Masuzaki Daigo, Nagata Toshiaki, Mafuné Fumitaka
Department of Basic Science, School of Arts and Sciences, The University of Tokyo , Komaba, Meguro, Tokyo 153-8902, Japan.
J Phys Chem A. 2017 Mar 16;121(10):2079-2085. doi: 10.1021/acs.jpca.6b12645. Epub 2017 Mar 3.
Thermal dissociation of cationic niobium oxide clusters (NbO) was investigated by gas phase thermal desorption spectrometry. The dominant species formed at 300 K were NbO (n = 2, 4, 6, ...; p = 0, 1, 2, ...) and NbO (n = 3, 5, ...; q = 0, 1, 2, ...). At higher temperatures, the more oxygen-rich clusters were observed to release O. However, the desorption of O from NbO was found to be insignificant in comparison with VO 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 NbO from NbO for odd values of n, whereas VO released O molecules instead. The energetics of the O and O release from the Nb and V oxide clusters, respectively, was consistent with the results of DFT calculations.
通过气相热脱附光谱法研究了阳离子氧化铌簇（NbO）的热解离。在300K时形成的主要物种是NbO（n = 2, 4, 6, ...; p = 0, 1, 2, ...）和NbO（n = 3, 5, ...; q = 0, 1, 2, ...）。在较高温度下，观察到富含氧的簇释放出O。然而，与VO相比，发现NbO中O的脱附不明显，因为Nb倾向于仅具有+5氧化态，而V可以具有+4和+5氧化态。对于奇数n值，从NbO形成NbO表现出释放O原子的倾向，而VO则释放O分子。分别从Nb和V氧化物簇中释放O和O的能量学与DFT计算结果一致。
