Cluster-size dependent phase transition of Co oxides on Au(111)

The surface structure of Co oxide nanoparticles supported on Au(111) was studied using scanning tunneling microscopy (STM) and ultra-violet photoelectron spectroscopy (UPS). Initial Co oxide growth at oxygen pressures orders of magnitude above those required to form bulk Co3O4 resulted solely in small 2-D CoO islands, exhibiting a moiré surface characteristic of the rocksalt (111) surface; continued growth led to a transition to fully oxidized 3-D Co3O4 spinel clusters. The CoO–Co3O4 transition is reversible by reduction in vacuum. It is shown that the stabilization of the reduced phase at low coverages can be explained by the higher surface energy of the support and the Co3O4 spinel structure; since a bilayer is the smallest repeat unit of this structure, oxidation increases the exposed area of the high surface energy substrate. In addition, the 2D to 3D transition required to form Co3O4 increases the occupancy of high energy edge sites, thus further stabilizing small CoO clusters against oxidation. The results show how support interactions and particle size can be used to tune the stability of oxide phases.