Evidence of the surface layer in tungstated zirconia

We characterized the structure of tungstated zirconia (WO_x–ZrO₂) by combining X-ray diffraction, Raman spectroscopy and High Resolution Electron Microscopy (HREM) together with molecular simulations. Our results indicate that the structure of this material consists of metastable tetragonal ZrO₂ nanoparticles (<20 nm in diameter) covered by a few-nanometers thick low-crystallinity surface layer formed by tungsten oxospecies (WO_x). Although the X-ray diffraction pattern matched the spectra of the tetragonal ZrO₂ bulk phase the lattice fringes of the ZrO₂ nanoparticles observed by HREM were locally distorted, presumably as a result of the interaction with the surface WO_x layer. The local interplanar distances of the surface layer were close to those present in different bulk tungsten oxocompounds, and its variability was also an indication of the WO_x–ZrO₂ interaction. Molecular simulations corroborated our structural assignment. The results presented here are a direct evidence for the presence of a surface WO_x layer in the case of WO_x–ZrO₂. PACS 68.35.Bs; 81.05.Ys; 82.65.Dp