Journal of Structural Chemistry

, Volume 60, Issue 10, pp 1599–1611 | Cite as

In situ Study of Structural Transformations of the Active Phase of VMoNbTeO Catalysts under Reduction Conditions

  • T. Yu. KardashEmail author
  • A. S. Marchuk
  • A. V. Ishchenko
  • A. A. Simanenko
  • E. V. Lazareva
  • D. A. Svintsitskiy


VMoNbTeO catalysts show high activity in the reactions of selective oxidation of ethane and propane. Time-resolved X-ray diffraction is used to study structural transformations of a mixed oxide with the composition (TeO)0.18(Mo0.7V0.22Nb0.08)20O56 and the structure of the active M1 phase upon heating in a hydrogen atmosphere (1% H2 in helium). It is shown that the structure of the M1 phase is destroyed in the presence of a reducing agent above 480 °C. The process is accompanied by structural distortions, diminishing of the size of crystalline blocks, elimination of tellurium (due to the reduction and sublimation), and the reduction by molybdenum and vanadium cations. As a result, VMoNb oxides with a disordered structure are formed and rapidly crystallized at T > 480 °C into the rutile-type monoclinic oxide (Mo,V,Nb)O2 with a variable composition. X-ray photoelectron spectroscopy and transmission electron microscopy data confirm heterogeneous compositions of oxides formed by the decomposition of the initial phase. The surface of the formed particles is enriched with vanadium and niobium present in the composition of the oxides with disordered structure.


VMoNbTeO catalysts M1 phase X-ray diffraction in situ 


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The authors thank the European Synchrotron Radiation Facility (ESRF) for providing the access to the experimental equipment and Dr. Yusenko for his help with the experiment.


This work was supported by the Russian Science Foundation (project No. 17-73-20073).

Conflict of Interests

The authors declare that they have no conflict of interests.

Supplementary material

10947_2019_1279_MOESM1_ESM.pdf (72 kb)
In situ Study of Structural Transformations of the Active Phase of VMoNbTeO Catalysts under Reduction Conditions


  1. 1.
    L. Kihlborg. Ark. Kemi., 1963, 21, 471–495.Google Scholar
  2. 2.
    M. A. Poraj-Koshits and L. O. Atovmyan. Crystal Chemistry and Stereochemistry of Molybdenum Coordination Compounds [in Russian]. Nauka: M., 1974.Google Scholar
  3. 3.
    W. Ueda, D. Vitry, and T. Katou. Catal. Today, 2004, 96, 235–240.CrossRefGoogle Scholar
  4. 4.
    Y. Zhu, W. Lu, H. Li, and H. Wan. J. Catal., 2007, 246, 382–389.CrossRefGoogle Scholar
  5. 5.
    X. Yang, R. Feng, W. Ji, and C. Au. J. Catal., 2008, 253, 57–65.CrossRefGoogle Scholar
  6. 6.
    H.-G. Lintz and S. P. Müller. Appl. Catal. A-Gen., 2009, 357, 178–183.CrossRefGoogle Scholar
  7. 7.
    P. DeSanto, D. Buttrey, R. K. Grasselli, C. G. Lugmair, A. F. Volpe Jr, B. H. Toby, and T. Vogt. Z. Kristallogr., 2004, 219, 152–165.Google Scholar
  8. 8.
    X. Li, D. J. Buttrey, D. A. Blom, and T. Vogt. Top. Catal., 2011, 54, 614–626.CrossRefGoogle Scholar
  9. 9.
    W. D. Pyrz, D. A. Blom, T. Vogt, and D. J. Buttrey. Angew. Chem., Int. Ed., 2008, 47, 2788–2791.CrossRefGoogle Scholar
  10. 10.
    T. Vogt, D. A. Blom, L. Jones, and D. J. Buttrey. Top. Catal., 2016, 59, 1489–1495.CrossRefGoogle Scholar
  11. 11.
    M. Hävecker, S. Wrabetz, J. Kröhnert, L.I. Csepei, R. Naumann D’Alnoncourt, Y. V. Kolen’ko, F. Girgsdies, R. Schlögl, and A. Trunschke. J. Catal., 2012, 285, 48–60.CrossRefGoogle Scholar
  12. 12.
    T. T. Nguyen, B. Deniau, M. Baca, and J. M. M. Millet. Top. Catal., 2016, 59, 1496–1505.CrossRefGoogle Scholar
  13. 13.
    B. Chu, L. Truter, and T. A. Nijhuis, Y. Cheng. Appl. Catal. A-Gen., 2015, 498, 99–106.CrossRefGoogle Scholar
  14. 14.
    J. Valente, H. Armendáriz-Herrera, R. Quintana-Solórzano, P. del Ángel, N. Nava, A. Masso, and J. M. L. Nieto. ACS Catal., 2014, 4, 1292–1301.CrossRefGoogle Scholar
  15. 15.
    I. I. Mishanin, A. N. Kalenchuk, K. I. Maslakov, V. V. Lunin, A. E. Koklin, E. D. Finashina, and V. I. Bogdan. Russ. J. Phys. Chem. A., 2016, 90, 1132–1136.CrossRefGoogle Scholar
  16. 16.
    E. V. Ishchenko, R. V. Gulyaev, T. Y. Kardash, A. V. Ishchenko, E. Y. Gerasimov, V. I. Sobolev, and V. M. Bondareva. Appl. Catal. A-Gen., 2017, 534, 58–69.CrossRefGoogle Scholar
  17. 17.
    E. V. Ishchenko, T. V. Andrushkevich, G. Y. Popova, Y. A. Chesalov, L. M. Plyasova, A. V. Ishchenko, T. Y. Kardash, and L. S. Dovlitova. Catal. Ind., 2011, 2, 291–298.CrossRefGoogle Scholar
  18. 18.
    E. V. Ishchenko, T. V. Andrushkevich, G. Y. Popova, T. Y. Kardash, A. V. Ishchenko, L. S. Dovlitova, and Y. A. Chesalov. Appl. Catal. A-Gen., 2014, 476, 91–102.CrossRefGoogle Scholar
  19. 19.
    G. Ashiotis, A. Deschildre, Z. Nawaz, J. P. Wright, D. Karkoulis, F. E. Picca, and J. Kieffer. J. Appl. Crystallogr., 2015, 48, 510–519.CrossRefGoogle Scholar
  20. 20.
    D. A. Svintsitskiy, L. S. Kibis, D. A. Smirnov, A. N. Suboch, O. A. Stonkus, O. Y. Podyacheva, A. I. Boronin, and Z. R. Ismagilov. Appl. Surf. Sci., 2018, 435, 1273–1284.CrossRefGoogle Scholar
  21. 21.
    D. A. Svintsitskiy, L. S. Kibis, A. I. Stadnichenko, V. I. Zaikovskii, S. V. Koshcheev, and A. I. Boronin. Kinet. Catal., 2013, 54, 497–504.CrossRefGoogle Scholar
  22. 22.
    D. A. Svintsitskiy, E. M. Slavinskaya, T. Y. Kardash, V. I. Avdeev, B. V. Senkovskiy, S. V. Koscheev, and A. I. Boronin. Appl. Catal. A-Gen., 2016, 510, 64–73.CrossRefGoogle Scholar
  23. 23.
    T. Y. Kardash, E. V. Lazareva, D. A. Svintsitskiy, A. V. Ishchenko, V. M. Bondareva, and R. B. Neder. RSC Adv., 2018, 8, 35903–35916.CrossRefGoogle Scholar
  24. 24.
    J. F. Moulder, W. F. Stickle, P. E. Sobol, and K. D. Bomben. Handbook of X-ray Photoelectron Spectroscopy. USA, Perkin-Elmer Corp, Eden Prairie: Minnesota, 1992.Google Scholar
  25. 25.
    T. Y. Kardash, L. M. Plyasova, V. M. Bondareva, and A. N. Shmakov. J. Struct. Chem., 2008, 49, 701–707.CrossRefGoogle Scholar
  26. 26.
    H. Werner, O. Timpe, D. Herein, and Y. Uchida. Catal. Lett., 1997, 44, 153–163.CrossRefGoogle Scholar
  27. 27.
    Celaya Sanfiz, T. W. Hansen, F. Girgsdies, O. Timpe, E. Rödel, T. Ressler, A. Trunschke, and R. Schlögl. Top. Catal., 2008, 50, 19–32.CrossRefGoogle Scholar
  28. 28.
    Powder Diffraction File. PDF-2. International Center for Diffraction Data, USA, 2009.Google Scholar
  29. 29.
    B. O. Marinder. Mater. Res. Bull., 1975, 10, 909–914.CrossRefGoogle Scholar
  30. 30.
    B. O. Marinder, E. Dorm, M. Seleborg, K. Motzfeldt, O. Theander, and H. Flood. Acta. Chem. Scand., 1962, 16, 293–296.CrossRefGoogle Scholar
  31. 31.
    A. A. Bolzan, B. J. Kennedy, and C. J. Howard. Aust. J. Chem., 1995, 48, 1473–1477.CrossRefGoogle Scholar
  32. 32.
    S. Ishikawa, D. Kobayashi, T. Konya, S. Ohmura, T. Murayama, N. Yasuda, M. Sadakane, and W. Ueda. J. Phys. Chem. C., 2015, 119, 7195–7206.CrossRefGoogle Scholar
  33. 33.
    P. Botella, J. M. Lopez Nieto, B. Solsona, A. Mifsud, and F. Marquez. J. Catal., 2002, 455, 445–455.CrossRefGoogle Scholar
  34. 34.
    N. S. McIntyre, D. D. Johnston, L. L. Coatsworth, R. D. Davidson, and J. R. Brown. Surf. Interface Anal., 1990, 15, 265–272.CrossRefGoogle Scholar
  35. 35.
    L. D. Lopez-Carren, G. Benıtez, L. Viscido, J. M. Heras, F. Yubero, J. P. Espino, and A. R. Gonzalez-Elipe. Surf. Sci., 1998, 402–404, 174–177.CrossRefGoogle Scholar
  36. 36.
    G. Silversmit, D. Depla, H. Poelman, G. B. Marin, and R. De Gryse. J. Electron Spectrosc., 2004, 135, 167–175.CrossRefGoogle Scholar
  37. 37.
    A. C. Sanfiz, T. W. Hansen, D. Teschner, P. Schnörch, F. Girgsdies, A. Trunschke, R. Schlögl, M.H. Looi, and B. A. H. Sharifah. J. Phys. Chem. C, 2010, 114, 1912–1921.CrossRefGoogle Scholar
  38. 38.
    M. Aufray, S. Menuel, Y. Fort, J. Eschbach, D. Rouxel, and B. Vincent. J. Nanosci. Nanotechnol., 2009, 9, 4780–4785.CrossRefGoogle Scholar
  39. 39.
    C. J. Hawley, B. R. Beatty, G. Chen, and J. E. Spanier. Cryst. Growth Des., 2012, 12, 2789–2793.CrossRefGoogle Scholar
  40. 40.
    T. Y. Kardash, L. M. Plyasova, V. M. Bondareva, T. V. Andrushkevich, A. V. Ishchenko, Y. A. Chesalov, and L. S. Dovlitova. Kinet. Catal., 2009, 50, 48–56.CrossRefGoogle Scholar

Copyright information

© Pleiades Publishing, Ltd. 2019

Authors and Affiliations

  • T. Yu. Kardash
    • 1
    • 2
    Email author
  • A. S. Marchuk
    • 1
    • 2
  • A. V. Ishchenko
    • 1
  • A. A. Simanenko
    • 1
    • 2
  • E. V. Lazareva
    • 1
  • D. A. Svintsitskiy
    • 1
    • 2
  1. 1.Boreskov Institute of Catalysis, Siberian BranchRussian Academy of SciencesNovosibirskRussia
  2. 2.Novosibirsk State UniversityNovosibirskRussia

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