Atomic Scale Insights into Reversible Oxygen Storage in Vanadium Oxide Thin Films

Monolayer vanadium oxide films grown on Pt(111) can be reversibly switched between an oxygen-poor and an oxygen-rich composition, equivalent to V₂O₃ and V₂O₅, respectively. While the overall oxygen storage capacity of the film is quantified by X-ray photoelectron spectroscopy, the atomic binding sites of the extra O species are determined by low-temperature scanning tunneling microscopy and electron diffraction. In the O-poor phase, the oxide takes the form of a honeycomb lattice that gets partially covered with vanadyl (V=O) groups at higher O exposure. Upon transition to the O-rich phase, isolated V₆O₁₂ rings emerge in the film first, which then evolves towards a disordered O-V-O trilayer on the Pt(111) surface. Our works thus unravels the microscopic nature of reversible oxygen storage in a model system for heterogeneous catalysis.