[Untitled]

The incorporation of transition-metal oxides into silica can give materials with useful optical, electronic or catalytic properties. For example, ZrO2-SiO2 and HfO2-SiO2 materials are of interest due to their high dielectric constants. Here we present a comparison of extended X-ray absorption fine structure and small-angle X-ray scattering results for acid-catalysed binary (MO2) x (SiO2)1 − x (M = Ti, Zr or Hf) xerogels, with x up to 0.4 and heat treatments up to 750°C. Detailed observations for TiO2-SiO2 and ZrO2-SiO2 xerogels provide a basis for interpretation of new results for HfO2-SiO2 xerogels. At low concentrations metal atoms are homogeneously incorporated into the silica network. Ti adopts coordinations of 4 or 6, and Zr and Hf both adopt higher coordination of 6 or 7 (the larger coordinations being due to ambient moisture). At higher concentrations, phase separation of metal oxide occurs. Such regions become clearly separated from the silica network for TiO2, but remain very finely mixed with silica network for ZrO2 and HfO2.