Korean Journal of Chemical Engineering

, Volume 14, Issue 6, pp 427–431 | Cite as

Recent topics in heterogeneous catalysis of heteropolyacids



First, the state of the art of the catalyst design based on heteropoly compounds is briefly overviewed. Then, selected topics of solid heteropoly catalysts, that is, the selective oxidation of isobutyric acid and isobutane over molybdovanadophosphoric acids, the methyl t-butyl ether synthesis in pseudoliquid of heteropolyacids, and the shape-selective and bifunctional (combined with noble metals) acid catalysis of cesium and ammonium salts of tungstophosphoric acid are described based on the recent studies from our laboratory.

Key words

Heteropolyacid Selective Oxidation Pseudoliquid Behavior Alkane Isomerization 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Centi, G., Lena, V. and Trifiró, F., “Active Form of 12-Vanadomolybdophosphoric Acids in n-Butane Selective Oxidation”,J. Chem. Soc, Faraday Trans.,86, 2775 (1990).CrossRefGoogle Scholar
  2. Inumaru, K., Kubo, Ono, A. and Misono, M., “The Structure and Redox Behaviour of Vanadium Speeies in Molybdovanadophosphoric Acid Catalysts during Partial Oxidation of Isobutane”, to be published.Google Scholar
  3. Inumaru, K., Nakajima, H., Ito, T. and Misono, M., “Porous Aggregates of Unidirectionally Oriented (NH4)3PW12O40 Microcrystallites: Epitaxial Self-Assembly”,Chem. Lett., 559 (1996).Google Scholar
  4. JP 1988-145249 (Asahi Chemical), 1991-106839 (Sumitomo Chemical).Google Scholar
  5. Koyano, G., Saito, T. and Misono, M., “In Stiu Raman Spectroscopic Investigation of Surface Redox Mechanism of Vanadyl Pyrophosphate ”,Chem. Lett., 415 (1997).Google Scholar
  6. Koyano, G., Yamaguchi, F., Okuhara, T. and Misono, M., “Anisotropic oxidation of crystallites of vanadyl pyrophosphate”,Catal. Lett.,41, 149 (1996).CrossRefGoogle Scholar
  7. Lee, K. Y., Arai, T., Nakata, S., Asaoka, S., Okuhara, T. and Misono, M., “Catalysis by Heteropoly Compounds. 20. An NMR Study of Ethanol Dehydration in the Pseudoliquid Phase of 12-Tungstophospheric Acid”,J. Am. Chem. Soc,114, 2836 (1992).CrossRefGoogle Scholar
  8. Lee, K. Y., Oishi, S. and Misono, M., “Acidic Cesium Salts of Molybdovanadophosphoric Acids as Effecient Catalysts for Oxidative Dehydrogenation of Isobutyric Acid ”,Catal. Today,33, 183 (1997).CrossRefGoogle Scholar
  9. Li, W. and Ueda, W., “Catalytic Oxidation of Isobutane to Methacrylic Acid with Melecular Oxygen over Activated Pyridinium 12-molybdophosphate”,Catal. Lett.,46, 261 (1991).CrossRefGoogle Scholar
  10. Liu, Y., Koyano, G., Na, K. and Makoto, M., “Isomerizations of n-Pentane and n-Hexane over Cesium Hydrogen Salt of 12-Tungstophosphoric Acid Promoted by Platinum”Appl. Catal. A., in press.Google Scholar
  11. Misono, M. and Okuhara, T., “Solid Superacid Catalysts”,Chemtech,Nov., 23 (1993).Google Scholar
  12. Mizuno, N. et al, “Oxidation of Isobutane Catalyzed by Csx-H3-xPMo12O40-based Heteropoly Compounds ”,J. Catal,163, 87 (1996);J. Mol. Catal,114, 309 (1996);Chem. Lett., 1121 (1996).CrossRefGoogle Scholar
  13. Mizuno, N. et al., “Catalytic Performance of Cs2.5Fe0.08H26-PVMo11O40 for Direct. Oxidation of Lower Alkanes ”,J. Mol. Catal. Google Scholar
  14. Mizuno, N. et al., “Selective Oxidative Dehydrogenation of Ethane Catalyzed by Cs2.5Mn0.08H134PVMo11O40”,Catalyst Precursor, Chem. Lett. Google Scholar
  15. Na, K., Okuhara, T. and Misono, M., “Skeletal Isomerization of N-Butane over Caesium Hydrogen Salts of 12-Tungestophosphoric Acid”,J. Chem. Soc., Faraday,91, 367 (1993).Google Scholar
  16. Na, K., Okuhara, T. and Misono, M., “Isomerization ofn- Butane over Bifunctional Platinum-heteropoly Compounds in Presence of Hydrogen ”,J. Chem. Soc. Chem. Comm., 1422 (1993);J. Catal,170, 96 (1997).Google Scholar
  17. Okuhara, T., Mizuno, N. and Misono, M., “Catalytic Chemistry of Heteropoly Compounds”Advan. Catal,41, 113 (1996).CrossRefGoogle Scholar
  18. Okuhara, T., Nishimura, T. and Misono, M., “Microporous Heteropoly Compound as a Shape Selective Catalyst: Cs2.2-H0 8PW12O40”,Chem. Lett.,155 (1995); Proc. 11th Intern. Congr. Catal., Baltimore,581, 1996.Google Scholar
  19. Okuhara, T., Nishimura, T. and Misono, M., “Insoluble Heteropoly Compounds as Highyl Active Catalysts for liquidphase Reactions”,J. Molec. Catal,74, 247 (1992).CrossRefGoogle Scholar
  20. Shikata, S., Nakata, S., Okuhara, T. and Misono, M., “Catalysis by Heteropoly Compounds. 32. Synthesis of Methyl tertButyl Ether Catalyzed by Heteropolyacids Supported on Silica”,J. Catal,166, 263 (1997).CrossRefGoogle Scholar
  21. Takahashi, K., Okuhara, T. and Misono, M., “Phase Transition-like Phenomenon Observed for “Pseudo-Liquid Phase” of Heteropoly Acid Catalysts”,Chem. Lett.,841 (1985).Google Scholar
  22. Tatematsu, S., Hibi, T., Okuhara, T. and Misono, M., “Preparation Process and Catalytic Activity of CsxH3-xPw12O40”,Chem. Lett.,865 (1984).Google Scholar

Copyright information

© Korean Institute of Chemical Engineering 1997

Authors and Affiliations

  1. 1.Department of Applied Chemistry, Graduate School of EngineeringThe University of TokyoTokyoJapan

Personalised recommendations