivity

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

Citation Formats

References (52)

Cited By (2)

Similar Records

Related Subjects