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The Surprising Stability of Cu3(btc)2 Metal–Organic Framework under Steam Flow at High Temperature

  • Raynald Giovine
    Raynald Giovine
    Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, France
  • Frédérique Pourpoint
    Frédérique Pourpoint
    Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, France
  • Sylvain Duval
    Sylvain Duval
    Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, France
  • Olivier Lafon
    Olivier Lafon
    Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, France
    Institut Universitaire de France, 1 rue Descartes, 75231 Cedex 05 Paris, France
  • Jean-Paul Amoureux
    Jean-Paul Amoureux
    Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, France
    Bruker, Biospin, 67160 Wissembourg, France
  • Thierry Loiseau
    Thierry Loiseau
    Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, France
  • , and 
  • Christophe Volkringer*
    Christophe Volkringer
    Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, France
    Institut Universitaire de France, 1 rue Descartes, 75231 Cedex 05 Paris, France
    *E-mail: [email protected]
Cite this: Cryst. Growth Des. 2018, 18, 11, 6681–6693
Publication Date (Web):October 2, 2018
https://doi.org/10.1021/acs.cgd.8b00931
Copyright © 2018 American Chemical Society

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    Abstract

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    It is widely admitted that metal–organic frameworks (MOFs) are water sensitive and that high temperatures accelerate the hydrolysis phenomena and the collapse of the porous network. We have investigated here the resistance of the prototypical HKUST-1 MOF under steam flow at temperatures ranging from RT to 200 °C. Surprisingly, the porous framework is not degraded at 200 °C, whereas temperatures close to 100 °C lead to the total destruction of the MOF. This unexpected behavior is assigned to the extended interaction of water with the porous framework at temperature about 100 °C, whereas above 150 °C the transient interactions between gaseous water and the HKUST-1 framework limit the decomposition process.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.8b00931.

    • Experimental setup, optical and SEM images, PXRD patterns, and IR spectra of HKUST-1 under dry flow, IR spectra of HKUST-1 under steam flow, evolution of IR spectra under steam flow at 100 °C for 24 h, 1H → 13C TEDOR sequence used in this work, 13C half-echo spectra and 2D 1H → 13C TEDOR spectrum at 9.4 T with MAS frequency of 30 kHz of as-synthesized HKUST-1, list of new 13C peaks observed on the HKUST-1 after an exposure time of 16 h and 24 h under steam flow, 2D 1H → 13C TEDOR spectrum at 9.4 T and MAS frequency of 30 kHz of HKUST-1 after an exposure time of 16 h and 24 h under steam flow and list of 13C–1H correlation peaks observed, specific surface area obtained with the BET and Langmuir models for HKUST-1 treated under dry flow or steam flow and evolution under steam flow for 24 h (PDF)

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