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  • 1 Department of Chemistry, Faculty of Science, M. S. University of Baroda, Vadodara 390 002, India
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Abstract

Zirconia supported dodecaphosphotungstate and undecaphosphotungstate were successfully used as heterogeneous catalysts for the liquid-phase solvent-free oxidation of styrene. A detailed kinetic study was carried out in order to study the effect of removal of one addenda atom from the parent Keggin unit. The supported catalysts were also systematically characterized by various physicochemical techniques to show that the Keggin unit remains intact even after supporting on the support. Thermal studies also indicate that the supported catalysts are stable up to 450 °C. Maximum conversion with a single selective product was obtained after 30 h for the undecaphosphotungstate and after 20 h for dodecaphosphotungstate. The rate constants as well as the activation energy for the reaction were determined. From the values of activation energy derived from the Arrhenius plot, different thermodynamic parameters such as enthalpy and Gibbs free energy were also calculated. From the above studies, supported dodecaphosphotungstate was found to be more active as compared to undecaphosphotungstate.

  • 1.

    Kholdeeva, O (2006) Top Catal. 40:229 .

  • 2.

    Grigoropoulou, G, Clark, J, Elings, J (2003) Green Chem. 5:1 .

  • 3.

    Noyori R , Aoki M, Sato K, (2003) Chem Commun 1977.

  • 4.

    Lane, B, Burgess, K (2003) Chem Rev. 103:2457 .

  • 5.

    Sato, K, Aoki, M, Noyori, R (1998) Science. 281:1646 .

  • 6.

    Centi, G, Misono, M (1998) Catal Today. 41:287 .

  • 7.

    Kholdeeva, O, Trubitsina, T, Timofeeva, M, Maksimov, G, Maksimovskaya, R, Rogov, V (2005) J Mol Catal A Chem. 232:173 .

  • 8.

    Pope, MT. 1983 Heteropoly and isopoly oxometalates Springer New York.

  • 9.

    Hill, CL, Prosser-McCartha, CM (1995) Coord Chem Rev. 143:407 .

  • 10.

    Hill CL (2004) Polyoxometalates: reactivity. In: Wedd AG (ed) Comprehensive coordination chemistry II, vol 4. Elsevier Science, New York, p 679.

    • Search Google Scholar
    • Export Citation
  • 11.

    Mizuno, N Misono 1998 Chem Rev. 98:199 .

  • 12.

    Rozner, DS, Witte, P, Alsters, PL, Neumann, R (2004) Adv Synth Catal. 346:339 .

  • 13.

    Harrup, MK, Hill, CL (1994) Inorg Chem. 33:5448 .

  • 14.

    Xinrong, L, Jinyu, X, Huizhang, L, Bin, Y, Songlin, J, Gaoyang, X (2000) J Mol Catal A Chem. 161:163 .

  • 15.

    Zhang, X, Chen, Q, Duncan, D et al (1997) Inorg Chem. 36:4381 .

  • 16.

    Neumann, R Abu-Grim 1990 J Am Chem Soc. 112:6025 .

  • 17.

    Indira, V, Halligudi, S, Gopinathan, S, Gopinathan, C (2001) React Kinet Catal Lett. 73:99 .

  • 18.

    Ishikawa, E, Yamase, T (1999) J Mol Catal A Chem. 142:61 .

  • 19.

    Gelbard, G, Breton, F, Quenard, M, Sherrington, D (2000) J Mol Catal A Chem. 153:7 .

  • 20.

    Gao, F, Yamase, T, Suzuki, H (2002) J Mol Catal A Chem. 180:97 .

  • 21.

    Cohen, M, Neumann, R (1999) J Mol Catal A Chem. 146:291 .

  • 22.

    Gelbard, G, Gauducheau, T, Vidal, E, Crossman, A, Pop, V (2002) J Mol Catal A Chem. 182:257 .

  • 23.

    Kamata, K, Yohehara, K, Sumida, Y, Yamaguchi, K, Hikichi, S, Mizuno, N (2003) Science. 300:964 .

  • 24.

    Mizuno, N, Hikichi, S, Yamaguchi, K, Uchida, S, Nakagawa, Y, Uehara, K, Kamata, K (2006) Catal Today. 117:32 .

  • 25.

    Kamata, K, Kotani, M, Yamaguchi, K, Hikichi, S, Mizuno, N (2007) Chem Eur J. 13:639 .

  • 26.

    Mizuno, N, Yamaguchi, K, Kamata, K (2005) Coord Chem Rev. 249:1944 .

  • 27.

    Nozaki, C, Kiyoto, I, Minai, Y, Misono, M, Mizuno, N (1999) Inorg Chem. 38:5724 .

  • 28.

    Yoshida, A, Hikichi, S, Mizuno, N (2007) J Organomet Chem. 692:455 .

  • 29.

    Massart, R, Contant, R, Fruchart, JM, Clabrini, JP, Fournier, M (1977) Inorg Chem. 16:2916 .

  • 30.

    Knoth, WH, Harlow, RL (1981) J Am Chem Soc. 103:1865 .

  • 31.

    Brevard, C, Schimpf, R, Tourne, G, Tourne, C (1983) J Am Chem Soc. 105:7059 .

  • 32.

    Okhuhara, T, Mizuno, N, Misono, M (1996) Adv Catal. 41:133.

  • 33.

    Shringarpure P , Patel A (2008) Dalton Trans 3953.

  • 34.

    Patel, S, Purohit, N, Patel, A (2003) J Mol Catal A Chem. 192:195 .

  • 35.

    Sharma, P, Patel, A (2006) Bull Mater Sci. 29:439 .

  • 36.

    Bhatt, N, Patel, A (2007) Catal Lett. 113:99 .

  • 37.

    Yadav, G, Bokade, V (1996) Appl Catal A. 147:299 .

  • 38.

    Okuhara, T, Mizuno, N, Misono, M (1996) Adv Catal. 41:113 .

  • 39.

    Edwards, J, Thiel, C, Benac, B, Knifton, J (1998) Catal Lett. 51:77 .

  • 40.

    Misono, M et al (1982) Bull Chem Soc Jpn. 55:400 .

  • 41.

    Sheldon, A, Walau, M, Arends, IWCE, Schuchurdt, U (1998) Acc Chem Res. 31:485 .

  • 42.

    Mizuno N (2008) Mechanisms in homogeneous and heterogeneous epoxidation catalysts. In: Ted S (ed) Oyama, chap 4. Elseiver, New York.

  • 43.

    Neumann, R, Gara, M (1995) J Am Chem Soc. 117:5066 .

  • 44.

    Gao, J, Chen, Y, Han, B, Feng, Z, Li, C, Zhou, N, Gao, S, Xi, S (2004) J Mol Catal A Chem. 210:197 .

  • 45.

    Ingle, RH, Kala Raj, NK (2008) J Mol Catal A Chem. 294:8 .

  • 46.

    Bond GC (1974) Heterogeneous catalysis: principles and applications, chap 3. Oxford Science Publications, Clarendon Press, Oxford, p 48.

    • Search Google Scholar
    • Export Citation
  • 47.

    Turek, W, Pomarzanska, ES, Pron, A, Haber, J (2000) J Catal. 189:297 .