Formation of hollow spheres upon oxidation of supported cobalt nanoparticles

Oxidation of cobalt nanoparticles supported on montmorillonite was studied using transmission electron microscopy and temperature programmed reduction of the oxide particles. It has been shown that hollow shells of cobalt oxide were formed in this process, consisting of the mixture of CoO and Co3O4 oxides. A linear relationship between the thickness of shells and the initial particles size was established which suggests that both diffusion of cobalt ions through the oxide layer and diffusion of the oxygen into cobalt occur, but particles sintering is negligible compared with the reverse diffusion of cobalt. The lower critical diameter of cobalt particles was estimated, above which formation of hollow shells occurred. The hollow shells formation is suggested to be the reason for cobalt redispersion upon oxidation-reduction cycling of supported heterogeneous catalysts.