Mechanistic aspects of photo-induced formation of peroxide ions on the surface of cubic Ln2O3 (Ln = Nd, Sm, Gd) under oxygen.

The photo-induced formation of peroxide ions on the surface of cubic Ln2O3 (Ln = Nd, Sm, Gd) was studied by in situ microprobe Raman spectroscopy using a 325 nm laser as excitation source. It was found that the Raman bands of peroxide ions at 833-843 cm(-1) began to grow at the expense of the Ln(3+)-O(2-) bands at 333-359 cm(-1) when the Ln2O3 samples under O2 were continuously irradiated with a focused 325 nm laser beam at temperatures between 25-150 °C. The intensity of the peroxide Raman band was found to increase with increasing O2 partial pressure, whereas no peroxide band was detected on the Ln2O3 under N2 as well as on the samples first irradiated with laser under Ar or N2 followed by exposure to O2 in the dark. The experiments using (18)O as a tracer further confirmed that the peroxide ions are generated by a photo-induced reaction between O2 and the lattice oxygen (O(2-)) species in Ln2O3. Under the excitation of 325 nm UV light, the transformation of O2 to peroxide ions on the surface of the above lanthanide sesquioxides can even take place at room temperature. Basicity of the lattice oxygen species on Ln2O3 also has an impact on the peroxide formation. Higher temperature or laser irradiation power is required to initiate the reaction between O2 and O(2-) species of weaker basicity.