Kinetics and Catalysis

, Volume 59, Issue 1, pp 70–82 | Cite as

Temperature Hysteresis in the Reaction of Methane Oxidation on a Palladium-Doped Manganese Hexaaluminate Catalyst

  • S. A. YashnikEmail author
  • Z. S. Vinokurov
  • A. V. Salnikov
  • A. V. Ishchenko
  • V. V. Kaichev
  • Z. R. Ismagilov


A study of the Pd-containing catalyst based on manganese hexaaluminate by X-ray diffraction analysis, transmission electron microscopy, thermo-programmed reduction with hydrogen, and thermoprogrammed oxidation showed the hysteresis manifested itself in a difference between the temperature dependences of its catalytic activity in the oxidation of methane under the conditions of sample heating or cooling is related to the decomposition of PdO to metallic palladium at temperatures higher than 700–800°C and the subsequent formation of PdO nanoparticles, which are localized on the surface of metallic Pd (30–50 nm) in the form of polycrystalline films with a thickness of 2–5 nm, at temperatures lower than 600–700°C. A near-surface oxide film is formed under the conditions of cooling in oxygen-containing atmospheres, including in the presence of methane. The value of the hysteresis depends on the heat treatment temperature of the catalyst, and it reaches a maximum on the catalysts calcined at 900 and 1000°C.


manganese hexaaluminate palladium doping methane oxidation thermal hysteresis TPR-O2 in situ XRD analysis 


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  1. 1.
    Pfefferle, L.D. and Pfefferle, W.C., Catal. Rev. Sci. Eng., 1987, vol. 29, p.219.CrossRefGoogle Scholar
  2. 2.
    Hicks, R.F., Qi, H., Young, M.L., and Lee, R.G., J. Catal., 1990, vol. 122, p.280.CrossRefGoogle Scholar
  3. 3.
    Hicks, R.F., Qi, H., Young, M.L., and Lee, R.G., J. Catal., 1990, vol. 122, p.295.CrossRefGoogle Scholar
  4. 4.
    Baldwin, T.H. and Burch, R., Appl. Catal., 1990, vol. 66, p.337.CrossRefGoogle Scholar
  5. 5.
    Baldwin, T.H. and Burch, R., Appl. Catal., 1990, vol. 66, p.359.CrossRefGoogle Scholar
  6. 6.
    Briot, P. and Primet, M., Appl. Catal., 1991, vol. 68, p.301.CrossRefGoogle Scholar
  7. 7.
    Oh, S.H., Mitchell, P.J., and Siewert, R.M., J. Catal., 1991, vol. 132, p.287.CrossRefGoogle Scholar
  8. 8.
    Lampert, J.K., Kazi, M.S., and Farrauto, R.J., Appl. Catal. B, vol. 14, p.211.Google Scholar
  9. 9.
    Garbowski, E., Feumi-Jantou, C., Mouaddib, N., and Primet, M., Appl. Catal. A, 1994, vol. 109, p.277.CrossRefGoogle Scholar
  10. 10.
    Burch, R. and Urbano, F.J., Appl. Catal. A, 1995, vol. 124, p.121.CrossRefGoogle Scholar
  11. 11.
    Burch, R., Loader, P.K., and Urbano, F.J., Catal. Today, 1996, vol. 27, p.243.CrossRefGoogle Scholar
  12. 12.
    McCarty, J.G., Catal. Today, 1995, vol. 26, p.283.CrossRefGoogle Scholar
  13. 13.
    Lyubovsky, M. and Pfefferle, L.D., Appl. Catal. A, 1998, vol. 173, p.107.CrossRefGoogle Scholar
  14. 14.
    Lyubovsky, M., Smith, L.L., Castaldi, M., Karim, H., Nentwick, B., Etemad, S., LaPierre, R., and Pfefferle, W.C., Catal. Today, 2003, vol. 83, p.71.CrossRefGoogle Scholar
  15. 15.
    Ismagilov, Z.R., Kerzhentsev, M.A., Sazonov, V.A., Tsykoza, L.T., Shikina, N.V., Kuznetsov, V.V., Ushakov, V.A., Mishanin, S.V., Kozhukhar, N.G., Russo, G., and Deutschmann, O., Korean J. Chem. Eng., 2003, vol. 20, p.461.CrossRefGoogle Scholar
  16. 16.
    Yashnik, S.A. and Ismagilov, Z.R., Top. Catal., 2012, vol. 55, p.818.CrossRefGoogle Scholar
  17. 17.
    McCarty, J.G., Gusman, M., Lowe, D.M., Hildenbrand, D.L., and Lau, K.N., Catal. Today, 1999, vol. 47, p.5.CrossRefGoogle Scholar
  18. 18.
    Yashnik, S.A., Ismagilov, Z.R., Kuznetsov, V.V., Ushakov, V.V., Rogov, V.A., and Ovsyannikova, I.A., Catal. Today, 2006, vol. 117, p.525.CrossRefGoogle Scholar
  19. 19.
    Yashnik, S.A., Chesalov, Yu.A., Ishchenko, A.V., Kaichev, V.V., and Ismagilov, Z.R., Appl. Catal. B, 2017, vol. 204, p.89.CrossRefGoogle Scholar
  20. 20.
    Yashnik, S.A., Shikina, N.V., Ismagilov, Z.R., Zagoruiko, A.N., Kerzhentsev, M.A., Parmon, V.N., Zakharov, V.M., Braynin, B.I., Favorski, O.N., and Gumerov, A.M., Catal. Today, 2009, vol. 147, p.237.CrossRefGoogle Scholar
  21. 21.
    Ismagilov, Z.R., Shikina, N.V., Yashnik, S.A., Zagoruiko, A.N., Kerzhentsev, M.A., Ushakov, V.A., Sazonov, V.A., Parmon, V.N., Zakharov, V.M., Braynin, B.I., and Favorskii, O.N., Catal. Today, 2010, vol. 155, p.35.CrossRefGoogle Scholar
  22. 22.
    Ismagilov, Z.R., Kerzhentsev, M.A., Yashnik, S.A., Shikina, N.V., Zagoruiko, A.N., Parmon, V.N., Zakharov, V.M., Braynin, B.I., and Favorski, O.N., Gas Turbines. Ed. Gurrapa I. Sciyo, 2010, Chapter 4, p.79.Google Scholar
  23. 23.
    Farrauto, R.J., Hobson, M.C., Kennelly, T., and Waterman, E.M., Appl. Catal. A, 1992, vol. 81, p.227.CrossRefGoogle Scholar
  24. 24.
    Farrauto, R.J., Lampert, J.K., Hobson, M.C., and Waterman, E.M., Appl. Catal. B, 1995, vol. 6, p.263.CrossRefGoogle Scholar
  25. 25.
    Rodriguez, N.M., Oh, S.G., Dallabetta, R.A., and Baker, R.T.K., J. Catal., 1995, vol. 157, p.676.CrossRefGoogle Scholar
  26. 26.
    Salmonsson, P., Johansson, S., and Kasemo, B., Catal. Lett., 1995, vol. 33, p.1.CrossRefGoogle Scholar
  27. 27.
    Ho, Y.S., Wang, C.-B., and Yeh, C.T., J. Mol. Catal. A, 1996, vol. 112, p.287.CrossRefGoogle Scholar
  28. 28.
    Lyubovsky, M. and Pfefferle, L., Catal. Today, 1999, vol. 47, p.29.CrossRefGoogle Scholar
  29. 29.
    Datye, A.K., Bravo, J., Nelson, T.R., Atanasova, P., Lyubovsky, M., and Pfefferle, L., Appl. Catal. A, 2000, vol. 198, p.179.CrossRefGoogle Scholar
  30. 30.
    Yang, S., Maroto-Valiente, A., Benito-Gonzalez, M., Rodriguez-Ramos, I., and Guerrero-Ruiz, A., Appl. Catal. B, 2000, vol. 28, p.223.CrossRefGoogle Scholar
  31. 31.
    Thevenin, P.O., Alcalde, A., Pettersson, L.J., Jaras, S.G., and Fierro, J.L.G., J. Catal., 2003, vol. 215, p.78.CrossRefGoogle Scholar
  32. 32.
    Simplicio, L.M.T., Brandao, S.T., Domingos, D., Bozon-Verduraz, F., and Sales, E.A., Appl. Catal. A, 2009, vol. 360, p.2.CrossRefGoogle Scholar
  33. 33.
    Colussi, S., Trovarelli, A., Vesselli, E., Baraldi, A., Comelli, G., Groppi, G., and Llorca, J., Appl. Catal. A, 2010, vol. 390, p.1.CrossRefGoogle Scholar
  34. 34.
    Widjaja, H., Sekizawa, K., Eguchi, K., and Arai, H., Catal. Today, 1999, vol. 47, p.95.CrossRefGoogle Scholar
  35. 35.
    Ismagilov, Z.R., Shikina, N.V., Yashnik, S.A., Parmon, V.N., Favorskii, O.N., Zakharov, V.M., and Branin, B.I., RF Patent no. 2372556, 2009.Google Scholar
  36. 36.
    Aulchenko, V.M., Evdokov, O.V., Kutovenko, V.D., Pirogov, B.Ya., Sharafutdinov, M.R., Titov, V.M., Tolochko, B.P., Vasiljev, A.V., Zhogin, I.A., and Zhulanov, V.V., Nucl. Instrum. Methods. Res. A, 2009, vol. 603, p.76.CrossRefGoogle Scholar
  37. 37.
    Chen, J.J. and Ruckenstein, E., J. Phys. Chem., 1981, vol. 85, p. 1606.CrossRefGoogle Scholar
  38. 38.
    Yashnik, S.A., Kuznetsov, V.V., Ismagilov, Z.R., Ushakov, V.V., Danchenko, N.M., and Denisov, S.P., Top. Catal., 2004, vol. 30-31, p.293.CrossRefGoogle Scholar
  39. 39.
    Yashnik, S.A., Ismagilov, Z.R., Porsin, A.V., Denisov, S.P., and Danchenko, N.M., Top. Catal., 2007, vol. 42–43, p.465.CrossRefGoogle Scholar
  40. 40.
    Ferrandon, M., Carno, J., Jaras, S., and Bjornbom, E., Appl. Catal. A, 1999, vol. 180, p.141.CrossRefGoogle Scholar
  41. 41.
    Alvarez-Galvan, M.C., de la Pena O’Shea, V.A., Fierro, J.L.G., and Arias, P.L., Catal. Commun., 2003, vol. 4, p.223.CrossRefGoogle Scholar
  42. 42.
    Kapteijn, F., van Langeveld, D., Moulijn, J.A., Andreini, A., Vuurman, M.A., Turek, A.M., Jehng, J., and Wachs, I.E., J. Catal., 1994, vol. 150, p.94.CrossRefGoogle Scholar
  43. 43.
    Yashnik, S.A., Denisov, S.P., Danchenko, N.M., and Ismagilov, Z.R., Top. Catal., 2007, vol. 42–43, p.465.CrossRefGoogle Scholar
  44. 44.
    Pinna, F., Signoretto, M., Strukul, G., Polizzi, S., and Pernicone, N., React. Kinet. Catal. Lett., 1997, vol. 60, p.9.CrossRefGoogle Scholar
  45. 45.
    Bonarowska, M., Pielaszek, J., Juszczyk, W., and Karpinski, J., J. Catal., 2000, vol. 195, p.304.CrossRefGoogle Scholar
  46. 46.
    Scholten, J.J.S. and Konvalinka, J.A., J. Catal., 1966, vol. 5, p.1.CrossRefGoogle Scholar
  47. 47.
    Tsikoza, L.T., Ismagilov, Z.R., Ushakov, V.A., Kuznetsov, V.V., and Ovsyannikova, I.A., Kinet. Katal., 2003, vol. 44, p.879.Google Scholar
  48. 48.
    Yashnik, S.A., Ushakov, V.V., Leonov, N.L., and Ismagilov, Z.R., Eurasian Chemico-Technological J., 2015, vol. 17, p.145.CrossRefGoogle Scholar
  49. 49.
    Rode, E.Ya., Kislorodnye soedineniya margantsa (Oxygen compounds of manganese), Moscow: Nauka, 1952.Google Scholar
  50. 50.
    Kaptejn, F., Singoredjo, L., Andreini, A., and Moulijn, J.A., Appl. Catal. B, 1994, vol. 3, p.173.CrossRefGoogle Scholar
  51. 51.
    Carroni, R., Griffin, T., Mantzaras, J., and Reinke, M., Catal. Today, 2003, vol. 83, p.157.CrossRefGoogle Scholar
  52. 52.
    Fujimoto, K., Ribeiro, F.H., Avalos-Borja, M., and Iglesia, E., J. Catal., 1998, vol. 179, p.431.CrossRefGoogle Scholar
  53. 53.
    Ersson, A., Kusar, H., Carroni, R., Griffin, T., and Jaras, S., Catal. Today, 2003, vol. 83, p.265.CrossRefGoogle Scholar
  54. 54.
    Su, S.C., Carstens, J.N., and Bell, A.T., J. Catal., 1998, vol. 176, p.125.CrossRefGoogle Scholar
  55. 55.
    Zhang, X. and Lee, C.S.-M., Mingos, D.M.P., Hayward, D.O., Appl. Catal. A, 2003, vol. 240, p.183.CrossRefGoogle Scholar
  56. 56.
    Wolf, M.M., Zhu, H., Green, W.H., and Jackson, G.S., Appl. Catal. A, 2003, vol. 244, p. 323.CrossRefGoogle Scholar

Copyright information

© Pleiades Publishing, Ltd. 2018

Authors and Affiliations

  • S. A. Yashnik
    • 1
    Email author
  • Z. S. Vinokurov
    • 1
  • A. V. Salnikov
    • 1
  • A. V. Ishchenko
    • 1
  • V. V. Kaichev
    • 1
  • Z. R. Ismagilov
    • 1
    • 2
  1. 1.Boreskov Institute of Catalysis, Siberian BranchRussian Academy of SciencesNovosibirskRussia
  2. 2.Institute of Coal Chemistry and Chemical Materials Science, Siberian BranchRussian Academy of SciencesKemerovoRussia

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