Selective Oxidation of Various Phenolic Contaminants by Activated Persulfate via the Hydrogen Abstraction Pathway

  • Cong Wang
    Cong Wang
    Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, P. R. China
    More by Cong Wang
  • Shao-Yi Jia
    Shao-Yi Jia
    Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, P. R. China
    More by Shao-Yi Jia
  • You Han
    You Han
    Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, P. R. China
    More by You Han
  • Yang Li
    Yang Li
    School of Environmental Science and Engineering, Tiangong University, Tianjin, 300387, P. R. China
    More by Yang Li
  • Yong Liu
    Yong Liu
    School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin, 300384, P. R. China
    More by Yong Liu
  • Hai-Tao Ren
    Hai-Tao Ren
    School of Textile Science and Engineering, Tiangong University, Tianjin, 300387, P. R. China
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  • Song-Hai Wu
    Song-Hai Wu
    Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, P. R. China
    College of Chemistry and Chemical Engineering, Xinjiang Normal University, Ü rümqi, 830054, Xinjiang, P. R. China
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  • , and 
  • Xu Han*
    Xu Han
    Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, P. R. China
    *Tel.: +86-15222072695. Email: [email protected]
    More by Xu Han
Cite this: ACS EST Engg. 2021, 1, 9, 1275–1286
Publication Date (Web):July 26, 2021
https://doi.org/10.1021/acsestengg.1c00091
Copyright © 2021 American Chemical Society
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Abstract

Enzymatic polymerization of phenolic contaminants to polyphenolics by H2O2 is an effective method to turn phenolic wastes to useful polymers. However, the sensitivities and the high costs of enzymes always limit their applications in the long-run treatment of industrial wastewater. In this study, a highly efficient CuO-persulfate (PS) system is reported to be a promising candidate for enzyme–H2O2 and shows high reactivity to polymerize various phenolic contaminants to polymers under alkaline conditions with the ratio of PS/phenolics less than 2.0. Compared with the generally accepted mechanism that the oxidizing species of SO4•– and ·OH generated during PS activation primarily contribute to the oxidation of various organic contaminants, quenching experiments, EPR (electron paramagnetic resonance) analysis and DFT calculations in this study indicate that PS is activated on CuO via a nonradical pathway under alkaline conditions, and the O–O bond in PS is moderately elongated from 1.45 to 1.58 Å. The inversely linear relationship between log kobs and BDEO–H values of various phenolics in the Hammett plot confirms H-abstraction from various phenolics under alkaline conditions. DFT calculations further reveal the formation of phenolic radicals after the activated PS abstracts H from phenolic −OH, followed by subsequent polymerization of phenoxyl radicals to polyphenolics. Characterizations of the oxidation products confirm that more than 80% phenolic contaminants have been transformed to polyphenolics. This study provides a new alternative for recovering various phenolic contaminants from industrial wastewater.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsestengg.1c00091.

  • Oxidation of various contaminants; DFT calculations; Mulliken charges and bond lengths during HAT; TEM and HRTEM images; XRD spectra; XPS spectra; zeta potential of CuO; oxidation activities of various systems; repeated experiments; effects of anions; chronoamperometry analysis; the ratio between consumed PS and removed phenolics; effect of pH; XPS spectra of the products (C 1s); quenching experiments and EPR analysis with TMP; configurations of phenol absorption and HAT; the optimized configurations of reactants; sedimentation after reaction; SEM images of CuO and products; schematic diagram of the CuO–PS system (PDF)

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