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Issue 38, 2010
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Methane activation by V3PO10˙+ and V4O10˙+ clusters: A comparative study

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Abstract

A series of vanadium and phosphorus heteronuclear oxide cluster cations (VxPyOz+) are prepared by laser ablation and the reactions of V3PO10˙+ and V4O10˙+ 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˙+ + CH4 → V4O10H+ + CH3˙, the observation of hydrogen atom pickup cluster V3PO10H+ suggests the reaction: V3PO10˙+ + CH4 → V3PO10H+ + CH3˙. The rate of the reaction of V4O10˙+ with CH4 is approximately 2.5 times faster than that of V3PO10˙+ with CH4. Density functional theory (DFT) calculations predict that structure of V3PO10˙+ is topologically similar to that of V4O10˙+, as well as that of P4O10˙+, which is very similar to V4O10˙+ 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 () in these clusters. Further theoretical study indicates that the radical (or spin density of the cluster) can transfer within the high symmetry V4O10˙+ and P4O10˙+ 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˙+ is thermodynamically forbidden. The experimentally observed reactivity difference is consistent with the theoretical consideration of the intra-cluster spin density transfer.

Graphical abstract: Methane activation by V3PO10˙+ and V4O10˙+ clusters: A comparative study

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Publication details

The article was received on 27 Apr 2010, accepted on 23 Jun 2010 and first published on 16 Aug 2010


Article type: Paper
DOI: 10.1039/C0CP00360C
Phys. Chem. Chem. Phys., 2010,12, 12223-12228

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    Methane activation by V3PO10˙+ and V4O10˙+ clusters: A comparative study

    J. Ma, X. Wu, X. Zhao, X. Ding and S. He, Phys. Chem. Chem. Phys., 2010, 12, 12223
    DOI: 10.1039/C0CP00360C

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