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

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) catal...

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Bibliographic Details
Published in:Environmental science & technology 2021-09, Vol.55 (18), p.12640-12651
Main Authors: Liu, Banghai, Guo, Wanqian, Jia, Wenrui, Wang, Huazhe, Si, Qishi, Zhao, Qi, Luo, Haichao, Jiang, Jin, Ren, Nanqi
Format: Article
Language:English
Subjects:
Antibiotics
Carbon nitride
Catalysts
Cobalt
Decontamination
Density functional theory
Electron transfer
Oxidation
Oxygenation
Peracetic acid
Species
Sulfonamides
Treatment and Resource Recovery
Water purification
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Summary: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.
ISSN:0013-936X
1520-5851
DOI:10.1021/acs.est.1c04091