Thermal Reactions of (V2O5)nO鈥?/sup> (n = 1鈥?) Cluster Anions with Ethylene and Propylene: Oxygen Atom Transfer Versus Molecular Association

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• 作者：Zhen Yuan ; Zi-Yu Li ; Zhen-Xun Zhou ; Qing-Yu Liu ; Yan-Xia Zhao ; Sheng-Gui He
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：July 10, 2014
• 年：2014
• 卷：118
• 期：27
• 页码：14967-14976
• 全文大小：537K
• ISSN：1932-7455

文摘

Vanadium oxide cluster ions are prepared by laser ablation and the (V₂O₅)_nO^{鈥?/sup> (n = 1鈥?) clusters (V₂O₆鈥?/sup>, V₄O₁₁鈥?/sup>, and V₆O₁₆鈥?/sup>) are selected by a quadrupole mass filter and interacted with ethylene (C₂H₄) and propylene (C₃H₆) in an ion trap reactor. Molecular association (MA) is observed for all of the reactions and oxygen atom transfer (OAT) is also observed for the V₄O₁₁鈥?/sup> and V₆O₁₆鈥?/sup> cluster systems. The branching ratio of the OAT versus the MA channel increases as the size of (V₂O₅)_nO鈥?/sup> increases and the OAT becomes the major channel in V₆O₁₆鈥?/sup> + C₂H₄ and V₆O₁₆鈥?/sup> + C₃H₆. Density functional theory computations are carried out for the reactions of V₂O₆鈥?/sup> and V₄O₁₁鈥?/sup> with C₂H₄ and the results are consistent with the experimental observations. Anionic metal oxide clusters are usually much less reactive than their cationic and neutral counterparts and this work is among the first to identify the OAT reactivity for cluster anions with hydrocarbon molecules under thermal collision conditions, to the best of our knowledge.}