Direct Formation of 2D-MnOx under Conditions of Water Oxidation Catalysis

  • 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, Technology, and Engineering, James Cook University, Townsville, Queensland 4811, Australia
    *E-mail: [email protected]
  • Rosalind J. Gummow
    Rosalind J. Gummow
    College of Science, Technology, and Engineering, James Cook University, Townsville, Queensland 4811, Australia
  • 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, Technology, and Engineering, James Cook University, Townsville, Queensland 4811, Australia
  • 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, Technology, and Engineering, James Cook University, Townsville, Queensland 4811, Australia
    University of Baghdad, College of Education for Pure Science—Ibn Al-Haitham, 10071 Baghdad, Iraq
    More by Mayada Sabri
  • Peter Kappen
    Peter Kappen
    Australian Synchrotron, ANSTO, 800 Blackburn Road Clayton, Victoria 3168, Australia
    More by Peter Kappen
  • Christian Dwyer
    Christian Dwyer
    Department of Physics, Arizona State University, Tempe, Arizona 85287, United States
  • , and 
  • Shery L. Y. Chang*
    Shery L. Y. Chang
    LeRoy Eyring Centre for Solid State Science, Arizona State University, Tempe, Arizona 85287, United States
    *E-mail: [email protected]
Cite this: ACS Appl. Nano Mater. 2018, 1, 4, 1603–1611
Publication Date (Web):April 5, 2018
https://doi.org/10.1021/acsanm.8b00095
Copyright © 2018 American Chemical Society
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Abstract

We describe the synthesis and characterization of a novel 2D-MnOx material using a combination of HR-TEM, XAS, XRD, and reactivity measurements. The ease with which the 2D material can be made and the conditions under which it can be made implies that water oxidation catalysts previously described as “birnessite-like” (3D) may be better thought of as 2D materials with very limited layer stacking. The distinction between the materials as being “birnessite-like” and “2D” is important because it impacts on our understanding of the function of these materials in the environment and as catalysts. The 2D-MnOx material is noted to be a substantially stronger chemical oxidant than previously noted for other birnessite-like manganese oxides. The material is shown to both “directly” and “catalytically” oxidize water in the presence of Ce4+, and to directly oxidize H2O2 in the absence of any other oxidant.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsanm.8b00095.

  • XANES and pre-edge of 2D-MnOx and K+ birnessite are compared to MnO (Mn2+), Mn2O3 (Mn3+), and MnO2 (Mn4+); XANES pre-edge and EXAFS data are compared to Spiccia’s catalyst, XAS data of the material taken under formation conditions; comparison of the XAS data with that of Biogenic MnOx formed by L. disophora SP6; EXAFS fits for both K+ Birnessite and 2D-MnOx; a blow up of the powder diffraction data; and electrochemical data of the material drop cast on ITO and the calculation of electrochemically active surface area is provided (PDF)

  • Video showing the reaction of 2D-MnOx, K+ birnessite and peroxide with peroxide (MP4)

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Cited By


This article is cited by 3 publications.

  1. Mayada Sabri, Hannah J. King, Rosalind J. Gummow, Xunyu Lu, Chuan Zhao, Michael Oelgemöller, Shery L. Y. Chang, Rosalie K. Hocking. 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. Chemistry of Materials 2018, 30 (22) , 8244-8256. https://doi.org/10.1021/acs.chemmater.8b03661
  2. Rukiye Babacan Tosun, Kadriye Özlem Hamaloğlu, Cengiz Kavaklı, Pınar Akkaş Kavaklı, Ali Tuncel. Reusable water oxidation catalyst with dual active center for enhanced water oxidation: Iridium oxide nanoparticles immobilized on monodisperse-porous Mn5O8 microspheres. International Journal of Hydrogen Energy 2021, 46 (29) , 15482-15496. https://doi.org/10.1016/j.ijhydene.2021.02.087
  3. Xin Bo, Kamran Dastafkan, Chuan Zhao. Design of Multi‐Metallic‐Based Electrocatalysts for Enhanced Water Oxidation. ChemPhysChem 2019, 20 (22) , 2936-2945. https://doi.org/10.1002/cphc.201900507