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Title: Critical Factors Driving the High Volumetric Uptake of Methane in Cu3(btc)2

Abstract

We report a thorough experimental and computational study has been carried out to elucidate the mechanistic reasons for the high volumetric uptake of methane in the metal–organic framework Cu3(btc)2 (btc3– = 1,3,5-benzenetricarboxylate; HKUST-1). Methane adsorption data measured at several temperatures for Cu3(btc)2, and its isostructural analogue Cr3(btc)2, show that there is little difference in volumetric adsorption capacity when the metal center is changed. In situ neutron powder diffraction data obtained for both materials were used to locate four CD4 adsorption sites that fill sequentially. This data unequivocally shows that primary adsorption sites around, and within, the small octahedral cage in the structure are favored over the exposed Cu2+ or Cr2+ cations. These results are supported by an exhaustive parallel computational study, and contradict results recently reported using a time-resolved diffraction structure envelope (TRDSE) method. Moreover, the computational study reveals that strong methane binding at the open metal sites is largely due to methane–methane interactions with adjacent molecules adsorbed at the primary sites instead of an electronic interaction with the metal center. Simulated methane adsorption isotherms for Cu3(btc)2 are shown to exhibit excellent agreement with experimental isotherms, allowing for additional simulations that show that modifications to the metal center, ligand, ormore » even tuning the overall binding enthalpy would not improve the working capacity for methane storage over that measured for Cu3(btc)2 itself.« less

Authors:
 [1];  [2];  [2];  [3];  [4];  [2];  [3];  [5];  [3];  [6]
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  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Georgetown Univ., Washington, DC (United States)
  5. Univ. of California, Berkeley, CA (United States); Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne (Switzerland)
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations (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). Chemical Sciences, Geosciences & Biosciences Division; National Institute of Standards and Technology (NIST); National Science Foundation (NSF)
OSTI Identifier:
1386971
Grant/Contract Number:  
SC0001015; FG02-12ER16362; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 33; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); metals; adsorption; molecules; screening assays; materials

Citation Formats

Hulvey, Zeric, Vlaisavljevich, Bess, Mason, Jarad A., Tsivion, Ehud, Dougherty, Timothy P., Bloch, Eric D., Head-Gordon, Martin, Smit, Berend, Long, Jeffrey R., and Brown, Craig M. Critical Factors Driving the High Volumetric Uptake of Methane in Cu3(btc)2. United States: N. p., 2015. Web. doi:10.1021/jacs.5b06657.
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Hulvey, Zeric, Vlaisavljevich, Bess, Mason, Jarad A., Tsivion, Ehud, Dougherty, Timothy P., Bloch, Eric D., Head-Gordon, Martin, Smit, Berend, Long, Jeffrey R., & Brown, Craig M. Critical Factors Driving the High Volumetric Uptake of Methane in Cu3(btc)2. United States. https://doi.org/10.1021/jacs.5b06657
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Hulvey, Zeric, Vlaisavljevich, Bess, Mason, Jarad A., Tsivion, Ehud, Dougherty, Timothy P., Bloch, Eric D., Head-Gordon, Martin, Smit, Berend, Long, Jeffrey R., and Brown, Craig M. Tue . "Critical Factors Driving the High Volumetric Uptake of Methane in Cu3(btc)2". United States. https://doi.org/10.1021/jacs.5b06657. https://www.osti.gov/servlets/purl/1386971.
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@article{osti_1386971,
title = {Critical Factors Driving the High Volumetric Uptake of Methane in Cu3(btc)2},
author = {Hulvey, Zeric and Vlaisavljevich, Bess and Mason, Jarad A. and Tsivion, Ehud and Dougherty, Timothy P. and Bloch, Eric D. and Head-Gordon, Martin and Smit, Berend and Long, Jeffrey R. and Brown, Craig M.},
abstractNote = {We report a thorough experimental and computational study has been carried out to elucidate the mechanistic reasons for the high volumetric uptake of methane in the metal–organic framework Cu3(btc)2 (btc3– = 1,3,5-benzenetricarboxylate; HKUST-1). Methane adsorption data measured at several temperatures for Cu3(btc)2, and its isostructural analogue Cr3(btc)2, show that there is little difference in volumetric adsorption capacity when the metal center is changed. In situ neutron powder diffraction data obtained for both materials were used to locate four CD4 adsorption sites that fill sequentially. This data unequivocally shows that primary adsorption sites around, and within, the small octahedral cage in the structure are favored over the exposed Cu2+ or Cr2+ cations. These results are supported by an exhaustive parallel computational study, and contradict results recently reported using a time-resolved diffraction structure envelope (TRDSE) method. Moreover, the computational study reveals that strong methane binding at the open metal sites is largely due to methane–methane interactions with adjacent molecules adsorbed at the primary sites instead of an electronic interaction with the metal center. Simulated methane adsorption isotherms for Cu3(btc)2 are shown to exhibit excellent agreement with experimental isotherms, allowing for additional simulations that show that modifications to the metal center, ligand, or even tuning the overall binding enthalpy would not improve the working capacity for methane storage over that measured for Cu3(btc)2 itself.},
doi = {10.1021/jacs.5b06657},
journal = {Journal of the American Chemical Society},
number = 33,
volume = 137,
place = {United States},
year = {Tue Aug 11 00:00:00 EDT 2015},
month = {Tue Aug 11 00:00:00 EDT 2015}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/jacs.5b06657
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Cited by: 59 works
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Figures / Tables:

Figure 1 Figure 1: Comparison of the total volumetric CH4 adsorption of Cr3(btc)2 (green) and Cu3(btc)2 (blue) at 25 °C. The solid black line corresponds to the amount of CH4 that would be present in a tank with no adsorbent.
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Works referenced in this record:

Methane storage in advanced porous materials
journal, January 2012

  • Makal, Trevor A.; Li, Jian-Rong; Lu, Weigang
  • Chemical Society Reviews, Vol. 41, Issue 23
  • DOI: 10.1039/c2cs35251f

Methane storage in metal organic frameworks
journal, January 2012

  • Konstas, Kristina; Osl, Theresa; Yang, Yunxia
  • Journal of Materials Chemistry, Vol. 22, Issue 33
  • DOI: 10.1039/c2jm32719h

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

Methane storage in metal–organic frameworks
journal, January 2014

  • He, Yabing; Zhou, Wei; Qian, Guodong
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00032C

A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
journal, February 1999

Highly-Selective and Reversible O2 Binding in Cr3(1,3,5-benzenetricarboxylate)2
journal, June 2010

  • Murray, Leslie J.; Dinca, Mircea; Yano, Junko
  • Journal of the American Chemical Society, Vol. 132, Issue 23, p. 7856-7857
  • DOI: 10.1021/ja1027925

Neutron Scattering and Spectroscopic Studies of Hydrogen Adsorption in Cr 3 (BTC) 2 —A Metal−Organic Framework with Exposed Cr 2+ Sites
journal, March 2011

  • Sumida, Kenji; Her, Jae-Hyuk; Dincă, Mircea
  • The Journal of Physical Chemistry C, Vol. 115, Issue 16
  • DOI: 10.1021/jp200638n

Hydrogen Storage in a Microporous Metal−Organic Framework with Exposed Mn 2+ Coordination Sites
journal, December 2006

  • Dincǎ, Mircea; Dailly, Anne; Liu, Yun
  • Journal of the American Chemical Society, Vol. 128, Issue 51
  • DOI: 10.1021/ja0656853

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

Methane Sorption in Nanoporous Metal−Organic Frameworks and First-Order Phase Transition of Confined Methane
journal, January 2009

  • Wu, Hui; Zhou, Wei; Yildirim, Taner
  • The Journal of Physical Chemistry C, Vol. 113, Issue 7
  • DOI: 10.1021/jp8103276

Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites
journal, March 2012

Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels
journal, May 2013

Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N 2 and CH 4
journal, December 2013

  • Lee, Kyuho; Isley, William C.; Dzubak, Allison L.
  • Journal of the American Chemical Society, Vol. 136, Issue 2
  • DOI: 10.1021/ja4102979

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

Methane storage mechanism in the metal-organic framework Cu3(btc)2: An in situ neutron diffraction study
journal, December 2010

Metal-Organic Frameworks with Exceptionally High Methane Uptake: Where and How is Methane Stored?
journal, March 2010

  • Wu, Hui; Simmons, Jason M.; Liu, Yun
  • Chemistry - A European Journal, Vol. 16, Issue 17
  • DOI: 10.1002/chem.200902719

Direct Measurement of Adsorbed Gas Redistribution in Metal–Organic Frameworks
journal, February 2015

  • Chen, Ying-Pin; Liu, Yangyang; Liu, Dahuan
  • Journal of the American Chemical Society, Vol. 137, Issue 8
  • DOI: 10.1021/ja5103579

Noble Gas Adsorption in Copper Trimesate, HKUST-1: An Experimental and Computational Study
journal, September 2013

  • Hulvey, Zeric; Lawler, Keith V.; Qiao, Zhiwei
  • The Journal of Physical Chemistry C, Vol. 117, Issue 39
  • DOI: 10.1021/jp408034u

Neutron Powder Diffraction Study of D 2 Sorption in Cu 3 (1,3,5-benzenetricarboxylate) 2
journal, December 2006

  • Peterson, Vanessa K.; Liu, Yun; Brown, Craig M.
  • Journal of the American Chemical Society, Vol. 128, Issue 49
  • DOI: 10.1021/ja0660857

Structural Study of D 2 within the Trimodal Pore System of a Metal Organic Framework
journal, April 2011

  • Peterson, Vanessa K.; Brown, Craig M.; Liu, Yun
  • The Journal of Physical Chemistry C, Vol. 115, Issue 17
  • DOI: 10.1021/jp2010937

Large-scale screening of hypothetical metal–organic frameworks
journal, November 2011

  • Wilmer, Christopher E.; Leaf, Michael; Lee, Chang Yeon
  • Nature Chemistry, Vol. 4, Issue 2, p. 83-89
  • DOI: 10.1038/nchem.1192

Thermodynamic analysis of Xe/Kr selectivity in over 137 000 hypothetical metal–organic frameworks
journal, January 2012

  • Sikora, Benjamin J.; Wilmer, Christopher E.; Greenfield, Michael L.
  • Chemical Science, Vol. 3, Issue 7
  • DOI: 10.1039/c2sc01097f

Structure–property relationships of porous materials for carbon dioxide separation and capture
journal, January 2012

  • Wilmer, Christopher E.; Farha, Omar K.; Bae, Youn-Sang
  • Energy & Environmental Science, Vol. 5, Issue 12, p. 9849-9856
  • DOI: 10.1039/c2ee23201d

Optimizing nanoporous materials for gas storage
journal, January 2014

  • Simon, Cory M.; Kim, Jihan; Lin, Li-Chiang
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 12
  • DOI: 10.1039/c3cp55039g

Exploring the Limits of Methane Storage and Delivery in Nanoporous Materials
journal, March 2014

  • Gómez-Gualdrón, Diego A.; Wilmer, Christopher E.; Farha, Omar K.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 13
  • DOI: 10.1021/jp502359q

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

Effects of Functionalization, Catenation, and Variation of the Metal Oxide and Organic Linking Units on the Low-Pressure Hydrogen Adsorption Properties of Metal−Organic Frameworks
journal, February 2006

  • Rowsell, Jesse L. C.; Yaghi, Omar M.
  • Journal of the American Chemical Society, Vol. 128, Issue 4, p. 1304-1315
  • DOI: 10.1021/ja056639q

EXPGUI , a graphical user interface for GSAS
journal, April 2001

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Van der Waals Density Functional for General Geometries
journal, June 2004

Higher-accuracy van der Waals density functional
journal, August 2010

Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995

Oxidation energies of transition metal oxides within the GGA + U framework
journal, May 2006

Projector augmented-wave method
journal, December 1994

UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
journal, December 1992

  • Rappe, A. K.; Casewit, C. J.; Colwell, K. S.
  • Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035
  • DOI: 10.1021/ja00051a040

Efficient Determination of Accurate Force Fields for Porous Materials Using ab Initio Total Energy Calculations
journal, January 2014

  • Kim, Jihan; Lin, Li-Chiang; Lee, Kyuho
  • The Journal of Physical Chemistry C, Vol. 118, Issue 5
  • DOI: 10.1021/jp412368m

After 155 Years, A Crystalline Chromium Carboxylate with a Supershort Cr−Cr Bond
journal, January 2000

  • Cotton, F. Albert; Hillard, Elizabeth A.; Murillo, Carlos A.
  • Journal of the American Chemical Society, Vol. 122, Issue 2
  • DOI: 10.1021/ja993755i

Liquid-Like Hydrogen Stored in Nanoporous Materials at 50 K Observed by in Situ Neutron Diffraction Experiments
journal, February 2013

  • Lee, Heeju; Choi, Yong Nam; Choi, Sang Beom
  • The Journal of Physical Chemistry C, Vol. 117, Issue 6
  • DOI: 10.1021/jp3128065

A Quasidegenerate Second-Order Perturbation Theory Approximation to RAS- n SF for Excited States and Strong Correlations
journal, January 2014

  • Mayhall, Nicholas J.; Goldey, Matthew; Head-Gordon, Martin
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 2
  • DOI: 10.1021/ct400898p

Ab Initio Prediction of Adsorption Isotherms for Small Molecules in Metal–Organic Frameworks: The Effect of Lateral Interactions for Methane/CPO-27-Mg
journal, September 2012

  • Sillar, Kaido; Sauer, Joachim
  • Journal of the American Chemical Society, Vol. 134, Issue 44
  • DOI: 10.1021/ja307076t

In silico Design of Porous Polymer Networks: High-Throughput Screening for Methane Storage Materials
journal, March 2014

  • Martin, Richard L.; Simon, Cory M.; Smit, Berend
  • Journal of the American Chemical Society, Vol. 136, Issue 13
  • DOI: 10.1021/ja4123939
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    Works referencing / citing this record:

    Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry
    journal, January 2019

    • Xue, Zi-Ling; Ramirez-Cuesta, Anibal J.; Brown, Craig M.
    • European Journal of Inorganic Chemistry, Vol. 2019, Issue 8
    • DOI: 10.1002/ejic.201801076

    Tailoring the pore geometry and chemistry in microporous metal–organic frameworks for high methane storage working capacity
    journal, January 2019

    • Shao, Kai; Pei, Jiyan; Wang, Jia-Xin
    • Chemical Communications, Vol. 55, Issue 76
    • DOI: 10.1039/c9cc06239d

    Insights into Selective Gas Sorbent Functionality Gained by Using Time-Resolved Neutron Diffraction
    journal, May 2018

    • Auckett, Josie E.; Duyker, Samuel G.; Turner, David R.
    • ChemPlusChem, Vol. 83, Issue 7
    • DOI: 10.1002/cplu.201800210

    Strategies for Overcoming Defects of HKUST‐1 and Its Relevant Applications
    journal, April 2019

    • Wang, Tianyi; Zhu, Haolin; Zeng, Qun
    • Advanced Materials Interfaces, Vol. 6, Issue 13
    • DOI: 10.1002/admi.201900423

    Preparation of a Composite Material AC/Cu-BTC with Improved Water Stability and n-Hexane Vapor Adsorption
    journal, September 2019

    Defect Creation in HKUST-1 via Molecular Imprinting: Attaining Anionic Framework Property and Mesoporosity for Cation Exchange Applications
    journal, September 2017

    • Tan, Ying Chuan; Zeng, Hua Chun
    • Advanced Functional Materials, Vol. 27, Issue 42
    • DOI: 10.1002/adfm.201703765

    High-pressure methane storage and selective gas adsorption in a cyclohexane-functionalised porous organic cage
    journal, June 2019

    Hydrogen Storage and Selective, Reversible O 2 Adsorption in a Metal-Organic Framework with Open Chromium(II) Sites
    journal, June 2016

    • Bloch, Eric D.; Queen, Wendy L.; Hudson, Matthew R.
    • Angewandte Chemie International Edition, Vol. 55, Issue 30
    • DOI: 10.1002/anie.201602950

    A Metal-Organic Framework with a Pore Size/Shape Suitable for Strong Binding and Close Packing of Methane
    journal, March 2016

    A Metal-Organic Framework with a Pore Size/Shape Suitable for Strong Binding and Close Packing of Methane
    journal, March 2016

    • Lin, Jiao-Min; He, Chun-Ting; Liu, Yan
    • Angewandte Chemie International Edition, Vol. 55, Issue 15
    • DOI: 10.1002/anie.201511006
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      Figure 5 (p. 7)figure
      Figure 6 (p. 7)figure
      Table 1 (p. 8)table
      Table 2 (p. 8)table
      Figure 7 (p. 9)figure
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