Skip to main content
SpringerLink
Log in

Comparative analysis of NdCaCoO4 phase formation from cryogel and from solid state precursors

  • Brief Communication: Sol-gel, hybrids and solution chemistries
  • Published:
Journal of Sol-Gel Science and Technology Aims and scope Submit manuscript

Abstract

In order to identify the reasons of the complicated synthesis of NdCaCoO4 by the cryogel method, the phase formation processes during thermal processing of precursors were investigated by in-situ X-ray diffraction analysis, Rietveld refinement and energy dispersive X-ray analysis of reaction products and intermediates. Formation of NdCaCoO4 from the cryogel precursor and from the mixture of oxides and CaCO3 is observed at 1000–1100 °C. The complicated phase formation from the cryogel precursor is associated with the low reactivity of (Nd,Ca)CoO3 intermediate of the precursor thermolysis. Precipitation by NaOH/Na2CO3 instead of KOH/K2CO3 results in the reduction of NdCaCoO4 formation temperature to 800 °C. According to energy dispersive X-ray analysis, the coprecipitation of Nd, Ca and Co is accompanied by the capture of Na ions followed by the formation of NaxCoO2 phase at 600–700 °C. The enhanced reactivity of (Nd,Ca)CoO3 in this case could be attributed to the enhanced ion mobility due to the simultaneous formation of NaxCoO2, CoO and NdCaCoO4 (Hedvall effect).

Graphical Abstract

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

References

  1. Dedov AG, Komissarenko DA, Loktev AS, Mazo GN, Moiseev II (2010) Method of producing synthesis gas. Patent RU2433950С1. https://patents.google.com/patent/RU2433950C1/en. Filing date 21-04-2010.

  2. Dedov AG, Loktev AS, Komissarenko DA, Mazo GN, Shlyakhtin OA, Parkhomenko KV, Kiennemann AA, Roger AC, Ishmurzin AV, Moiseev II (2015) Partial oxidation of methane to produce syngas over a neodymium–calcium cobaltate-based catalyst. Appl Catal A Gen 489:140–146

    Article  Google Scholar 

  3. Taguchi H, Kido H, Tabata K (2004) Relationship between crystal structure and electricalproperty of K2NiF4-type (Ca1-xNd1+x)CoO4-δ. Physica B 344:271–277

    Article  Google Scholar 

  4. Borovskikh LV, Putilin SN, Leonova LS, Mazo GN (2008) Synthesis, structure and transport properties of NdCaCoO4. Inorg Mater Appl Res 5:54–59

    Google Scholar 

  5. Mazo GN, Kolchina LM, Lyskov NV, Leonova LS et al. (2013) Features of high temperature behavior in NdCaCoO4 — the catalyst of the partial oxidation of methane to syngas. Rus. J Phys Chem 87:1976–1982

    Google Scholar 

  6. James M, Tedesco A, Cassidy D, Colella M, Smythe PJ (2006) The phase diagram and crystal chemistry of strontium-doped rare earth cobaltates: Ln2-xSrxCoO4+δ (Ln = La-Dy). J Alloys Compd 419:201–207

    Article  Google Scholar 

  7. Shlyakhtin OA, Mazo GN, Kaluzhskikh MS, Komissarenko DA, Loktev AS, Dedov AG (2012) Compositional boundaries of Nd2-x CaxCoO4±δ at 900–1200°C. Mater Lett 75:20–22

    Article  Google Scholar 

  8. Thorogood GJ, Orain PY, Ouvry M, Piriou B, Tedesco T, Wallwork KS, Herrmann J, James M (2011) Structure, crystal chemistry and magnetism of rare earth calcium-doped cobaltates: Ln2-xCaxCoO4+δ (Ln . Pr, Nd, Sm, Eu and Gd). Solid State Sci 13:2113–2123

    Article  Google Scholar 

  9. Shlyakhtin OA, Mazo GN, Malyshev SA, Kolchina LM, Knot’ko AV, Loktev AS, Dedov AG (2013) Cryogel synthesis and solid state reactivity of NdCaCoO4. Mater Res Bull 48:245–249

    Article  Google Scholar 

  10. Wong-Ng W, Laws W, Talley KR, Huang Q, Yan Y, Martin J, Kaduk JA (2014) Phase equilibria and crystal chemistry of the CaO–1/2Nd2O3–CoOz system at 885 C in air. J Solid State Chem 215:128–134

    Article  Google Scholar 

  11. Berar JF, Lelann P (1991) ESDs and estimated probable-error obtained in Rietveld refinements with local correlations. J Appl Cryst. 24:1–5

    Article  Google Scholar 

  12. Kundu AK, Sampathkumaran EV, Gopalakrishnan KV, Rao CNR (2004) Inhomogeneous magnetic behavior of Pr0.7Ca0.3CoO3 and Nd0.7 Ca0.3CoO3. J Magn Magn Mater 281:261–266

    Article  Google Scholar 

  13. Zhang L, Tang X, Gao W (2009) Formation and growth mechanism of highly tiled γ-NaxCo2O4 crystals by a novel sodium alginate gel template method. J Phys Chem C 113:7930–7934

    Article  Google Scholar 

  14. Huang Q, Khaykovich B, Chou FC, Cho JH, Lynn JW, Lee YS (2004) Structural transition in NaxCoO2 with x near 0.75 due to Na rearrangement. Phys Rev B: Condens Matter 70(134115):1–6

    Google Scholar 

  15. Gallagher PK, Johnson DW (1982) Solid-State Reactivity in the System Na2CO3-CaCO3. J Phys Chem 86:295–297

    Article  Google Scholar 

  16. Vecera J, Dohnalova Z, Mikulasek P, Sulcova P (2013) Anatase–rutile transformation at the synthesis of rutile pigments (Ti,Cr,Nb)O2 and their color properties. J Therm Anal Calorim 113:61–67

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the Russian Foundation for Basic Research (grant No 13-03-12406) and by the Russian Science Foundation (project 14-13-01007). The M.V. Lomonosov Moscow State University Program of Development is gratefully acknowledged for the partial support.

Author information

Authors and Affiliations

  1. Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow, 119991, Russia

    Sergey A. Malyshev, Oleg A. Shlyakhtin, Galina N. Mazo & Andrey V. Mironov

  2. Department of Materials Sciences, M.V. Lomonosov Moscow State University, Moscow, 119991, Russia

    Alexey V. Garshev

  3. Gubkin Russian State University of Oil and Gas (National Research University), Moscow, 119991, Russia

    Alexey S. Loktev & Alexey G. Dedov

Authors
  1. Sergey A. Malyshev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Oleg A. Shlyakhtin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Galina N. Mazo
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Alexey V. Garshev
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Andrey V. Mironov
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Alexey S. Loktev
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Alexey G. Dedov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Oleg A. Shlyakhtin.

Ethics declarations

Conflict of interest

The authors declare that they have no competing interests.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Malyshev, S.A., Shlyakhtin, O.A., Mazo, G.N. et al. Comparative analysis of NdCaCoO4 phase formation from cryogel and from solid state precursors. J Sol-Gel Sci Technol 81, 372–377 (2017). https://doi.org/10.1007/s10971-016-4224-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10971-016-4224-8

Keywords

Search

Navigation