Unveiling the Photodegradation Mechanism of Monochlorinated Naphthalenes under UV-C Irradiation: Affecting Factors Analysis, the Roles of Hydroxyl Radicals, and DFT Calculation

揭示一氯萘在UV-C照射下的光降解机理:影响因素分析、羟基自由基的作用及DFT计算

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Abstract

Polychlorinated naphthalenes (PCNs) are a new type of persistent organic pollutant (POP) characterized by persistence, bioaccumulation, dioxin-like toxicity, and long-range atmospheric transport. Focusing on one type of PCN, monochlorinated naphthalenes (CN-1, CN-2), this study aimed to examine their photodegradation in the environment. In this work, CN-1 and CN-2 were employed as the model pollutants to investigate their photodegradation process under UV-C irradiation. Factors like the pH, initial concentrations of CN-1, and inorganic anions were investigated. Next, the roles of hydroxyl radicals ((•)OH), superoxide anion radicals (O(2)(•-)), and singlet oxygen ((1)O(2)) in the photodegradation process were discussed and proposed via theory computation. The results show that the photodegradation of CN-1 and CN-2 follows pseudo-first-order kinetics. Acidic conditions promote the photodegradation of CN-1, while the effects of pH on the photodegradation of CN-2 are not remarkable. Cl(-), NO(3)(-), and SO(3)(2-) accelerate the photodegradation of CN-1, whereas the effect of SO(4)(2-) and CO(3)(2-) is not significant. Additionally, the contributions of (•)OH and O(2)(•-) to the photodegradation of CN-1 are 20.47% and 38.80%, while, for CN-2, the contribution is 16.40% and 16.80%, respectively. Moreover, the contribution of (1)O(2) is 15.7%. Based on DFT calculations, C4 and C6 of the CN-1 benzene ring are prioritized attack sites for (•)OH, while C2 and C9 of CN-2 are prioritized attack sites.

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