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Enhanced Hydrothermal Stability of γ-Al2O3 Catalyst Supports with Alkyl Phosphonate Coatings
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    Enhanced Hydrothermal Stability of γ-Al2O3 Catalyst Supports with Alkyl Phosphonate Coatings
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    • Tim Van Cleve
      Tim Van Cleve
      Department of Chemical and Biological Engineering, University of Colorado Boulder, JSCBB D125, 3415 Colorado Avenue, Boulder, Colorado 80303, United States
    • Devon Underhill
      Devon Underhill
      Department of Chemical and Biological Engineering, University of Colorado Boulder, JSCBB D125, 3415 Colorado Avenue, Boulder, Colorado 80303, United States
    • Mariana Veiga Rodrigues
      Mariana Veiga Rodrigues
      School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
      Instituto de Química de Araraquara (UNESP), Rua Prof. Francisco Degni 55, 14800-900 Araraquara, SP Brazil
    • Carsten Sievers
      Carsten Sievers
      School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
    • J. Will Medlin*
      J. Will Medlin
      Department of Chemical and Biological Engineering, University of Colorado Boulder, JSCBB D125, 3415 Colorado Avenue, Boulder, Colorado 80303, United States
      *E-mail: [email protected]
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    Langmuir

    Cite this: Langmuir 2018, 34, 12, 3619–3625
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    https://doi.org/10.1021/acs.langmuir.8b00465
    Published March 7, 2018
    Copyright © 2018 American Chemical Society

    Abstract

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    In this study, monolayers formed from organophosphonic acids were employed to stabilize porous γ-Al2O3, both as a single component and as a support for Pt nanoparticle catalysts, during exposure to hydrothermal conditions. To provide a baseline, structural changes of uncoated γ-Al2O3 catalysts under model aqueous phase reforming conditions (liquid water at 200 °C and autogenic pressure) were examined over the course of 20 h. These changes were characterized by X-ray diffraction, NMR spectroscopy, N2 physisorption, and IR spectroscopy. It was demonstrated that γ-alumina was rapidly converted into a hydrated boehmite (AlOOH) phase with significantly decreased surface area. Deposition of alkyl phosphonate groups on γ-alumina drastically inhibited the formation of boehmite, thereby maintaining its high specific surface area over 20 h of treatment. 27Al MAS NMR spectra demonstrated that hydrothermal stability increased with alkyl tail length despite lower P coverages. Although the inhibition of boehmite formation by the phosphonic acids was attributed primarily to the formation of Al2O3–POx bonds, it was found that use of longer-chain octadecylphosphonic acids led to the most pronounced effect. Phosphonate coatings on Pt/γ-Al2O3 improved stability without adversely affecting the rate of a model reaction, catalytic hydrogenation of 1-hexene.

    Copyright © 2018 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.langmuir.8b00465.

    • DRIFT and 27Al NMR spectra of as-synthesized and hydrothermal-treated Al2O3 samples; relative surface area changes over course of hydrothermal treatment; DRIFT spectra of Pt/Al2O3 catalysts; calculation and comparison of P coverage based on ICP results; 31P NMR of Al2O3@C1PA and Al2O3@C18PA (PDF)

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    Langmuir

    Cite this: Langmuir 2018, 34, 12, 3619–3625
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.langmuir.8b00465
    Published March 7, 2018
    Copyright © 2018 American Chemical Society

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