MOLYBDATES AND TUNGSTATES OF THE ALLUAUDITE FAMILY: CRYSTAL CHEMISTRY, COMPOSITION, AND IONIC MOBILITY

MOLYBDATES AND TUNGSTATES OF THE ALLUAUDITE FAMILY: CRYSTAL CHEMISTRY, COMPOSITION, AND IONIC MOBILITY Full article

Journal

Journal of Structural Chemistry
ISSN: 1573-8779 , E-ISSN: 0022-4766

Output data

Year: 2022, Volume: 63, Number: 7, Pages: 1101-1133 Pages count : 33 DOI: 10.1134/s0022476622070071

Tags

alluaudite family, crystal structure, molybdates, tungstates, non-stoichiometry, structure distortion, superstructure, bond-valence sum maps, NMR, ab initio calculations, ion mobility.

Authors

Solodovnikov S.F. ¹ , Gulyaeva O.A. ¹ , Savina A.A. ^2,3 , Yudin V.N. ¹ , Buzlukov A.L. ^4,5 , Solodovnikova Z.A. ¹ , Zolotova E.S. ¹ , Spiridonova T.S. ² , Khaikina E.G. ² , Stefanovich S.Yu. ⁶ , Medvedeva N.I. ⁵ , Baklanova Ya.V. ⁵ , Denisova T.A. ⁵

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2	Baikal Institute of Nature Management, BINM SB RAS, Ulan-Ude, Russia
3	Skolkovo Institute of Science and Technology, Moscow, Russia
4	M. N. Mikheev Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
5	Institute of Solid State Chemistry, Urals Branch, Russian Academy of Sciences, Ekaterinburg, Russia
6	Lomonosov Moscow State University, Moscow, Russia

The work reviews the structure, non-stoichiometry, and ionic mobility of molybdates, tungstates, and other compounds crystallizing in the structure type of alluaudite (Na, Ca)(Fe, Mn, Mg)3(PO4)3 with the general Moore's crystal chemical formula X(2)X(1)M(1)M(2)2(TO4)3, where X are large cations Na+, Ca2+, K+, Pb2+, etc., with the coordination number 8; M are octahedral cations, T = P, As, V, S, Mo, W. Using this formula and the corresponding site occupancies, possible limits of double molybdate and tungstate compositions of the alluaudite family are determined. Various types of distortions (superstructures) of alluaudite are considered; several groups of phases with different symmetries, numbers of anions in the unit cell, and vector relations with the unit cell of the original alluaudite structure are distinguished. It is shown that chains of partially defective positions X(2) and X(1) aligned along axis c play a key role in the transport of sodium cations in the alluaudite type phases. Phosphates and sulfates with alluaudite structure exhibit mainly 1D transport of sodium ions; however, calculations of the bond-valence sum maps, NMR data, and ab initio calculations show that 2D transport in the (100) plane is possible in complex molybdates and tungstates due to the transport of Na+ ions between X(2)–X(2) and X(1)–X(1) channels through the bridging site M(1). It is shown that the family of alluaudite-related (pseudo)orthorhombic triple molybdates Na10Cs4M5(MoO4)12 (M = Mn, Co) and Na25Cs8R5(MoO4)24 (R = Fe, Sc, In) also exhibits 2D diffusion of sodium ions via successive zigzag ion hoppings and that 3D transport may appear at elevated temperatures.

Solodovnikov S.F. , Gulyaeva O.A. , Savina A.A. , Yudin V.N. , Buzlukov A.L. , Solodovnikova Z.A. , Zolotova E.S. , Spiridonova T.S. , Khaikina E.G. , Stefanovich S.Y. , Medvedeva N.I. , Baklanova Y.V. , Denisova T.A.
MOLYBDATES AND TUNGSTATES OF THE ALLUAUDITE FAMILY: CRYSTAL CHEMISTRY, COMPOSITION, AND IONIC MOBILITY
Journal of Structural Chemistry. 2022. V.63. N7. P.1101-1133. DOI: 10.1134/s0022476622070071 WOS OpenAlex

Солодовников С.Ф. , Гуляева О.А. , Савина А.А. , Юдин В.Н. , Бузлуков А.Л. , Солодовникова З.А. , Золотова Е.С. , Спиридонова Т.С. , Хайкина Е.Г. , Стефанович С.Ю. , Медведева Н.И. , Бакланова Я.В. , Денисова Т.А.
Молибдаты и вольфраматы семейства аллюодита: кристаллохимия, состав и ионная подвижность
Журнал структурной химии. 2022. Т.63. №7. 96516 :1-35. DOI: 10.26902/jsc_id96516 OpenAlex

Submitted:	Mar 1, 2022
Accepted:	Mar 31, 2022

Web of science:	WOS:000832695800007
OpenAlex:	W4288456968

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Web of science	5
OpenAlex	6