New data on protonation and hydration of perovskite-type layered oxide KCa2Nb3O10


Protonation and hydration processes of layered perovskite-like oxide KCa2Nb3O10 during the reaction with nitric acid solutions with different concentrations were studied by means of TG, STA + MS, XRD, SEM, EDX and ICP methods. It was found that despite the absence of significant changes in crystal structure, treatment of KCa2Nb3O10 with water leads to the partial substitution of K+ with H+ (about 15% exchange), while a number of new hydrated protonated phases HxK1−xCa2Nb3O10·yH2O with higher exchange (50–90%) may be obtained using moderate acid concentrations (0.1–3 M HNO3) varying reaction time. It was shown that production of the fully protonated form requires the minimum 3 M concentration of the acid and 24 h reaction time.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6


  1. 1.

    Liu Y, Mao Z-Q. Unconventional superconductivity in Sr2RuO4. Phys C. 2015;514:339–53.

    CAS  Article  Google Scholar 

  2. 2.

    Ogino H, Sato S, Kishio K, Shimoyama J. Relationship between crystal structures and physical properties in iron arsenides with perovskite-type layers. Phys Proc. 2012;36:722–6.

    CAS  Article  Google Scholar 

  3. 3.

    Moritomo Y, Asamitsu A, Kuwahara H, Tokura Y. Giant magnetoresistance of manganese oxides with a layered perovskite structure. Nature. 1996;380:141–4.

    CAS  Article  Google Scholar 

  4. 4.

    Lacz A. Structure, chemical stability and electrical properties of BaCe0.9Y0.1O3-ß modified with V2O5. J Therm Anal Calorim. 2019.

    Article  Google Scholar 

  5. 5.

    Manonmani M, Jaikumar V, Gokul Raj S, Ramesh Kumar G. Crystallization, non-isothermal kinetics and structural analysis of nanocrystalline multiferroic bismuth ferrite (BiFeO3) synthesized by combustion method. J Therm Anal Calorim. 2019.

    Article  Google Scholar 

  6. 6.

    Rodionov IA, Zvereva IA. Photocatalytic activity of layered perovskite-like oxides in practically valuable chemical reactions. Russ Chem Rev. 2016;85:248–79.

    CAS  Article  Google Scholar 

  7. 7.

    Belina P, Sadovska G, Krejcıkova V, Dohnalova Z, Sulcova P. Preparation of LaNiO3 perovskite by oxalate and carbonate precursor method for utilization as catalyst for high-temperature decomposition of N2O. J Therm Anal Calorim. 2019.

    Article  Google Scholar 

  8. 8.

    Chen Y, Luo Q, Ke X-Y, Chen Q, Gong H, Zhang C-C, et al. Excellent high curie temperature BiTi3O6+1.5 (x = 3.96, 3.98, 4.0, 4.02, 4.04) ferroelectric ceramics with low-loss dielectric properties. Ceram Int. 2017;43:15556–60.

    CAS  Article  Google Scholar 

  9. 9.

    Thangadurai V, Schmid-Beurmann P, Weppner W. Synthesis, structure, and electrical conductivity of A′[A2B2O10] (A′ = Rb, Cs; A = Sr, Ba; B = Nb, Ta): new members of Dion-Jacobson type layered perovskites. J Solid State Chem. 2001;158:279–98.

    CAS  Article  Google Scholar 

  10. 10.

    Kim SY, Oh J, Park J, Byeon S. Structure of new layered oxides MII0.5LaTiO4 (M = Co, Cu, and Zn) synthesized by the ion-exchange reaction. Society. 2002;4:1643–8.

    Google Scholar 

  11. 11.

    Mahler CH, Cushing BL, Lalena JN, Wiley JB. Divalent ion exchange of alkaline-earth cations into the triple-layered perovskite RbCa2Nb3O10. Mater Res Bull. 1998;33:1581.

    CAS  Article  Google Scholar 

  12. 12.

    Sato M, Abo J, Jin T, Ohta M. Structure and ionic conductivity of MLaNb2O7 (M ≡ K, Na, Li, H). J Alloys Compd. 1993;192:81–3.

    CAS  Article  Google Scholar 

  13. 13.

    Mangamma G, Bhat V, Gopalakrishnan J, Bhat S. NMR study of fast protonic conduction in layered HLa2NbTi2O10·1.5H2O. Solid State Ion. 1992;58:303–9.

    CAS  Article  Google Scholar 

  14. 14.

    Oshima T, Yokoi T, Eguchid M. Synthesis and photocatalytic activity of K2CaNaNb3O10, a new Ruddlesden–Popper phase layered perovskite. Dalton Trans R Soc Chem. 2017;46:10594–601.

    CAS  Article  Google Scholar 

  15. 15.

    Wang Y, Wang C, Wang L, Hao Q, Zhu X, Chen X, et al. Preparation of interlayer surface tailored protonated double-layered perovskite H2CaTa2O7 with n-alcohols, and their photocatalytic activity. RSC Adv. 2014;4:4047–54.

    CAS  Article  Google Scholar 

  16. 16.

    Huang Y, Wu J, Wei Y, Hao S, Huang M, Lin J. Synthesis and photocatalytic activity of hydrated layered perovskite K2−xLa2Ti3−xNbxO10 (x = 0–1) and protonated derivatives. Scr Mater. 2007;57:437–40.

    CAS  Article  Google Scholar 

  17. 17.

    Schaak RE, Mallouk TE. KLnTiO4 (Ln = La, Nd, Sm, Eu, Gd, Dy): a new series of Ruddlesden–Popper phases synthesized by ion-exchange of HLnTiO4. J Solid State Chem. 2001;161:225–32.

    CAS  Article  Google Scholar 

  18. 18.

    Gopalakrishnan J, Bhat V. A2Ln2Ti3O10 (A = potassium or rubidium; Ln = lanthanum or rare earth): a new series of layered perovskites exhibiting ion exchange. Inorg Chem. 1987;26:4299–301.

    CAS  Article  Google Scholar 

  19. 19.

    Silyukov OI, Abdulaeva LD, Burovikhina AA, Rodionov IA, Zvereva IA. Phase transformations during HLnTiO4 (Ln = La, Nd) thermolysis and photocatalytic activity of obtained compounds. J Solid State Chem. 2015;226:101–6.

    CAS  Article  Google Scholar 

  20. 20.

    Thangadurai V, Gopalakrishnan J, Subbanna GN. Ln2Ti2O7 (Ln = La, Nd, Sm, Gd): a novel series of defective Ruddlesden–Popper phases formed by topotactic dehydration of HLnTiO4. Chem Commun. 1998;7:1299–300.

    Article  Google Scholar 

  21. 21.

    Matsuda M, Hioki T, Okada K, Nishimoto S, Miyake M. Hydrous protonated forms derived from n = 3 Dion–Jacobson-type layered perovskite titanotantalate RbLa2Ti2TaO10: interlayer reactivity with n-alkylamine. J Phys Chem Solids. 2006;67:1325–9.

    CAS  Article  Google Scholar 

  22. 22.

    Jacobson AJ, Johnson JW, Lewandowski J. Intercalation of the layered solid acid HCa2Nb3O10 by organic amines. Mater Res Bull. 1987;22:45–51.

    CAS  Article  Google Scholar 

  23. 23.

    Tahara S, Ichikawa T, Kajiwara G, Sugahara Y. Reactivity of the Ruddlesden–Popper phase H2La2Ti3O10 with organic compounds: intercalation and grafting reactions. Chem Mater. 2007;19:2352–8.

    CAS  Article  Google Scholar 

  24. 24.

    Tahara S, Sugahara Y. Interlayer surface modification of the protonated triple-layered perovskite HCa2Nb3O10·xH2O with n-alcohols. Langmuir. 2003;19:9473–8.

    CAS  Article  Google Scholar 

  25. 25.

    Shimizu K, Itoh S, Hatamachi T, Kitayama Y, Kodama T. Pillaring of Ruddlesden–Popper perovskite tantalates, H2ATa2O7 (A = Sr or La2/3), with n-alkylamines and oxidenanoparticles. J Mater Chem. 2006;16:773–9.

    CAS  Article  Google Scholar 

  26. 26.

    Lee W-J, Yeo HJ, Kim D-Y, Paek S-M, Kim Y-I. Exfoliation of Dion–Jacobson layered perovskite into macromolecular nanoplatelet. Bull Korean Chem Soc. 2013;34:2041–3.

    CAS  Article  Google Scholar 

  27. 27.

    Dion M, Ganne M, Tournoux M. Nouvelles familles de phases MIMII2Nb3O10 a feuillets “perovskites”. Mater Res Bull. 1981;16:1429–35.

    CAS  Article  Google Scholar 

  28. 28.

    Fukuoka H, Isami T, Yamanaka S. Crystal structure of a layered perovskite niobate KCa2Nb3O10. J Solid State Chem. 2000;151:40–5.

    CAS  Article  Google Scholar 

  29. 29.

    Jacobson AJ, Lewandowski JT, Johnson JW. Ion exchange of the layered perovskite KCa2Nb3O10 by protons. J Less Common Met. 1986;116:137–46.

    CAS  Article  Google Scholar 

  30. 30.

    Jacobson AJ, Johnson JW, Lewandowski JT. Interlayer chemistry between thick transition-metal oxide layers: synthesis and intercalation reactions of K[Ca2Nan−3NbnO3n+1]. Inorg Chem. 1985;24:3727–9.

    CAS  Article  Google Scholar 

  31. 31.

    Schaak RE, Mallouk TE. Prying apart Ruddlesden − Popper phases: exfoliation into sheets and nanotubes for assembly of perovskite thin films. Chem Mater. 2000;12:3427–34.

    CAS  Article  Google Scholar 

  32. 32.

    Domen K, Yoshimura J, Sekine T, Kondo J, Tanaka A, Maruya K, et al. A novel series of photocatalysts with an ion-exchangeable layered structure of niobate. Catal Lett. 1993;75:2159–62.

    CAS  Google Scholar 

  33. 33.

    Oshima T, Ishitani O, Maeda K. Non-sacrificial water photo-oxidation activity of lamellar calcium niobate induced by exfoliation. Adv Mater Interfaces. 2014;1:2–5.

    Article  CAS  Google Scholar 

  34. 34.

    Sabio EM, Chamousis RL, Browning ND, Osterloh FE. Photocatalytic water splitting with suspended calcium niobium oxides: why nanoscale is better than bulk—a kinetic analysis. J Phys Chem C. 2012;116:3161–70.

    CAS  Article  Google Scholar 

  35. 35.

    Ohisa S, Hikichi T, Pu YJ, Chiba T, Kido J. Two-dimensional Ca2Nb3O10 perovskite nanosheets for electron injection layers in organic light-emitting devices. ACS Appl Mater Interfaces. 2018;10:27885–93.

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  36. 36.

    Rabin NN, Ida S, Karim MR, Islam MS, Ohtani R, Nakamura M, et al. Super dielectric materials of two-dimensional TiO2 or Ca2Nb3O10 nanosheet hybrids with reduced graphene oxide. ACS Omega. 2018;3:2074–83.

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  37. 37.

    Zhang Z, Wang D, Yang M, Liu L, Ma J, Wang M, et al. Electrostatic self-assembly deposition of ayered calcium niobate intercalated with task-specific ionic liquid and Its electrocatalytic activity. Chem Lett. 2017;46:506–8.

    CAS  Article  Google Scholar 

  38. 38.

    Nguyen MD, Yuan H, Houwman EP, Dekkers M, Koster G, Ten Elshof JE, et al. Highly oriented growth of piezoelectric thin films on silicon using two-dimensional nanosheets as growth template Layer. ACS Appl Mater Interfaces. 2016;8:31120–7.

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  39. 39.

    Sakaki M, Okubi R, Feng Y, Kajiyoshi K. Hydrothermal synthesis followed by post heat-treatment: a novel route for the fabrication of KCa2Nb3O10 layered compound. Solid State Sci. 2018;82:59–64.

    CAS  Article  Google Scholar 

  40. 40.

    Igarashi S, Sato S, Takashima T, Ogawa M. Preparation of finite particles of layered niobate (KCa 2Nb3O10) for improved materials performance. Ind Eng Chem Res. 2013;52:3329–33.

    CAS  Article  Google Scholar 

  41. 41.

    Utkina T, Chislov M, Silyukov O, Burovikhina A, Zvereva I. TG and DSC investigation of water intercalation and protonation processes in perovskite-like layered structure of titanate K2Nd2Ti3O10. J Therm Anal Calorim. 2016;125:281–7.

    CAS  Article  Google Scholar 

  42. 42.

    Utkina T, Chislov M, Myshenkov M, Rodionov I, Zvereva I. Water sorption by the perovskite-like layered titanate K2Nd2Ti3O10 in humid atmosphere. J Therm Anal Calorim. 2018;134:323–31.

    CAS  Article  Google Scholar 

  43. 43.

    Silyukov O, Chislov M, Burovikhina A, Utkina T, Zvereva I. Thermogravimetry study of ion exchange and hydration in layered oxide materials. J Therm Anal Calorim. 2012;110:187–92.

    CAS  Article  Google Scholar 

  44. 44.

    Zvereva I, Silyukov O, Chislov M. Ion-exchange reactions in the structure of perovskite-like layered oxides: i. Protonation of NaNdTiO4 complex oxide. Russ J Gen Chem. 2011;81:1434–41.

    CAS  Article  Google Scholar 

  45. 45.

    Rodionov I, Mechtaeva E, Burovikhina A, Silyukov O, Toikka M, Zvereva I. Effect of protonation on the photocatalytic activity of the K2La2Ti3O10 layered oxide in the reaction of hydrogen production. Monatshefte für Chemie Chem Mon. 2018;149:475–82.

    CAS  Article  Google Scholar 

  46. 46.

    Rodionov I, Silyukov O, Utkina T, Chislov M, Sokolova Y, Zvereva I. Photocatalytic properties and hydration of perovskite-type layered titanates A2Ln2Ti3O10 (A = Li, Na, K; Ln = La, Nd). Russ J Gen Chem. 2012;82:1191–6.

    CAS  Article  Google Scholar 

  47. 47.

    Makó É, Senkár Z, Kristóf J, Vágvölgyi V. Surface modification of mechanochemically activated kaolinites by selective leaching. J Colloid Interface Sci. 2006;294:362–70.

    PubMed  Article  CAS  PubMed Central  Google Scholar 

  48. 48.

    Abdulaeva LD, Silyukov OI, Petrov YV, Zvereva IA. Low-temperature transformations of protonic forms of layered complex oxides HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd). J Nanomater. 2013;2013:1–8.

    Article  CAS  Google Scholar 

Download references


This work was supported by the Russian Science Foundation (Grant No. 19-13-00184). Authors also are grateful to Saint Petersburg State University Research Park. TG and DSC studies were carried out in Center of Thermal Analysis and Calorimetry, XRD study was carried out in Research Centre for X-ray Diffraction Studies, SEM images were obtained in Interdisciplinary Resource Center for Nanotechnology, ICP study was carried out in Center for chemical analysis and materials research.

Author information



Corresponding author

Correspondence to Irina A. Zvereva.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 441 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Yafarova, L.V., Silyukov, O.I., Myshkovskaya, T.D. et al. New data on protonation and hydration of perovskite-type layered oxide KCa2Nb3O10. J Therm Anal Calorim 143, 87–93 (2021).

Download citation


  • Thermogravimetry
  • Layered perovskite-type oxides
  • Niobates
  • Protonation
  • Hydration