Kinetic Investigation of the Catalytic Cycles of Iron Tetraamido Macrocyclic Ligand Catalysts (Fe-T AML) in activating hydrogen peroxide and hypochlorite to oxidize Polycyclic Aromatic Hydrocarbons (PAHs)

<p dir="ltr">This thesis comprises three chapters. Each chapter has its own abstract. Here, a brief overview of the whole content is presented. Iron tetraamido macrocyclic ligands (Fe-TAMLs), initially designed by Prof. Collins of Carnegie Mellon University and co-workers, are synthetic catalysts that are high performance functional mimics of nature's peroxidase enzymes. Fe-TAMLs undergo rapid activation by the principal activator, hydrogen peroxide (H₂O₂), at high pH for most known TAMLs. To shift the pH of optimum activation toward environmentally relevant pH, I explored another strategy than TAML ligand development, namely that of using a different oxidizing agent, hypochlorous acid (HOCl). The corresponding experimental findings and their implications have been laid out in Chapter 1 of this thesis. Moreover, studies of the effect of commonly found chloride anion in environmental aquatic systems on the activation process of Fe-TAML by H₂O₂ is also presented in the first chapter. Chapter 1 additionally includes the comparative kinetic analyses for the reaction of a dye, Orange II, with Fe-TAML activated by both H₂O₂ and HOCl. The next two chapters include the results and discussion for the objective suggested in the thesis proposal, i.e., the exploration of the efficiency of Fe-TAML catalyst in the oxidative removal of a ubiquitous class of pollutants, polycyclic aromatic hydrocarbons (PAHs). Chapter 2 focuses on the oxidation of the most water-soluble PAH with the highest ionization potential (IP), naphthalene, by Fe-TAML activated by H₂O₂ and HOCl, and includes a scanning of the reactivity of other PAHs. Chapter 3 includes a discussion on the performance of Fe-TAML/H₂O₂ toward oxidative degradation of 12 PAHs in hydro-organic mixtures</p>