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Oxygen Incorporation and Release in Metastable Bixbyite V2O3 Nanocrystals

Bergerud, Amy; Selbach, Sverre Magnus; Milliron, Delia J.
Journal article
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URI
http://hdl.handle.net/11250/2465959
Date
2016
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  • Institutt for materialteknologi [1570]
  • Publikasjoner fra CRIStin - NTNU [19849]
Original version
ACS Nano. 2016, 10 (6), 6147-6155.   10.1021/acsnano.6b02093
Abstract
A new, metastable polymorph of V2O3 with a bixbyite structure was recently stabilized in colloidal nanocrystal form. Here, we report the reversible incorporation of oxygen in this material, which can be controlled by varying temperature and oxygen partial pressure. Based on X-ray diffraction (XRD) and thermogravimetric analysis, we find that oxygen occupies interstitial sites in the bixbyite lattice. Two oxygen atoms per unit cell can be incorporated rapidly and with minimal changes to the structure while the addition of three or more oxygen atoms destabilizes the structure, resulting in a phase change that can be reversed upon oxygen removal. Density functional theory (DFT) supports the reversible occupation of interstitial sites in bixbyite by oxygen, and the 1.1 eV barrier to oxygen diffusion predicted by DFT matches the activation energy of the oxidation process derived from observations by in situ XRD. The observed rapid oxidation kinetics are thus facilitated by short diffusion paths through the bixbyite nanocrystals. Due to the exceptionally low temperatures of oxidation and reduction, this earth-abundant material is proposed for use in oxygen storage applications.
Publisher
American Chemical Society
Journal
ACS Nano

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