Skip to main content
SpringerLink
Log in

The structure of vanadium oxide species on γ-alumina; an in situ X-ray absorption study during catalytic oxidation

  • Published:
Topics in Catalysis Aims and scope Submit manuscript

Abstract

The mechanism of catalytic oxidation reactions was studied using in situ X-ray absorption spectroscopy (XAFS) over a 17.5 wt% V2O5/Al2O3 catalyst, i.e., at reaction temperatures and in the presence of reactants. It was found that X-ray absorption near-edge structure (XANES) is a powerful tool to study changes in the local environment and the oxidation state of the vanadium centres during catalytic oxidation. At 623 K, the catalyst follows the associative mechanism in CO oxidation. XAFS revealed that the Mars–van Krevelen mechanism is operative at 723 K for CO oxidation. The extended X-ray absorption fine structure (EXAFS) results showed that the structure of the supported V2O5 phase consists of monomeric tetrahedral (Al–O)3–V=O units after dehydration in air at 623 K. However, the residuals of the EXAFS analysis indicate that an extra contribution has to be accounted for. This contribution probably consists of polymeric vanadate species. The structure remains unchanged during steady-state CO oxidation at 623 and 723 K. Furthermore, when oxygen was removed from the feed at 623 K, no changes in the spectra occurred. However, when oxygen is removed from the feed at 723 K, reduction of the vanadium species was observed, i.e., the vanadyl oxygen atom is removed. The V3+ ion subsequently migrates into the γ-Al2O3 lattice, where it is positioned at an Al3+ octahedral position. This migration process appears to be reversible; so the (Al–O)3–V=O units are thus restored by re-oxidation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. X. Gao, S.R. Bare, B.M. Weckhuysen and I.E. Wachs, J. Phys. Chem. B 102 (1998) 10842.

    Article  CAS  Google Scholar 

  2. I.E. Wachs, Catal. Today 27 (1996) 437.

    Article  CAS  Google Scholar 

  3. G.T. Went and S.T. Oyama, J. Phys. Chem. 94 (1990) 4240.

    Article  CAS  Google Scholar 

  4. F. Roozeboom, M.C. Mittelmeijer-Hazeleger, J.A. Moulijn, J. Medema, V.H.J. de Beer and P.J. Gellings, J. Phys. Chem. 84 (1980) 2783.

    Article  CAS  Google Scholar 

  5. G. Busca, Mater. Chem. Phys. 19 (1988) 157.

    Article  CAS  Google Scholar 

  6. A.A. Davydov, Kinet. Katal. 34 (1993) 951.

    Google Scholar 

  7. T. Tanaka, H. Yamashita, R. Tsuchitani, T. Funabiki and S. Yoshida, J. Chem. Soc. Faraday Trans. I 84 (1988) 2987.

    Article  CAS  Google Scholar 

  8. S. Yoshida, T. Tanaka, Y. Nishimura, H. Mizutani and T. Funabiki, Proc. ICC IX (1988) p. 1473.

    Google Scholar 

  9. S. Yoshida, T. Tanaka, T. Hanada, T. Hiraiwa and H. Kanai, Catal. Lett. 12 (1992) 277.

    Article  CAS  Google Scholar 

  10. R. Kozlowski, R.F. Pettifer and J.M. Thomas, J. Phys Chem. 87 (1983) 5176.

    Article  CAS  Google Scholar 

  11. J. Haber, A. Kozlowska and R. Kozlowski, J. Catal. 102 (1986) 52.

    Article  CAS  Google Scholar 

  12. N. Das, H. Eckert, H. Hu, I.E. Wachs, J.F. Walzer and F.J. Feher, J. Phys. Chem. 97 (1993) 8240.

    Article  CAS  Google Scholar 

  13. H. Eckert and I.E. Wachs, Mater. Res. Soc. Symp. Proc. 111 (1988) 455.

    Google Scholar 

  14. H. Eckert and I.E. Wachs, J. Phys. Chem. 93 (1989) 6796.

    Article  CAS  Google Scholar 

  15. L.R. Le Costumer, B. Taouk, M. Le Meur, E. Payen, M. Guelton and J.M. Grimblot, J. Phys. Chem. 92 (1988) 1230.

    Article  Google Scholar 

  16. B.M. Weckhuysen, I.P. Vannijvel and R.A. Schoonheydt, Zeolites 15 (1995) 482.

    Article  CAS  Google Scholar 

  17. U. Scharf, M. Schraml-Merth, A. Wokaun and A. Baiker, J. Chem. Soc. Faraday Trans. 87 (1991) 3299.

    Article  CAS  Google Scholar 

  18. G. Catana, R. Ramachandra Rao, B.M. Weckhuysen, P. van der Voort, E. Vansant and R. Schoonheydt, J. Phys. Chem. B 102 (1998) 8005.

    Article  CAS  Google Scholar 

  19. M.F. Hazenkamp and G. Blasse, J. Phys. Chem. 96 (1992) 3442.

    Article  CAS  Google Scholar 

  20. M. Anpo, M. Sunamoto and M. Che, J. Phys. Chem. 93 (1989) 1187.

    Article  CAS  Google Scholar 

  21. G. Busca and E. Giamello, Mater. Chem. Phys. 25 (1990) 475.

    Article  CAS  Google Scholar 

  22. B.I. Wittington and J.R. Anderson, J. Phys. Chem. 97 (1993) 1032.

    Article  Google Scholar 

  23. J.M. Jehng, G. Deo, B.M. Weckhuysen and I.E. Wachs, J. Mol. Catal. A 110 (1996) 41.

    Article  CAS  Google Scholar 

  24. I.E. Wachs and B.M. Weckhuysen, Appl. Catal. A 157 (1997) 67.

    Article  CAS  Google Scholar 

  25. S.S. Chan, I.E. Wachs, L.L. Murrell, L. Wang and W.K. Hall, J. Phys. Chem. 88 (1984) 5831.

    Article  CAS  Google Scholar 

  26. X. Gao, S.R. Bare, B.M. Weckhuysen and I.E. Wachs, J. Phys. Chem. B 102 (1998) 10684.

    Google Scholar 

  27. T. Kataoka and J.A. Dumesic, J. Catal. 112 (1988) 66.

    Article  CAS  Google Scholar 

  28. G.C. Bond, J. Perez Zurita, S. Flamerz, P.J. Gellings, H. Bosch, J.G. van Ommen and B.J. Kip, Appl. Catal. 22 (1986) 361.

    Article  CAS  Google Scholar 

  29. W. Fluhr, M. Schraml-Marth, A. Wokaun and A. Baiker, Ber. Bunsenges Phys. Chem. 8 (1989) 852.

    Google Scholar 

  30. I.E. Wachs, G. Deo, B.M. Weckhuysen, V.V. Guliants and J.B. Benziger, Catal. Today 32 (1996) 47.

    Article  CAS  Google Scholar 

  31. G. Ramis, C. Cristiani, P. Forzatti and G. Busca, J. Catal. 124 (1990) 574.

    Article  CAS  Google Scholar 

  32. I.E. Wachs, R.Y. Saleh, S.S. Chan and C.C. Chersich, Appl. Catal. 15 (1985) 339.

    Article  CAS  Google Scholar 

  33. K. Mori, M. Inomata, A. Miyamoto and Y. Murakami, J. Chem. Soc. Faraday Trans. I 80 (1984) 2666.

    Article  Google Scholar 

  34. T. Tanaka, Y. Nishimura, S. Kawasaki, M. Oe, T. Funabiki and S. Yoshida, J. Catal. 118 (1989) 327.

    Article  CAS  Google Scholar 

  35. S.L. Kaliaguine, B.N. Shelimov and B. Kazansky, J. Catal. 55 (1978) 384.

    Article  CAS  Google Scholar 

  36. A.A. Siddiqi and J.W. Tenini, Hydrocarbon Process. 60 (1984) 649.

    Google Scholar 

  37. M. Iwamoto, J. Hirata, K. Matsukami and S. Kagawa, J. Phys. Chem. 87 (1983) 903.

    Article  CAS  Google Scholar 

  38. G.I. Golodets, Stud. Surf. Sci. Catal. 55 (1990) 693.

    Article  Google Scholar 

  39. P. Mars and D.W. van Krevelen, Chem. Eng. Sci. (Special Suppl.) 3 (1954) 41.

    CAS  Google Scholar 

  40. A.J. Van Dillen, Catalytic oxidation of carbon monoxide over oxides of indium and vanadium, Thesis, Utrecht University (1977).

  41. L.V. Azararoff and D.M. Pease, in: X-Ray Spectroscopy, ed. L.V. Azaroff (McGraw Hil, New York, 1974).

    Google Scholar 

  42. J. Wong, F.W. Lytle, R.P. Mesmer and D.H. Maylotte, Phys. Rev. B 30 (1984) 5596.

    Article  CAS  Google Scholar 

  43. J. Wong, R.P. Mesmer, D.H. Maylotte and F.W. Lytle, in: EXAFS and Near Edge Structure, eds. A. Bianconi, L. Inoccia and S. Stipcich (Springer, Berlin, 1983) p. 130.

    Google Scholar 

  44. J. Wong, D.H. Maylotte, F.W. Lytle, R.B. Greegor and R.L. St. Peters, in: EXAFS and Near Edge Structure, eds. A. Bianconi, L. Inoccia and S. Stipcich (Springer, Berlin, 1983) p. 206.

    Google Scholar 

  45. I. Davoli, S. Stizza, M. Benfatto, O. Gzowski, L. Murawski and A. Bianconi, in: EXAFS and Near Edge Structure, eds. A. Bianconi, L. Inoccia and S. Stipcich (Springer, Berlin, 1983) p. 162.

    Google Scholar 

  46. M. Ruitenbeek, R.A. Overbeek, A.J. van Dillen, D.C. Koningsberger and J.W. Geus, Recl. Trav. Chim. Pays-Bas 115 (1996) 519.

    CAS  Google Scholar 

  47. J. van den Berg, Stoichiometry and catalytic activity of vanadia-based oxides for the oxidation of CO and H2, Thesis, Utrecht University (1984).

  48. I.E. Wachs, J.-M. Jehng, G. Deo, B.M. Weckhuysen, V.V. Guliants, J.B. Benziger and S. Sundaresan, J. Catal. 170 (1997) 75.

    Article  CAS  Google Scholar 

  49. F.W.H. Kampers, T.M.J. Maas, J. van Grondelle, P. Brinkgreve and D.C. Koningsberger, Rev. Sci. Instrum. 60 (1989) 2635.

    Article  Google Scholar 

  50. M. Vaarkamp, B.L. Mojet, F.S. Modica, J.T. Miler and D.C. Koningsberger, J. Phys. Chem. 99 (1995) 16067.

    Article  CAS  Google Scholar 

  51. http://www.xs4all.nl/_xsi/.

  52. M. Vaarkamp, I. Dring, R.J. Oldman, E.A. Stern and D.C. Koningsberger, Phys. Rev. B 50 (1994) 7872.

    Article  CAS  Google Scholar 

  53. J.W. Cook, Jr. and D.E. Sayers, J. Appl. Phys. 52 (1981) 5024.

    Article  CAS  Google Scholar 

  54. J.B.A.D. van Zon, D.C. Koningsberger, H.F.J. van' t Blik and D.E. Sayers, J. Chem. Phys. 82 (1985) 5742.

    Article  CAS  Google Scholar 

  55. E. Vogt, Preparation and properties of catalysts supported on modified silica, Thesis, Utrecht University (1988).

  56. B.L. Mojet, Metal support interactions, a step closer to the origin, Thesis, Utrecht University (1997).

  57. F.W.H. Kampers, EXAFS in catalysis, instrumentation and applications, Thesis, TU Eindhoven (1988).

  58. J.N. Fiedor, A. Proctor, M. Houalla and D.M. Hercules, Surf. Interface Anal. 20 (1993) 1.

    Article  CAS  Google Scholar 

  59. S.J. Scierka, A. Proctor, J.N. Fiedor and D.M. Hercules, Surf. Interface Anal. 20 (1993) 901.

    Article  CAS  Google Scholar 

  60. M.A. Eberhardt, A. Proctor, M. Houalla and D.M. Hercules, J. Catal. 160 (1996) 27.

    Article  CAS  Google Scholar 

  61. M.J. Fay, A. Proctor, D.P. Hoffmann, M. Houalla and D.M. Hercules, Mikrochim. Acta 109 (1992) 281.

    Article  CAS  Google Scholar 

  62. E.R. Malinowski, Factor Analysis in Chemistry, 2nd Ed. (Wiley, New York, 1991).

    Google Scholar 

  63. E.R. Malinowski, J. Chemom. 3 (1988) 49.

    Article  CAS  Google Scholar 

  64. E.R. Malinowski, J. Chemom. 4 (1990) 102.

    Google Scholar 

  65. F.M. Dautzenberg, ACS Symposium Series 421 (1989) 277.

    Google Scholar 

  66. M. Ruitenbeek, Characterisation of vanadium-based oxidation catalysts, Thesis, Utrecht University (1999).

  67. D.E. Ramaker, B.L. Mojet, D.C. Koningsberger and W.E. O'Grady, J. Phys. Condens. Matter 10 (1998) 8753.

    Article  CAS  Google Scholar 

  68. F.M.F. de Groot, M. Ruitenbeek and D.C. Koningsberger, to be published.

  69. H. Praliaud and M.-V. Mathieu, J. Chim. Phys. 73 (1976) 689.

    CAS  Google Scholar 

  70. F. Lemoigno, E. Prouzet, Z.Y. Wu, P. Gressier and G. Ouvrard, J. Phys. IV France 7 (1997) 263.

    Article  CAS  Google Scholar 

  71. W.A. Caliebe, C.-C. Kao, J.B. Hastings, M. Taguchi, A. Kotani, T. Uozumi and F.M.F. de Groot, Phys. Rev. B 58 (1998) 13452.

    Article  CAS  Google Scholar 

  72. J. Haber, in: Catalytic Oxidation, Principles and Applications, eds. R.A. Sheldon and R.A. van Santen (World Scientific, London, 1995) p. 17.

    Google Scholar 

  73. R.E. Newnham and Y.M. de Haan, Z. Kristall. 117 (1962) 235.

    Article  CAS  Google Scholar 

  74. N.W. Hurst, S.J. Gentry, A. Jones and B.D. McNicol, Catal. Rev. Sci. Eng. 24 (1982) 233.

    CAS  Google Scholar 

  75. W.S. Xia, H.L. Wan and Y. Chen, J. Mol. Catal. A 138 (1999) 185.

    Article  CAS  Google Scholar 

  76. B.M. Weckhuysen, L.M. de Ridder, P.J. Grobet and R.A. Schoonheydt, J. Phys. Chem. 99 (1995) 320.

    Article  CAS  Google Scholar 

  77. B.M. Weckhuysen and R.A. Schoonheydt, Catal. Today 51 (1999) 223.

    Article  CAS  Google Scholar 

  78. A.F. Reid and T.M. Sabine, J. Solid State Chem. 2 (1970) 203.

    Article  CAS  Google Scholar 

  79. B. Reuter, R. Aust, G. Collsmann and Ch. Neuwald, Z. Anorg. Allg. Chem. 500 (1983) 188.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Debye Institute, Department of Inorganic Chemistry and Catalysis, Utrecht University, PO Box 80083, 3508 TB, Utrecht, The Netherlands

    M. Ruitenbeek, A.J. van Dillen, F.M.F. de Groot, J.W. Geus & D.C. Koningsberger

  2. Zettlemoyer Center for Surface Studies, Department of Chemical Engineering, Lehigh University, 7 Asa Drive, Bethlehem, PA, 18015, USA

    I.E. Wachs

Authors
  1. M. Ruitenbeek
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A.J. van Dillen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. F.M.F. de Groot
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. I.E. Wachs
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. J.W. Geus
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. D.C. Koningsberger
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ruitenbeek, M., van Dillen, A., de Groot, F. et al. The structure of vanadium oxide species on γ-alumina; an in situ X-ray absorption study during catalytic oxidation. Topics in Catalysis 10, 241–254 (2000). https://doi.org/10.1023/A:1019180504770

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1019180504770

Search

Navigation