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Sol—Gel Synthesis and Structure Formation of Manganese Zirconium (Titanium) Phosphates

  • Synthesis and Properties of Inorganic Compounds
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Abstract

Compounds Mn0.5Ti2(PO4)3 and Mn0.5Zr2(PO4)3 and Mn0.5+2xZr2 – x(PO4)3 (0 < x ≤0.35) solid solution were prepared by two variants of the sol-gel method using inorganic and organic reagents and were characterized using X-ray diffraction and IR spectroscopy. Mn0.5Ti2(PO4)3, a compound with an NaZr2(PO4)3 (NZP) structure, is formed at 600°C and is stable up to 950°C. Mn0.5Zr2(PO4)3 has dimorphism; its low-temperature phase having the Sc2(WO4)3 (SW) structure was prepared at 650°C, and the high-temperature NZP phase, at 1200°C. Mn0.5 + 2xZr2−x(PO4)3 solid solution crystallizes in an SW-type structure; it is thermally unstable at temperatures above 900°C. The thermal stability of samples decays as x rises. p ]The numbers of the stretching and bending vibrations in an \({\rm{PO}}_4^{3 - }\) ion in the IR spectra of NZP and SW ortho-phosphates agree with factor-group analysis for space group R3̅ and P21/n. Structure refinement was carried out for the low-temperature Mn0.5Zr2(PO4)3 phase (space group P21/n, a = 8.861(3) Å, b = 8.869(2) Å, c = 12.561(3) Å, β = 89.51(2)°) and for the solid solution. The basis of the structures is a framework built of corner-sharing tetrahedra PO4 and octahedra ZrO6 or (Mn,Zr)O6. The framework interstices are occupied by cations Mn2+ in tetrahedral oxygen coordination. A comparative crystal-chemical analysis of the morpho-tropic series of M0.5Zr2(PO4)3 phosphates (M stands for a metal in the oxidation state +2) elucidated a relationship between structural features.

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Authors and Affiliations

  1. National Research Nizhny Novgorod State University, Nizhny Novgorod, 603950, Russia

    V. I. Pet’kov, D. A. Lavrenov & M. V. Sukhanov

  2. National Research and Technology University “MISiS”, Moscow, 119049, Russia

    A. M. Koval’skii

  3. Moscow State University, Moscow, 119991, Russia

    E. Yu. Borovikova

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  1. V. I. Pet’kov
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  2. D. A. Lavrenov
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  3. M. V. Sukhanov
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Correspondence to V. I. Pet’kov.

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Russian Text © V.I. Pet’kov, D.A. Lavrenov, M.V. Sukhanov, A.M. Koval’skii, E.Yu. Borovikova, 2019, published in Zhurnal Neorganicheskoi Khimii, 2019, Vol. 64, No. 2, pp. 137–145.

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Pet’kov, V.I., Lavrenov, D.A., Sukhanov, M.V. et al. Sol—Gel Synthesis and Structure Formation of Manganese Zirconium (Titanium) Phosphates. Russ. J. Inorg. Chem. 64, 170–178 (2019). https://doi.org/10.1134/S0036023619020165

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