Mixing properties of Al₂O₃(0001)-supportedM₂O₃andMM'O₃monolayers (M,M' = Ti, V, Cr, Fe)

Considering the importance of sub-monolayer transition metal oxides supported on another oxide in many industrial processes, with the help of a DFT +Uapproach, we provide information on the structural and electronic properties of pureM₂O₃and mixedMM'O₃oxide monolayers (M,M' = Ti, V, Cr, Fe) supported on anα-Al₂O₃(0001) support. With their structure in the prolongation of the alumina corundum lattice, the monolayers have non-equivalent surface and interface cations, which leads to two different cation configurations in the mixed oxides. In all cases, the interfacial charge transfer is weak, but strong cation-cation electron redistributions may take place as in TiVO₃, TiFeO₃, VFeO₃, and TiCrO₃in which actual redox processes lead to cation oxidation states different from the expected +3 value. We show that the tendency to mixing relies on the interplay between two very different driving forces. Cation-cation redox reactions, in most cases, strongly stabilise mixed configurations, but preference for a given cation position in the monolayer, because of surface energy reasons, may strengthen, weaken or even block the mixing tendency. By comparison with results obtained in bulk ilmenite, in free-standing monolayers and in MLs deposited on transition metal substrates, we evidence the flexibility of their electronic structure as a function of size, dimensionality and nature of support, as a lever to tune their properties for specific applications.