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Title: New series of triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) with framework structures and mobile silver ion sublattices

Abstract

Triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg{sub 3}In(MoO{sub 4}){sub 5} type were synthesized and single crystals of AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) were grown. In their structures, the MoO{sub 4} tetrahedra, pairs and trimers of edge-shared (Mg, R)O{sub 6} octahedra are connected by common vertices to form a 3D framework. Large framework cavities involve Ag{sup +} cations disordered on three nearby positions with CN=3+1 or 4+1. Alternating (Mg, R)O{sub 6} octahedra and MoO{sub 4} tetrahedra in the framework form quadrangular windows penetrable for Ag{sup +} at elevated temperatures. Above 653–673 K, the newly obtained molybdates demonstrate abrupt reduction of the activation energy to 0.4–0.6 eV. At 773 K, AgMg{sub 3}Al(MoO{sub 4}){sub 5} shows electric conductivity 2.5·10{sup −2} S/cm and E{sub a}=0.39 eV compatible with characteristics of the best ionic conductors of the NASICON type. - Graphical abstract: Triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg{sub 3}In(MoO{sub 4}){sub 5} type were synthesized, AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) were structurally characterized, ion-conductive properties of AgMg{sub 3}Al(MoO{sub 4}){sub 5} were measured. Display Omitted - Highlights: • Triple molybdates AgA{sub 3}R(MoO{submore » 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg{sub 3}In(MoO{sub 4}){sub 5} type were synthesized. • Single crystals of AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) were grown and their crystal structures were determined. • Disordering Ag{sup +} ions and penetrable framework structures of AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) suggest 2D-character of silver-ion mobility. • Measured ion-conductive properties of AgMg{sub 3}Al(MoO{sub 4}){sub 5} are compatible with characteristics of the best ionic conductors of the NASICON type.« less

Authors:
 [1];  [2];  [3];  [2];  [3]; ;  [4];  [1];  [2];  [1];  [2]
  1. Baikal Institute of Nature Management, Siberian Branch, Russian Academy of Sciences, Sakh’yanova St. 6, Ulan-Ude 670047, Buryat Republic (Russian Federation)
  2. (Russian Federation)
  3. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Acad. Lavrentiev Ave. 3, Novosibirsk 630090 (Russian Federation)
  4. Lomonosov Moscow State University, Leninskie Gory 1, Moscow 119991 (Russian Federation)
Publication Date:
OSTI Identifier:
22584110
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 238; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACTIVATION ENERGY; CARBON NITRIDES; CATIONS; CRYSTAL STRUCTURE; CYANIDES; ELECTRIC CONDUCTORS; ION MOBILITY; IONIC CONDUCTIVITY; MOLYBDATES; MONOCRYSTALS; SILVER; SILVER IONS; SYNTHESIS

Citation Formats

Kotova, Irina Yu., Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic, Solodovnikov, Sergey F., Novosibirsk State University, Pirogov St. 2, Novosibirsk 630090, Solodovnikova, Zoya A., Belov, Dmitry A., Stefanovich, Sergey Yu., Savina, Aleksandra A., E-mail: alex551112@mail.ru, Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic, Khaikina, Elena G., and Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic. New series of triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) with framework structures and mobile silver ion sublattices. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.03.003.
Kotova, Irina Yu., Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic, Solodovnikov, Sergey F., Novosibirsk State University, Pirogov St. 2, Novosibirsk 630090, Solodovnikova, Zoya A., Belov, Dmitry A., Stefanovich, Sergey Yu., Savina, Aleksandra A., E-mail: alex551112@mail.ru, Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic, Khaikina, Elena G., & Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic. New series of triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) with framework structures and mobile silver ion sublattices. United States. doi:10.1016/J.JSSC.2016.03.003.
Kotova, Irina Yu., Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic, Solodovnikov, Sergey F., Novosibirsk State University, Pirogov St. 2, Novosibirsk 630090, Solodovnikova, Zoya A., Belov, Dmitry A., Stefanovich, Sergey Yu., Savina, Aleksandra A., E-mail: alex551112@mail.ru, Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic, Khaikina, Elena G., and Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic. 2016. "New series of triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) with framework structures and mobile silver ion sublattices". United States. doi:10.1016/J.JSSC.2016.03.003.
@article{osti_22584110,
title = {New series of triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) with framework structures and mobile silver ion sublattices},
author = {Kotova, Irina Yu. and Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic and Solodovnikov, Sergey F. and Novosibirsk State University, Pirogov St. 2, Novosibirsk 630090 and Solodovnikova, Zoya A. and Belov, Dmitry A. and Stefanovich, Sergey Yu. and Savina, Aleksandra A., E-mail: alex551112@mail.ru and Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic and Khaikina, Elena G. and Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic},
abstractNote = {Triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg{sub 3}In(MoO{sub 4}){sub 5} type were synthesized and single crystals of AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) were grown. In their structures, the MoO{sub 4} tetrahedra, pairs and trimers of edge-shared (Mg, R)O{sub 6} octahedra are connected by common vertices to form a 3D framework. Large framework cavities involve Ag{sup +} cations disordered on three nearby positions with CN=3+1 or 4+1. Alternating (Mg, R)O{sub 6} octahedra and MoO{sub 4} tetrahedra in the framework form quadrangular windows penetrable for Ag{sup +} at elevated temperatures. Above 653–673 K, the newly obtained molybdates demonstrate abrupt reduction of the activation energy to 0.4–0.6 eV. At 773 K, AgMg{sub 3}Al(MoO{sub 4}){sub 5} shows electric conductivity 2.5·10{sup −2} S/cm and E{sub a}=0.39 eV compatible with characteristics of the best ionic conductors of the NASICON type. - Graphical abstract: Triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg{sub 3}In(MoO{sub 4}){sub 5} type were synthesized, AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) were structurally characterized, ion-conductive properties of AgMg{sub 3}Al(MoO{sub 4}){sub 5} were measured. Display Omitted - Highlights: • Triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg{sub 3}In(MoO{sub 4}){sub 5} type were synthesized. • Single crystals of AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) were grown and their crystal structures were determined. • Disordering Ag{sup +} ions and penetrable framework structures of AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) suggest 2D-character of silver-ion mobility. • Measured ion-conductive properties of AgMg{sub 3}Al(MoO{sub 4}){sub 5} are compatible with characteristics of the best ionic conductors of the NASICON type.},
doi = {10.1016/J.JSSC.2016.03.003},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 238,
place = {United States},
year = 2016,
month = 6
}
  • Subsolidus phase relations in the systems Li{sub 2}MoO{sub 4}-K{sub 2}MoO{sub 4}-Ln{sub 2}(MoO{sub 4}){sub 3} (Ln=La, Nd, Dy, Er) were determined. Formation of LiKLn{sub 2}(MoO{sub 4}){sub 4} was confirmed in the systems with Ln=Nd, Dy, Er at the LiLn(MoO{sub 4}){sub 2}-KLn(MoO{sub 4}){sub 2} joins. No intermediate phases of other compositions were found. No triple molybdates exist in the system Li{sub 2}MoO{sub 4}-K{sub 2}MoO{sub 4}-La{sub 2}(MoO{sub 4}){sub 3}. The join LiLa(MoO{sub 4}){sub 2}-KLa(MoO{sub 4}){sub 2} is characterized by formation of solid solutions. Triple molybdates LiKLn{sub 2}(MoO{sub 4}){sub 4} for Ln=Nd-Lu, Y were synthesized by solid state reactions (single phases with ytterbium andmore » lutetium were not prepared). Crystal and thermal data for these molybdates were determined. Compounds LiKLn{sub 2}(MoO{sub 4}){sub 4} form isostructural series and crystallized in the monoclinic system with the unit cell parameters a=5.315-5.145A, b=12.857-12.437A, c=19.470-19.349A, {beta}=92.26-92.98{sup o}. When heated, the compounds decompose in solid state to give corresponding double molybdates. The dome-shaped curve of the decomposition temperatures of LiMLn{sub 2}(MoO{sub 4}){sub 4} has the maximum in the Gd-Tb-Dy region. While studying the system Li{sub 2}MoO{sub 4}-K{sub 2}MoO{sub 4}-Dy{sub 2}(MoO{sub 4}){sub 3} we revealed a new low-temperature modification of KDy(MoO{sub 4}){sub 2} with the triclinic structure of {alpha}-KEu(MoO{sub 4}){sub 2} (a=11.177(2)A, b=5.249(1)A, c=6.859(1)A, {alpha}=112.33(2){sup o}, {beta}=111.48(1){sup o}, {gamma}=91.30(2){sup o}, space group P1-bar , Z=2)« less
  • In this study, the magnetic properties and magnetic structures of the R 5Ni 2In 4 and the microfibrous R 11Ni 4In 9 compounds with R = Tb and Ho have been examined using magnetization, heat capacity, and neutron diffraction data. Rare earth atoms occupy three and five symmetrically inequivalent rare earth sites in R 5Ni 2In 4 and R 11Ni 4In 9 compounds, respectively. As a result of the intra- and inter-magnetic sublattice interactions, the magnetic exchange interactions are different for various rare earth sites; this leads to a cascade of magnetic transitions with a strong hierarchy in the temperaturemore » dependence of the magnetic orderings.« less
  • Three new compounds AgLnMo{sub 2}O{sub 8}(Ln=Eu,Gd,Tb) crystallize with a tetragonal scheelite-type structure characterized by MoO{sub 4} tetrahedra. The IR spectra show three absorption bands, which correspond respectively to the v{sub 1}, v{sub 2}, and v{sub 3} modes of the tetrahedral-MoO{sub 4}{sup 2-} groups. The emission of AgGdMo{sub 2}O{sub 8} shows the band of the MoO{sub 4}{sup 2-} groups around 600 nm wavelength with very weak intensity. Both AgEuMo{sub 2}O{sub 8} and AgTbMo{sub 2}O{sub 8} emit intensely, and the concentration quenchings of both Eu{sup 3+} and Tb{sup 3+} luminescences are very weak. For all compounds, Ag{sup +} luminescence is not observed.
  • The composition and structure of compounds formed in MMoO/sub 4/ - UO/sub 2/MoO/sub 4/ - H/sub 2/O system where M=Zn, Mg, Ca, or Sr were investigated. Structure were determined by the heavy-atom method, and the coordinates of the U and Mo atoms were determined from an analysis of the 3-dimensional Patterson function. The compounds have a layer-type structure; and in the system in which M=Zn, the uranyl groups were almost symmetrical and linear but differ crystallographically in that those within a layer are bound to 5 MoO/sub 4/ tetrahedrons and those located between the layers are bound to 4 MoO/submore » 4/ groups and one H/sub 2/O molecule. H/sub 2/O molecules not appearing within the skeleton of the compound are found in zigzag channels in the structure giving rise to a zeolite structure. The compound containing Mg had a more clearly expressed layered nature, but there were no uranyl groups located between the layers. It was noted that a decrease in the metal:U ratio results in an increase in the number of UO/sub 2//sup 2 +/ groups between the layers. Attempts to synthesize analogs of the natural minerals, calcurmolite and kunzinite, by the synthetic procedure were not successful. (BLM)« less
  • A three-dimensional triply interpenetrated mixed metal-organic framework, Zn{sub 2}(BBA){sub 2}(CuPyen) {center_dot} G{sub x} (M'MOF-20; BBA = biphenyl-4,4'-dicarboxylate; G = guest solvent molecules), of primitive cubic net was obtained through the solvothermal reaction of Zn(NO{sub 3}){sub 2}, biphenyl-4,4'-dicarboxylic acid, and the salen precursor Cu(PyenH{sub 2})(NO{sub 3}){sub 2} by a metallo-ligand approach. The triple framework interpenetration has stabilized the framework in which the activated M'MOF-20a displays type-I N{sub 2} gas sorption behavior with a Langmuir surface area of 62 m{sup 2} g{sup -1}. The narrow pores of about 3.9 {angstrom} and the open metal sites on the pore surfaces within M'MOF-20a collaborativelymore » induce its highly selective C{sub 2}H{sub 2}/CH{sub 4} and CO{sub 2}/CH{sub 4} gas separation at ambient temperature.« less