New families of lithium-containing triple molybdates and the stabilizing role of lithium in their structure formation

Солодовников, С. Ф.; Хайкина, Е. Г.; Солодовникова, З. А.; Kadyrova, Yulia M.; Khal'baeva, K. M.; Золотова, Е. С.

doi:10.1134/s0012500807090029

Cited by 18 publications

(16 citation statements)

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“…Исследования фазовых равновесий в многокомпонентных системах позволяют получить данные по формированию новых фаз и играют большую роль в поиске новых соединений. Важное место среди большого класса неорганических соединений представляют молибдаты, перспективные как лазерные, сцинтилляционные, сегнетоактивные, нелинейно-оптические и люминесцентные материалы [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. Комплексные молибдаты, содержащие щелочные металлы, обладают ионопроводящими свойствами [1, 3 -7].…”

Section: Introductionunclassified

New molybdates in the Rb2MoO4–MI2MoO4–Zr(MoO4)2 (MI – Na, K) systems as promising ion-conducting materials

Dorzhieva¹,

Базаров²,

Bazarova³

2019

LOM

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Phase equilibria in the Rb 2 MoO 4-Na 2 MoO 4-Zr(MoO 4) 2 system were studied for the first time, quasi-binary cuts in the concentration triangle were determined, and triangulation was performed. The formation of a new phase of molybdate Rb 5 Na 1 / 3 Zr 5 / 3 (MoO 4) 6 was established in the system. New triple molybdates Rb 5 M I 1 / 3 Zr 5 / 3 (MoO 4) 6 (M I-Na,K) were synthesized by the solid-phase reaction in the temperature interval 400-510°C. The physicochemical characteristics of the prepared materials were carried out by Х-ray diffraction, differential scanning calorimetry, IR-spectroscopy, and scanning electron microscopy. It was established that synthesized molybdates crystallized in the trigonal space group R-3С, Z = 6. The crystal structure consists of MoO 4-tetrahedra and octahedrally coordinated MO 6-polyhedra. Rubidium cations are located in the cavities of the framework. Cation (sodium, potassium) and zirconium atoms are statistically distributed in M positions. The curves of differential-scanning calorimetry are characterized by endothermic effects corresponding to phase transitions and melting of the samples. The phase transitions found in the high-temperature region as a result of multiple measurements in the heating and cooling modes without melting the samples belong to the first-order phase transitions due to the temperature hysteresis. The IR spectra contain intense absorption bands associated with stretching vibrations of MoO bonds in MoO 4-tetrahedra. In the final annealing product, the particle size is 80-400 nm, as measured at electron micrographs. The identified compounds of the composition Rb 5 M I 1 / 3 Zr 5 / 3 (MoO 4) 6 (M I-Na, K) have a framework structure with channels appropriate for ion transport, which is a prerequisite for ion-conducting properties and use of the compounds as promising solid electrolytes.

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Section: Introductionunclassified

New molybdates in the Rb2MoO4–MI2MoO4–Zr(MoO4)2 (MI – Na, K) systems as promising ion-conducting materials

Dorzhieva¹,

Базаров²,

Bazarova³

2019

LOM

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“…The structures of molybdates Li 2 M 2 II (MoO 4 ) 3 (M = Mg, Mn, Co, Ni, Cu, Zn), [12][13][14][15][16], Li 3 M III (MoO 4 ) 3 (M = Al, Cr, Ga, Sc, In, Co), [17][18][19] and Li 2 M IV (MoO 4 ) 3 (M = Ti, Zr, Hf) closely related to the orthorhombic NaCo 2.31 (MoO 4 ) 3 [20], contain open frameworks formed by MoO 4 tetrahedra, NaO 6 and CoO 6 octahedra. Since then, both powder and single-crystal X-ray and neutron diffraction studies have been performed to establish the structure of others triple molybdates.…”

Section: Introductionmentioning

confidence: 99%

New molybdate Li2Co2−x Nix (MoO4)3 (0⩽x⩽2) materials with a lyonsite structure: X-ray diffraction and Raman spectroscopy studies

Bensaid¹,

Bouari²,

Benmokhtar

et al. 2013

Journal of Molecular Structure

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“…Double tungstates and molybdates containing alkaline elements and di-or trivalent metals are well known in the literature and are interesting due to their important properties and applications, such as laser hosts (Kaminskii, 2007), ferroelectrics and ferroelastics (Isupov, 2005a,b), phosphors (Shi et al, 2014), materials for Li(Na)-ion batteries (Mikhailova et al, 2010;Masquelier & Croguennec, 2013) and photocatalysts (Lu et al, 2015). In recent years, dozens of triple molybdates (three kinds of cations and MoO 4 anions) have been synthesized, a number of which are promising functional materials (see, for example, Solodovnikov et al, 2007;Sarapulova et al, 2014;Ines et al, 2015). A fruitful approach for synthesizing new triple molybdates is insertion of small cations like Li + into the structural cavities of double molybdates using aliovalent substitutions.…”

Section: Introductionmentioning

confidence: 99%

“…4M 2+ + 2Li + and 5Zn 2+ + & ! 2R 3+ + 4Li + (Solodovnikov et al, 2007). The first scheme is realized in A 3 LiZn 2 (MoO 4 ) 4 (A = Rb, Cs) and Cs 3 LiCo 2 (MoO 4 ) 4 (space group I43d, Z = 4), with disordered distributions of M 2+ and Li + on the Zn positions of the parent structure (Solodovnikova et al, 2006).…”

Section: Introductionmentioning

confidence: 99%

“…The first scheme is realized in A 3 LiZn 2 (MoO 4 ) 4 (A = Rb, Cs) and Cs 3 LiCo 2 (MoO 4 ) 4 (space group I43d, Z = 4), with disordered distributions of M 2+ and Li + on the Zn positions of the parent structure (Solodovnikova et al, 2006). The second scheme leads to the formation of triple molybdates A 3 Li 2 R(MoO 4 ) 4 (AR = TlAl, RbAl, RbGa, CsAl, CsGa, CsFe), with complete ordering of the tetrahedral R 3+ and Li + cations in the space group I42d (Z = 4) (Solodovnikov et al, 2007). The structures of the mentioned compounds are open three-dimensional frameworks of MoO 4 , LiO 4 and M(R)O 4 tetrahedra, with 12-coordinated A + ions located in the cuboctahedral cavities.…”

Section: Introductionmentioning

confidence: 99%

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Cs₃LiZn₂(WO₄)₄ and Rb₃Li₂Ga(MoO₄)₄: different filled derivatives of the cation-deficient Cs₆Zn₅(MoO₄)₈ structure

et al. 2017

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Two new compounds, namely cubic tricaesium lithium dizinc tetrakis(tetraoxotungstate), CsLiZn(WO), and tetragonal trirubidium dilithium gallium tetrakis(tetraoxomolybdate), RbLiGa(MoO), belong to the structural family of CsZn(MoO) (space group I-43d, Z = 4), with a partially incomplete (Zn□) position. In CsLiZn(WO), this position is fully statistically occupied by (ZnLi), and in RbLiGa(MoO), the 2Li + Ga atoms are completely ordered in two distinct sites of the space group I-42d (Z = 4). In the same way, the crystallographically equivalent A cations (A = Cs, Rb) in CsZn(MoO), CsLiZn(WO) and isostructural ALiZn(MoO) and CsLiCo(MoO) are divided into two sites in RbLiGa(MoO), as in other isostructural ALiR(MoO) compounds (AR = TlAl, RbAl, CsAl, CsGa, CsFe). In the title structures, the WO and (Zn,Li)O or LiO, GaO and MoO tetrahedra share corners to form open three-dimensional frameworks with the caesium or rubidium ions occupying cuboctahedral cavities. The tetrahedral frameworks are related to that of mayenite 12CaO·7AlO and isotypic compounds. Comparison of isostructural CsMZn(MoO) (M = Li, Na, Ag) and CsZn(MoO) shows a decrease of the cubic lattice parameter and an increase in thermal stability with the filling of the vacancies by Li in the Zn position of the CsZn(MoO) structure, while filling of the cation vacancies by larger Na or Ag ions plays a destabilizing role. The series ALiR(MoO) shows second harmonic generation effects compatible with that of β'-Gd(MoO) and may be considered as nonlinear optical materials with a modest nonlinearity.

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New families of lithium-containing triple molybdates and the stabilizing role of lithium in their structure formation

Cited by 18 publications

References 6 publications

New molybdates in the Rb2MoO4–MI2MoO4–Zr(MoO4)2 (MI – Na, K) systems as promising ion-conducting materials

New molybdates in the Rb2MoO4–MI2MoO4–Zr(MoO4)2 (MI – Na, K) systems as promising ion-conducting materials

New molybdate Li2Co2−x Nix (MoO4)3 (0⩽x⩽2) materials with a lyonsite structure: X-ray diffraction and Raman spectroscopy studies

Cs₃LiZn₂(WO₄)₄ and Rb₃Li₂Ga(MoO₄)₄: different filled derivatives of the cation-deficient Cs₆Zn₅(MoO₄)₈ structure

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New families of lithium-containing triple molybdates and the stabilizing role of lithium in their structure formation

Cited by 18 publications

References 6 publications

New molybdates in the Rb2MoO4–MI2MoO4–Zr(MoO4)2 (MI – Na, K) systems as promising ion-conducting materials

New molybdates in the Rb2MoO4–MI2MoO4–Zr(MoO4)2 (MI – Na, K) systems as promising ion-conducting materials

New molybdate Li2Co2−x Nix (MoO4)3 (0⩽x⩽2) materials with a lyonsite structure: X-ray diffraction and Raman spectroscopy studies

Cs3LiZn2(WO4)4 and Rb3Li2Ga(MoO4)4: different filled derivatives of the cation-deficient Cs6Zn5(MoO4)8 structure

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Cs₃LiZn₂(WO₄)₄ and Rb₃Li₂Ga(MoO₄)₄: different filled derivatives of the cation-deficient Cs₆Zn₅(MoO₄)₈ structure