Oxidant or Catalyst for Oxidation? A Study of How Structure and Disorder Change the Selectivity for Direct versus Catalytic Oxidation Mediated by Manganese(III,IV) Oxides

  • Mayada Sabri
    Mayada Sabri
    Department of Chemistry and Biotechnology, Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, Melbourne, Victoria 3122, Australia
    College of Science and Engineering, James Cook University, Townsville, Queensland 4811, Australia
    College of Education for Pure Science-Ibn Al-Haitham, University of Baghdad, Baghdad 10071, Iraq
    More by Mayada Sabri
  • Hannah J. King
    Hannah J. King
    Department of Chemistry and Biotechnology, Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, Melbourne, Victoria 3122, Australia
    College of Science and Engineering, James Cook University, Townsville, Queensland 4811, Australia
  • Rosalind J. Gummow
    Rosalind J. Gummow
    College of Science and Engineering, James Cook University, Townsville, Queensland 4811, Australia
  • Xunyu Lu
    Xunyu Lu
    School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia
    More by Xunyu Lu
  • Chuan Zhao
    Chuan Zhao
    School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia
    More by Chuan Zhao
  • Michael Oelgemöller
    Michael Oelgemöller
    College of Science and Engineering, James Cook University, Townsville, Queensland 4811, Australia
  • Shery L. Y. Chang
    Shery L. Y. Chang
    LeRoy Eyring Center for Microscopy, Arizona State University, Tempe, Arizona 85287, United States
  • , and 
  • Rosalie K. Hocking*
    Rosalie K. Hocking
    Department of Chemistry and Biotechnology, Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, Melbourne, Victoria 3122, Australia
    College of Science and Engineering, James Cook University, Townsville, Queensland 4811, Australia
    *E-mail: [email protected]
Cite this: Chem. Mater. 2018, 30, 22, 8244–8256
Publication Date (Web):October 24, 2018
https://doi.org/10.1021/acs.chemmater.8b03661
Copyright © 2018 American Chemical Society
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Abstract

Structure type and disorder have become important questions in catalyst design, with the most active catalysts often noted to be “disordered” or “amorphous” in nature. To quantify the effects of disorder and structure type systematically, a test set of manganese(III,IV) oxides was developed and their reactivity as oxidants and catalysts tested against three substrates: methylene blue, hydrogen peroxide, and water. We find that disorder destabilizes the materials thermodynamically, making them stronger chemical oxidants but not necessarily better catalysts. For the disproportionation of H2O2 and the oxidative decomposition of methylene blue, MnOx-mediated direct oxidation competes with catalytically mediated oxidation, making the most disordered materials the worst catalysts, whereas for water oxidation, the most disordered materials and the strongest chemical oxidants are also the best catalysts. Even though the manganese(III,IV) oxide materials were able to oxidize both methylene blue and peroxides directly, the same materials were able to act as catalysts for the oxidation of methylene blue in the presence of peroxides. This implies that effects of electron transfer time scales are important and strongly affected by structure type and disorder. This is discussed in the context of catalyst design.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b03661.

  • A photograph showing our gas buret for monitoring the volume of gas that evolved, XANES data showing the reaction between methylene blue and manganese oxides when methylene blue is in 3-fold excess relative to Mn, a plot showing reactions between methylene blue and MnOx in the absence of O2, an expansion of Figure 8 to three pH values, and XANES data taken after the addition of Ce4+ to MnOx (PDF)

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