skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Combined Nuclear Magnetic Resonance and Molecular Dynamics Study of Methane Adsorption in M2 (dobdc) Metal–Organic Frameworks

Abstract

We investigate the diffusion of methane in the metal-organic frameworks M2 (dobdc) (M = Mg, Ni, Zn; dobdc4- = 2,5-dioxido-1,4-benzenedicarboxylate) as a function of methane loading through a combination of nuclear magnetic resonance and molecular dynamics simulations. At low gas densities, our results suggest that favorable CH4 -CH4 interactions lower the free energy barrier for methane hopping between coordinatively unsaturated metal sites and thus enhance the translational motion of methane down the c-axis. At higher gas densities, CH4 -CH4 interactions become more significant, CH4 -CH4 collisions become more frequent, and the gas self-diffusion begins to decrease. Lastly, we determine that the self-diffusion coefficient of methane is inversely related to the binding energy at the coordinatively unsaturated metal sites, such that diffusion is most rapid in the Zn2(dobdc) framework.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1];  [3]; ORCiD logo [4]; ORCiD logo [5]
  1. Univ. of California, Berkeley, CA (United States)
  2. Ecole Polytechnique Federale Lausanne (Switzlerland)
  3. RWTH Aachen Univ. (Germany)
  4. Univ. of California, Berkeley, CA (United States); Ecole Polytechnique Federale Lausanne (Switzlerland)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Aachen-California Network of Academic Exchange (DAAD Germany)
OSTI Identifier:
1542406
Grant/Contract Number:  
AC02-05CH11231; SC0001015; DGE-1752814; DGE-1106400
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 19; 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

Witherspoon, Velencia J., Mercado, Rocío, Braun, Efrem, Mace, Amber, Bachman, Jonathan, Long, Jeffrey R., Blümich, Bernhard, Smit, Berend, and Reimer, Jeffrey A.. Combined Nuclear Magnetic Resonance and Molecular Dynamics Study of Methane Adsorption in M2 (dobdc) Metal–Organic Frameworks. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpcc.9b01733.
Witherspoon, Velencia J., Mercado, Rocío, Braun, Efrem, Mace, Amber, Bachman, Jonathan, Long, Jeffrey R., Blümich, Bernhard, Smit, Berend, & Reimer, Jeffrey A.. Combined Nuclear Magnetic Resonance and Molecular Dynamics Study of Methane Adsorption in M2 (dobdc) Metal–Organic Frameworks. United States. https://doi.org/10.1021/acs.jpcc.9b01733
Witherspoon, Velencia J., Mercado, Rocío, Braun, Efrem, Mace, Amber, Bachman, Jonathan, Long, Jeffrey R., Blümich, Bernhard, Smit, Berend, and Reimer, Jeffrey A.. Tue . "Combined Nuclear Magnetic Resonance and Molecular Dynamics Study of Methane Adsorption in M2 (dobdc) Metal–Organic Frameworks". United States. https://doi.org/10.1021/acs.jpcc.9b01733. https://www.osti.gov/servlets/purl/1542406.
@article{osti_1542406,
title = {Combined Nuclear Magnetic Resonance and Molecular Dynamics Study of Methane Adsorption in M2 (dobdc) Metal–Organic Frameworks},
author = {Witherspoon, Velencia J. and Mercado, Rocío and Braun, Efrem and Mace, Amber and Bachman, Jonathan and Long, Jeffrey R. and Blümich, Bernhard and Smit, Berend and Reimer, Jeffrey A.},
abstractNote = {We investigate the diffusion of methane in the metal-organic frameworks M2 (dobdc) (M = Mg, Ni, Zn; dobdc4- = 2,5-dioxido-1,4-benzenedicarboxylate) as a function of methane loading through a combination of nuclear magnetic resonance and molecular dynamics simulations. At low gas densities, our results suggest that favorable CH4 -CH4 interactions lower the free energy barrier for methane hopping between coordinatively unsaturated metal sites and thus enhance the translational motion of methane down the c-axis. At higher gas densities, CH4 -CH4 interactions become more significant, CH4 -CH4 collisions become more frequent, and the gas self-diffusion begins to decrease. Lastly, we determine that the self-diffusion coefficient of methane is inversely related to the binding energy at the coordinatively unsaturated metal sites, such that diffusion is most rapid in the Zn2(dobdc) framework.},
doi = {10.1021/acs.jpcc.9b01733},
journal = {Journal of Physical Chemistry. C},
number = 19,
volume = 123,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Systematic Functionalization of a Metal−Organic Framework via a Postsynthetic Modification Approach
journal, July 2008

  • Tanabe, Kristine K.; Wang, Zhenqiang; Cohen, Seth M.
  • Journal of the American Chemical Society, Vol. 130, Issue 26, p. 8508-8517
  • DOI: 10.1021/ja801848j

Postsynthetic modification of metal–organic frameworks
journal, January 2009

  • Wang, Zhenqiang; Cohen, Seth M.
  • Chemical Society Reviews, Vol. 38, Issue 5
  • DOI: 10.1039/b802258p

Postsynthetic Modification of a Metal–Organic Framework for Stabilization of a Hemiaminal and Ammonia Uptake
journal, August 2011

  • Morris, William; Doonan, Christian J.; Yaghi, Omar M.
  • Inorganic Chemistry, Vol. 50, Issue 15, p. 6853-6855
  • DOI: 10.1021/ic200744y

Metal–Organic Frameworks as A Tunable Platform for Designing Functional Molecular Materials
journal, August 2013

  • Wang, Cheng; Liu, Demin; Lin, Wenbin
  • Journal of the American Chemical Society, Vol. 135, Issue 36
  • DOI: 10.1021/ja308229p

Postsynthetic Modification of Zirconium Metal-Organic Frameworks: Postsynthetic Modification of Zirconium Metal-Organic Frameworks
journal, July 2016

  • Marshall, Ross J.; Forgan, Ross S.
  • European Journal of Inorganic Chemistry, Vol. 2016, Issue 27
  • DOI: 10.1002/ejic.201600394

Introduction to Metal–Organic Frameworks
journal, September 2011

  • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
  • DOI: 10.1021/cr300014x

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Methane Storage in Metal–Organic Frameworks: Current Records, Surprise Findings, and Challenges
journal, July 2013

  • Peng, Yang; Krungleviciute, Vaiva; Eryazici, Ibrahim
  • Journal of the American Chemical Society, Vol. 135, Issue 32, p. 11887-11894
  • DOI: 10.1021/ja4045289

Evaluating metal–organic frameworks for natural gas storage
journal, January 2014

  • Mason, Jarad A.; Veenstra, Mike; Long, Jeffrey R.
  • Chemical Science, Vol. 5, Issue 1, p. 32-51
  • DOI: 10.1039/c3sc52633j

Potential applications of metal-organic frameworks
journal, December 2009

  • Kuppler, Ryan J.; Timmons, Daren J.; Fang, Qian-Rong
  • Coordination Chemistry Reviews, Vol. 253, Issue 23-24
  • DOI: 10.1016/j.ccr.2009.05.019

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M 2 (dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)
journal, January 2014

  • Queen, Wendy L.; Hudson, Matthew R.; Bloch, Eric D.
  • Chem. Sci., Vol. 5, Issue 12
  • DOI: 10.1039/c4sc02064b

The materials genome in action: identifying the performance limits for methane storage
journal, January 2015

  • Simon, Cory M.; Kim, Jihan; Gomez-Gualdron, Diego A.
  • Energy & Environmental Science, Vol. 8, Issue 4
  • DOI: 10.1039/c4ee03515a

The role of metal–organic frameworks in a carbon-neutral energy cycle
journal, April 2016


Force Field Development from Periodic Density Functional Theory Calculations for Gas Separation Applications Using Metal–Organic Frameworks
journal, June 2016

  • Mercado, Rocio; Vlaisavljevich, Bess; Lin, Li-Chiang
  • The Journal of Physical Chemistry C, Vol. 120, Issue 23
  • DOI: 10.1021/acs.jpcc.6b03393

High-Capacity Methane Storage in Metal−Organic Frameworks M 2 (dhtp): The Important Role of Open Metal Sites
journal, April 2009

  • Wu, Hui; Zhou, Wei; Yildirim, Taner
  • Journal of the American Chemical Society, Vol. 131, Issue 13
  • DOI: 10.1021/ja900258t

Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design
journal, January 2015

  • Lee, Kyuho; Howe, Joshua D.; Lin, Li-Chiang
  • Chemistry of Materials, Vol. 27, Issue 3, p. 668-678
  • DOI: 10.1021/cm502760q

Solid-state NMR: A powerful tool for characterization of metal–organic frameworks
journal, February 2013


Reprint of: Transient breakthroughs of CO 2 /CH 4 and C 3 H 6 /C 3 H 8 mixtures in fixed beds packed with Ni-MOF-74
journal, March 2015


Benefit of Microscopic Diffusion Measurement for the Characterization of Nanoporous Materials
journal, October 2009

  • Kärger, J.; Caro, J.; Cool, P.
  • Chemical Engineering & Technology, Vol. 32, Issue 10
  • DOI: 10.1002/ceat.200900160

Perspectives on NMR studies of CO2 adsorption
journal, January 2018


Ex Situ NMR Relaxometry of Metal-Organic Frameworks for Rapid Surface-Area Screening
journal, September 2013

  • Chen, Joseph J.; Kong, Xueqian; Sumida, Kenji
  • Angewandte Chemie International Edition, Vol. 52, Issue 46
  • DOI: 10.1002/anie.201305247

NMR studies of carbon dioxide and methane self-diffusion in ZIF-8 at elevated gas pressures
journal, September 2012


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
  • DOI: 10.1002/anie.200502553

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
  • DOI: 10.1021/ja306822p

Understanding CO 2 Dynamics in Metal-Organic Frameworks with Open Metal Sites
journal, March 2013


NMR relaxation and diffusion studies of methane and carbon dioxide in nanoporous ZIF-8 and ZSM-58
journal, March 2015


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
  • DOI: 10.1021/jacs.7b09453

Characteristic features of molecular transport in MOF ZIF-8 as revealed by IR microimaging
journal, November 2015


Influence of adsorption thermodynamics on guest diffusivities in nanoporous crystalline materials
journal, January 2013

  • Krishna, Rajamani; van Baten, Jasper M.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 21
  • DOI: 10.1039/c3cp50449b

M 2 ( m -dobdc) (M = Mn, Fe, Co, Ni) Metal–Organic Frameworks as Highly Selective, High-Capacity Adsorbents for Olefin/Paraffin Separations
journal, October 2017

  • Bachman, Jonathan E.; Kapelewski, Matthew T.; Reed, Douglas A.
  • Journal of the American Chemical Society, Vol. 139, Issue 43
  • DOI: 10.1021/jacs.7b06397

Pulsed field gradient stimulated echo methods for improved NMR diffusion measurements in heterogeneous systems
journal, June 1989


NMR imaging, NMR diffraction and applications of pulsed gradient spin echoes in porous media
journal, January 1996


Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


A new perspective on the order- n algorithm for computing correlation functions
journal, October 2009

  • Dubbeldam, David; Ford, Denise C.; Ellis, Donald E.
  • Molecular Simulation, Vol. 35, Issue 12-13
  • DOI: 10.1080/08927020902818039

Automated Multiscale Approach To Predict Self-Diffusion from a Potential Energy Field
journal, February 2019

  • Mace, Amber; Barthel, Senja; Smit, Berend
  • Journal of Chemical Theory and Computation, Vol. 15, Issue 4
  • DOI: 10.1021/acs.jctc.8b01255

Statistical mechanics of isomerization dynamics in liquids and the transition state approximation
journal, January 1978

  • Chandler, David
  • The Journal of Chemical Physics, Vol. 68, Issue 6
  • DOI: 10.1063/1.436049

Proton-spin-lattice relaxation and self-diffusion in methanes
journal, February 1971


Proton Spin–Lattice Relaxation in Polyatomic Gases
journal, August 1961

  • Bloom, M.; Lipsicas, M.; Muller, B. H.
  • Canadian Journal of Physics, Vol. 39, Issue 8
  • DOI: 10.1139/p61-125

Proton and Deuteron Field-Cycling NMR Relaxometry of Liquids in Porous Glasses: Evidence for Lévy-Walk Statistics
journal, October 1995


Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions
journal, January 2012

  • Xiang, Shengchang; He, Yabing; Zhang, Zhangjing
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1956