Crystal structure of the low-temperature forms of cesium and rubidium orthophosphates

Воронин, В. И.; Berger, I. F.; Proskurnina, N. V.; Sheptyakov, Denis; Goshchitskii, B. N.; Бурмакин, Е. И.; Stroev, S. S.; Shekhtman, G. Sh.

doi:10.1134/s0020168508060186

Cited by 11 publications

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“…The structures of both the modifications are based on a three dimensional network of isolated tetrahedra [PO 4 ], coordinated by rubidium ions. The low temperature γ modification has a orthorhombic structure [8] similar to the γ forms of potassium and cesium orthophosphates [9]; the space group is Pnma. The high temperature cubic β form, judging from the similarity of X ray diffraction patters, is isostructural to the β modification of potassium and cesium ortho phosphates.…”

Section: Sample Preparation and Experimental Techniquementioning

confidence: 99%

Rubidium-cation conductivity in Rb3−2x M x PO4 (M = Zn, Cd) solid solutions

Бурмакин

Shekhtman

2015

Phys. Solid State

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New ceramic materials with a high rubidium cation conductivity in Rb 3 -2x M x PO 4 (M = Zn, Cd) systems have been synthesized and studied. It has been found that the introduction of Zn 2+ and Cd 2+ cations leads to a sharp increase in the electrical conductivity of rubidium orthophosphate due to the formation of cation vacancies and the stabilization of the high temperature cubic modification of Rb 3 PO 4 . The maximum conductivity has been observed in compositions with x = 0.15-0.30 and has the values of 10 -1 S cm -1 at 700°C and (2.0-2.5) × 10 -2 S cm -1 at 400°C. The factors influencing the transport properties of the materials under study have been discussed.

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Section: Sample Preparation and Experimental Techniquementioning

confidence: 99%

Rubidium-cation conductivity in Rb3−2x M x PO4 (M = Zn, Cd) solid solutions

Бурмакин

Shekhtman

2015

Phys. Solid State

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“…Низкотемпературные упорядоченные γ-модификации принадлежат к орторомбической син-гонии (пространственная группа Pmna [9,10]). В от-личие от них высокотемпературные β-формы имеют кубическую структуру (пространственная группа F-43m) и характеризуются ориентационным разупорядочением тетраэдров [PO 4 ], что было доказано как прецизион-ными нейтронографическими исследованиями [12][13][14], так и анализом данных по проводимости для широкого круга систем (см., например, [15]). Это ориентацион-ное разупорядочение, по сути, означает вращательное движение тетраэдров [PO 4 ], приводящее к появлению дополнительного механизма ионного переноса за счет проталкивания при вращении тетраэдров щелочных ка-тионов на соседние вакантные позиции.…”

Section: результаты и их обсуждениеunclassified

Рубидий-катионная проводимость твердых растворов Rb-=SUB=-3-2x-=/SUB=-Pb-=SUB=-x-=/SUB=-PO-=SUB=-4-=/SUB=-

Shekhtman¹,

Бурмакин²

2017

Физика Твердого Тела

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Синтезированы и исследованы новые керамические материалы на основе Rb3PO4 с высокой проводимостью по катионам рубидия в системе Rb3-2xPbxPO4. Введение катионов Pb2+ приводит к резкому возрастанию электропроводности ортофосфата рубидия за счет образования катионных вакансий, а при температурах 350-550oC и за счет стабилизации высокотемпературной кубической модификации Rb3PO4. В области высоких температур полученные электролиты обладают очень высокой ионной проводимостью, превышающей 10-1 S·cm-1 при 700oC, что выше значений, полученных ранее в аналогичных системах с добавками ионов цинка и кадмия. Обсуждаются факторы, влияющие на транспортные свойства исследованных материалов. DOI: 10.21883/FTT.2017.07.44599.402

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“…Numerous caesium phosphates have been completely structurally characterized so far, viz. the low-temperature form of Cs 3 (PO 4 ) [6], Cs 2 (HPO 4 )(H 2 O) 2 [7], Cs(H 2 PO 4 ) in its low-and room-temperature forms [8][9][10], as a superprotonic conductor phase [11] and in its high-pressure forms [12], CsH 5 (PO 4 ) 2 [13], Cs(H 3 P 2 O 7 )(H 2 O) [14], Cs 2 (H 2 P 2 O 7 ) [15], Cs 6 (P 6 O 18 )(H 2 O) 6 [16], Cs 3 (P 3 O 9 )(H 2 O) [17], Cs 4 (P 4 O 12 )(H 2 O) 4 [18], and Cs 8 (P 8 O 24 )(H 2 O) 8 [19].…”

Section: Introductionmentioning

confidence: 99%

The caesium phosphates Cs3(H1.5PO4)2(H2O)2, Cs3(H1.5PO4)2, Cs4P2O7(H2O)4, and CsPO3

Weil

Stöger

2020

Monatsh Chem

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The caesium phosphates Cs3(H1.5PO4)2(H2O)2 and Cs3(H1.5PO4)2 were obtained from aqueous solutions, and Cs4P2O7(H2O)4 and CsPO3 from solid state reactions, respectively. Cs3(H1.5PO4)2, Cs4P2O7(H2O)4, and CsPO3 were fully structurally characterized for the first time on basis of single-crystal X-ray diffraction data recorded at − 173 °C. Monoclinic Cs3(H1.5PO4)2 (Z = 2, C2/m) represents a new structure type and comprises hydrogen phosphate groups involved in the formation of a strong non-symmetrical hydrogen bond (accompanied by a disordered H atom over a twofold rotation axis) and a very strong symmetric hydrogen bond (with the H atom situated on an inversion centre) with symmetry-related neighbouring anions. Triclinic Cs4P2O7(H2O)4 (Z = 2, P$$\bar{1}$$ 1 ¯ ) crystallizes also in a new structure type and is represented by a diphosphate group with a P–O–P bridging angle of 128.5°. Although H atoms of the water molecules were not modelled, O···O distances point to hydrogen bonds of medium strengths in the crystal structure. CsPO3 is monoclinic (Z = 4, P21/n) and belongs to the family of catena-polyphosphates (MPO3)n with a repetition period of 2. It is isotypic with the room-temperature modification of RbPO3. The crystal structure of Cs3(H1.5PO4)2(H2O)2 was re-evaluated on the basis of single-crystal X-ray diffraction data at − 173 °C, revealing that two adjacent hydrogen phosphate anions are connected by a very strong and non-symmetrical hydrogen bond, in contrast to the previously described symmetrical bonding situation derived from room temperature X-ray diffraction data. In the four title crystal structures, coordination numbers of the caesium cations range from 7 to 12. Graphic abstract

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Crystal structure of the low-temperature forms of cesium and rubidium orthophosphates

Cited by 11 publications

References 3 publications

Rubidium-cation conductivity in Rb3−2x M x PO4 (M = Zn, Cd) solid solutions

Rubidium-cation conductivity in Rb3−2x M x PO4 (M = Zn, Cd) solid solutions

Рубидий-катионная проводимость твердых растворов Rb-=SUB=-3-2x-=/SUB=-Pb-=SUB=-x-=/SUB=-PO-=SUB=-4-=/SUB=-

The caesium phosphates Cs3(H1.5PO4)2(H2O)2, Cs3(H1.5PO4)2, Cs4P2O7(H2O)4, and CsPO3

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