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Activation of Hydrogen Peroxide by a Titanium Oxide-Supported Iron Catalyst: Evidence for Surface Fe(IV) and Its Selectivity

  • Hak-Hyeon Kim
    Hak-Hyeon Kim
    Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
  • Hongshin Lee
    Hongshin Lee
    Department of Civil, Environmental, and Architectural Engineering, Korea University, Seoul 02841, Republic of Korea
    More by Hongshin Lee
  • Donghyun Lee
    Donghyun Lee
    School of Chemical and Biological Engineering, Institute of Chemical Process (ICP), Seoul National University, Seoul 08826, Republic of Korea
    More by Donghyun Lee
  • Young-Jin Ko
    Young-Jin Ko
    Center for Electronic Materials, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea
    More by Young-Jin Ko
  • Heesoo Woo
    Heesoo Woo
    Center for Water Resource Cycle Research, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea
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  • Jaesang Lee
    Jaesang Lee
    Department of Civil, Environmental, and Architectural Engineering, Korea University, Seoul 02841, Republic of Korea
    More by Jaesang Lee
  • Changha Lee*
    Changha Lee
    School of Chemical and Biological Engineering, Institute of Chemical Process (ICP), Seoul National University, Seoul 08826, Republic of Korea
    *Email: [email protected]. Tel: +82-2-880-8630.
    More by Changha Lee
  • , and 
  • Anh Le-Tuan Pham*
    Anh Le-Tuan Pham
    Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
    *Email: [email protected]. Tel: +1-519-888-4567. (ext. 30337).
Cite this: Environ. Sci. Technol. 2020, 54, 23, 15424–15432
Publication Date (Web):November 12, 2020
https://doi.org/10.1021/acs.est.0c04262
Copyright © 2020 American Chemical Society
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Abstract

Iron immobilized on supports such as silica, alumina, titanium oxide, and zeolite can activate hydrogen peroxide (H2O2) into strong oxidants. However, the role of the support and the nature of the oxidants produced in this process remain elusive. This study investigated the activation of H2O2 by a TiO2-supported catalyst (FeTi-ox). Characterizing the catalyst surface in situ using X-ray absorption spectroscopy (XAS), together with X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR), revealed that the interaction between H2O2 and the TiO2 phase played a key role in the H2O2 activation. This interaction generated a stable peroxo–titania ≡Fe(III)–Ti–OOH complex, which reacted further with H2O to produce a surface oxidant, likely ≡Fe[IV] ═ O2+. The oxidant effectively degraded acetaminophen, even in the presence of chloride, bicarbonate, and organic matter. Unexpectedly, contaminant oxidation continued after the H2O2 in the solution was depleted, owing to the decomposition of ≡Fe(III)–Ti–OOH by water. In addition, the FeTi-ox catalyst effectively degraded acetaminophen over five testing cycles. Overall, new insights gained in this study may provide a basis for designing more effective catalysts for H2O2 activation.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.0c04262.

  • SEM and EDS images of FeTi-ox; formation of p-HBA in the FeTi-ox system; formation of PMSO2 by Amor. Fe-ox, Amor. Ti-ox, and FeTi-ox in the presence of H2O2; production of PMSO2; and XPS spectra (PDF)

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This article is cited by 11 publications.

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  2. Zhichao Yang, Jieshu Qian, Chao Shan, Hongchao Li, Yuyang Yin, Bingcai Pan. Toward Selective Oxidation of Contaminants in Aqueous Systems. Environmental Science & Technology 2021, 55 (21) , 14494-14514. https://doi.org/10.1021/acs.est.1c05862
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