ICCAS OpenIR
Methane activation by V3PO10 center dot+ and V4O10 center dot+ clusters: A comparative study
Ma, Jia-Bi1,2; Wu, Xiao-Nan1,2; Zhao, Xian-Xia1,2; Ding, Xun-Lei1; He, Sheng-Gui1
2010
Source PublicationPHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN1463-9076
Volume12Issue:38Pages:12223-12228
AbstractA 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.
DOI10.1039/c0cp00360c
Indexed BySCI
Language英语
WOS IDWOS:000282103200047
PublisherROYAL SOC CHEMISTRY
Citation statistics
Cited Times:65[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/71220
Collection中国科学院化学研究所
Corresponding AuthorHe, Sheng-Gui
Affiliation1.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
Recommended Citation
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.
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