Photoinduced electron transfer at solid surfaces: the TiO2-SiO2 system

Small particles of TiO2 have been synthesized on porous silica. XRD and spectral measurements place the sizes of the particles at about 50 A. With these small particles the band gap of the semiconductor material is markedly blue shifted with respect to bulk TiO2. This enables the direct excitation of co-adsorbed arenes on the TiO2-SiO2 material. Direct excitation of TiO2 leads to Ti3+, by photoinduced extraction from the SiO2. Direct excitation of pyrene on the material leads to a shortened fluorescence lifetime and lower quantum yield. Meanwhile, the yield of pyrene cation radical increases compared to that on pure SiO2. The production of Ti3+ on the pyrene samples, by direct excitation of the TiO2, leads to a shortened pyrene fluorescence lifetime and decreased quantum yield, the quantum yield decreasing to zero at high enough Ti3+. Removal of Ti3+ by O2 causes the original properties of the pyrene fluorescence to return.