Journal
CHEMICAL ENGINEERING JOURNAL
Volume 410, Issue -, Pages -Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2020.128181
Keywords
Superoxide radical; In situ long-path spectroscopy; Aqueous solution; Reactivities; Mechanism; Kinetics
Categories
Funding
- National Natural Science Foundation of China [21976212]
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A method to generate O-2(center dot-) was developed, and its reaction kinetics and mechanism with CCl4 were investigated. The results showed that O-2(center dot-) exhibited lower reactivity towards CCl4 compared to other radicals, with nucleophilic substitution as the major pathway and solvation effect playing an important role in the reaction.
Contemporary studies emphasize that superoxide radical (O-2(center dot-)) exhibits the potential to degrade organic contaminants, but practical application of this radical in engineered waters require an in-depth understanding of its kinetic profiles in a quantitative way. Here, we developed, for the first time, a convenient and reliable approach to generate micromolar level O-2(center dot-) in aqueous solution by photolysis of formate and H2O2. The presence of O-2(center dot-) was confirmed by comparing the UV spectra under pulse radiolysis and chromogenic reaction. We then constructed an in situ long-path spectroscopy to investigate the kinetics and mechanisms of O(2)(center dot-)mediated degradation of carbon tetrachloride (CCl4), a halogenated model contaminant. The rate constant for the reaction of O-2(center dot-) and CCl4 was determined to be 478 M-1 s(-1). In addition, we employed the transition state theory to model the reaction rate constants. Both results show that O center dot-2 exhibited low reactivity towards CCl4 with bimolecular rate constant lower by at least one order of magnitude than those radicals generated in typical advanced oxidation processes such as hydroxyl and sulfate radicals. Our results also indicate that nucleophilic substitution is the major pathway, and the solvation effect plays an important role in the reaction. The complementary experimental and theoretical approaches provide a mechanistic basis for better understanding aqueous-phase O-2(center dot-) chemistry and a holistic evaluation on the application of O-2(center dot-) for the degradation of organic contaminants of emerging concern.
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