A study of Pt, Rh, Ni and Ir dispersion on anatase TiO2(101) and the role of water

Abstract

Understanding how metal atoms are stabilized on metal oxide supports is important for predicting the stability of “single-atom” catalysts. In this study, we use scanning tunnelling microscopy (STM) and x-ray photoelectron spectroscopy (XPS) to investigate four catalytically active metals – platinum, rhodium, nickel and iridium – on the anatase TiO2(101) surface. The metals were vapor deposited at room temperature in ultrahigh vacuum (UHV) conditions, and also with a background water pressure of 2 × 10−8 mbar. Pt and Ni exist as a mixture of adatoms and nanoparticles in UHV at low coverage, with the adatoms immobilized at defect sites. Water has no discernible effect on the Pt dispersion, but significantly increases the amount of Ni single atoms. Ir is highly dispersed, but sinters to nanoparticles in the water vapor background leading to the formation of large clusters at step edges. Rh forms clusters on the terrace of anatase TiO2(101) irrespective of the environment. We conclude that introducing defect sites into metal oxide supports could be a strategy to aid the dispersion of single atoms on metal-oxide surfaces, and that the presence of water should be taken into account in the modelling of single-atom catalysts.