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Novel Nonradical Oxidation of Sulfonamide Antibiotics with Co(II)-Doped g-C3N4-Activated Peracetic Acid: Role of High-Valent Cobalt–Oxo Species

  • Banghai Liu
    Banghai Liu
    State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
    More by Banghai Liu
  • Wanqian Guo*
    Wanqian Guo
    State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
    *Email: [email protected]
    More by Wanqian Guo
  • Wenrui Jia
    Wenrui Jia
    State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
    More by Wenrui Jia
  • Huazhe Wang
    Huazhe Wang
    State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
    More by Huazhe Wang
  • Qishi Si
    Qishi Si
    State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
    More by Qishi Si
  • Qi Zhao
    Qi Zhao
    State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
    More by Qi Zhao
  • Haichao Luo
    Haichao Luo
    State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
    More by Haichao Luo
  • Jin Jiang*
    Jin Jiang
    Key Laboratory for City Cluster Environmental Safety and Green Development of the Ministry of Education, Institute of Environmental and Ecological Engineering, Guangdong University of Technology, Guangzhou 510006, China
    *Email: [email protected]
    More by Jin Jiang
  • , and 
  • Nanqi Ren
    Nanqi Ren
    State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
    More by Nanqi Ren
Cite this: Environ. Sci. Technol. 2021, 55, 18, 12640–12651
Publication Date (Web):August 31, 2021
https://doi.org/10.1021/acs.est.1c04091
Copyright © 2021 American Chemical Society
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Abstract

Herein, we report that Co(II)-doped g-C3N4 can efficiently trigger peracetic acid (PAA) oxidation of various sulfonamides (SAs) in a wide pH range. Quite different from the traditional radical-generating or typical nonradical-involved (i.e., singlet oxygenation and mediated electron transfer) catalytic systems, the PAA activation follows a novel nonradical pathway with unprecedented high-valent cobalt–oxo species [Co(IV)] as the dominant reactive species. Our experiments and density functional theory calculations indicate that the Co atom fixated into the nitrogen pots of g-C3N4 serves as the main active site, enabling dissociation of the adsorbed PAA and conversion of the coordinated Co(II) to Co(IV) via a unique two-electron transfer mechanism. Considering Co(IV) to be highly electrophilic in nature, different substituents (i.e., five-membered and six-membered heterocyclic moieties) on the SAs could affect their nucleophilicity, thus leading to the differences in degradation efficiency and transformation pathway. Also, benefiting from the selective oxidation of Co(IV), the established oxidative system exhibits excellent anti-interference capacity and achieves satisfactory decontamination performance under actual water conditions. This study provides a new nonradical approach to degrade SAs by efficiently activating PAA via heterogeneous cobalt-complexed catalysts.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.1c04091.

  • Details of materials and methods; chemicals and reagents; electrochemical measurements; 18O isotope-labeled experiments; operation methods for reactive intermediate analysis by EPR; computational methods; fraction of 1O2 involving in SMX degradation; operation parameters for organic contaminant analysis with UPLC; HOMO and LUMO calculated based on DFT; condensed dual descriptor of the SMX and SDZ molecules; mass-to-charge ratio, chemical formula, and proposed structure of the detected transformation products; TEM images of the resultant catalysts; degradation of SMX; zeta potentials; degradation of SMX; removal of CBZ; UPLC/MS chromatogram; removal of SMX during the PAA/CCN4 process; HPLC-QTOF-MS analyses; EPR spectra; spin-trapping EPR spectra for O2; LSV curves of CCN4 under different conditions; removal of various SAs by PAA alone; HPLC-QTOF-MS analyses; difference in geometries between the five-membered ring of isoxazole in SMX and the six-membered ring of pyrimidine in SDZ; SMX and SDZ degradation in deionized water, tap water, and river water; and illustrations of experimental results (PDF)

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