Prediction of reaction mechanism for OH radical-mediated phenol oxidation using quantum chemical calculation

Understanding the reaction mechanism of OH•-mediated oxidation of organic micropollutants (OMPs) contributes to the assessment and development of advanced oxidation processes (AOPs) for removal of OMPs in water environment. In this study, a theoretical approach using quantum chemical calculation (QCC) was employed to investigate the prediction accuracy of the reaction mechanism (i.e., reaction site and rate) for OH•-mediated oxidation of phenol, where the hydroquinone and catechol are generated as transformation products (TPs) via radical and electrophilic reactions. We compared three different levels of theory (Hartree-Fock, B3LYP, and M06-2X) with 6-311 + G (2d,2p)/SMD, and the reaction site and rate constants were predicted by the Fukui function and transition state theory, respectively. Overall, the prediction accuracy of the TPs formation mechanism was the highest in the calculations using M06-2X. For example, the initial OH• addition to phenol was predicted to occur with a probability of 77% for the ortho position and 23% for the para position, which was consistent with the experimental observation. By applying the transition state theory, the rate constants toward TPs formation pathway can be reasonably reproduced, suggesting that M06-2X has an effective function for polycyclic reactions. However, the observed discrepancies in rate constants are inferred from dispersion effects and the multi-reference property in the computational system or derived from mismatch of target reactions between theoretical calculations and experiments. Overall, this study provides an insight into QCC application for investigating the formation mechanism of TPs in AOPs for removal of OMPs in water environment.