State Key Laboratory of Pollution Control and Resources Reuse, School of Environment, Nanjing University, No. 163 Xianlin Avenue, Qixia District, Nanjing, Jiangsu 210023, People's Republic of China.
Environ Sci Technol. 2015 Apr 7;49(7):4209-17. doi: 10.1021/es505111r. Epub 2015 Mar 13.
This study found that decabromodiphenyl ether (BDE 209) could be oxidized effectively by potassium permanganate (KMnO4) in sulfuric acid medium. A total of 15 intermediate oxidative products were detected. The reaction pathways were proposed, which primarily included cleavage of the ether bond to form pentabromophenol. Direct oxidation on the benzene ring also played an important role because hydroxylated polybrominated diphenyl ethers (PBDEs) were produced during the oxidation process. The degradation occurred dramatically in the first few minutes and fitted pseudo-first-order kinetics. Increasing the water content decelerated the reaction rate, whereas increasing the temperature facilitated the reaction. In addition, density functional theory (DFT) was employed to determine the frontier molecular orbital (FMO) and frontier electron density (FED) of BDE 209 and the oxidative products. The theoretical calculation results confirmed the proposed reaction pathways.
这项研究发现，十溴二苯醚（BDE-209）在硫酸介质中可以被高锰酸钾（KMnO4）有效氧化。共检测到 15 种中间氧化产物。提出了反应途径，主要包括醚键的断裂形成五溴苯酚。苯环的直接氧化也起着重要作用，因为在氧化过程中产生了羟基化多溴二苯醚（PBDEs）。在最初的几分钟内，降解剧烈发生，符合假一级动力学。增加水含量会降低反应速率，而升高温度则有利于反应。此外，还采用密度泛函理论（DFT）确定了 BDE-209 和氧化产物的前线分子轨道（FMO）和前线电子密度（FED）。理论计算结果证实了所提出的反应途径。
