Investigating Reactive Superoxide Units Bound to Zirconium Oxide Cations

The structure and reactivity properties of a series of clusters ZrxO2x+1+(x= 1–3) are investigated using DFT calculations and guided-ion-beam mass spectrometry. Calculations determine the cluster structures containing two oxygen atoms sharing a spin unpaired electron known as a superoxide (O2–). Experiment and theory provide evidence that the size of the cluster has marked influence over the reactivity properties toward C3H6, C4H6, and C2H2. In particular, Zr2O5+is highly reactive for the oxidation of the three hydrocarbons, while ZrO3+only presents substantial reactivity toward butadiene. In addition, Zr3O7+primarily associates the reactants, revealing minor oxidation channels.