Kinetics and Catalysis

, Volume 41, Issue 4, pp 546–552 | Cite as

Heterogeneous selective oxidation of formaldehyde on oxide catalysts:In situ FTIR study of formaldehyde surface species on a V-Ti-O catalyst and oxygen effect

  • G. Ya. Popova
  • Ya. A. Chesalov
  • T. V. Andrushkevich
  • E. S. Stoyanov


The interaction of formaldehyde with a highly selective V-Ti-O catalyst for the oxidation of formaldehyde to formic acid is studied by Fourier-transform infrared (FTIR) spectroscopy at 70–200‡C. In a flow of formaldehyde/oxygen mixture and in a mixture without oxygen at optimal temperatures for formic acid formation (100–140‡C), methoxy groups and other oxygenates are formed in small amounts. These are two bidentate formates and covalently bound monodentate formate. The fact that similar oxygenates are observed independently of the presence of oxygen in the reaction mixture suggests the participation of the catalyst oxygen in their formation. Oxygen accelerates the desorption of bidentate formates. Bidentate formates of one type decompose in a flow of air at 100–150‡C, and bidentate formates of the other type decompose at 170–200‡C.


Formic Acid Oxide Catalyst Methoxy Group Surface Species Methanol Synthesis 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Popova, G.Ya., Andrushkevich, T.V., and Zenkovets, G.A.,Kinet. Katal., 1997, vol. 38, no. 2, p. 285.Google Scholar
  2. 2.
    Busca, G., Lamotte, J., Lavalley, J.-C., and Lorenzelli, V.,J. Am. Chem. Soc., 1987, vol. 109, p. 5197.CrossRefGoogle Scholar
  3. 3.
    Lavalley, J.C., Lamotte, J., Busca, G., and Lorenzelli, V.,J. Chem. Soc., Chem. Commun., 1986, p. 1006.Google Scholar
  4. 4.
    Groff, R.P. and Manogue, W.H.,J. Catal., 1983, vol. 79, no. 2, p. 462.CrossRefGoogle Scholar
  5. 5.
    Manuera, G.,J. Catal., 1970, vol. 18, no. 1, p. 19.CrossRefGoogle Scholar
  6. 6.
    Onishi, H., Aruga, T., and Iwasawa, Y.,J. Catal., 1994, vol. 146, no. l,p. 557.CrossRefGoogle Scholar
  7. 7.
    Kim, K.S. and Barteau, M.A.,Langmuir, 1990, vol. 6, no. 8, p. 1485.CrossRefGoogle Scholar
  8. 8.
    Forzatti, P., Tronconi, E., Elmi, A.S., and Busca, G.,Appl. Catal A., 1997, vol. 157, nos. 1-2, p. 387.CrossRefGoogle Scholar
  9. 9.
    Loffer, D.G. and Schmidt, L.D.,Surf. Scl., 1976, vol. 59, p. 195.CrossRefGoogle Scholar
  10. 10.
    Gland, J.L. and Korchak, V.N.,J. Catal., 1978, vol. 55, p. 342.CrossRefGoogle Scholar
  11. 11.
    Otto, K.J. and Yao, H.C.,J. Catal., 1980, vol. 66, p. 229.CrossRefGoogle Scholar
  12. 12.
    Taylor, K.S. and Klimisch, R.L.,J. Catal., 1973, vol. 30, p. 478.CrossRefGoogle Scholar
  13. 13.
    Ku, R. and Gjostein, N.A.,Surf. Sci., 1977, vol. 64, p. 465.CrossRefGoogle Scholar
  14. 14.
    Obuchi, A., Naiton, S., Onishi, T., and Tamaru, K.,Surf. Scl., 1982, vol. 122, p. 235.CrossRefGoogle Scholar
  15. 15.
    Busca, G., Elmy, A.S., and Forzatti, P.,J. Phys. Chem., 1987, vol. 91, p. 5263.CrossRefGoogle Scholar
  16. 16.
    Feil, F.S., Ommen, J.G., and Ross, J.R.H.,Langmuir, 1987, vol. 3, p. 668.CrossRefGoogle Scholar
  17. 17.
    Busca, G. and Lorenzelly, V., J. Catal., 1980, vol. 66, p. 155.CrossRefGoogle Scholar
  18. 18.
    Kishi, K., Ogawa, T., and Hirota, K.,J. Catal., 1966, vol. 5, p. 464.CrossRefGoogle Scholar
  19. 19.
    Li, K., Domen, K., Maruya, K., and Onishi, T.,J. Catal., 1990, vol. 125, p. 445.CrossRefGoogle Scholar
  20. 20.
    Stuve, E.M. and Madix, R.J.,Surf. Scl., 1982, vol. 119, p. 279.CrossRefGoogle Scholar
  21. 21.
    Jianyi Lin, Koon Gee Neoh, Wah Koon Teo,J. Chem. Soc., Faraday Trans., 1994, vol. 90(2), p. 358.Google Scholar
  22. 22.
    Andrushkevich, T.V., Popova, G.Ya., Al’kaeva, E.M., et al.,Khim. Prom-st, 1996, no. 3 (165), p. 21.Google Scholar
  23. 23.
    Krylov, O.V. and Matyshak, V.A.,Promezhutochnye soedineniya v geterogennom katalize (Intermediates in Heterogeneous Catalysis), Moscow: Nauka, 1996.Google Scholar
  24. 24.
    Saur, O., Travert, J., Lavalley, J.C., and Sheppard, N.,Spectrochim. Acta, Part A, 1973, vol. 29, p. 243.CrossRefGoogle Scholar
  25. 25.
    Khoskhoo, H. and Nixon, E.R.,Spectrochim. Acta, Part A, 1973, vol. 29, p. 603.CrossRefGoogle Scholar
  26. 26.
    Nukada, K.,Spectrochim. Acta, Part B, 1983, vol. 18, p. 745.Google Scholar
  27. 27.
    Zambony, V. and Zerbi, A.J.,Polym. Sci., 1963, vol. 7, p. 153.Google Scholar
  28. 28.
    Idriss, H., Kim, K.S., and Barteau, M.A.,Surf. Sci., 1992, vol. 262, p. 113.CrossRefGoogle Scholar
  29. 29.
    Clark, D.B. and Bell, A.T.,J. Catal., 1995, vol. 154, no. 1, p. 314.CrossRefGoogle Scholar

Copyright information

© MAIK “Nauka/Interperiodica” 2000

Authors and Affiliations

  • G. Ya. Popova
    • 1
  • Ya. A. Chesalov
    • 1
  • T. V. Andrushkevich
    • 1
  • E. S. Stoyanov
    • 1
  1. 1.Boreskov Institute of Catalysis, Siberian DivisionRussian Academy of SciencesNovosibirskRussia

Personalised recommendations