Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Overcoming Metastable CO2 Adsorption in a Bulky Diamine-Appended Metal-Organic Framework

Abstract

We report carbon capture at fossil fuel-fired power plants is a critical strategy to mitigate anthropogenic contributions to global warming, but widespread deployment of this technology is hindered by a lack of energy-efficient materials that can be optimized for CO2 capture from a specific flue gas. As a result of their tunable, step-shaped CO2 adsorption profiles, diamine-functionalized metal-organic frameworks (MOFs) of the form diamine-Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are among the most promising materials for carbon capture applications. Here, we present a detailed investigation of dmen-Mg2(dobpdc) (dmen = 1,2-diamino-2-methylpropane), one of only two MOFs with an adsorption step near the optimal pressure for CO2 capture from coal flue gas. While prior characterization suggested that this material only adsorbs CO2 to half capacity (0.5 CO2 per diamine) at 1 bar, we show that the half-capacity state is actually a metastable intermediate. Under appropriate conditions, the MOF adsorbs CO2 to full capacity, but conversion from the half-capacity structure happens on a very slow time scale, rendering it inaccessible in traditional adsorption measurements. Data from solid-state magic angle spinning nuclear magnetic resonance spectroscopy, coupled with van der Waals-corrected density functional theory, indicate that ammonium carbamate chains formed at half capacity and full capacity adoptmore » opposing configurations, and the need to convert between these states likely dictates the sluggish post-half-capacity uptake. By use of the more symmetric parent framework Mg2(pc-dobpdc) (pc-dobpdc4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate), the metastable trap can be avoided and the full CO2 capacity of dmen-Mg2(pc-dobpdc) accessed under conditions relevant for carbon capture from coal-fired power plants.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [1]; ORCiD logo [3];  [4];  [1];  [4]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of Cambridge (United Kingdom)
  3. Korea Institute of Science and Technology (KIST), Seoul (Korea, Republic of)
  4. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH); National Institute of General Medical Sciences (NIGMS); Korean Institute of Science and Technology (KIST)
OSTI Identifier:
1843008
Grant/Contract Number:  
AC02-05CH11231; SC0019992; S10OD024998; S10OD023532; AC02-06CH1135; F32GM120799; 2E30460; KSC-2019-CRE-0149
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 143; Journal Issue: 37; 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; adsorption; chemical structure; organic compounds; cations; materials

Citation Formats

Dinakar, Bhavish, Forse, Alexander C., Jiang, Henry H., Zhu, Ziting, Lee, Jung-Hoon, Kim, Eugene J., Parker, Surya T., Pollak, Connor J., Siegelman, Rebecca L., Milner, Phillip J., Reimer, Jeffrey A., and Long, Jeffrey R. Overcoming Metastable CO2 Adsorption in a Bulky Diamine-Appended Metal-Organic Framework. United States: N. p., 2021. Web. doi:10.1021/jacs.1c06434.
Copy to clipboard
Dinakar, Bhavish, Forse, Alexander C., Jiang, Henry H., Zhu, Ziting, Lee, Jung-Hoon, Kim, Eugene J., Parker, Surya T., Pollak, Connor J., Siegelman, Rebecca L., Milner, Phillip J., Reimer, Jeffrey A., & Long, Jeffrey R. Overcoming Metastable CO2 Adsorption in a Bulky Diamine-Appended Metal-Organic Framework. United States. https://doi.org/10.1021/jacs.1c06434
Copy to clipboard
Dinakar, Bhavish, Forse, Alexander C., Jiang, Henry H., Zhu, Ziting, Lee, Jung-Hoon, Kim, Eugene J., Parker, Surya T., Pollak, Connor J., Siegelman, Rebecca L., Milner, Phillip J., Reimer, Jeffrey A., and Long, Jeffrey R. Tue . "Overcoming Metastable CO2 Adsorption in a Bulky Diamine-Appended Metal-Organic Framework". United States. https://doi.org/10.1021/jacs.1c06434. https://www.osti.gov/servlets/purl/1843008.
Copy to clipboard
@article{osti_1843008,
title = {Overcoming Metastable CO2 Adsorption in a Bulky Diamine-Appended Metal-Organic Framework},
author = {Dinakar, Bhavish and Forse, Alexander C. and Jiang, Henry H. and Zhu, Ziting and Lee, Jung-Hoon and Kim, Eugene J. and Parker, Surya T. and Pollak, Connor J. and Siegelman, Rebecca L. and Milner, Phillip J. and Reimer, Jeffrey A. and Long, Jeffrey R.},
abstractNote = {We report carbon capture at fossil fuel-fired power plants is a critical strategy to mitigate anthropogenic contributions to global warming, but widespread deployment of this technology is hindered by a lack of energy-efficient materials that can be optimized for CO2 capture from a specific flue gas. As a result of their tunable, step-shaped CO2 adsorption profiles, diamine-functionalized metal-organic frameworks (MOFs) of the form diamine-Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are among the most promising materials for carbon capture applications. Here, we present a detailed investigation of dmen-Mg2(dobpdc) (dmen = 1,2-diamino-2-methylpropane), one of only two MOFs with an adsorption step near the optimal pressure for CO2 capture from coal flue gas. While prior characterization suggested that this material only adsorbs CO2 to half capacity (0.5 CO2 per diamine) at 1 bar, we show that the half-capacity state is actually a metastable intermediate. Under appropriate conditions, the MOF adsorbs CO2 to full capacity, but conversion from the half-capacity structure happens on a very slow time scale, rendering it inaccessible in traditional adsorption measurements. Data from solid-state magic angle spinning nuclear magnetic resonance spectroscopy, coupled with van der Waals-corrected density functional theory, indicate that ammonium carbamate chains formed at half capacity and full capacity adopt opposing configurations, and the need to convert between these states likely dictates the sluggish post-half-capacity uptake. By use of the more symmetric parent framework Mg2(pc-dobpdc) (pc-dobpdc4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate), the metastable trap can be avoided and the full CO2 capacity of dmen-Mg2(pc-dobpdc) accessed under conditions relevant for carbon capture from coal-fired power plants.},
doi = {10.1021/jacs.1c06434},
journal = {Journal of the American Chemical Society},
number = 37,
volume = 143,
place = {United States},
year = {Tue Sep 07 00:00:00 EDT 2021},
month = {Tue Sep 07 00:00:00 EDT 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jacs.1c06434
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

We have the technology
journal, October 2017

Enhancement of CO 2 binding and mechanical properties upon diamine functionalization of M 2 (dobpdc) metal–organic frameworks
journal, January 2018

  • Lee, Jung-Hoon; Siegelman, Rebecca L.; Maserati, Lorenzo
  • Chemical Science, Vol. 9, Issue 23
  • DOI: 10.1039/C7SC05217K

CO2 Capture in the Cement Industry
journal, February 2009

Projector augmented-wave method
journal, December 1994

Post-combustion CO2 capture with chemical absorption: A state-of-the-art review
journal, September 2011

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Modelling one- and two-dimensional solid-state NMR spectra: Modelling 1D and 2D solid-state NMR spectra
journal, December 2001

  • Massiot, Dominique; Fayon, Franck; Capron, Mickael
  • Magnetic Resonance in Chemistry, Vol. 40, Issue 1
  • DOI: 10.1002/mrc.984

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
  • DOI: 10.1021/jacs.7b09983

Powder crystallography of pharmaceutical materials by combined crystal structure prediction and solid-state 1H NMR spectroscopy
journal, January 2013

  • Baias, Maria; Widdifield, Cory M.; Dumez, Jean-Nicolas
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 21
  • DOI: 10.1039/c3cp41095a

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

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

Overcoming double-step CO 2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg 2 (dobpdc)
journal, January 2018

  • Milner, Phillip J.; Martell, Jeffrey D.; Siegelman, Rebecca L.
  • Chemical Science, Vol. 9, Issue 1
  • DOI: 10.1039/C7SC04266C

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994

Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999

Exceptional CO 2 working capacity in a heterodiamine-grafted metal–organic framework
journal, January 2015

  • Lee, Woo Ram; Jo, Hyuna; Yang, Li-Ming
  • Chemical Science, Vol. 6, Issue 7
  • DOI: 10.1039/C5SC01191D

"Special points for Brillouin-zone integrations"—a reply
journal, August 1977

CO2 Capture and Utilization in Cement and Iron and Steel Industries
journal, January 2014

Kinetics of cooperative CO 2 adsorption in diamine-appended variants of the metal–organic framework Mg 2 (dobpdc)
journal, January 2020

  • Martell, Jeffrey D.; Milner, Phillip J.; Siegelman, Rebecca L.
  • Chemical Science, Vol. 11, Issue 25
  • DOI: 10.1039/D0SC01087A

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
  • DOI: 10.1021/jacs.7b05858

Adsorption Properties and Microscopic Mechanism of CO 2 Capture in 1,1-Dimethyl-1,2-ethylenediamine-Grafted Metal–Organic Frameworks
journal, March 2020

  • Zhang, Hui; Yang, Li-Ming; Ganz, Eric
  • ACS Applied Materials & Interfaces, Vol. 12, Issue 16
  • DOI: 10.1021/acsami.0c01927

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
  • DOI: 10.1021/jacs.7b07612

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
  • DOI: 10.1038/nature14327

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
  • DOI: 10.1021/ja300034j

Ab initiomolecular dynamics for liquid metals
journal, January 1993

15N chemical shift referencing in solid state NMR
journal, July 2014

  • Bertani, Philippe; Raya, Jésus; Bechinger, Burkhard
  • Solid State Nuclear Magnetic Resonance, Vol. 61-62
  • DOI: 10.1016/j.ssnmr.2014.03.003

Cooperative carbon capture and steam regeneration with tetraamine-appended metal–organic frameworks
journal, July 2020

  • Kim, Eugene J.; Siegelman, Rebecca L.; Jiang, Henry Z. H.
  • Science, Vol. 369, Issue 6502
  • DOI: 10.1126/science.abb3976

Water Enables Efficient CO 2 Capture from Natural Gas Flue Emissions in an Oxidation-Resistant Diamine-Appended Metal–Organic Framework
journal, July 2019

  • Siegelman, Rebecca L.; Milner, Phillip J.; Forse, Alexander C.
  • Journal of the American Chemical Society, Vol. 141, Issue 33
  • DOI: 10.1021/jacs.9b05567

Density-functional energies and forces with Gaussian-broadened fractional occupations
journal, May 1994

Carbon capture and storage update
journal, January 2014

  • Boot-Handford, Matthew E.; Abanades, Juan C.; Anthony, Edward J.
  • Energy Environ. Sci., Vol. 7, Issue 1
  • DOI: 10.1039/C3EE42350F

Amine Scrubbing for CO2 Capture
journal, September 2009

Photochemical Removal of Mercury from Flue Gas
journal, October 2002

  • Granite, Evan J.; Pennline, Henry W.
  • Industrial & Engineering Chemistry Research, Vol. 41, Issue 22
  • DOI: 10.1021/ie020251b

Elucidating CO 2 Chemisorption in Diamine-Appended Metal–Organic Frameworks
journal, December 2018

  • Forse, Alexander C.; Milner, Phillip J.; Lee, Jung-Hoon
  • Journal of the American Chemical Society, Vol. 140, Issue 51
  • DOI: 10.1021/jacs.8b10203

Influence of reservoir size on the adsorption path in an ideal pore
journal, September 2009

  • Puibasset, Joël; Kierlik, Edouard; Tarjus, Gilles
  • The Journal of Chemical Physics, Vol. 131, Issue 12
  • DOI: 10.1063/1.3236510
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: