Skip to main content
SpringerLink
Log in

Synthesis, crystal structure, and spectroscopic study of K0.92(2) Zn0.08(2) H1.92(2) (PO4) (Zn-KDP)

  • Review
  • Published:
Ionics Aims and scope Submit manuscript

Abstract

The structure of K0.92(2) Zn0.08(2) H1.92(2) (PO4) was determined using single-crystal X-ray diffraction. The crystal structure of the Zn-KDP belonged to the tetragonal space group \( \mathrm{I}\overline{4}2\mathrm{d} \), with cell parameters of a = b = 7.4487(5) Å and c = 6.9703(5) Å, 386.73(5) Å3, Z = 4, and R = 0.023. Zn2+ ions were used as substitutes for K+ ions with hydrogen vacancy. The Zn-KDP single crystals were submitted to further Raman, infrared, and 1H NMR studies to investigate chemical group functionalisation, possible bonding between the organic and inorganic materials, and partial substitution of K+ by Zn2+. The latter partial substitution was confirmed by the deviation of IR frequencies for O–H stretching, the variation of IR and Raman frequencies for stretching and bending vibrations ν(PO4) of H2PO4, and the appearance of additional Raman (147, 386 and 481 cm−1) vibrational bands. Electrical conductivity measurements were performed on polycrystalline pellets of Zn-KDP and pure KDP at room temperatures (RT) of up to 473K. In both cases, a conductivity jump close to 453K was observed, and a stronger increase of conductivity was measured.

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
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Ponomareva VG, Martsinkevich VV, Chesalov YA (2011) Transport and thermal characteristics of Cs1 – x Rb x H2PO4 1. J Electrochem 47:645–653

    Google Scholar 

  2. Botez CE, Carbajal D, Adiraju VAK, Tackett RJ, Chianelli RR (2010) Intermediate-temperature polymorphic phase transition in KH2PO4: a synchrotron X-ray diffraction study. J Phys Chem Solids 71:1576–1580

    Article  CAS  Google Scholar 

  3. Subramony JA, Scott L, Kahr B (1998) Polymorphism of potassium dihydrogen phosphate. J Chem Mater 10:2053–2057

    Article  CAS  Google Scholar 

  4. Anand Subramony J, Lovell S, Kaminsky W, Kahr B (2004) Structure of a high temperature phase of potassium dideuteriophosphate (DKDP). J Solid State Commun 132:827–830

    Article  Google Scholar 

  5. Park J-H (2002) Separation of surface and bulk electrical conductivity in KH2PO4 and KH2AsO4 crystals at high temperatures. J Solid State Commun 123:291–294

    Article  CAS  Google Scholar 

  6. Guzman LA, Maeda K, Hirota S, Kubota N (1998) Adsorption of growth suppressor chromium (III) on potassium sulfate crystals in aqueous solution. J Cryst Growth 186:438–445

    Article  CAS  Google Scholar 

  7. Rashkovich LN, Kronsky NV (1997) Influence of of Fe 3+ and Al 3+ ions on the kinetics of steps on the faces of KDP. J Cryst Growth 182:434–441

    Article  CAS  Google Scholar 

  8. Zaitseva N, Carman L, Smolsky I, Torres R, Yan M (1999) The effect of impurities and supersaturation on the rapid growth of KDP crystals. J Cryst Growth 204:512–524

    Article  CAS  Google Scholar 

  9. Guzman LA, Maeda K, Hirota S, Yokota M, Kubota N (1997) Unsteady-state impurity effect of chromium (III) on the growth rate of potassium sulfate crystal in aqueous solution. J Cryst Growth 181:272–280

    Article  CAS  Google Scholar 

  10. Lai X, Roberts KJ, Bedzyk MJ, Lyman PF, Cardoso LP, Sasaki JM (2005) Structure of habit-modifying trivalent transition metal cations (Mn3+, Cr3+) in nearly perfect single crystals of potassium dihydrogen phosphate as examined by X-ray standing waves, X-ray absorption spectroscopy, and molecular modeling. J Chem Mater 17:4053–4061

    Article  CAS  Google Scholar 

  11. Garces NY, Stevens KT, Halliburton LE, Yan M, Zaitseva NP, DeYoreo JJ (2001) Optical absorption and electron paramagnetic resonance of Feions in KDP crystals. J Cryst Growth 225:435–439

    Article  CAS  Google Scholar 

  12. Asakuma Y, Takeda S, Maeda K, Fukui K (2009) Kinetic and theoretical studies of metal ion adsorption in KDP solution. J Appl Surf Sci 225:4140–4144

    Article  Google Scholar 

  13. Eremina TA, Kuznetsov VA, Eremin NN, Okhrimenko TM, Furmanova NG, Efremovaa EP, Rak M (2005) On the mechanism of impurity influence on growth kinetics and surface morphology of KDP crystals-II: experimental study of influence of bivalent and trivalent impurity ions on growth kinetics and surface morphology of KDP crystals. J Cryst Growth 273:586–593

    Article  CAS  Google Scholar 

  14. Benedict JB, Wallace PM, Reid PJ, Jang S-H, Kahr B (2003) Up-conversion luminescence in dye doped crystals of potassium hydrogen phthalate. J Adv Mater 15:1068–1070

    Article  CAS  Google Scholar 

  15. Pritula I, Gayvoronsky V, Gromov Y, Kopylovsky M, Kolybaeva M, Puzikov V, Kosinova A, Savvin Y, Velikhov Y, Levchenko A (2009) Linear and nonlinear optical properties of dye-doped KDP crystals: effect of thermal treatment. J Optics Commun 282:1141–1147

    Article  CAS  Google Scholar 

  16. Asakuma Y, Nishimura M, Li Q, Ming Ang H, Tade M, Maeda K, Fukui K (2007) Colouring mechanism of dyed KDP crystal by quantum chemistry. J Mol Struct (THEOCHEM) 810:7–13

    Article  CAS  Google Scholar 

  17. Zaitseva N, Carman L, Rapid growth of KDP-type crystals (2001) Rapid growth of KDP-type crystals. J Mater 43:1–118

    CAS  Google Scholar 

  18. Velikhov Y, Pritula I, Ganina I, Kolybayeva M, Puzikov V, Levchenko AN (2007) Growth and properties of dyed KDP crystals. J Cryst Res Technol 42:27–33

    Article  CAS  Google Scholar 

  19. Nelmes RJ (1987) Ferroelectrics 71:87

    Article  CAS  Google Scholar 

  20. Sheldrick GM (1997) SHELXTL-97 Program for Refining Crystal Structure, University of Göttingen. Göttingen, Germany

    Google Scholar 

  21. Kawahata Y, Tominaga Y (2008) Dynamical mechanism of ferroelectric phase transition in KDP/DKDP mixed crystals and distortion of PO4 tetrahedron. J Solid State Commun 145:218–222

    Article  CAS  Google Scholar 

  22. Dongli X, Xue D, Ratajczak H (2005) Morphology and structure studies of KDP and ADP crystallites in the water and ethanol solutions. J Mol Struct 740:37–45

    Article  Google Scholar 

  23. Kumaresan P, Moorthy Babu S, Anbarasan PM (2008) Growth and characterization of metal ions and dyes doped KDP single crystals for laser applications. J Mater Res Bull 43:1716–1723

    Article  CAS  Google Scholar 

  24. Frost RLM, Bouzaid JM, Reddy BJ (2007) Vibrational spectroscopy of the sorosilicate mineral hemimorphite Zn4(OH)2Si2O7.H2O. J Polyhedron 26(12):2405–2412

    Article  CAS  Google Scholar 

  25. Muralidharan P, Venkateswarlu M, Satyanarayana N (2005) Acid catalyst concentration effect on structure and ion relaxation studies of Li2O–O5–O3–SiO2 glasses synthesized by sol–gel process. J Non-Cryst Solid 351:583–594

    Article  CAS  Google Scholar 

  26. O'Keefee M, Perrino CT (1967) Proton conductivity in pur and doped KH2PO4. J Phys Chem Solids 28:211–218

    Article  Google Scholar 

  27. Mathew M, Wong-Ng W (1995) Crystal structure of a new monoclinic form of potassium dihydrogen phosphate containing orthophosphacidiumion, [H4PO4]+1. J Solid State Chem 114:219–223

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors wish to express their gratitude to Mr. Anouar Smaoui and Mrs Hanen Ben Salem from the Faculty of Science, Sfax, Tunisia for their constructive proofreading and language polishing services. Thanks are also due to the Raman spectroscopy Unit at FSS Sfax for their valuable help with the measuring of Raman spectra.

Author information

Authors and Affiliations

  1. Laboratoire de L’Etat Solide (LES), Université du Sfax, Faculté des Sciences de Sfax, Route de Soukra Km 3.5, BP 802, 3018, Sfax, Tunisia

    Houda Ettoumi, Mohamed Toumi & Tahar Mhiri

  2. Unité de Recherche de Chimie Industrielle, Université Elmanar, Faculté des Sciences de Tunis, 1060, Tunis, Tunisia

    Faouzi Ben Brahim

Authors
  1. Houda Ettoumi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Faouzi Ben Brahim
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mohamed Toumi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tahar Mhiri
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Houda Ettoumi.

Appendix A. Supplementary data

Appendix A. Supplementary data

CSD-423866 contains the supplementary crystallographic data for this paper. CIF and structure factor deposits may be made using online service: http://journals.iucr.org/services/cif/checkcif.html, or from the Fachinformationszentrum Karlsruhe (FIZ) 76344 Eggenstein-Leopoldshafen, Germany; tel: +49-(0)7247/808-205; or e-mail: crysdata@fiz-karlsruhe.de

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ettoumi, H., Brahim, F.B., Toumi, M. et al. Synthesis, crystal structure, and spectroscopic study of K0.92(2) Zn0.08(2) H1.92(2) (PO4) (Zn-KDP). Ionics 19, 193–200 (2013). https://doi.org/10.1007/s11581-012-0824-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11581-012-0824-7

Keywords

Search

Navigation