Pivotal Roles of Metal Oxides in the Formation of Environmentally Persistent Free Radicals.

Environmentally persistent free radicals (EPFRs) are emerging pollutants that can adversely affect human health. Although the pivotal roles of metal oxides in EPFR formation have been identified, few studies have investigated the influence of the metal oxide species, size, or concentration on the formation of EPFRs. In this study, EPFR formation from a polyaromatic hydrocarbon with chlorine and hydroxyl substituents (2,4-dichloro-1-naphthol) was investigated using electron paramagnetic resonance spectroscopy. The effect of the metal oxide on the EPFR species and its lifetime and yield were evaluated. The spectra obtained with catalysis by CuO, Al2O3, ZnO, and NiO were obviously different, indicating that different EPFRs formed. The abilities of the metal oxides to promote EPFR formation were in the order Al2O3 > ZnO > CuO > NiO, which were in accordance with the oxidizing strengths of the metal cations. A decay study showed that the generated radicals were persistent, with a maximum 1/e lifetime of 108 days on the surface of Al2O3. The radical yields were dependent on the concentration and particle size of the metal oxide. Metal oxide nanoparticles increased the EPFR concentrations more than micrometer-sized particles.