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

Abstract

Herein we present a detailed study of the hydrogen adsorption properties of Cu-BTTri, a robust crystalline metal-organic framework containing open metal-coordination sites. Diffraction techniques, carried out on the activated framework, reveal a structure that is different from what was previously reported. Further, combining standard hydrogen adsorption measurements with in-situ neutron diffraction techniques provides molecular level insight into the hydrogen adsorption process. The diffraction experiments unveil the location of four D2 adsorption sites in Cu-BTTri and shed light on the structural features that promote hydrogen adsorption in this material. Density functional theory (DFT), used to predict the location and strength of binding sites, corroborate the experimental findings. By decomposing binding energies in different sites in various energetic contributions, we show that van der Waals interactions play a crucial role, suggesting a possible route to enhancing the binding energy around open metal coordination sites.

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [1];  [1];  [3];  [1];  [1]; ORCiD logo [4];  [5]; ORCiD logo [1]
  1. Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), -1051 Sion Switzerland
  2. Institute of Materials, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne Switzerland; Institut Charles Gerhardt Montpellier UMR 5253 CNRS, Université de Montpellier, Place E. Bataillon 34095 Montpellier Cedex 05 France
  3. National Institute of Standards and Technology, Center for Neutron Research, 20899 Gaithersburg Maryland USA; National Renewable Energy Laboratory, 80401 Golden Colorado USA
  4. National Institute of Standards and Technology, Center for Neutron Research, 20899 Gaithersburg Maryland USA
  5. Institute of Materials, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne Switzerland
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1493694
Report Number(s):
NREL/JA-5900-73224
Journal ID: ISSN 1434-1948
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: none; Journal Issue: none; Journal ID: ISSN 1434-1948
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal-organic frameworks; hydrogen; neutron diffraction; density functional calculations

Citation Formats

Asgari, Mehrdad, Semino, Rocio, Schouwink, Pascal, Kochetygov, Ilia, Trukhina, Olga, Tarver, Jacob D., Bulut, Safak, Yang, Shuliang, Brown, Craig M., Ceriotti, Michele, and Queen, Wendy L. An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri: An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri. United States: N. p., 2019. Web. doi:10.1002/ejic.201801253.
Asgari, Mehrdad, Semino, Rocio, Schouwink, Pascal, Kochetygov, Ilia, Trukhina, Olga, Tarver, Jacob D., Bulut, Safak, Yang, Shuliang, Brown, Craig M., Ceriotti, Michele, & Queen, Wendy L. An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri: An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri. United States. doi:10.1002/ejic.201801253.
Asgari, Mehrdad, Semino, Rocio, Schouwink, Pascal, Kochetygov, Ilia, Trukhina, Olga, Tarver, Jacob D., Bulut, Safak, Yang, Shuliang, Brown, Craig M., Ceriotti, Michele, and Queen, Wendy L. Tue . "An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri: An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri". United States. doi:10.1002/ejic.201801253.
@article{osti_1493694,
title = {An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri: An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri},
author = {Asgari, Mehrdad and Semino, Rocio and Schouwink, Pascal and Kochetygov, Ilia and Trukhina, Olga and Tarver, Jacob D. and Bulut, Safak and Yang, Shuliang and Brown, Craig M. and Ceriotti, Michele and Queen, Wendy L.},
abstractNote = {Herein we present a detailed study of the hydrogen adsorption properties of Cu-BTTri, a robust crystalline metal-organic framework containing open metal-coordination sites. Diffraction techniques, carried out on the activated framework, reveal a structure that is different from what was previously reported. Further, combining standard hydrogen adsorption measurements with in-situ neutron diffraction techniques provides molecular level insight into the hydrogen adsorption process. The diffraction experiments unveil the location of four D2 adsorption sites in Cu-BTTri and shed light on the structural features that promote hydrogen adsorption in this material. Density functional theory (DFT), used to predict the location and strength of binding sites, corroborate the experimental findings. By decomposing binding energies in different sites in various energetic contributions, we show that van der Waals interactions play a crucial role, suggesting a possible route to enhancing the binding energy around open metal coordination sites.},
doi = {10.1002/ejic.201801253},
journal = {European Journal of Inorganic Chemistry},
issn = {1434-1948},
number = none,
volume = none,
place = {United States},
year = {2019},
month = {1}
}

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

Hydrogen Storage in Metal–Organic Frameworks
journal, September 2011

  • Suh, Myunghyun Paik; Park, Hye Jeong; Prasad, Thazhe Kootteri
  • Chemical Reviews, Vol. 112, Issue 2, p. 782-835
  • DOI: 10.1021/cr200274s

Strong CO2 Binding in a Water-Stable, Triazolate-Bridged Metal−Organic Framework Functionalized with Ethylenediamine
journal, July 2009

  • Demessence, Aude; D’Alessandro, Deanna M.; Foo, Maw Lin
  • Journal of the American Chemical Society, Vol. 131, Issue 25, p. 8784-8786
  • DOI: 10.1021/ja903411w

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


Metal–Organic Frameworks as Efficient Materials for Drug Delivery
journal, September 2006

  • Horcajada, Patricia; Serre, Christian; Vallet-Regí, María
  • Angewandte Chemie International Edition, Vol. 45, Issue 36, p. 5974-5978
  • DOI: 10.1002/anie.200601878

Metal–organic framework materials as catalysts
journal, January 2009

  • Lee, JeongYong; Farha, Omar K.; Roberts, John
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
  • DOI: 10.1039/b807080f

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Hydrogen storage in metal–organic frameworks
journal, January 2009

  • Murray, Leslie J.; Dincă, Mircea; Long, Jeffrey R.
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1294-1314
  • DOI: 10.1039/b802256a

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

Hydrogen Storage in Microporous Metal-Organic Frameworks
journal, May 2003

  • Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed
  • Science, Vol. 300, Issue 5622, p. 1127-1129
  • DOI: 10.1126/science.1083440

Selective gas adsorption and separation in metal–organic frameworks
journal, January 2009

  • Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504
  • DOI: 10.1039/b802426j

Hydrogen Storage in Microporous Metal-Organic Frameworks with Exposed Metal Sites
journal, August 2008

  • Dincă, Mircea; Long, Jeffrey R.
  • Angewandte Chemie International Edition, Vol. 47, Issue 36, p. 6766-6779
  • DOI: 10.1002/anie.200801163

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

Hybrid porous solids past, present, future
journal, January 2008

  • Férey, Gérard
  • Chem. Soc. Rev., Vol. 37, Issue 1, p. 191-214
  • DOI: 10.1039/B618320B

Hydrogen storage and carbon dioxide capture in an iron-based sodalite-type metal–organic framework (Fe-BTT) discovered via high-throughput methods
journal, January 2010

  • Sumida, Kenji; Horike, Satoshi; Kaye, Steven S.
  • Chemical Science, Vol. 1, Issue 2, p. 184-191
  • DOI: 10.1039/c0sc00179a

Engineering Metal Organic Frameworks for Heterogeneous Catalysis
journal, August 2010

  • Corma, A.; García, H.; Llabrés i Xamena, F. X.
  • Chemical Reviews, Vol. 110, Issue 8, p. 4606-4655
  • DOI: 10.1021/cr9003924

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

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


Strategies for Hydrogen Storage in Metal-Organic Frameworks
journal, July 2005

  • Rowsell, Jesse L. C.; Yaghi, Omar M.
  • Angewandte Chemie International Edition, Vol. 44, Issue 30, p. 4670-4679
  • DOI: 10.1002/anie.200462786