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Catalytic Implications for Keggin and Dawson Ions: A Theoretical Study of Stability Factors of Heteropolyoxoanions

Published online by Cambridge University Press:  15 February 2011

Shu-Hsien Wang  and
Susan A. Jansen
Shu-Hsien Wang
Affiliation:
Chemistry Department, Temple University, Philadelphia, PA 19122 Shu-Li Wang
Susan A. Jansen
Affiliation:
Department of Bioengineering, University of Pennsylvania, Philadelphia, PA 19104
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Abstract

Hetreropolyoxoanions(HPAs) have received wide spread attention due to their unique oxidation-reduction properties in catalysis. Two main structural motifs groups of HPAs have been described by Keggin and Dawson. The first is composed of twelve distorted, octahedrallycoordinated metal atoms forming trimeric and tetrameric subunits connected such that a closed shell results. The second is formed by fusing two Keggin units. The most common Keggin ions(XM12O40n−,) with Td symmetry and the Dawson ions(X2M18O62n−) with D3h symmetry are the α-isomers; while the β-isomers are generated by rotating one trimer 60° along its C3 axis, thus producing the Cs, symmetry for β-Keggin ions and D34 symmetry for β-Dawson ions. Here, M is the framework metal atom, usually Mo, W, and X is the central heteroatom which can be the metal or nonmetal. From our previous studies, the instability of β-isomers caused by the “rotated” trimer can not be compensated by other coordination effects within the cluster and therefore defect states are retained between the HOMO-LUMO gap relative to the α-isomer. This enhances catalytic properties and causes thermal/photo lability. The catalytic function of a-Keggin ions are well studied; however, related research reports about Dawson ions are rare. The α-Dawson ion possesses stronger oxidizing ability and higher activities in oxidative dehydrogenation and oxygen addition reactions than the α-Keggin ions; the β-isomers have a greater tendency to be reduced than the α-isomers. Most of the characterization methods applied have not yielded the electronic or the structural requisites for the catalytic properties of the HPAs. In this work, the theoretical analysis is done through the application of crystal/tight binding theory coupled with the extended HMckel methodology. The stability trends and the redox behaviors provided by this work reliably trace the experimental data. In addition, the intrinsic instability and the redox effects in the β-isomers with respect to the α-isomers is assessed and a rationale for the observed catalytic and electronic develpoment of structrual function is also offered.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 368: Symposium T – Synthesis and Properties of Advanced Catalytic Materials , 1994 , 229
Copyright
Copyright © Materials Research Society 1995

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References

1. Misono, M. and Mizuno, N., J. Mol. CataL, 86, 309(1994).Google Scholar
2. Buckley, R. I. and Clark, R. J. H., Coord. Chem. Rev., 65, 167(1985).Google Scholar
3. Pope, M. T. and Mttller, A., Angew. Chem. Int. Ed. Engl., 30, 34(1991).Google Scholar
4. Ghosh, A. K. and J. Moffat, B., J. Catal., 101, 238(1986).Google Scholar
5. Prados, R. A. and Pope, M. T., Inorg. Chem., 15, 2547(1976).Google Scholar
6. Lyon, D. K., Miller, W. K., Novet, T., Domaille, P. J., Evitt, E., Johnson, D. C., and Finke, R. G., J. Am. Chem. Soc., 113, 7209 and 7222(1991).Google Scholar
7. Contant, R. and Thouvenot, R., Inorg. Chim. Acta, 212, 41(1993).Google Scholar
8. Finke, R. G., Droege, M. W., and Domaille, P. J., Inorg. Chem., 26, 3886(1987).Google Scholar
9. Barrows, J.N. and Pope, M. T., Inorg. Chim. Acta, 213, 91(1993).Google Scholar
10. Wang, S.–H. and Jansen, S. A., Chem. Mater. 6, 146 and 2130(1994).Google Scholar
11. Wang, S.–H., Singh, D., and Jansen, S. A., J. Catal.(submitted).Google Scholar
12. Wang, S.–H. and Jansen, S. A., Inorg. Chem.(in preparation).Google Scholar
13. Matsumoto, K. Y., Kobayashi, A., and Sasaki, Y., Bull. Chem. Soc. Jpn., 48, 3146(1975).Google Scholar
14. Yamase, T., Ozeki, T., and Motomura, S., Bull. Chem. Soc. Jpn., 65, 1453(1992).Google Scholar
15. Dawson, B., Acta Cryst., 6, 113, (1953).Google Scholar
16. S. Jansen, A. and Hoffmann, R., Surface Sci., 197, 474(1988).Google Scholar