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Title: Probing the mechanism of CO 2 capture in diamine-appended metal–organic frameworks using measured and simulated X-ray spectroscopy

Abstract

Diamine-appended metal–organic frameworks display great promise for carbon capture applications, due to unusual step-shaped adsorption behavior that was recently attributed to a cooperative mechanism in which the adsorbed CO 2 molecules insert into the metal–nitrogen bonds to form ordered ammonium carbamate chains. We present a detailed study of this mechanism by in situ X-ray absorption spectroscopy and density functional theory calculations. Distinct spectral changes at the N and O K-edges are apparent upon CO 2 adsorption in both mmen-Mg 2(dobpdc) and mmen-Mn 2(dobpdc), and these are evaluated based upon computed spectra from three potential adsorption structures. The computations reveal that the observed spectral changes arise from specific electronic states that are signatures of a quasi-trigonal planar carbamate species that is hydrogen bonded to an ammonium cation. This eliminates two of the three structures studied, and confirms the insertion mechanism. Here, we note the particular sensitivity of X-ray absorption spectra to the insertion step of this mechanism, underpinning the strength of the technique for examining subtle chemical changes upon gas adsorption.

Authors:
 [1];  [2];  [3];  [1];  [1];  [1];  [3];  [4];  [1];  [5];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. Grenoble Alpes, Grenoble (France)
  3. Univ. of California, Berkeley, CA (United States)
  4. Univ. of Minnesota, Minneapolis, MN (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
High Performance Computing Services Group; GENCI; Beamline 6.3.2; National Energy Research Scientific Computing Center
OSTI Identifier:
1488857
Grant/Contract Number:  
FG02-12ER16362; SC0008688
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 17; Journal Issue: 33; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Drisdell, Walter S., Poloni, Roberta, McDonald, Thomas M., Pascal, Tod A., Wan, Liwen F., Pemmaraju, C. Das, Vlaisavljevich, Bess, Odoh, Samuel O., Neaton, Jeffrey B., Long, Jeffrey R., Prendergast, David, and Kortright, Jeffrey B. Probing the mechanism of CO2 capture in diamine-appended metal–organic frameworks using measured and simulated X-ray spectroscopy. United States: N. p., 2015. Web. doi:10.1039/C5CP02951A.
Drisdell, Walter S., Poloni, Roberta, McDonald, Thomas M., Pascal, Tod A., Wan, Liwen F., Pemmaraju, C. Das, Vlaisavljevich, Bess, Odoh, Samuel O., Neaton, Jeffrey B., Long, Jeffrey R., Prendergast, David, & Kortright, Jeffrey B. Probing the mechanism of CO2 capture in diamine-appended metal–organic frameworks using measured and simulated X-ray spectroscopy. United States. doi:10.1039/C5CP02951A.
Drisdell, Walter S., Poloni, Roberta, McDonald, Thomas M., Pascal, Tod A., Wan, Liwen F., Pemmaraju, C. Das, Vlaisavljevich, Bess, Odoh, Samuel O., Neaton, Jeffrey B., Long, Jeffrey R., Prendergast, David, and Kortright, Jeffrey B. Thu . "Probing the mechanism of CO2 capture in diamine-appended metal–organic frameworks using measured and simulated X-ray spectroscopy". United States. doi:10.1039/C5CP02951A. https://www.osti.gov/servlets/purl/1488857.
@article{osti_1488857,
title = {Probing the mechanism of CO2 capture in diamine-appended metal–organic frameworks using measured and simulated X-ray spectroscopy},
author = {Drisdell, Walter S. and Poloni, Roberta and McDonald, Thomas M. and Pascal, Tod A. and Wan, Liwen F. and Pemmaraju, C. Das and Vlaisavljevich, Bess and Odoh, Samuel O. and Neaton, Jeffrey B. and Long, Jeffrey R. and Prendergast, David and Kortright, Jeffrey B.},
abstractNote = {Diamine-appended metal–organic frameworks display great promise for carbon capture applications, due to unusual step-shaped adsorption behavior that was recently attributed to a cooperative mechanism in which the adsorbed CO2 molecules insert into the metal–nitrogen bonds to form ordered ammonium carbamate chains. We present a detailed study of this mechanism by in situ X-ray absorption spectroscopy and density functional theory calculations. Distinct spectral changes at the N and O K-edges are apparent upon CO2 adsorption in both mmen-Mg2(dobpdc) and mmen-Mn2(dobpdc), and these are evaluated based upon computed spectra from three potential adsorption structures. The computations reveal that the observed spectral changes arise from specific electronic states that are signatures of a quasi-trigonal planar carbamate species that is hydrogen bonded to an ammonium cation. This eliminates two of the three structures studied, and confirms the insertion mechanism. Here, we note the particular sensitivity of X-ray absorption spectra to the insertion step of this mechanism, underpinning the strength of the technique for examining subtle chemical changes upon gas adsorption.},
doi = {10.1039/C5CP02951A},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 33,
volume = 17,
place = {United States},
year = {Thu Jul 23 00:00:00 EDT 2015},
month = {Thu Jul 23 00:00:00 EDT 2015}
}

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Works referenced in this record:

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

The Mechanism of Carbon Dioxide Adsorption in an Alkylamine-Functionalized Metal�Organic Framework
journal, April 2013

  • Planas, Nora; Dzubak, Allison L.; Poloni, Roberta
  • Journal of the American Chemical Society, Vol. 135, Issue 20, p. 7402-7405
  • DOI: 10.1021/ja4004766

Projector augmented-wave method
journal, December 1994


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


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

Carbon Dioxide Capture: Prospects for New Materials
journal, July 2010

  • D'Alessandro, Deanna?M.; Smit, Berend; Long, Jeffrey?R.
  • Angewandte Chemie International Edition, Vol. 49, Issue 35, p. 6058-6082
  • DOI: 10.1002/anie.201000431

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


Evaluating metal�organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption
journal, January 2011

  • Mason, Jarad A.; Sumida, Kenji; Herm, Zoey R.
  • Energy & Environmental Science, Vol. 4, Issue 8, p. 3030-3040
  • DOI: 10.1039/c1ee01720a

Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites
journal, November 2009

  • Britt, D.; Furukawa, H.; Wang, B.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 49, p. 20637-20640
  • DOI: 10.1073/pnas.0909718106

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

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


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

  • Dietzel, Pascal D. C.; Besikiotis, Vasileios; Blom, Richard
  • Journal of Materials Chemistry, Vol. 19, Issue 39, p. 7362-7370
  • DOI: 10.1039/b911242a

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
  • DOI: 10.1021/ja8036096