Skip to main content
SpringerLink
Log in

Synthesis and catalytic properties of M0.5(1 + x)Fe x Ti2 − x (PO4)3 (M = Co, Ni, Cu; 0 ≤ x ≤ 2) for methanol conversion reactions

  • Published:
Inorganic Materials Aims and scope

Abstract

New phosphates with the general formula M0.5(1 + x )Fe x Ti2 − x (PO4)3 (M = Co, Ni, Cu; 0 ≤ x ≤ 2) have been synthesized by a sol-gel process. We have studied phase relations in these systems and determined the composition stability limits of NASICON-type solid solutions. The catalytic properties of the phosphates for methanol dehydration and dehydrogenation reactions have been investigated in an inert atmosphere.

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. Pet’kov, V.I. and Orlova, A.I., Crystal-chemical approach to predicting the thermal expansion of compounds in the NZP family, Inorg. Mater., 2003, vol. 39, no. 10, pp. 1013–1023.

    Article  Google Scholar 

  2. Yaroslavtsev, A.B. and Stenina, I.A., Complex phosphates with the NASICON structure (MxA2(PO4)3), Russ. J. Inorg. Chem., 2006, vol. 51,suppl. 1, pp. 97–116.

    Article  Google Scholar 

  3. Goodenough, J.B., Hong, H.Y.-P., and Kafalas, J.A., Fast Na+-ion transport in skeleton structures, Mater. Res. Bull., 1976, vol. 11, pp. 203–220.

    Article  CAS  Google Scholar 

  4. Robertson, A.D., West, A.R., and Ritchie, A.G., Review of crystalline lithium-ion conductors suitable for high temperature battery applications, Solid State Ionics, 1997, vol. 104, pp. 1–11.

    Article  CAS  Google Scholar 

  5. Ivanov-Shitz, A.K. and Murin, I.V., Ionika tverdogo tela (Solid-State Ionics), St. Petersburg: S.-Peterburg. Gos. Univ., 2001, vol. 1.

    Google Scholar 

  6. Imanaka, N., Ueda, T., and Adachi, G., Tetravalent Zr4+ ion conduction in NASICON-type phosphate solids, J. Solid State Electrochem., 2003, vol. 7, pp. 239–243.

    Article  CAS  Google Scholar 

  7. Anantharamulu, N., Koteswara Rao, K., Rambabu, G., Vijaya Kumar, B., Radha, V., and Vithal, M., A wideranging review on Nasicon type materials, J. Mater. Sci., 2011, vol. 46, no. 9, pp. 2821–2837.

    Article  CAS  Google Scholar 

  8. Stenina, I.A., Zhizhin, M.G., Lazoryak, B.I., and Yaroslavtsev, A.B., Phase transitions, structure and ion conductivity of zirconium hydrogen phosphates with the NASICON structure, H1 ± x Zr2 − x Mx(PO4)3 · H2O (M = Nb, Y), Mater. Res. Bull., 2009, vol. 44, no. 7, pp. 1608–1612.

    Article  CAS  Google Scholar 

  9. Pinus, I.Yu., Khoroshilov, A.V., Gavrichev, K.S., Tarasov, V.P., and Yaroslavtsev, A.B., On cationic mobility in Nasicon phosphates LiTi2(PO4)3 and Li0.9Ti1.9Nb0.1(PO4)3, Solid State Ionics, 2012, vol. 212, pp. 112–116.

    Article  CAS  Google Scholar 

  10. Svitan’ko, A.I., Novikova, S.A., Stenina, I.A., Skopets, V.A., and Yaroslavtsev, A.B., Microstructure and ion transport in Li1+x Ti2−x Mx(PO4)3 (M = Cr, Fe, Al) NASICON-type materials, Inorg. Mater., 2014, vol. 50, no. 3, pp. 273–279.

    Article  Google Scholar 

  11. Ziyad, M., Arsalane, S., Kacimi, M., Couduriere, G., Miller, J.M., and Vedrine, J.C., Behaviour of silver-thorium phosphate AgTh2(PO4)3 in butane-2-ol conversion, Appl. Catal., A, 1996, vol. 147, pp. 363–373.

    Article  CAS  Google Scholar 

  12. Ienealem, S.N., Gul’yanova, S.G., Chekhlova, T.K., Ermilova, M.M., Orlova, A.I., Pet’kov, V.I., and Timakin, A.G., Catalytic activity and selectivity of combined zirconium-3d transition metal phosphates in isopropanol conversion, Russ. J. Phys. Chem. A, 2000, vol. 74, no. 12, pp. 2082–2084.

    Google Scholar 

  13. Brik, Y., Kacimi, M., Bozon-Verduraz, F., and Ziyad, M., Characterization of active sites on AgTh2(PO4)3 in butane-2-ol conversion, Microporous Mesoporous Mater., 2001, vol. 43, pp. 103–112.

    Article  CAS  Google Scholar 

  14. Sadykov, V.A., Pavlova, S.N., Zabolotnaya, G.V., Chaikina, M.V., Maksimovskaya, R.I., Tsybulya, S.V., Burgina, E.B., Zaikovskii, V.I., Litvak, G.S., Frolova, Yu.V., Kochubei, D.I., Kriventsov, V.V., Paukshtis, E.A., Kolomiichuk, V.N., Lunin, V.V., Kuznetsova, N.N., Agraval, D., and Roi, R., Scientific bases for the synthesis of highly dispersed framework zirconium phosphate catalysts for paraffin isomerization and selective oxidation, Kinet. Katal., 2001, vol. 42, no. 3, pp. 390–398.

    Article  CAS  Google Scholar 

  15. Sukhanov, M.V., Ermilova, M.M., Orekhova, N.V., Pet’kov, V.I., and Tereshchenko, G.F., Catalytic properties of zirconium phosphate and double phosphates of zirconium and alkali metals with a NaZr2(PO4)3 structure, Russ. J. Appl. Chem., 2006, vol. 79, no. 4, pp. 614–618.

    Article  CAS  Google Scholar 

  16. Sukhanov, M.V., Ermilova, M.M., Orekhova, N.V., Tereshchenko, G.F., Pet’kov, V.I., and Shchelokov, I.A., Catalytic properties of zirconium-containing framework phosphates for methanol dehydration, Vestn. Nizhegorod. Univ. im. N.I. Lobachevskogo, 2007, no. 1, pp. 89–94.

    Google Scholar 

  17. Pet’kov, V.I., Sukhanov, M.V., Ermilova, M.M., Orekhova, N.V., and Tereshchenko, G.F., Development and synthesis of bulk and membrane catalysts based on framework phosphates and molybdates, Russ. J. Appl. Chem., 2010, vol. 83, no. 10, pp. 1731–1741.

    Article  Google Scholar 

  18. Povarova, E.I., Pylinina, A.I., and Mikhalenko, I.I., Catalytic dehydrogenation of propanol-2 on Na-Zr phosphates containing Cu, Co, and Ni, Russ. J. Phys. Chem. A, 2012, vol. 86, no. 6, pp. 935–941.

    Article  CAS  Google Scholar 

  19. Ermilova, M.M., Sukhanov, M.V., Borisov, R.S., Orekhova, N.V., Pet’kov, V.I., Novikova, S.A., Il’in, A.B., and Yaroslavtsev, A.B., Synthesis of the new framework phosphates and their catalytic activity in ethanol conversion into hydrocarbons, Catal. Today, 2012, vol. 193, pp. 37–41.

    Article  CAS  Google Scholar 

  20. Ogorodnikov, S.K., Formal’degid (Formaldehyde), Leningrad: Khimiya, 1984.

    Google Scholar 

  21. Spravochnik neftekhimika (Pedtrochemist’s Handbook), Ogorodnikov, S.K., Ed., Leningrad, 1978, vol. 2, pp. 249–251.

  22. Pet’kov, V.I., Complex phosphates formed by metal cations in oxidation states I and IV, rus. Chem. Rev., 2012, vol. 81, no. 7, pp. 606–637.

    Google Scholar 

  23. Olazcuaga, R., Le Flem, G., Boireau, A., and Soubeyroux, J.L., The structure of the high temperature forms of Cu(II)0.5Ti2(PO4)3 and D0.5Cu(I)0.5Zr2(PO4)3, Adv. Mater. Res., 1994, no. 1, pp. 177–188.

    Google Scholar 

  24. El Bouari, A., El Jazouli, A., Dance, J.M., Le Flem, G., and Olazcuaga, R., A new Nasicon-like phosphate Co0.5Ti2(PO4)3, Adv. Mater. Res., 1994, no. 1, pp. 173–176.

    Google Scholar 

  25. Shchelokov, I., Asabina, E., Sukhanov, M., Ermilova, M., Orekhova, N., Pet’kov, V., and Tereshchenko, G., Synthesis, surface properties and catalytic activity of phosphates Cu0.5(1 + y)FeyZr2 − y (PO4)3 in methanol conversion, Solid State Sci., 2008, vol. 10, no. 4, pp. 513–517.

    Article  CAS  Google Scholar 

  26. Ziyad, M., Rouimi, M., and Portefaix, J.-L., Isomerization of n-butene over ferrierite zeolite modified by silicon tetrachloride treatment, Appl. Catal., A, 1999, vol. 183, no. 1, pp. 93–105.

    Article  CAS  Google Scholar 

  27. Ramos, F.S., Duarte de Farias, A.M., Borges, L.E.P., Monteiro, J.L., Fraga, M.A., Sousa-Aguiar, E.F., and Appel, L.G., Role of dehydration catalyst acid properties on one-step DME synthesis over physical mixtures, Catal. Today, 2005, vol. 101, pp. 39–44.

    Article  CAS  Google Scholar 

  28. Tanabe, K., Solid Acids and Bases, Their Catalytic Properties, New York: Academic, 1970.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Lobachevsky State University, pr. Gagarina 23, Nizhni Novgorod, 603950, Russia

    E. A. Asabina, V. I. Pet’kov & I. O. Glukhova

  2. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991, Russia

    N. V. Orekhova, M. M. Ermilova, N. A. Zhilyaeva & A. B. Yaroslavtsev

  3. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119991, Russia

    A. B. Yaroslavtsev

Authors
  1. E. A. Asabina
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. N. V. Orekhova
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. M. Ermilova
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. V. I. Pet’kov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. I. O. Glukhova
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. N. A. Zhilyaeva
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. A. B. Yaroslavtsev
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A. B. Yaroslavtsev.

Additional information

Original Russian Text © E.A. Asabina, N.V. Orekhova, M.M. Ermilova, V.I. Pet’kov, I.O. Glukhova, N.A. Zhilyaeva, A.B. Yaroslavtsev, 2015, published in Neorganicheskie Materialy, 2015, Vol. 51, No. 8, pp. 864–869.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Asabina, E.A., Orekhova, N.V., Ermilova, M.M. et al. Synthesis and catalytic properties of M0.5(1 + x)Fe x Ti2 − x (PO4)3 (M = Co, Ni, Cu; 0 ≤ x ≤ 2) for methanol conversion reactions. Inorg Mater 51, 793–798 (2015). https://doi.org/10.1134/S002016851508004X

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S002016851508004X

Keywords

Search

Navigation