Vibrational and Structural Studies of Environmentally Persistent Free Radicals Formed by Phenol-Dosed Metal Oxide Nanoparticles

Environmentally persistent free radicals (EPFRs) are formed by the adsorption of substituted aromatic precursors on the surface of metal oxides and are known to have significant health and environmental impact due to their unique stability. In this article, the formation of EPFRs is studied by adsorption of phenol on ZnO, CuO, Fe2O3, and TiO2 nanoparticles (similar to 10-50 nm) at high temperatures. Electron paramagnetic resonance indicates the formation of phenoxyl-type radicals. Fourier transform infrared spectroscopy provides further evidence of EPFR formation by the disappearance of -OH groups, indicating the chemisorption of the organic precursor on the metal oxide surface. These results are further confirmed by inelastic neutron scattering, which shows both ring out-of-plane bend and C-H in plane bend motions characteristic of phenol adsorption on the studied systems. Also, the changes in the oxidation state of the metal cations are investigated by X-ray photoelectron spectroscopy, which shows that the direction of electron transfer (redox) during phenol chemisorption is strongly dependent on surface properties as well as surface defects of the metal oxide surface.