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Title: Generation and applications of structure envelopes for porous metal–organic frameworks

Abstract

The synthesis of polycrystalline, as opposed to single-crystalline, porous materials, such as zeolites and metal–organic frameworks (MOFs), is usually beneficial because the former have shorter synthesis times and higher yields. However, the structural determination of these materials using powder X-ray diffraction (PXRD) data is usually complicated. Recently, several methods for the structural investigation of zeolite polycrystalline materials have been developed, taking advantage of the structural characteristics of zeolites. Nevertheless, these techniques have rarely been applied in the structure determination of a MOF even though, with the electron-density contrast between the metal-containing units and pore regions, the construction of a structure envelope, the surface between high- and low-electron-density regions, should be straightforward for a MOF. Herein an example of such structure solution of MOFs based on PXRD data is presented. To start, a Patterson map was generated from powder diffraction intensities. From this map, structure factor phases for several of the strongest reflections were extracted and a structure envelope (SE) of a MOF was subsequently constructed. This envelope, together with all extracted reflection intensities, was used as input to theSUPERFLIPsoftware and a charge-flipping (CF) structure solution was performed. This structure solution method has been tested on the PXRD data of bothmore » activated (solvent removed from the pores;d min= 0.78 Å) and as-synthesized (d min= 1.20 Å) samples of HKUST-1. In both cases, our method has led to structure solutions. In fact, charge-flipping calculations using SE provided correct solutions in minutes (6 min for activated and 3 min for as-synthesized samples), while regular charge flipping or charge flipping with histogram matching calculation provided meaningful solutions only after several hours. To confirm the applicability of structure envelopes to low-symmetry MOFs, the structure of monoclinic PCN-200 has been solvedviaCF+SE calculations.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1382459
DOE Contract Number:  
SC0001015
Resource Type:
Journal Article
Journal Name:
Journal of Applied Crystallography
Additional Journal Information:
Journal Volume: 46; Journal Issue: 2; 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 0021-8898
Publisher:
International Union of Crystallography
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)

Citation Formats

Yakovenko, Andrey A., Reibenspies, Joseph H., Bhuvanesh, Nattamai, and Zhou, Hong-Cai. Generation and applications of structure envelopes for porous metal–organic frameworks. United States: N. p., 2013. Web. doi:10.1107/S0021889812050935.
Yakovenko, Andrey A., Reibenspies, Joseph H., Bhuvanesh, Nattamai, & Zhou, Hong-Cai. Generation and applications of structure envelopes for porous metal–organic frameworks. United States. doi:10.1107/S0021889812050935.
Yakovenko, Andrey A., Reibenspies, Joseph H., Bhuvanesh, Nattamai, and Zhou, Hong-Cai. Thu . "Generation and applications of structure envelopes for porous metal–organic frameworks". United States. doi:10.1107/S0021889812050935.
@article{osti_1382459,
title = {Generation and applications of structure envelopes for porous metal–organic frameworks},
author = {Yakovenko, Andrey A. and Reibenspies, Joseph H. and Bhuvanesh, Nattamai and Zhou, Hong-Cai},
abstractNote = {The synthesis of polycrystalline, as opposed to single-crystalline, porous materials, such as zeolites and metal–organic frameworks (MOFs), is usually beneficial because the former have shorter synthesis times and higher yields. However, the structural determination of these materials using powder X-ray diffraction (PXRD) data is usually complicated. Recently, several methods for the structural investigation of zeolite polycrystalline materials have been developed, taking advantage of the structural characteristics of zeolites. Nevertheless, these techniques have rarely been applied in the structure determination of a MOF even though, with the electron-density contrast between the metal-containing units and pore regions, the construction of a structure envelope, the surface between high- and low-electron-density regions, should be straightforward for a MOF. Herein an example of such structure solution of MOFs based on PXRD data is presented. To start, a Patterson map was generated from powder diffraction intensities. From this map, structure factor phases for several of the strongest reflections were extracted and a structure envelope (SE) of a MOF was subsequently constructed. This envelope, together with all extracted reflection intensities, was used as input to theSUPERFLIPsoftware and a charge-flipping (CF) structure solution was performed. This structure solution method has been tested on the PXRD data of both activated (solvent removed from the pores;dmin= 0.78 Å) and as-synthesized (dmin= 1.20 Å) samples of HKUST-1. In both cases, our method has led to structure solutions. In fact, charge-flipping calculations using SE provided correct solutions in minutes (6 min for activated and 3 min for as-synthesized samples), while regular charge flipping or charge flipping with histogram matching calculation provided meaningful solutions only after several hours. To confirm the applicability of structure envelopes to low-symmetry MOFs, the structure of monoclinic PCN-200 has been solvedviaCF+SE calculations.},
doi = {10.1107/S0021889812050935},
journal = {Journal of Applied Crystallography},
issn = {0021-8898},
number = 2,
volume = 46,
place = {United States},
year = {2013},
month = {2}
}

Works referenced in this record:

Using a structure envelope to facilitate structure solution from powder diffraction data
journal, December 1997

  • Brenner, S.; McCusker, L. B.; Baerlocher, C.
  • Journal of Applied Crystallography, Vol. 30, Issue 6
  • DOI: 10.1107/S0021889897011291

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


Isomerism in Metal–Organic Frameworks: “Framework Isomers”
journal, June 2011

  • Makal, Trevor A.; Yakovenko, Andrey A.; Zhou, Hong-Cai
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 14
  • DOI: 10.1021/jz200424h

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Ab initio structure solution by charge flipping
journal, March 2004

  • Oszlányi, Gábor; Sütő, András
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 60, Issue 2
  • DOI: 10.1107/S0108767303027569

Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993


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

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

SUPERFLIP – a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions
journal, July 2007


Unit-cell refinement from powder diffraction scans
journal, December 1981


Reticular synthesis and the design of new materials
journal, June 2003

  • Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.
  • Nature, Vol. 423, Issue 6941, p. 705-714
  • DOI: 10.1038/nature01650

Highly controlled acetylene accommodation in a metal–organic microporous material
journal, July 2005

  • Matsuda, Ryotaro; Kitaura, Ryo; Kitagawa, Susumu
  • Nature, Vol. 436, Issue 7048
  • DOI: 10.1038/nature03852

The current status of hydrogen storage in metal–organic frameworks—updated
journal, January 2011

  • Sculley, Julian; Yuan, Daqiang; Zhou, Hong-Cai
  • Energy & Environmental Science, Vol. 4, Issue 8
  • DOI: 10.1039/c1ee01240a

Potential applications of metal-organic frameworks
journal, December 2009

  • Kuppler, Ryan J.; Timmons, Daren J.; Fang, Qian-Rong
  • Coordination Chemistry Reviews, Vol. 253, Issue 23-24
  • DOI: 10.1016/j.ccr.2009.05.019

Ab-initio structure determination of LiSbWO6 by X-ray powder diffraction
journal, March 1988


Powder Diffraction Data and Crystal Chemical Information Combined in an Automated Structure Determination Procedure for Zeolites
journal, December 1997

  • Grosse-Kunstleve, R. W.; McCusker, L. B.; Baerlocher, Ch.
  • Journal of Applied Crystallography, Vol. 30, Issue 6
  • DOI: 10.1107/S0021889897005013

FOX , `free objects for crystallography': a modular approach to ab initio structure determination from powder diffraction
journal, November 2002

  • Favre-Nicolin, Vincent; Černý, Radovan
  • Journal of Applied Crystallography, Vol. 35, Issue 6
  • DOI: 10.1107/S0021889802015236

Functional Porous Coordination Polymers
journal, April 2004

  • Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
  • Angewandte Chemie International Edition, Vol. 43, Issue 18, p. 2334-2375
  • DOI: 10.1002/anie.200300610

Carbon dioxide capture-related gas adsorption and separation in metal-organic frameworks
journal, August 2011

  • Li, Jian-Rong; Ma, Yuguang; McCarthy, M. Colin
  • Coordination Chemistry Reviews, Vol. 255, Issue 15-16
  • DOI: 10.1016/j.ccr.2011.02.012

High H2 Adsorption in a Microporous Metal-Organic Framework with Open Metal Sites
journal, July 2005

  • Chen, Banglin; Ockwig, Nathan W.; Millward, Andrew R.
  • Angewandte Chemie International Edition, Vol. 44, Issue 30, p. 4745-4749
  • DOI: 10.1002/anie.200462787

Low-Energy Selective Capture of Carbon Dioxide by a Pre-designed Elastic Single-Molecule Trap
journal, September 2012

  • Wriedt, Mario; Sculley, Julian P.; Yakovenko, Andrey A.
  • Angewandte Chemie International Edition, Vol. 51, Issue 39
  • DOI: 10.1002/anie.201202992

Using electron microscopy to complement X-ray powder diffraction data to solve complex crystal structures
journal, January 2009

  • McCusker, Lynne B.; Baerlocher, Christian
  • Chemical Communications, Issue 12
  • DOI: 10.1039/b821716e