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Investigating Reactive Superoxide Units Bound to Zirconium Oxide Cations

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journal contribution
posted on 10.11.2011, 00:00 by Eric C. Tyo, Melanie Nossler, Christopher L. Harmon, Roland Mitrić, Vlasta Bonačić-Koutecký, A. W. Castleman
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.