A Comparative Study on the Oxidation Mechanisms of Substituted Phenolic Pollutants by Ferrate(VI) through Experiments and Density Functional Theory Calculations

In this work, the oxidation of five phenolic contaminants by ferrate(VI) was comparatively investigated to explore the possible reaction mechanisms by combined experimental results and theoretical calculations. The second-order rate constants were positively correlated with the energy of the highest occupied molecular orbital. Considering electronic effects of different substituents, the easy oxidation of phenols by ferrate(VI) could be ranked as the electron-donating group (-R) > weak electron withdrawing group (-X) > strong electron-withdrawing group (-(C=O)-). The contributions of reactive species (Fe(VI), Fe(V)/ (IV), and center dot OH) were determined, and Fe(VI) was found to dominate the reaction process. Four main reaction mechanisms including single-oxygen transfer (SOT), double-oxygen transfer (DOT), center dot OH attack, and electron-transfer-mediated coupling reaction were proposed for the ferrate(VI) oxidation process. According to density functional theory calculation results, the presence of-(C=O)- was more conducive for the occurrence of DOT and center dot OH attack reactions than -R and -X, while the tendency of SOT for different substituents was -R >-(C=O)- > -X and that of e--transfer reaction was -R > -X >-(C=O)-. Moreover, the DOT pathway was found in the oxidation of all four substituted phenols, indicating that it may be a common reaction mechanism during the ferrate(VI) oxidation of phenolic compounds.

Automated summary

In this study, the oxidation of five phenolic contaminants using ferrate(VI) was investigated to understand the reaction mechanisms. Experimental and theoretical calculations revealed that the reaction rate constants were correlated with the energy of the highest occupied molecular orbital. Electron-donating groups (-R) were found to be more easily oxidized by ferrate(VI) compared to weak electron withdrawing groups (-X) and strong electron-withdrawing groups (-(C=O)-). The dominance of Fe(VI) in the reaction process was determined, and four main reaction mechanisms, including single-oxygen transfer, double-oxygen transfer, ·OH attack, and electron-transfer-mediated coupling reaction, were proposed. Density functional theory calculations suggested that the presence of -(C=O)- facilitated the occurrence of double-oxygen transfer and ·OH attack reactions, while the tendency of single-oxygen transfer and electron-transfer reaction varied with different substituents. Furthermore, the double-oxygen transfer pathway was found to be a common reaction mechanism during the ferrate(VI) oxidation of phenolic compounds.