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Desorption of Oxygen from Cationic Niobium Oxide Clusters Revealed by Gas Phase Thermal Desorption Spectrometry and Density Functional Theory Calculations.
Journal of Physical Chemistry. A 2017 March 17
Thermal dissociation of cationic niobium oxide clusters (Nbn Om + ) was investigated by gas phase thermal desorption spectrometry. The dominant species formed at 300 K were Nbn O(5/2)n+p + (n = 2, 4, 6, ...; p = 0, 1, 2, ...) and Nbn O((5/2)n-1/2)+q + (n = 3, 5, ...; q = 0, 1, 2, ...). At higher temperatures, the more oxygen-rich clusters were observed to release O2 . However, the desorption of O2 from Nbn Om + was found to be insignificant in comparison with Vn Om + because Nb tends to have a +5 oxidation state exclusively, whereas V can have both +4 and +5 oxidation states. The propensity for the release of O atoms was manifested in the formation of Nbn O(5/2)n-1/2 + from Nbn O((5/2)n-1/2)+1 + for odd values of n, whereas Vn O((5/2)n-1/2)+1 + released O2 molecules instead. The energetics of the O and O2 release from the Nb and V oxide clusters, respectively, was consistent with the results of DFT calculations.
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