Soft X-ray absorption spectroscopy of titanium dioxide nanopowders with cobalt impurities

The charge states of the cobalt ions in TiO2 nanopowders with the anatase lattice are studied by soft X-ray absorption spectroscopy. It is found that, at a low cobalt impurity concentration (1.8 at %), the cobalt ions with an oxidation state 2+ are mainly located in the tetrahedral (Td) environment of oxygen ions. Amorphous titanium dioxide exists on the sample surface before heat treatment. Annealing in vacuum or hydrogen leads to the enrichment of the nanoparticle surfaces with Co2+ ions, a change in the coordination of the remaining part of cobalt ions from octahedral to tetrahedral, stabilization of the anatase structure, and the disappearance of the amorphous phase. The crystal lattice of the samples with a relatively high cobalt concentration (12 at %) is distorted, and annealing does not cause the disappearance of the amorphous phase of TiO2. Cobalt is reduced to its metallic state upon hydrogen annealing of the samples with a high cobalt concentration.