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Systematic Preparation Of Polyoxometalate Pillared Layered Double Hydroxides Via Direct Aqueous Reaction

Published online by Cambridge University Press:  15 February 2011

Jiandang Wang ,
Ying Tian ,
Ren-Chain Wang ,
Jorge L. Colón  and
Abraham Clearfield
Jiandang Wang
Affiliation:
Department of Chemistry, Texas A&M University College Station, Texas 77843
Ying Tian
Affiliation:
Department of Chemistry, Texas A&M University College Station, Texas 77843
Ren-Chain Wang
Affiliation:
Department of Chemistry, Texas A&M University College Station, Texas 77843
Jorge L. Colón
Affiliation:
Department of Chemistry, Texas A&M University College Station, Texas 77843
Abraham Clearfield
Affiliation:
Department of Chemistry, Texas A&M University College Station, Texas 77843
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Abstract

The series of layered double hydroxides, MgnAl(OH)2n+2X (n = 2–5, X = NO3− or Cl−) and NinAl(OH) 2n+2X (n = 2–4, X = NO3− or Cl−), were pillared with polyoxometalate ions of the Keggin structure, ranging from [PW12O40]3− to [PV4W8O40]7−, in aqueous solution. Full exchange of the Keggin ions into the layers is achieved as evidenced by X-ray powder diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Also, partial exchange was observed for Ni5Al(OH)12NO3 The key factor that effects these reactions is the pre-swelling step. Thus, when the layered double hydroxides are thoroughly wet either by preparing wet solids or by soaking the dried products for an extended period, pillaring reactions proceed with great ease. Relations can be extracted between the water content and the separation between the layers, as well as between layer charge density and the charge of the Keggin ion. The pillared layered double hydroxides were found generally to have interlayer distances ranging from 11.0 to 13.5 Å, which is smaller than the numerical sum of the Keggin ion diameter and the ideal thickness of the hydroxide layer. This fact and the low crystallinity are attributed to strong interaction between the basic layered double hydroxides and the acidic Keggin ions. A more crystalline phase with the expected 14.5 Å interlayer spacing was also obtained as a mixture with the lower spaced products.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 233: Symposium U – Synthesis/Characterization and Novel Applications of Molecular Sieve Materials , 1991 , 63
Copyright
Copyright © Materials Research Society 1991

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References

REFERENCES

1. Vaughan, D.E.W., Catal. Today 2, 187 (1988).Google Scholar
2. Catalysis Today - Pillared Clays edited by Burch, R. (Elsevier, Amsterdam, 1988) Vol.2, pp 199–295.Google Scholar
3. Figueras, F., Catal. Rev. Sci. Eng. 30, 457 (1988).CrossRefGoogle Scholar
4. Adams, J.M., Appl. Clay Sci. 2, 309 (1987).CrossRefGoogle Scholar
5. Cataylsis Today - Pillared Clays. edited by Burch, R. (Elsevier, Amsterdam,1988) Vol.2, pp 297–355.Google Scholar
6. Clearfield, A. and Roberts, B.D., Inorg. Chem. 27, 3237 (1988).Google Scholar
7. Cheng, S. and Wang, T.-C., Inorg. Chem., 28 1283 1989).Google Scholar
8. Jones, W. and Chibwe, M., in Pillared Layered Structures edited by Mitchell, I.V. (Elsevier, London, 1990) pp 67–77.Google Scholar
9. Allmann, R., Chimia 27, 4628 (1970).Google Scholar
10. Drezdzon, M.A., Inorg. Chem. 227, 4628 (1988).Google Scholar
11. Kwon, T. and Pinnavaia, T.J., Chem. Mater. 1, 381(1989).Google Scholar
12. Dimotakis, E.D. and Pinnavaia, T.J., Inorg. Chem. 29 2393 (1990).Google Scholar
13. Shriver, D.F. and Drezdzon, M.A., The Manipulation of Air-Sensitive Compounds, 2nd ed. (Wiley, New York, 1986).Google Scholar
14. Pope, M.T., Heteropoly and Isopoly Oxometalates (Springer-Verlag, New York, 1983).CrossRefGoogle Scholar
15. (a) Domaille, P.J. and Watunya, G., Inorg. Chem., 25 1239 (1986). (b) D.P. Smith and M.T. Pope, Inorg. Chem. 12, 331(1973).Google Scholar
16. (a) Pope, M.T. and Varga, G.M. Jr.,, Inorg. Chem. 5, 1249 (1960). (b) H. Wu, J. Biol. Chem., 43, 189 (1920).Google Scholar
17. Clearfield, A., Kieke, M., Kwan, J., Colón, J.L. and Wang, R.-C., J. Inclusion Phenom., submitted.Google Scholar
18. Wang, R.-C. and Clearfield, A., Patent pending and manuscript in preparation.Google Scholar
19. In one experiment with highly crystalline Mg2AI(OH)6CI, our colleague Shea, W.-L. obtained a series of XPD patterns during the process of slow air drying of the wet sample. Very sharp reflections were observed at both d = 15.0,Å and 9.0 Å on the first, wettest sample.Google Scholar
20. Theng, B.K.G., The Chemistry of Clay-Organic Reactions (Wiley, New York, 1974).Google Scholar
21. An error is obvious in reference 11 in which Kwon and Pinnavaia claimed that “for Zn2Al[NO3 −] the area per unit charge is only 16.6 Å2” when it actually should be 25.0 Å2 confirmed by both our calculations and experiments.Google Scholar
22. Based on crystallographic data in the literature: (a) Brown, G.M., Noe-Spirlet, M.-R., Busing, W.R., Levy, H.A., Acta Cryst. B33, 1038 (1977). (b) H. D'Amour and R. Allmann, Z. Krist 143, 1 (1977). (c) J. Fuchs, A. Thiele and R. Palm, Z. Naturforsch. 366 161 (1981).Google Scholar