Theoretical and experimental insights into the ·OH-mediated mineralization mechanism of flutriafol

- A complete ·OH-mediated degradation pathway of flutriafol is proposed.
- Computational approach is effective to reveal the favorable transformation process.
- The electrochemical experiments well verify the theoretical results.

Flutriafol is one of the widely used triazole fungicides in global pesticides market, and its degradation mechanisms are important to develop powerful technologies to remove it. Insight into the kinetics and mechanisms of ·OH-mediated mineralization of flutriafol have been obtained using quantum chemical calculation and electrochemical experiment methods. The complete ·OH-mediated degradation pathway of flutriafol was proposed by density functional theory (DFT) simulation and the potential energy surface was mapped out for possible reactions. On the basis of DFT calculations, the optimal ·OH-mediated mineralization mechanism of flutriafol was revealed, and a series of intermediates were observed accumulated in the degradation process, most significance among which were (2-fluorophenyl) (4-fluorophenyl)-Methanone, phenol, dihydroxybenzenes, benzoquinones, muconic acids, maleic acids, oxalic acids and formic acid. To give deeper insight into the ·OH-mediated reaction mechanism, the electrostatic potential (ESP) and average local ionization energy (ALIE) analysis were conducted for o-benzoquinone and p-benzoquinone. The proposed mechanism was further validated by electrochemical experiments at TiO2-NTs/SnO2-Sb/PbO2 anode. The main intermediates were identified and quantified by experimental method, indicating that the proposed ·OH-mediated degradation mechanism derived from DFT calculations was feasible. These detailed findings could be instrumental for a comprehensive understanding of the ·OH-mediated mineralization mechanism of flutriafol and the similar contaminants.

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