Hydrogen-Atom Abstraction from Methane by Stoichiometric Vanadium-Silicon Heteronuclear Oxide Cluster Cations
文献类型：期刊论文
| 作者 | Ding, Xun-Lei1; Zhao, Yan-Xia1,2; Wu, Xiao-Nan1,2; Wang, Zhe-Chen1,2; Ma, Jia-Bi1,2; He, Sheng-Gui1 |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2010 |
| 卷号 | 16期号:37页码:11463-11470 |
| 关键词 | C-h Activation Cluster Compounds Density Functional Calculations Mass Spectrometry Methane Activation Radicals |
| ISSN号 | 0947-6539 |
| DOI | 10.1002/chem.201001297 |
| 英文摘要 | Vanadium-silicon heteronuclear oxide cluster cations were prepared by laser ablation of a V/Si mixed sample in an O-2 background. Reactions of the heteronuclear oxide cations with methane in a fast-flow reactor were studied with a time-of-flight (TOF) mass spectrometer to detect the cluster distribution before and after the reactions. Hydrogen abstraction reactions were identified over stoichiometric cluster cations [(V2O5)(n)(SiO2)(m)](+) (n = 1, m=1-4; n=2, m=1), and the estimated first-order rate constants for the reactions were close to that of the homonuclear oxide cluster V4O10+ with methane. Density functional calculations were performed to study the structural, bonding, electronic, and reactivity properties of these stoichiometric oxide clusters. Terminal-oxygen-centered radicals (O-t(center dot)) were found in all of the stable isomers. These O-t(center dot) radicals are active sites of the clusters in reaction with CH4 center dot The O-t(center dot) radicals in [V2O5(SiO2)(1-4)](+) clusters are bonded with Si rather than V atoms. All the hydrogen abstraction reactions are favorable both thermodynamically and kinetically. This work reveals the unique properties of metal/nonmetal heteronuclear oxide clusters, and may provide new insights into CH4 activation on silica-supported vanadium oxide catalysts. |
| 语种 | 英语 |
| WOS记录号 | WOS:000283386600030 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/70699]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | He, Sheng-Gui |
| 作者单位 | 1.Chinese Acad Sci, State Key Lab Struct Chem Unstable & Stable Speci, Beijing Natl Lab Mol Sci, Inst Chem, Beijing 100190, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China |
| 推荐引用方式 GB/T 7714 | Ding, Xun-Lei,Zhao, Yan-Xia,Wu, Xiao-Nan,et al. Hydrogen-Atom Abstraction from Methane by Stoichiometric Vanadium-Silicon Heteronuclear Oxide Cluster Cations[J]. CHEMISTRY-A EUROPEAN JOURNAL,2010,16(37):11463-11470. |
| APA | Ding, Xun-Lei,Zhao, Yan-Xia,Wu, Xiao-Nan,Wang, Zhe-Chen,Ma, Jia-Bi,&He, Sheng-Gui.(2010).Hydrogen-Atom Abstraction from Methane by Stoichiometric Vanadium-Silicon Heteronuclear Oxide Cluster Cations.CHEMISTRY-A EUROPEAN JOURNAL,16(37),11463-11470. |
| MLA | Ding, Xun-Lei,et al."Hydrogen-Atom Abstraction from Methane by Stoichiometric Vanadium-Silicon Heteronuclear Oxide Cluster Cations".CHEMISTRY-A EUROPEAN JOURNAL 16.37(2010):11463-11470. |
入库方式： OAI收割
来源：化学研究所
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