Determination of the V2p XPS binding energies for different vanadium oxidation states (V5+ to V0+)

Silversmit, Geert; Depla, Diederik; Poelman, Hilde; Marin, Guy; Gryse, Roger De

doi:10.1016/j.elspec.2004.03.004

Cited by 1,575 publications

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“…Spectra with a different degree of reduction were obtained by Ar + bombardment of the V 2 O 5 (0 0 1) surface due to the preferential sputtering of the oxygen atoms and are discussed in Section 3.2. Analysis of the set of XPS spectra confirms the transferability of the V2p fit parameters reported in [1]. However, asymmetric line shapes for the V 3+ 2p core line proved necessary.…”

Section: Introductionmentioning

confidence: 48%

“…However, asymmetric line shapes for the V 3+ 2p core line proved necessary. Moreover, the asymmetric line shape for the V 3+ 2p photoline is supported by re-analysis of representative V 3+ 2p spectra from [1].…”

Section: Introductionmentioning

confidence: 97%

“…A review on this topic is given in [2]. Recently we have shown that the V2p BE positions for the V 5+ , V 4+ and V 3+ oxidation states can be determined by studying a pressed V 2 O 3 pellet under an Ar + bombardment [1].…”

Section: Introductionmentioning

confidence: 99%

“…The reducing effect of the Al Ka X-rays on the vanadium oxidation state of a fresh in vacuum cleaved V 2 O 5 (0 0 1) crystal is therefore determined beforehand in Section 3.1. In order to test the transferability of the V2p fit parameters from [1], derived mostly on a V 2 O 3 powder pellet, to other vanadium oxide systems, a V 2 O 5 (0 0 1) single crystal sample was used in this work. Spectra with a different degree of reduction were obtained by Ar + bombardment of the V 2 O 5 (0 0 1) surface due to the preferential sputtering of the oxygen atoms and are discussed in Section 3.2.…”

Section: Introductionmentioning

confidence: 99%

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An XPS study on the surface reduction of V2O5(001) induced by Ar+ ion bombardment

et al. 2006

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The effect of the irradiation with Al Ka X-rays during an XPS measurement upon the surface vanadium oxidation state of a fresh in vacuum cleaved V 2 O 5 (0 0 1) crystal was examined. Afterwards, the surface reduction of the V 2 O 5 (0 0 1) surface under Ar + bombardment was studied. The degree of reduction of the vanadium oxide was determined by means of a combined analysis of the O1s and V2p photoelectron lines. Asymmetric line shapes were needed to fit the V 3+ 2p photolines, due to the metallic character of V 2 O 3 at ambient temperature. Under Ar + bombardment, the V 2 O 5 (0 0 1) crystal surface reduces rather fast towards the V 2 O 3 stoichiometry, after which a much slower reduction of the vanadium oxide occurs.

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Section: Introductionmentioning

confidence: 48%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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An XPS study on the surface reduction of V2O5(001) induced by Ar+ ion bombardment

et al. 2006

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“…The peak at ~527 eV corresponds to a vanadium satellite while the peak at ~532 eV can be assigned to the oxygen-containing oleate ligands bound to the surface of the nanocrystals. 33,34 Density Functional Theory: DFT 35,36 calculations were performed using the Vienna Ab initio Simulation Package (VASP) with a plane-wave basis set expanded up to a cutoff energy of 550 eV. 37,38 The projector augmented wave (PAW) method was used, treating 13 valence electrons for vanadium (3s 2 3p 6 4s 2 3d 3 ) and 6 valence electrons for oxygen (2s 2 2p 4 ).…”

Section: Methodsmentioning

confidence: 99%

Oxygen Incorporation and Release in Metastable Bixbyite V₂O₃ Nanocrystals

2016

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A new, metastable polymorph of V 2 O 3 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 interstitials 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. Thus, the observed rapid oxidation kinetics are facilitated by short diffusion paths through the bixbyite nanocrystals. Due to the exceptionally low temperatures of oxidation and reduction, this earthabundant material is proposed for use in oxygen storage applications.The oxides of vanadium are known for both their structural complexity and fascinating properties, as manifested in the many stable and metastable phases and phase transitions that exist in these materials. Vanadium sesquioxide (V 2 O 3 ) is one such oxide, transforming from the antiferromagnetic, insulating monoclinic phase to the paramagnetic, metallic corundum phase at 170 K. [1][2][3] This phase transformation is of great fundamental importance due to its model Mott-Hubbard transition behavior. 4 Recently, a metastable phase of V 2 O 3 with a cubic, bixbyite structure was discovered. 5 This new polymorph has since been the subject of several studies, both fundamental and applied, including its proposed use as a p-type conductor and battery electrode. 6,7 Synthesizing V 2 O 3 nanocrystals stabilizes the metastable phase and allowed us, in 2013, to prepare phase pure bixbyite. 8 Using our colloidal synthetic method, we now demonstrate low temperature, reversible oxidation and reduction of bixbyite V 2 O 3 nanocrystals, a phenomenon which could be harnessed for oxygen storage.The bixbyite structure has a body-centered cubic lattice with space group Ia-3. Often described as anion deficient fluorite, bixbyite is comparable to a 2 x 2 x 2 fluorite supercell with a quarter of the anions removed, as demonstrated in Figure 1. These vacated sites are the 16c Wyckoff positions in the Ia-3 space group, which are inherently unfilled in bixbyite. 9 Cations in the bixbyite structure populate two symmetry inequivalent positions-the 8b and 24d Wyckoff positions, otherwise known as b-and d-sites,

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Vanadium Oxidation State Determination by X‐Ray Absorption Spectroscopy

Duchesne

Nakano

et al. 2016

Advances in Molten Slags, Fluxes, and Salts

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Determination of the V2p XPS binding energies for different vanadium oxidation states (V5+ to V0+)

Cited by 1,575 publications

References 23 publications

An XPS study on the surface reduction of V2O5(001) induced by Ar+ ion bombardment

An XPS study on the surface reduction of V2O5(001) induced by Ar+ ion bombardment

Oxygen Incorporation and Release in Metastable Bixbyite V₂O₃ Nanocrystals

Vanadium Oxidation State Determination by X‐Ray Absorption Spectroscopy

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Determination of the V2p XPS binding energies for different vanadium oxidation states (V5+ to V0+)

Cited by 1,575 publications

References 23 publications

An XPS study on the surface reduction of V2O5(001) induced by Ar+ ion bombardment

An XPS study on the surface reduction of V2O5(001) induced by Ar+ ion bombardment

Oxygen Incorporation and Release in Metastable Bixbyite V2O3 Nanocrystals

Vanadium Oxidation State Determination by X‐Ray Absorption Spectroscopy

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Product

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About

Oxygen Incorporation and Release in Metastable Bixbyite V₂O₃ Nanocrystals