Surface Coverage- and Excitation Laser Wavelength-Dependent Luminescence Properties of U(VI) Species Adsorbed on Amorphous SiO2

Abstract

Time-resolved luminescence spectroscopy is usefully used to identify U(VI) surface species adsorbed on SiO2. However, the cause of the inconsistent luminescence lifetimes and spectral shapes reported previously remains undetermined. In this study, the U(VI) surface coverage (Gamma) and excitation laser wavelength (lambda(ex)) were examined as the predominant factors governing the luminescence properties of U(VI) surface species. At neutral pH, the luminescence lifetimes of U(VI) surface species increased with decreasing Gamma. In the low-Gamma region, where a relatively large number of adjacent surface sites are involved in the formation of multidentate surface complexes, the displacement of more number of coordinated water molecules in the equatorial plane of U(VI) results in a longer lifetime. The pH-dependent luminescence lifetimes of U(VI) surface species at the same U(VI) to SiO2 concentration ratio in the pH range of 4.5-7.5 also explain the effect of the surface binding sites on the luminescence lifetime. The time-resolved luminescence properties of the U(VI) surface species were also investigated at different excitation wavelengths. Continued irradiation of the SiO2 surface with a UV laser beam at lambda(ex) = 266 nm considerably reduced the luminescence intensities of the U(VI) surface species. The higher the laser pulse energy, the greater the decrease in luminescence intensity. Laser-induced thermal desorption (LITD) of U(VI) surface species is suggested to be the origin of the decrease in luminescence intensity. LITD effects were not observed at lambda(ex) = 355 and 422 nm, even at high laser pulse energies.