Degradation mechanism of tris(2-chloroethyl) phosphate (TCEP) as an emerging contaminant in advanced oxidation processes: a DFT modelling approach

Xia, Hui, Zhang, Wenjing, Yang, Yuesuo, Purchase, Diane ORCID: https://orcid.org/0000-0001-8071-4385, Zhao, Chuanqi, Song, Xiaoming and Wang, Yuanyuan (2021) Degradation mechanism of tris(2-chloroethyl) phosphate (TCEP) as an emerging contaminant in advanced oxidation processes: a DFT modelling approach. Chemosphere, 273 , 129674. pp. 1-12. ISSN 0045-6535 [Article] (doi:10.1016/j.chemosphere.2021.129674)

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Abstract

As a typical toxic organophosphate and emerging contaminant, tris(2-chloroethyl) phosphate (TCEP) is resistant to conventional water treatment processes. Studies on advanced oxidation processes (AOPs) to degrade TCEP have received increasing attention, but the detailed mechanism is not yet fully understood. This study investigated the mechanistic details of TCEP degradation promoted by ·OH using the density functional theory (DFT) method. Our results demonstrated that in the initial step, energy barriers of the hydrogen abstraction pathways were no more than 7 kcal/mol. Cleavage of the P-O or C-Cl bond was verified to be possible to occur, whilst the C-O or C-C cleavage had to overcome an energy barrier above 50 kcal/mol, which was too high for mild experimental conditions. The bond dissociation energy (BDE) combined with the distortion/interaction energy (DIE) analysis disclosed origin of the various reactivities of each site of TCEP. The systematic calculations on the transformation of products generated in the initial step showed remarkable exothermic property. The systematic calculations on the transformation of products generated in the initial step showed remarkable exothermic property. The novel information at molecular level provides insight on how these products are generated and offers valuable theoretical guidance to help develop more effective AOPs to degrade TCEP or other emerging environmental contaminant.

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