Complexation Enhances Cu(II)-Activated Peroxydisulfate: A Novel Activation Mechanism and Cu(III) Contribution

  • Jiabin Chen
    Jiabin Chen
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, P. R. China
    More by Jiabin Chen
  • Xuefei Zhou
    Xuefei Zhou
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, P. R. China
    More by Xuefei Zhou
  • Peizhe Sun
    Peizhe Sun
    School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, P. R. China
    More by Peizhe Sun
  • Yalei Zhang*
    Yalei Zhang
    State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, P. R. China
    *E-mail: [email protected]. Phone: 86-21-65980624. Fax: 86-21-65989961 (Y.Z.).
    More by Yalei Zhang
  • , and 
  • Ching-Hua Huang*
    Ching-Hua Huang
    School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta Georgia 30332, United States
    *E-mail: [email protected]. Phone: 404-894-7694. Fax: 404-358-7087 (C.-H.H.).
Cite this: Environ. Sci. Technol. 2019, 53, 20, 11774–11782
Publication Date (Web):September 16, 2019
https://doi.org/10.1021/acs.est.9b03873
Copyright © 2019 American Chemical Society
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Abstract

While aqueous free Cu(II) ion is known to be ineffective to activate peroxydisulfate (PDS), here we report for the first time that Cu(II) complexes are potentially effective activators for PDS when the coordination involves suitable ligands. Using cefalexin (CFX) as a representative, studies show that the complex of Cu(II) with CFX can efficiently activate PDS to induce rapid degradation of CFX. Transformation products of CFX by PDS/Cu(II) differ substantially from those generated from the typical radical oxidation process, for example, PDS/Ag(I), but quite resemble the products from oxidation of CFX by Cu(III). Complexation with CFX increases the electron density of Cu(II), favoring electron transfer from Cu(II) to PDS to generate radicals and Cu(III). The produced Cu(III), rather than radicals, plays the primary role in the overall CFX degradation and regenerates Cu(II) in a catalytic cycle. This novel activation process can occur for a wide range of contaminants (cephalosporin, penicillin, and tetracycline antibiotics) and ligands when coordinated with Cu(II), and N-containing functional groups (e.g. amines) were found to form effective Cu(II) complexes for PDS activation. The new findings of this study further broaden the knowledge on PDS activation by aqueous Cu(II), and verify the contribution of Cu(III) to contaminant elimination.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.9b03873.

  • Details of chemicals; real water samples; LC–MS conditions; EPR analysis; PDS analysis; UV–vis spectra of complexation; 363 products; characteristics of water samples; HPLC method parameters; EPR spectra of PDS or Cu(II); CFX degradation (A) and the corresponding PDS decomposition (B); effect of Cu(II) concentration on CFX degradation (A) and PDS decomposition (B) in the PDS/Cu(II)/CFX system; effect of humic acid (A) and Cl- (B) on CFX degradation by PDS/Cu(II); and the degradation of CFX at relatively low concentration by PDS/Cu(II) (C); effect of real water matrices on CFX degradation; EPR spectra of the activated PDS solution (A), and the effect of MeOH on CFX degradation by PDS/Cu(II) (B); transformation products of CFX by PDS/Cu(II); MS2 spectrum of the 335 product; MS2 spectrum of 206a (A) and 206b (B); effect of pH on Cu(II)-promoted degradation of CFX (without PDS); effect of pH on the degradation of CFX by PDS/Cu(II) in the absence or presence of MeOH radical quencher; effect of oxygen on CFX degradation and PDS decomposition in the PDS/Cu(II)/CFX system; effect of Cu(III) concentration (A), and pH (B) on UV–vis spectra of Cu(III) solution; Cu(III)-induced degradation of CFX at pH 7 (A), and effect of Cu(III) concentration (B) and pH (C) on Cu(III)-oxidized CFX; transformation products of CFX by Cu(III); effect of pH on the complexation of CFX with Cu(II); effect of pH on the degradation of anisole by PDS/Cu(II); degradation of 7-ACA and phenylglycine; oxidation of 7-ACA and phenylglycine; chemical structures of the investigated contaminants (PDF)

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