Mechanistic study of a manganese porphyrin catalyst for on-demand production of chlorine dioxide in water

A water-soluble manganese porphyrin complex was examined for the catalytic formation of chlorine dioxide from chlorite under ambient temperature at pH 5.00 and 6.90. Quantitative kinetic modeling allowed for the deduction of a mechanism that accounts for all experimental observations. Catalysis is initiated via an OAT (Oxygen Atom Transfer) reaction resulting in formation of a putative manganese(V) oxo species, which undergoes ET (Electron Transfer) with chlorite to form chlorine dioxide. As chlorine dioxide accumulates in solution, chlorite consumption slows down and ClO2 reaches a maximum as the system reaches equilibrium. In phosphate buffer at pH 6.90, manganese(IV) oxo accumulates and its reaction with ClO2 gives ClO3-. However, at pH 5.00 acetate buffer proton coupled electron transfer (PCET) from chlorite to manganese(IV) oxo is fast and irreversible leading to chlorate formation only via the putative manganese(V) oxo species. These differences underscore how PCET rates affect reaction pathways and mechanism. The ClO2 product can be collected from the aqueous reaction mixture via purging with an inert gas, allowing for the preparation of chlorine dioxide on-demand.