Density Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO2(101) Surface

Experimental studies have shown the possible production of hydrogen through photocatalytic water splitting using metal oxide (MOy) nanoparticles attached to an anatase TiO2 surface. In this work, we performed density functional theory (DFT) calculations to provide a detailed description of the stability and geometry of MxOy clusters M = Cu, Ni, Co, Fe and Mn, x = 1–5, and y = 0–5 on the anatase TiO2(101) surface. It is found that unsaturated 2-fold-coordinated O-sites may serve as nucleation centers for the growth of metal clusters. The formation energy of Ni-containing clusters on the anatase surface is larger than for other M clusters. In addition, the Nin adsorption energy increases with cluster size n, which makes the formation of bigger Ni clusters plausible as confirmed by transition electron microscopy images. Another particularity for Ni-containing clusters is that the adsorption energy per atom gets larger when the O-content is reduced, while for other M atoms it remains almost constant or, as for Mn, even decreases. This trend is in line with experimental results. Also provided is a discussion of the oxidation states of M5Oy clusters based on their magnetic moments and Bader charges and their possible reduction with oxygen depletion.