Binding and stability of MgO monomers on anatase TiO₂(101)

In catalysis, MgO is often used to modify the acid-base properties of support oxides and to stabilize supported metal atoms and particles on oxides. In this study, we show how the sublimation of MgO powder can be used to deposit MgO monomers, hither on anatase TiO₂(101). A combination of x-ray electron spectroscopy, high-resolution scanning tunneling microscopy, and density functional theory is employed to gain insight into the MgO monomer binding, electronic and vibrational properties, and thermal stability. In the most stable configuration, the Mg and O of the MgO monomer bind to two surface oxygens and one undercoordinated surface titanium, respectively. The additional binding weakens the Mg-O monomer bond and makes Mg more ionic. The monomers are thermally stable up to 600 K, where the onset of diffusion into the TiO₂ bulk is observed. The monomeric MgO species on TiO₂(101) represent an ideal atomically precise system with modified acid-base properties and will be employed in our future catalytic studies.