Revisiting the Iron(II)/Cobalt(II)-Based Homogenous Fenton-like Processes from the Standpoint of Diverse Metal-Oxygen Complexes.
Environ Sci Technol
; 58(37): 16589-16599, 2024 Sep 17.
Article
em En
| MEDLINE
| ID: mdl-39238135
ABSTRACT
The aqueous FeIV-oxo complex and FeIII-peroxy complex (e.g., ligand-assisted or interfacial FeIII-hydroperoxo intermediates) have been recognized as crucial reactive intermediates for decontamination in iron-based Fenton-like processes. Intermediates with terminal oxo ligands can undergo the oxygen atom exchange process with water molecules, whereas peroxides are unable to induce such exchanges. Therefore, these distinct metal-oxygen complexes can be distinguished based on the above feature. In this study, we identified previously unknown intermediates with a peroxy moiety and cobalt center that were generated during peroxymonosulfate (PMS) activation via aqueous CoII ions under acidic conditions. Results of theoretical calculations and tip-enhanced Raman spectroscopy revealed that the CoII ion tended to coordinate with the PMS anion to form a bidentate complex with a tetrahedral structure. These reactive cobalt intermediates were collectively named the CoII-PMS* complex. Depending on the inherent characteristics of the target contaminants, the CoII-PMS* complex can directly oxidize organic compounds or trigger PMS disproportionation to release hydroxyl radicals and sulfate radicals for collaborative decontamination. This work provides a comparative study between iron- and cobalt-based Fenton-like processes and proposes novel insights from the standpoint of diverse metal-oxygen complexes.
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Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Oxigênio
/
Cobalto
/
Ferro
Idioma:
En
Revista:
Environ Sci Technol
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
China