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Unraveling the Overlooked Involvement of High-Valent Cobalt-Oxo Species Generated from the Cobalt(II)-Activated Peroxymonosulfate Process

  • Yang Zong
    Yang Zong
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science & Engineering, Tongji University, Shanghai 200092, P. R. China
    More by Yang Zong
  • Xiaohong Guan
    Xiaohong Guan
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science & Engineering, Tongji University, Shanghai 200092, P. R. China
    Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, P. R. China
  • Jun Xu
    Jun Xu
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science & Engineering, Tongji University, Shanghai 200092, P. R. China
    More by Jun Xu
  • Yong Feng
    Yong Feng
    School of Environment, South China Normal University, University Town, Guangzhou 510631, China
    More by Yong Feng
  • Yunfeng Mao
    Yunfeng Mao
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science & Engineering, Tongji University, Shanghai 200092, P. R. China
    More by Yunfeng Mao
  • Longqian Xu
    Longqian Xu
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science & Engineering, Tongji University, Shanghai 200092, P. R. China
    More by Longqian Xu
  • Huaqiang Chu
    Huaqiang Chu
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science & Engineering, Tongji University, Shanghai 200092, P. R. China
    Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, P. R. China
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  • , and 
  • Deli Wu*
    Deli Wu
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science & Engineering, Tongji University, Shanghai 200092, P. R. China
    Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, P. R. China
    *Email: [email protected]. Phone: +86-21-65980872. Fax: +86-21-65983602.
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Cite this: Environ. Sci. Technol. 2020, 54, 24, 16231–16239
Publication Date (Web):November 23, 2020
https://doi.org/10.1021/acs.est.0c06808
Copyright © 2020 American Chemical Society
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Abstract

Sulfate radical (SO4•–) is widely recognized as the predominant species generated from the cobalt(II)-activated peroxymonosulfate (PMS) process. However, in this study, it was surprisingly found that methyl phenyl sulfoxide (PMSO) was readily oxidized to the corresponding sulfone (PMSO2) with a transformation ratio of ∼100% under acidic conditions, which strongly implied the generation of high-valent cobalt-oxo species [Co(IV)] instead of SO4•– in the Co(II)/PMS process. Scavenging experiments using methanol (MeOH), tert-butyl alcohol, and dimethyl sulfoxide further suggested the negligible role of SO4•– and hydroxyl radical (OH) but favored the generation of Co(IV). By employing 18O isotope-labeling technique, the formation of Co(IV) was conclusively verified and the oxygen atom exchange reaction between Co(IV) and H2O was revealed. Density functional theory calculation determined that the formation of Co(IV) was thermodynamically favorable than that of SO4•– and OH in the Co(II)/PMS process. The generated Co(IV) species was indicated to be highly reactive due to the existence of oxo-wall and capable of oxidizing the organic pollutant that is rather recalcitrant to SO4•– attack, for example, nitrobenzene. Additionally, the degradation intermediates of sulfamethoxazole (SMX) in the Co(II)/PMS process under acidic conditions were identified to further understand the interaction between Co(IV) and the representative contaminant. The developed kinetic model successfully simulated PMSO loss, PMSO2 production, SMX degradation, and/or PMS decomposition under varying conditions, which further supported the proposed mechanism. This study might shed new light on the Co(II)/PMS process.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.0c06808.

  • Details regarding chemicals and analytical methods used in this study; HPLC conditions for organic compounds analysis; coordinate data of the atoms; transformation ratio; PMSO consumption and PMSO2 production; comparison of PMSO degradation, PMSO2 generation and SMX removal; model sketches; and MS spectrum and MS2 spectrum (PDF)

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