Heteropolyoxometalate Catalysts for Oxidation of Alcohols with H2O2 Under Green Condition
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heteropolyoxometalate oxidation alcohols hydrogen peroxide
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Abstract
This work describes the use of hydrogen peroxide as an oxidant for the selective oxidation of cyclohexanoland benzyl alcohol under green condition using heteropolyoxometalates catalysts. The results showed thatcatalytic activity depended on types of countercation and metal of the catalysts. For transition metal-substitutedpolyoxotungstates [(n-C4H9)4N]4H[PW11M(H2O)O39], the catalytic order is Ni > Co > Mn. For a series ofvanadium(V)-substituted polyoxotungstates [(n-C4H9)4N)]3+x[PW12-xVxO40], the catalytic activity decreasedwith increasing numbers of vanadium atoms in the catalyst. Using the [(n-C4H9)4N]4H[PW11Ni(H2O)O39] as acatalyst, cyclohexanol was oxidized to cyclohexanone with 98% yield and 100% selectivity at 90°C in 5 hwhereas benzyl alcohol was oxidized to benzaldehyde with 96% yield and 37% selectivity to benzaldehyde and 63% selectivity to benzoic acid at 90°C in 12 h.
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Kanjina, W., & Trakarnpruk, W. (2013). Heteropolyoxometalate Catalysts for Oxidation of Alcohols with H2O2 Under Green Condition. Science, Engineering and Health Studies, 3(1), 7–12. https://doi.org/10.14456/sustj.2009.1
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References
Deltcheff, C. R., Fournier, M., Franck, R., and Thouvenot, R. (1983). Vibration investigations of polyoxometalates. 2. Evidence for Anion-Anion interactions in molybdenum (VI) and tungsten (VI) compounds related to the Keggin structure. Inorganic Chemistry, 22: 207-216.
Hill, C. L., Kim, G. S., Prosser-McCartha, C. M., and Judd, D. (1994). Polyoxometalates: From platonic solids to anti-retroviral activity. (Pope M. T., Muller A., eds.), pp. 307. Kluwer Academic Publishers, Dordrecht.
Himeno, S. and Ishiro, N. A. (1998). Voltammetric Study on the formation of V(V) and V(IV) sub stituted molybdophosphate (V) complexes in aqueous solution. Journal of Electrical Chemistry, 451: 203-209.
Ishii, Y., Yamawaki, K., Ura, T., Yamada, H., Yoshida, T., and Ogawa, M. (1988). Hydrogen peroxide oxidation catalyzed by heteropoly acids combined with cetylpyridinium chloride. Epoxidation of olefins and allylic alcohols, ketonization of alcohols and diols, and oxidative cleavage of 1,2-diols and olefins. Journal of Organic Chemistry, 53(15): 3587-3591.
Komintarachat, C. and Trakarnpruk, W. (2006). Oxidative desulfurization using polyoxometalates. Industrial & Engineering Chemistry Research, 45: 1853-1857.
Kozhevnikov, I. V. (1995). Heteropolyacids and related compounds as catalysts for fine chemical synthesis. Catalysis Reviews: Science Engineering, 37: 311-316.
Lingaiah, N., Reddy, K. M., Babu, N. S., Rao, K. N., Suryanarayana, I. P., and Prasad, S. S. (2006). Aerobic selective oxidation of benzyl alcohol over vanadium substituted ammonium salt of 12-molybdophosphoric acid. Catalysis Communications, 7: 245-249.
Maldotti, A., Molinari, A., Varani, G., Lenarda, M., Storaro, L., Bigi, F., Maggi, R., Mazzacani, A., and Sartori, G. (2002). Immobilization of (n-Bu4N) 4W10O32 on mesoporous MCM-41 andamorphous silicas for photocatalytic oxidation of cycloalkanes with molecular oxygen. Journal of Catalysis, 209: 210-216.
Manyar, H. G., Chaure, G. S., and Kumar, A. (2006). Supported polyperoxometallates: Highly selective catalyst for oxidation of alcohols to aldehydes. Journal of Molecular Catalysis A: Chemical, 243: 244-248.
Neumann, R. and Gara, M. (1995). Catalytic oxidation with hydrogen peroxide catalyzed by ‘Sandwich’ type transition metal substituted polyoxometalates. Journal of American Chemical Society, 117: 5074-5080.
Peng, G. Y., Wang, C., Hu, Wang, E., Feng., Zhou, S., Ding, Y. H., and Liu., Y. (2001). Heteropolyoxometalates which are included in microporous silica, CsxH3-xPMo12O40/SiO2 and CsyH5-yPMo10V2O40/SiO2, as insoluble solid bifunctional catalysts: synthesis and selective oxidation of benzyl alcohol in liquid–solid systems. Applied Catalysis A: General, 218: 91-96.
Sheldon, R. A., Arends, I. W. C. E., and Dijksman, A. (2000). New developments in catalytic alcohol oxidations for fine chemicals synthesis. Catalysis Today, 57: 157-166.
Sloboda-Rozner, D., Neimann, K., and Neumann, R. (2007). Aerobic oxidation of aldehydes catalyzedby -Keggin type polyoxometalates [Mo12VO39(μ2-OH)10H2{XII(H2O)3}4] (X = Ni, Co, Mn and Cu) as heterogeneous catalysts. Journal of Molecular Catalysis A: Chemical, 262: 109-115.
Silviani, E. and Burns, R. C. (2004). Synthesis and characterization of soluble alkali metal, alkaline earth metal and related Keggin-type [PMo12O40]3- salts for heterogeneous catalysis reactions. Journal of Molecular Catalysis A: Chemical, 219: 327-342.
SimÕes, M. M. O., Conceição, C. M. M., Gamelas, J. A. F., Domingues, P. M. D. N., Cavaleiro, A. M. V., Cavaleiro, J. A. S., Ferrer-Correia, A. J. V., and Johnstone, R. A. W. (1999). Keggin-type polyoxotungstates as catalysts in the oxidation of cyclohexane by dilute aqueous hydrogen peroxide. Journal of Molecular Catalysis A: Chemical, 144: 461-468.
Song, K. and Barteau, M. A. (2004). Redox properties of Keggin-type heteropolyacid (HPA) catalysts: effect of counter-cation, heteroatom, and polyatom substitution. Journal of Molecular Catalysis A: Chemical, 212: 229-236.
Trost, B. M. and Masuyama, Y. (1984). Chemoselectivity in molybdenum catalyzed alcohol and aldehyde oxidations. Tetrahedron Letter, 25: 173-176.
Venturello, C. and Gambaro, M. (1991). Selective oxidation of alcohols and aldehydes with hydrogen peroxide catalyzed by methyltrioctylammonium tetrakis (oxodiperoxotungsto) phosphate(3-) undertwo-phase conditions. Journal of Organic Chemistry, 56: 5924-5930.
Wang, J., Yan, L., Li, G., Wang, X., Ding, Y., and Suo, J. (2005). Polyoxometalate compound: a highly efficient heterogeneous catalyst for aerobic alcohol oxidation. Tetrahedron Letter, 46: 7023-7027.
Weng, Z., Wang, J., and Jian, X. (2008). A reusable and active lacunary derivative [PW11O39]7- as benzyl alcohol oxidation catalyst with hydrogen peroxide. Catalysis Communications, 9: 1688-1693.
Weng, Z., Liao, G., Wang, J., and Jian, X. (2007). Selective oxidation of benzyl alcohol with hydrogen peroxide over reaction-controlled phase-transfer catalyst. Catalysis Communications, 8: 1493-1497.
Yadav, G. D. and Mistry, C. K. (2001). Oxidation of benzyl alcohol under a synergism of phase transfer catalysis and heteropolyacids. Journal of Molecular Catalysis A: Chemical, 172: 135-139.
Yang, J. I., Lee, D., Lee, J., Hyun, J. C., and Lee, K. (2000). Selective and high catalytic activity of CsnH4-nPMo11VO40 (n≥3) for oxidation of ethanol. Applied Catalysis A: General, 123: 194-200.
Zhang, S., Zhao, G., Gao, S., Xi, Z., and Xu, J. (2008). Secondary alcohols oxidation with hydrogen peroxide catalyzed by [n-C16H33N(CH3)3]3PW12O40: Transform-and-retransform process between catalytic precursor and catalytic activity species. Journal of Molecular Catalysis A: Chemical, 289: 22-27.
Zhang, S., Gao, S., Xi, Z., and Xu, J. (2007). Solvent-free oxidation of alcohols catalyzed by an efficient and reusable heteropolyphosphatotungstate. Catalysis Communication, 8: 531-534.
Hill, C. L., Kim, G. S., Prosser-McCartha, C. M., and Judd, D. (1994). Polyoxometalates: From platonic solids to anti-retroviral activity. (Pope M. T., Muller A., eds.), pp. 307. Kluwer Academic Publishers, Dordrecht.
Himeno, S. and Ishiro, N. A. (1998). Voltammetric Study on the formation of V(V) and V(IV) sub stituted molybdophosphate (V) complexes in aqueous solution. Journal of Electrical Chemistry, 451: 203-209.
Ishii, Y., Yamawaki, K., Ura, T., Yamada, H., Yoshida, T., and Ogawa, M. (1988). Hydrogen peroxide oxidation catalyzed by heteropoly acids combined with cetylpyridinium chloride. Epoxidation of olefins and allylic alcohols, ketonization of alcohols and diols, and oxidative cleavage of 1,2-diols and olefins. Journal of Organic Chemistry, 53(15): 3587-3591.
Komintarachat, C. and Trakarnpruk, W. (2006). Oxidative desulfurization using polyoxometalates. Industrial & Engineering Chemistry Research, 45: 1853-1857.
Kozhevnikov, I. V. (1995). Heteropolyacids and related compounds as catalysts for fine chemical synthesis. Catalysis Reviews: Science Engineering, 37: 311-316.
Lingaiah, N., Reddy, K. M., Babu, N. S., Rao, K. N., Suryanarayana, I. P., and Prasad, S. S. (2006). Aerobic selective oxidation of benzyl alcohol over vanadium substituted ammonium salt of 12-molybdophosphoric acid. Catalysis Communications, 7: 245-249.
Maldotti, A., Molinari, A., Varani, G., Lenarda, M., Storaro, L., Bigi, F., Maggi, R., Mazzacani, A., and Sartori, G. (2002). Immobilization of (n-Bu4N) 4W10O32 on mesoporous MCM-41 andamorphous silicas for photocatalytic oxidation of cycloalkanes with molecular oxygen. Journal of Catalysis, 209: 210-216.
Manyar, H. G., Chaure, G. S., and Kumar, A. (2006). Supported polyperoxometallates: Highly selective catalyst for oxidation of alcohols to aldehydes. Journal of Molecular Catalysis A: Chemical, 243: 244-248.
Neumann, R. and Gara, M. (1995). Catalytic oxidation with hydrogen peroxide catalyzed by ‘Sandwich’ type transition metal substituted polyoxometalates. Journal of American Chemical Society, 117: 5074-5080.
Peng, G. Y., Wang, C., Hu, Wang, E., Feng., Zhou, S., Ding, Y. H., and Liu., Y. (2001). Heteropolyoxometalates which are included in microporous silica, CsxH3-xPMo12O40/SiO2 and CsyH5-yPMo10V2O40/SiO2, as insoluble solid bifunctional catalysts: synthesis and selective oxidation of benzyl alcohol in liquid–solid systems. Applied Catalysis A: General, 218: 91-96.
Sheldon, R. A., Arends, I. W. C. E., and Dijksman, A. (2000). New developments in catalytic alcohol oxidations for fine chemicals synthesis. Catalysis Today, 57: 157-166.
Sloboda-Rozner, D., Neimann, K., and Neumann, R. (2007). Aerobic oxidation of aldehydes catalyzedby -Keggin type polyoxometalates [Mo12VO39(μ2-OH)10H2{XII(H2O)3}4] (X = Ni, Co, Mn and Cu) as heterogeneous catalysts. Journal of Molecular Catalysis A: Chemical, 262: 109-115.
Silviani, E. and Burns, R. C. (2004). Synthesis and characterization of soluble alkali metal, alkaline earth metal and related Keggin-type [PMo12O40]3- salts for heterogeneous catalysis reactions. Journal of Molecular Catalysis A: Chemical, 219: 327-342.
SimÕes, M. M. O., Conceição, C. M. M., Gamelas, J. A. F., Domingues, P. M. D. N., Cavaleiro, A. M. V., Cavaleiro, J. A. S., Ferrer-Correia, A. J. V., and Johnstone, R. A. W. (1999). Keggin-type polyoxotungstates as catalysts in the oxidation of cyclohexane by dilute aqueous hydrogen peroxide. Journal of Molecular Catalysis A: Chemical, 144: 461-468.
Song, K. and Barteau, M. A. (2004). Redox properties of Keggin-type heteropolyacid (HPA) catalysts: effect of counter-cation, heteroatom, and polyatom substitution. Journal of Molecular Catalysis A: Chemical, 212: 229-236.
Trost, B. M. and Masuyama, Y. (1984). Chemoselectivity in molybdenum catalyzed alcohol and aldehyde oxidations. Tetrahedron Letter, 25: 173-176.
Venturello, C. and Gambaro, M. (1991). Selective oxidation of alcohols and aldehydes with hydrogen peroxide catalyzed by methyltrioctylammonium tetrakis (oxodiperoxotungsto) phosphate(3-) undertwo-phase conditions. Journal of Organic Chemistry, 56: 5924-5930.
Wang, J., Yan, L., Li, G., Wang, X., Ding, Y., and Suo, J. (2005). Polyoxometalate compound: a highly efficient heterogeneous catalyst for aerobic alcohol oxidation. Tetrahedron Letter, 46: 7023-7027.
Weng, Z., Wang, J., and Jian, X. (2008). A reusable and active lacunary derivative [PW11O39]7- as benzyl alcohol oxidation catalyst with hydrogen peroxide. Catalysis Communications, 9: 1688-1693.
Weng, Z., Liao, G., Wang, J., and Jian, X. (2007). Selective oxidation of benzyl alcohol with hydrogen peroxide over reaction-controlled phase-transfer catalyst. Catalysis Communications, 8: 1493-1497.
Yadav, G. D. and Mistry, C. K. (2001). Oxidation of benzyl alcohol under a synergism of phase transfer catalysis and heteropolyacids. Journal of Molecular Catalysis A: Chemical, 172: 135-139.
Yang, J. I., Lee, D., Lee, J., Hyun, J. C., and Lee, K. (2000). Selective and high catalytic activity of CsnH4-nPMo11VO40 (n≥3) for oxidation of ethanol. Applied Catalysis A: General, 123: 194-200.
Zhang, S., Zhao, G., Gao, S., Xi, Z., and Xu, J. (2008). Secondary alcohols oxidation with hydrogen peroxide catalyzed by [n-C16H33N(CH3)3]3PW12O40: Transform-and-retransform process between catalytic precursor and catalytic activity species. Journal of Molecular Catalysis A: Chemical, 289: 22-27.
Zhang, S., Gao, S., Xi, Z., and Xu, J. (2007). Solvent-free oxidation of alcohols catalyzed by an efficient and reusable heteropolyphosphatotungstate. Catalysis Communication, 8: 531-534.