Revisiting Anisotropic Diffusion of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc)
Abstract
The diffusion of gases confined in nanoporous materials underpins membrane and adsorption-based gas separations, yet relatively few measurements of diffusion coefficients in the promising class of materials, metal–organic frameworks (MOFs), have been reported to date. Recently we reported self-diffusion coefficients for 13CO2 in the MOF Zn2(dobpdc) (dobpdc4– = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) which has one-dimensional channels with a diameter of approximately 2 nm [Forse, A. C.; J. Am. Chem. Soc. 2018, 140, 1663-1673]. By analyzing the evolution of the residual 13C chemical shift anisotropy line shape at different gradient strengths, we obtained self-diffusion coefficients both along (D∥) and between (D⊥) the one-dimensional MOF channels. The observation of nonzero D⊥ was unexpected based on the single crystal X-ray diffraction structure and flexible lattice molecular dynamics simulations, and we proposed that structural defects may be responsible for self-diffusion between the MOF channels. In this paper we revisit this analysis and show that homogeneous line broadening must be taken into account to obtain accurate values for D⊥. In the presence of homogeneous line broadening, intensity at a particular NMR frequency represents signal from crystals with a range of orientations relative to the applied magnetic field and magnetic gradient field. To quantify these effects, we perform spectralmore »
- Authors:
-
- Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering. Berkeley Energy and Climate Inst.
- ABQMR, Inc., Albuquerque, NM (United States)
- RWTH Aachen Univ. (Germany). Inst. of Technical and Macromolecular Chemistry (ITMC)
- Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1464169
- Grant/Contract Number:
- AC02-05CH11231; SC0001015
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 27; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Forse, Alexander C., Altobelli, Stephen A., Benders, Stefan, Conradi, Mark S., and Reimer, Jeffrey A. Revisiting Anisotropic Diffusion of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc). United States: N. p., 2018.
Web. doi:10.1021/acs.jpcc.8b02843.
Forse, Alexander C., Altobelli, Stephen A., Benders, Stefan, Conradi, Mark S., & Reimer, Jeffrey A. Revisiting Anisotropic Diffusion of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc). United States. https://doi.org/10.1021/acs.jpcc.8b02843
Forse, Alexander C., Altobelli, Stephen A., Benders, Stefan, Conradi, Mark S., and Reimer, Jeffrey A. Mon .
"Revisiting Anisotropic Diffusion of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc)". United States. https://doi.org/10.1021/acs.jpcc.8b02843. https://www.osti.gov/servlets/purl/1464169.
@article{osti_1464169,
title = {Revisiting Anisotropic Diffusion of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc)},
author = {Forse, Alexander C. and Altobelli, Stephen A. and Benders, Stefan and Conradi, Mark S. and Reimer, Jeffrey A.},
abstractNote = {The diffusion of gases confined in nanoporous materials underpins membrane and adsorption-based gas separations, yet relatively few measurements of diffusion coefficients in the promising class of materials, metal–organic frameworks (MOFs), have been reported to date. Recently we reported self-diffusion coefficients for 13CO2 in the MOF Zn2(dobpdc) (dobpdc4– = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) which has one-dimensional channels with a diameter of approximately 2 nm [Forse, A. C.; J. Am. Chem. Soc. 2018, 140, 1663-1673]. By analyzing the evolution of the residual 13C chemical shift anisotropy line shape at different gradient strengths, we obtained self-diffusion coefficients both along (D∥) and between (D⊥) the one-dimensional MOF channels. The observation of nonzero D⊥ was unexpected based on the single crystal X-ray diffraction structure and flexible lattice molecular dynamics simulations, and we proposed that structural defects may be responsible for self-diffusion between the MOF channels. In this paper we revisit this analysis and show that homogeneous line broadening must be taken into account to obtain accurate values for D⊥. In the presence of homogeneous line broadening, intensity at a particular NMR frequency represents signal from crystals with a range of orientations relative to the applied magnetic field and magnetic gradient field. To quantify these effects, we perform spectral simulations that take into account homogeneous broadening and allow improved D⊥ values to be obtained. Finally, our new analysis best supports nonzero D⊥ at all studied dosing pressures and shows that our previous analysis overestimated D⊥.},
doi = {10.1021/acs.jpcc.8b02843},
journal = {Journal of Physical Chemistry. C},
number = 27,
volume = 122,
place = {United States},
year = {Mon Jun 11 00:00:00 EDT 2018},
month = {Mon Jun 11 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Diffusion in Nanoporous Materials
book, April 2012
- Kärger, Jörg; Ruthven, Douglas M.; Theodorou, Doros N.
Cooperative insertion of CO2 in diamine-appended metal-organic frameworks
journal, March 2015
- McDonald, Thomas M.; Mason, Jarad A.; Kong, Xueqian
- Nature, Vol. 519, Issue 7543
A spin transition mechanism for cooperative adsorption in metal–organic frameworks
journal, September 2017
- Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia
- Nature, Vol. 550, Issue 7674
Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites
journal, December 2016
- Yoon, Ji Woong; Chang, Hyunju; Lee, Seung-Joon
- Nature Materials, Vol. 16, Issue 5
Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels
journal, May 2013
- Herm, Z. R.; Wiers, B. M.; Mason, J. A.
- Science, Vol. 340, Issue 6135, p. 960-964
Large-Pore Apertures in a Series of Metal-Organic Frameworks
journal, May 2012
- Deng, H.; Grunder, S.; Cordova, K. E.
- Science, Vol. 336, Issue 6084, p. 1018-1023
Maximizing the right stuff: The trade-off between membrane permeability and selectivity
journal, June 2017
- Park, Ho Bum; Kamcev, Jovan; Robeson, Lloyd M.
- Science, Vol. 356, Issue 6343
Diffusion of Small Molecules in Metal Organic Framework Materials
journal, January 2013
- Canepa, Pieremanuele; Nijem, Nour; Chabal, Yves J.
- Physical Review Letters, Vol. 110, Issue 2
Role of Hydrogen Bonding on Transport of Coadsorbed Gases in Metal–Organic Frameworks Materials
journal, January 2018
- Tan, Kui; Jensen, Stephanie; Zuluaga, Sebastian
- Journal of the American Chemical Society, Vol. 140, Issue 3
Diffusion of CO 2 in Large Crystals of Cu-BTC MOF
journal, September 2016
- Tovar, Trenton M.; Zhao, Junjie; Nunn, William T.
- Journal of the American Chemical Society, Vol. 138, Issue 36
Self and Transport Diffusivity of CO 2 in the Metal−Organic Framework MIL-47(V) Explored by Quasi-elastic Neutron Scattering Experiments and Molecular Dynamics Simulations
journal, December 2009
- Salles, Fabrice; Jobic, Hervé; Devic, Thomas
- ACS Nano, Vol. 4, Issue 1
Experimental Evidence Supported by Simulations of a Very High Diffusion in Metal Organic Framework Materials
journal, June 2008
- Salles, F.; Jobic, H.; Maurin, G.
- Physical Review Letters, Vol. 100, Issue 24
Observation of single-file diffusion in a MOF
journal, January 2016
- Jobic, H.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 26
Intracrystalline Diffusivities and Surface Permeabilities Deduced from Transient Concentration Profiles: Methanol in MOF Manganese Formate
journal, June 2007
- Kortunov, Pavel V.; Heinke, Lars; Arnold, Mirko
- Journal of the American Chemical Society, Vol. 129, Issue 25
Quantitative Predictions of Molecular Diffusion in Binary Mixed-Linker Zeolitic Imidazolate Frameworks Using Molecular Simulations
journal, February 2018
- Verploegh, Ross J.; Wu, Ying; Boulfelfel, Salah Eddine
- The Journal of Physical Chemistry C, Vol. 122, Issue 10
The predictive power of classical transition state theory revealed in diffusion studies with MOF ZIF-8
journal, May 2016
- Chmelik, Christian; Kärger, Jörg
- Microporous and Mesoporous Materials, Vol. 225
NMR Studies on the Diffusion of Hydrocarbons on the Metal-Organic Framework Material MOF-5
journal, March 2006
- Stallmach, Frank; Gröger, Stefan; Künzel, Volker
- Angewandte Chemie International Edition, Vol. 45, Issue 13, p. 2123-2126
13C NMR study of diffusion anisotropy of carbon dioxide adsorbed in nanoporous DMOF-1
journal, March 2015
- Peksa, Mikuláš; Lang, Jan; Stallmach, Frank
- Microporous and Mesoporous Materials, Vol. 205
Relationship between long-range diffusion and diffusion in the ZIF-8 and polymer phases of a mixed-matrix membrane by high field NMR diffusometry
journal, March 2015
- Mueller, Robert; Zhang, Suihua; Zhang, Chen
- Journal of Membrane Science, Vol. 477
Microscopic diffusion of pure and mixed methane and carbon dioxide in ZIF-11 by high field diffusion NMR
journal, August 2017
- Forman, Evan M.; Pimentel, Brian R.; Ziegler, Kirk J.
- Microporous and Mesoporous Materials, Vol. 248
Mixture diffusion of adsorbed organic compounds in metal-organic frameworks as studied by magic-angle spinning pulsed-field gradient nuclear magnetic resonance
journal, April 2011
- Gratz, Marcel; Hertel, Stefan; Wehring, Markus
- New Journal of Physics, Vol. 13, Issue 4
Unexpected Diffusion Anisotropy of Carbon Dioxide in the Metal–Organic Framework Zn 2 (dobpdc)
journal, January 2018
- Forse, Alexander C.; Gonzalez, Miguel I.; Siegelman, Rebecca L.
- Journal of the American Chemical Society, Vol. 140, Issue 5
NMR studies of carbon dioxide and methane self-diffusion in ZIF-8 at elevated gas pressures
journal, September 2012
- Pusch, Anne-Kristin; Splith, Tobias; Moschkowitz, Lutz
- Adsorption, Vol. 18, Issue 5-6
Self-Diffusion Studies in CuBTC by PFG NMR and MD Simulations
journal, May 2010
- Wehring, M.; Gascon, J.; Dubbeldam, D.
- The Journal of Physical Chemistry C, Vol. 114, Issue 23
Molecular Dynamics Phenomena of Water in the Metalorganic Framework MIL-100(Al), as Revealed by Pulsed Field Gradient NMR and Atomistic Simulation
journal, August 2017
- Splith, Tobias; Pantatosaki, Evangelia; Kolokathis, Panagiotis D.
- The Journal of Physical Chemistry C, Vol. 121, Issue 33
Translational Dynamics and Magnetic Resonance: Principles of Pulsed Gradient Spin Echo NMR
book, September 2011
- Callaghan, Paul T.
NMR methods applied to anisotropic diffusion: NMR methods applied to anisotropic diffusion
journal, November 2002
- Furó, István; Dvinskikh, Sergey V.
- Magnetic Resonance in Chemistry, Vol. 40, Issue 13
diffusion constant in the superionic conductor N measured by NMR
journal, September 1984
- Bechtold-Schweickert, E.; Mali, M.; Roos, J.
- Physical Review B, Vol. 30, Issue 5
Diffusion processes in the superionic conductor N: An NMR study
journal, November 1982
- Brinkmann, D.; Mali, M.; Roos, J.
- Physical Review B, Vol. 26, Issue 9
PFG n.m.r. study of diffusion anisotropy in oriented ZSM-5 type zeolite crystallites
journal, November 1991
- Hong, U.; Kärger, J.; Kramer, R.
- Zeolites, Vol. 11, Issue 8
Evidence of Anisotropic Self-Diffusion of Guest Molecules in Nanoporous Materials of MCM-41 Type
journal, September 2000
- Stallmach, Frank; Kärger, Jörg; Krause, Cordula
- Journal of the American Chemical Society, Vol. 122, Issue 38
PFG NMR diffusion measurements of CH4 and CO2 through large ZSM-58-crystals
journal, December 2013
- Bleken, Bjørn-Tore Lønstad; Lillerud, Karl Petter; Splith, Tobias
- Microporous and Mesoporous Materials, Vol. 182
Quantitative in vivo assessment of lung microstructure at the alveolar level with hyperpolarized 3He diffusion MRI
journal, February 2002
- Yablonskiy, D. A.; Sukstanskii, A. L.; Leawoods, J. C.
- Proceedings of the National Academy of Sciences, Vol. 99, Issue 5
The measurement of diffusion using deuterium pulsed field gradient nuclear magnetic resonance
journal, December 1983
- Callaghan, P. T.; Le Gros, M. A.; Pinder, D. N.
- The Journal of Chemical Physics, Vol. 79, Issue 12
Measurement of the Principal Values of the Anisotropic Diffusion Tensor in an Unoriented Sample by Exploiting the Chemical Shift Anisotropy: 19F PGSE NMR with Homonuclear Decoupling
journal, January 2001
- Dvinskikh, S. V.; Furó, I.
- Journal of Magnetic Resonance, Vol. 148, Issue 1
Molecular Mechanism of Lateral Diffusion of Fluorosurfactants. A 19 F NMR Study
journal, June 2002
- Kadi, M.; Dvinskikh, S. V.; Furó, I.
- Langmuir, Vol. 18, Issue 12
Capture of Carbon Dioxide from Air and Flue Gas in the Alkylamine-Appended Metal–Organic Framework mmen-Mg2(dobpdc)
journal, April 2012
- McDonald, Thomas M.; Lee, Woo Ram; Mason, Jarad A.
- Journal of the American Chemical Society, Vol. 134, Issue 16, p. 7056-7065
Application of a High-Throughput Analyzer in Evaluating Solid Adsorbents for Post-Combustion Carbon Capture via Multicomponent Adsorption of CO 2 , N 2 , and H 2 O
journal, April 2015
- Mason, Jarad A.; McDonald, Thomas M.; Bae, Tae-Hyun
- Journal of the American Chemical Society, Vol. 137, Issue 14
Controlling Cooperative CO 2 Adsorption in Diamine-Appended Mg 2 (dobpdc) Metal–Organic Frameworks
journal, July 2017
- Siegelman, Rebecca L.; McDonald, Thomas M.; Gonzalez, Miguel I.
- Journal of the American Chemical Society, Vol. 139, Issue 30
A Diaminopropane-Appended Metal–Organic Framework Enabling Efficient CO 2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism
journal, September 2017
- Milner, Phillip J.; Siegelman, Rebecca L.; Forse, Alexander C.
- Journal of the American Chemical Society, Vol. 139, Issue 38
CO 2 induced phase transitions in diamine-appended metal–organic frameworks
journal, January 2015
- Vlaisavljevich, Bess; Odoh, Samuel O.; Schnell, Sondre K.
- Chemical Science, Vol. 6, Issue 9
Fine-Tuning of the Carbon Dioxide Capture Capability of Diamine-Grafted Metal-Organic Framework Adsorbents Through Amine Functionalization
journal, December 2016
- Jo, Hyuna; Lee, Woo Ram; Kim, Nam Woo
- ChemSusChem, Vol. 10, Issue 3
Adsorption of Carbon Dioxide on Unsaturated Metal Sites in M 2 (dobpdc) Frameworks with Exceptional Structural Stability and Relation between Lewis Acidity and Adsorption Enthalpy
journal, April 2016
- Yoo, Ga Young; Lee, Woo Ram; Jo, Hyuna
- Chemistry - A European Journal, Vol. 22, Issue 22
Tuning carbon dioxide capture capability with structural and compositional design in mmen-(Mg,Zn) (dobpdc) metal-organic framework: density functional theory investigation: Original Research Article: Tuning carbon dioxide capture capability with structural and compositional design
journal, March 2018
- Pramchu, Sittichain; Jaroenjittichai, Atchara P.; Laosiritaworn, Yongyut
- Greenhouse Gases: Science and Technology, Vol. 8, Issue 3
Enantioselective Recognition of Ammonium Carbamates in a Chiral Metal–Organic Framework
journal, October 2017
- Martell, Jeffrey D.; Porter-Zasada, Leo B.; Forse, Alexander C.
- Journal of the American Chemical Society, Vol. 139, Issue 44
CO 2 Dynamics in Pure and Mixed-Metal MOFs with Open Metal Sites
journal, October 2017
- Marti, Robert M.; Howe, Joshua D.; Morelock, Cody R.
- The Journal of Physical Chemistry C, Vol. 121, Issue 46
CO 2 Dynamics in a Metal–Organic Framework with Open Metal Sites
journal, August 2012
- Kong, Xueqian; Scott, Eric; Ding, Wen
- Journal of the American Chemical Society, Vol. 134, Issue 35
Understanding CO 2 Dynamics in Metal-Organic Frameworks with Open Metal Sites
journal, March 2013
- Lin, Li-Chiang; Kim, Jihan; Kong, Xueqian
- Angewandte Chemie International Edition, Vol. 52, Issue 16
Rotational and translational dynamics of CO2 adsorbed in MOF Zn2(bdc)2(dabco)
journal, November 2015
- Peksa, Mikuláš; Burrekaew, Sareeya; Schmid, Rochus
- Microporous and Mesoporous Materials, Vol. 216
Solid-State NMR Spectroscopy of Metal–Organic Framework Compounds (MOFs)
journal, November 2012
- Hoffmann, Herbert; Debowski, Marta; Müller, Philipp
- Materials, Vol. 5, Issue 12
Characteristics of flexibility in metal-organic framework solid solutions of composition [Zn2(BME-bdc)x(DB-bdc)2−xdabco]n: In situ powder X-ray diffraction, in situ NMR spectroscopy, and molecular dynamics simulations
journal, November 2015
- Bon, Volodymyr; Pallmann, Julia; Eisbein, Emanuel
- Microporous and Mesoporous Materials, Vol. 216
Understanding The Fascinating Origins of CO 2 Adsorption and Dynamics in MOFs
journal, August 2016
- Chen, Shoushun; Lucier, Bryan E. G.; Boyle, Paul D.
- Chemistry of Materials, Vol. 28, Issue 16
Deducing CO 2 motion, adsorption locations and binding strengths in a flexible metal–organic framework without open metal sites
journal, January 2016
- Zhang, Yue; Lucier, Bryan E. G.; Huang, Yining
- Physical Chemistry Chemical Physics, Vol. 18, Issue 12
Sizable dynamics in small pores: CO 2 location and motion in the α-Mg formate metal–organic framework
journal, January 2017
- Lu, Yuanjun; Lucier, Bryan E. G.; Zhang, Yue
- Phys. Chem. Chem. Phys., Vol. 19, Issue 8
SIMPSON: A General Simulation Program for Solid-State NMR Spectroscopy
journal, December 2000
- Bak, Mads; Rasmussen, Jimmy T.; Nielsen, Niels Chr
- Journal of Magnetic Resonance, Vol. 147, Issue 2
Pulsed field gradient stimulated echo methods for improved NMR diffusion measurements in heterogeneous systems
journal, June 1989
- Cotts, R. M.; Hoch, M. J. R.; Sun, T.
- Journal of Magnetic Resonance (1969), Vol. 83, Issue 2
Works referencing / citing this record:
In Operando Analysis of Diffusion in Porous Metal‐Organic Framework Catalysts
journal, December 2018
- Gao, Wen‐Yang; Cardenal, Ashley D.; Wang, Chen‐Hao
- Chemistry – A European Journal, Vol. 25, Issue 14