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Title: An experimental and computational study of CO 2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites

Abstract

We present a comprehensive investigation of the CO2 adsorption properties of an isostructural series of metal-organic frameworks, M-BTT (M = Cr, Mn, Fe, Cu; BTT3-= 1,3,5-benzenetristetrazolate), which exhibit a high density of open metal sites capable of polarizing and binding guest molecules. Coupling gas adsorption measurements with in situ neutron and X-ray diffraction experiments provides molecular-level insight into the adsorption process and enables rationalization of the observed adsorption isotherms. In particular, structural data confirms that the high initial isosteric heats of CO2 adsorption for the series are directly correlated with the presence of open metal sites and further reveals the positions and orientations of as many as three additional adsorption sites. Density functional theory calculations that include van der Waals dispersion corrections quantitatively support the observed structural features associated with the primary and secondary CO2 binding sites, including CO2 positions and orientations, as well as the experimentally determined isosteric heats of CO2 adsorption.The work provides molecular level insight into the CO2adsorption properties of an isostructural series of MOFs, known as M-BTT.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4];  [5];  [6]; ORCiD logo [7]; ORCiD logo [8]; ORCiD logo [1]
  1. Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), Switzerland
  2. Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), Switzerland, Department of Chemical and Biomolecular Engineering, University of California
  3. Department of Chemistry, University of California, Berkeley, USA, Department of Chemistry and Biochemistry
  4. National Institute of Standards and Technology, Center for Neutron Research, Gaithersburg, USA
  5. Canadian Neutron Beam Centre, National Research Council, Chalk River Laboratories, Canada
  6. Department of Chemistry, University of South Dakota, USA
  7. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, USA, Department of Chemistry
  8. National Institute of Standards and Technology, Center for Neutron Research, Gaithersburg, USA, Department of Chemical Engineering
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)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1435854
Alternate Identifier(s):
OSTI ID: 1465423
Grant/Contract Number:  
SC0001015; AC02-05CH11231
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 20; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Asgari, Mehrdad, Jawahery, Sudi, Bloch, Eric D., Hudson, Matthew R., Flacau, Roxana, Vlaisavljevich, Bess, Long, Jeffrey R., Brown, Craig M., and Queen, Wendy L. An experimental and computational study of CO 2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites. United Kingdom: N. p., 2018. Web. doi:10.1039/C8SC00971F.
Asgari, Mehrdad, Jawahery, Sudi, Bloch, Eric D., Hudson, Matthew R., Flacau, Roxana, Vlaisavljevich, Bess, Long, Jeffrey R., Brown, Craig M., & Queen, Wendy L. An experimental and computational study of CO 2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites. United Kingdom. https://doi.org/10.1039/C8SC00971F
Asgari, Mehrdad, Jawahery, Sudi, Bloch, Eric D., Hudson, Matthew R., Flacau, Roxana, Vlaisavljevich, Bess, Long, Jeffrey R., Brown, Craig M., and Queen, Wendy L. 2018. "An experimental and computational study of CO 2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites". United Kingdom. https://doi.org/10.1039/C8SC00971F.
@article{osti_1435854,
title = {An experimental and computational study of CO 2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites},
author = {Asgari, Mehrdad and Jawahery, Sudi and Bloch, Eric D. and Hudson, Matthew R. and Flacau, Roxana and Vlaisavljevich, Bess and Long, Jeffrey R. and Brown, Craig M. and Queen, Wendy L.},
abstractNote = {We present a comprehensive investigation of the CO2 adsorption properties of an isostructural series of metal-organic frameworks, M-BTT (M = Cr, Mn, Fe, Cu; BTT3-= 1,3,5-benzenetristetrazolate), which exhibit a high density of open metal sites capable of polarizing and binding guest molecules. Coupling gas adsorption measurements with in situ neutron and X-ray diffraction experiments provides molecular-level insight into the adsorption process and enables rationalization of the observed adsorption isotherms. In particular, structural data confirms that the high initial isosteric heats of CO2 adsorption for the series are directly correlated with the presence of open metal sites and further reveals the positions and orientations of as many as three additional adsorption sites. Density functional theory calculations that include van der Waals dispersion corrections quantitatively support the observed structural features associated with the primary and secondary CO2 binding sites, including CO2 positions and orientations, as well as the experimentally determined isosteric heats of CO2 adsorption.The work provides molecular level insight into the CO2adsorption properties of an isostructural series of MOFs, known as M-BTT.},
doi = {10.1039/C8SC00971F},
url = {https://www.osti.gov/biblio/1435854}, journal = {Chemical Science},
issn = {2041-6520},
number = 20,
volume = 9,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1039/C8SC00971F

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Cited by: 39 works
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Works referenced in this record:

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Projector augmented-wave method
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Strong and Reversible Binding of Carbon Dioxide in a Green Metal–Organic Framework
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Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework
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Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design
journal, January 2015


Hydrogen Storage in the Expanded Pore Metal–Organic Frameworks M 2 (dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn)
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Selective Binding of O 2 over N 2 in a Redox–Active Metal–Organic Framework with Open Iron(II) Coordination Sites
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Enhanced Binding Affinity, Remarkable Selectivity, and High Capacity of CO2 by Dual Functionalization of a rht-Type Metal-Organic Framework
journal, December 2011


The chemistry of metal–organic frameworks for CO2 capture, regeneration and conversion
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Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores
journal, August 2008

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Solvothermal growth of a ruthenium metal–organic framework featuring HKUST-1 structure type as thin films on oxide surfaces
journal, January 2011


Recent Advances in Carbon Capture with Metal–Organic Frameworks
journal, May 2015


Hydrogen Storage and Selective, Reversible O 2 Adsorption in a Metal-Organic Framework with Open Chromium(II) Sites
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Metal–organic frameworks for artificial photosynthesis and photocatalysis
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Rod Packings and Metal−Organic Frameworks Constructed from Rod-Shaped Secondary Building Units
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Carbon dioxide adsorption on MIL-100(M) (M=Cr, V, Sc) metal–organic frameworks: IR spectroscopic and thermodynamic studies
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journal, November 2011


An In-Depth Structural Study of the Carbon Dioxide Adsorption Process in the Porous Metal-Organic Frameworks CPO-27-M
journal, March 2017


Critical Factors Driving the High Volumetric Uptake of Methane in Cu 3 (btc) 2
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High-Enthalpy Hydrogen Adsorption in Cation-Exchanged Variants of the Microporous Metal−Organic Framework Mn 3 [(Mn 4 Cl) 3 (BTT) 8 (CH 3 OH) 10 ] 2
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Oxidation energies of transition metal oxides within the GGA + U framework
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Synthesis and properties of the metal-organic framework Mo3(BTC)2 (TUDMOF-1)
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Application of metal–organic frameworks with coordinatively unsaturated metal sites in storage and separation of methane and carbon dioxide
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Impact of Metal and Anion Substitutions on the Hydrogen Storage Properties of M-BTT Metal–Organic Frameworks
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Works referencing / citing this record:

An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri : An
journal, January 2019


Ligand-Assisted Enhancement of CO 2 Capture in Metal–Organic Frameworks
journal, April 2012


An In-Depth Structural Study of the Carbon Dioxide Adsorption Process in the Porous Metal-Organic Frameworks CPO-27-M
journal, March 2017


RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials
journal, February 2015


Impact of Metal and Anion Substitutions on the Hydrogen Storage Properties of M-BTT Metal–Organic Frameworks
journal, January 2013


Rod Packings and Metal−Organic Frameworks Constructed from Rod-Shaped Secondary Building Units
journal, February 2005


Base-Induced Formation of Two Magnesium Metal-Organic Framework Compounds with a Bifunctional Tetratopic Ligand
journal, August 2008


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


Selective Binding of O 2 over N 2 in a Redox–Active Metal–Organic Framework with Open Iron(II) Coordination Sites
journal, September 2011


Strong and Reversible Binding of Carbon Dioxide in a Green Metal–Organic Framework
journal, October 2011

  • Gassensmith, Jeremiah J.; Furukawa, Hiroyasu; Smaldone, Ronald A.
  • Journal of the American Chemical Society, Vol. 133, Issue 39, p. 15312-15315
  • https://doi.org/10.1021/ja206525x

Electrostatic Potential Derived Atomic Charges for Periodic Systems Using a Modified Error Functional
journal, August 2009


Application of metal–organic frameworks with coordinatively unsaturated metal sites in storage and separation of methane and carbon dioxide
journal, January 2009


Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous Metal–Organic Frameworks
journal, March 2008


The chemistry of metal–organic frameworks for CO2 capture, regeneration and conversion
journal, July 2017


A multifunctional Zr( iv )-based metal–organic framework for highly efficient elimination of Cr( vi ) from the aqueous phase
journal, January 2019


Guest-Induced Emergent Properties in Metal–Organic Frameworks
journal, March 2015


Solvothermal growth of a ruthenium metal–organic framework featuring HKUST-1 structure type as thin films on oxide surfaces
journal, January 2011


Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework
journal, January 2006


Understanding Trends in CO 2 Adsorption in Metal–Organic Frameworks with Open-Metal Sites
journal, February 2014


High-Enthalpy Hydrogen Adsorption in Cation-Exchanged Variants of the Microporous Metal−Organic Framework Mn 3 [(Mn 4 Cl) 3 (BTT) 8 (CH 3 OH) 10 ] 2
journal, September 2007


Observation of Cu2+–H2 Interactions in a Fully Desolvated Sodalite-Type Metal–Organic Framework
journal, February 2007


Carbon dioxide adsorption on MIL-100(M) (M=Cr, V, Sc) metal–organic frameworks: IR spectroscopic and thermodynamic studies
journal, May 2014


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


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


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


Critical Factors Driving the High Volumetric Uptake of Methane in Cu 3 (btc) 2
journal, August 2015


Reconciling the Discrepancies between Crystallographic Porosity and Guest Access As Exemplified by Zn-HKUST-1
journal, November 2011


Synthesis and properties of the metal-organic framework Mo3(BTC)2 (TUDMOF-1)
journal, January 2006


Hydrogen Storage in the Expanded Pore Metal–Organic Frameworks M 2 (dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn)
journal, February 2016


Enhanced H2 Adsorption in Isostructural Metal−Organic Frameworks with Open Metal Sites: Strong Dependence of the Binding Strength on Metal Ions
journal, November 2008


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


Enhanced Binding Affinity, Remarkable Selectivity, and High Capacity of CO2 by Dual Functionalization of a rht-Type Metal-Organic Framework
journal, December 2011


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


Recent Advances in Carbon Capture with Metal–Organic Frameworks
journal, May 2015


M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni) Metal–Organic Frameworks Exhibiting Increased Charge Density and Enhanced H2 Binding at the Open Metal Sites
journal, August 2014

  • Kapelewski, Matthew T.; Geier, Stephen J.; Hudson, Matthew R.
  • Journal of the American Chemical Society, Vol. 136, Issue 34, p. 12119-12129
  • https://doi.org/10.1021/ja506230r

Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores
journal, August 2008

  • Caskey, Stephen R.; Wong-Foy, Antek G.; Matzger, Adam J.
  • Journal of the American Chemical Society, Vol. 130, Issue 33, p. 10870-10871
  • https://doi.org/10.1021/ja8036096

An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri : An
journal, January 2019


A multifunctional Zr( iv )-based metal–organic framework for highly efficient elimination of Cr( vi ) from the aqueous phase
journal, January 2019


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


Neutron diffraction structural study of CO 2 binding in mixed-metal CPM-200 metal–organic frameworks
journal, January 2020