Structure and thermal behavior of novel double ceriс phosphates RbCe2(PO4)3 and Rb2Ce(PO4)2 · xH2O

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Abstract

New double cerium(IV)-rubidium phosphates, RbCe2(PO4)3 and Rb2Ce(PO4)2 · хH2O, have been obtained under hydrothermal conditions. Using the crystallographic parameters of isostructural compounds, the unit cell parameters of RbCe2(PO4)3 and Rb2Ce(PO4)2 · хH2O were calculated from X-ray powder diffraction data. The following values were obtained: for RbCe2(PO4)3, a = 17.494(1) A, b = 6.7759(5) A, c = 7.9831(5) A, β = 102.875(4)°, V = 922.51(10), A3, Z = 4 (space group C2/c); for Rb2Ce(PO4)2 · хH2O, a = b = 6.8663(1) A, c = 17.6562(5) A, V = 832.42(3) A3, Z = 4 (space group I41/amd). Thermal behavior analysis of the synthesized compounds was performed, including phase composition determination of the thermolysis products. The results demonstrate that the initial structures exhibit relative thermal stability, with decomposition onset temperatures of approximately 500°C. At higher temperatures, progressive thermolysis leads to the formation of CePO4 alongside RbPO3 or Rb4P2O7, depending on conditions.

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About the authors

D. N. Vasilyeva

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences; National Research University “Higher School of Economics”

Email: taisiya@igic.ras.ru
Russian Federation, Moscow, 119991; Moscow, 101000

D. A. Kozlov

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: taisiya@igic.ras.ru
Russian Federation, Moscow, 119991

M. R. Protsenko

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences; National Research University “Higher School of Economics”

Email: taisiya@igic.ras.ru
Russian Federation, Moscow, 119991; Moscow, 101000

N. P. Simonenko

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: taisiya@igic.ras.ru
Russian Federation, Moscow, 119991

T. O. Kozlova

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Author for correspondence.
Email: taisiya@igic.ras.ru
Russian Federation, Moscow, 119991

V. K. Ivanov

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: taisiya@igic.ras.ru
Russian Federation, Moscow, 119991

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Supplementary files

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2. Fig. 1. Full-profile analysis of the diffraction pattern of the product of hydrothermal treatment of the reaction mixture obtained by mixing the cerium phosphate solution with 1 M aqueous RbOH. The positions of the Bragg peaks for RbCe2(PO4)3 and monazite CePO4 (PDF2 00-032-199) are marked at the bottom. The inset shows the crystal structure of RbCe2(PO4)3 along the a-axis. CeO9 polyhedra are highlighted in yellow, PO4 tetrahedra are highlighted in gray, rubidium atoms are shown as purple spheres, and oxygen atoms are shown as red.

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3. Fig. 2. Full-profile analysis of the diffraction pattern of the product of hydrothermal treatment of the reaction mixture obtained by mixing the cerium phosphate solution with 3 M aqueous RbOH. The positions of the Bragg peaks for Rb2Ce(PO4)2 and monazite CePO4 (PDF2 [00-032-199]) are marked at the bottom. The inset shows the crystal structure of Rb2Ce(PO4)2 along the c-axis. CeO9 polyhedra are highlighted in yellow, PO4 tetrahedra are highlighted in gray, rubidium atoms are shown as purple spheres, and oxygen atoms are shown as red.

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4. Fig. 3. Scanning electron microscopy data for the products of hydrothermal treatment of the reaction mixture obtained by mixing the cerium phosphate solution with 1 M (a), 3 M (b) aqueous solution of RbOH.

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5. Fig. 4. Results of thermogravimetric analysis of the products of hydrothermal treatment of the reaction mixture obtained by mixing the cerium phosphate solution with 1 M (a), 3 M (b) aqueous solution of RbOH.

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6. Fig. 5. IR spectra of the products of hydrothermal treatment of the reaction mixture obtained by mixing the cerium phosphate solution with 1 M (a), 3 M (b) aqueous solution of RbOH, before and after annealing.

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7. Fig. 6. Diffraction patterns of the products of hydrothermal treatment of the reaction mixture obtained by mixing the cerium phosphate solution with 1 M (a), 3 M (b) aqueous solution of RbOH, before and after annealing. The positions of the Bragg peaks for RbCe2(PO4)3, Rb2Ce(PO4)2, RbPO3 [50] and monazite CePO4 (PDF2 [00-032-199]) are marked at the bottom.

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