Methane activation by V3PO10 center dot+ and V4O10 center dot+ clusters: A comparative study
文献类型：期刊论文
| 作者 | Ma, Jia-Bi1,2; Wu, Xiao-Nan1,2; Zhao, Xian-Xia1,2; Ding, Xun-Lei1; He, Sheng-Gui1 |
| 刊名 | PHYSICAL CHEMISTRY CHEMICAL PHYSICS
 |
| 出版日期 | 2010 |
| 卷号 | 12期号:38页码:12223-12228 |
| ISSN号 | 1463-9076 |
| DOI | 10.1039/c0cp00360c |
| 英文摘要 | A series of vanadium and phosphorus heteronuclear oxide cluster cations (VxPyOz+) are prepared by laser ablation and the reactions of V3PO10 center dot+ and V4O10 center dot+ with methane in a fast flow reactor under the same conditions are studied. A time of flight mass spectrometer is used to detect the cluster distribution before and after reactions. In addition to previously identified reaction of V4O10 center dot+ + CH4 -> V4O10H+ + CH3 center dot, the observation of hydrogen atom pickup cluster V3PO10H+ suggests the reaction: V3PO10 center dot+ + CH4 -> V3PO10H+ + CH3 center dot. The rate of the reaction of V4O10 center dot+ with CH4 is approximately 2.5 times faster than that of V3PO10 center dot+ with CH4. Density functional theory (DFT) calculations predict that structure of V3PO10 center dot+ is topologically similar to that of V4O10 center dot+, as well as that of P4O10 center dot+, which is very similar to V4O10 center dot+ in terms of methane activation in previous studies. The facile methane activation by the homo-and hetero-nuclear oxide clusters can all be attributed to the presence of an oxygen-centered radical (O-center dot) in these clusters. Further theoretical study indicates that the O-center dot radical (or spin density of the cluster) can transfer within the high symmetry V4O10 center dot+ and P4O10 center dot+ clusters quite easily, and CH4 molecule further enhances the rate of intra-cluster spin density transfer. In contrast, the intra-cluster spin density transfer within low symmetry V3PO10 center dot+ is thermodynamically forbidden. The experimentally observed reactivity difference is consistent with the theoretical consideration of the intra-cluster spin density transfer. |
| 语种 | 英语 |
| 出版者 | ROYAL SOC CHEMISTRY |
| WOS记录号 | WOS:000282103200047 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/71219]  |
| 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, Inst Chem, BNLMS, State Key Lab Struct Chem Unstable & Stable Speci, 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 | Ma, Jia-Bi,Wu, Xiao-Nan,Zhao, Xian-Xia,et al. Methane activation by V3PO10 center dot+ and V4O10 center dot+ clusters: A comparative study[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2010,12(38):12223-12228. |
| APA | Ma, Jia-Bi,Wu, Xiao-Nan,Zhao, Xian-Xia,Ding, Xun-Lei,&He, Sheng-Gui.(2010).Methane activation by V3PO10 center dot+ and V4O10 center dot+ clusters: A comparative study.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,12(38),12223-12228. |
| MLA | Ma, Jia-Bi,et al."Methane activation by V3PO10 center dot+ and V4O10 center dot+ clusters: A comparative study".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 12.38(2010):12223-12228. |
入库方式： OAI收割
来源：化学研究所
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