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Title: The Na{sub 2}O-SrO-B{sub 2}O{sub 3} diagram in the B-rich part and the crystal structure of NaSrB{sub 5}O{sub 9}

Abstract

The subsolidus phase relations in the B-rich part of the ternary system, Na{sub 2}O-SrO-B{sub 2}O{sub 3}, are investigated by the powder X-ray diffraction method. Four ternary compounds: NaSrBO{sub 3}, NaSr{sub 4}B{sub 3}O{sub 9}, Na{sub 3}SrB{sub 5}O{sub 10} and NaSrB{sub 5}O{sub 9} were found in it, the two lasts are new. NaSrB{sub 5}O{sub 9} crystallizes in the monoclinic space group P2{sub 1} /c, with the lattice parameters a=6.4963(1) A, b=13.9703(2) A, c=8.0515(1) A, {beta}=106.900(1){sup o}. Na{sub 3}SrB{sub 5}O{sub 9} is also monoclinic, space group C2, a=7.290(1) A, b=13.442(2) A, c=9.792(1) A, {beta}=109.60(1). NaSrB{sub 5}O{sub 9} is isostructural with another pentaborate NaCaB{sub 5}O{sub 9}, and its structure was refined by Rietveld method based on the structural model of NaCaB{sub 5}O{sub 9}. The fundamental building units are [B{sub 5}O{sub 9}]{sup 3-} anionic groups, forming complex thick anionic sheets, extending parallel to the ac plane. The Na and Sr atoms are all eight-coordinated with O atoms, forming trigonal dodecahedra. The [NaO{sub 8}] polyhedra are distributed between the B-O sheets, while the [SrO{sub 8}] polyhedra located in the sheets and connect with each other by edges to form infinite chains along the c-axis. - Graphical abstract: The subsolidus phase relations in the B-rich part ofmore » Na{sub 2}O-SrO-B{sub 2}O{sub 3} system has been investigated by powder diffraction. At the same time, two new pentaborates, NaSrB{sub 5}O{sub 9} and Na{sub 3}SrB{sub 5}O{sub 10}, have been successfully synthesized by standard solid-state reaction, and the crystal structure of NaSrB{sub 5}O{sub 9} has been refined by Rietveld method based on the structural model of NaCaB{sub 5}O{sub 9}. It crystallizes in the monoclinic space group P2{sub 1} /c with lattice parameters: a=6.4963(1) A, b=13.9703(2) A, c=8.0515(1) A, {beta}=106.900(1){sup o}. The fundamental building units are [B{sub 5}O{sub 9}]{sup 3-} anionic groups, and structure is composed of separated [BO] sheets, with Na atoms located in between the sheets and Sr atoms surrounded by the [BO] groups.« less

Authors:
 [1];  [2];  [2];  [3];  [3];  [3];  [2]
  1. Key Laboratory of Weak-Light Nonlinear Photonics, Nankai University, Tianjin 300457, Ministry of Education (China), E-mail: lwu@nankai.edu.cn
  2. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100080 (China)
  3. Key Laboratory of Weak-Light Nonlinear Photonics, Nankai University, Tianjin 300457, Ministry of Education (China)
Publication Date:
OSTI Identifier:
21015798
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 4; Other Information: DOI: 10.1016/j.jssc.2007.02.014; PII: S0022-4596(07)00088-6; Copyright (c) 2007 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; BORON OXIDES; LATTICE PARAMETERS; MONOCLINIC LATTICES; SODIUM OXIDES; SPACE GROUPS; STRONTIUM OXIDES; STRUCTURAL MODELS; X-RAY DIFFRACTION

Citation Formats

Wu, L., Zhang, Y., Chen, X.L., Kong, Y.F., Sun, T.Q., Xu, J.J., and Xu, Y.P.. The Na{sub 2}O-SrO-B{sub 2}O{sub 3} diagram in the B-rich part and the crystal structure of NaSrB{sub 5}O{sub 9}. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2007.02.014.
Wu, L., Zhang, Y., Chen, X.L., Kong, Y.F., Sun, T.Q., Xu, J.J., & Xu, Y.P.. The Na{sub 2}O-SrO-B{sub 2}O{sub 3} diagram in the B-rich part and the crystal structure of NaSrB{sub 5}O{sub 9}. United States. doi:10.1016/j.jssc.2007.02.014.
Wu, L., Zhang, Y., Chen, X.L., Kong, Y.F., Sun, T.Q., Xu, J.J., and Xu, Y.P.. Sun . "The Na{sub 2}O-SrO-B{sub 2}O{sub 3} diagram in the B-rich part and the crystal structure of NaSrB{sub 5}O{sub 9}". United States. doi:10.1016/j.jssc.2007.02.014.
@article{osti_21015798,
title = {The Na{sub 2}O-SrO-B{sub 2}O{sub 3} diagram in the B-rich part and the crystal structure of NaSrB{sub 5}O{sub 9}},
author = {Wu, L. and Zhang, Y. and Chen, X.L. and Kong, Y.F. and Sun, T.Q. and Xu, J.J. and Xu, Y.P.},
abstractNote = {The subsolidus phase relations in the B-rich part of the ternary system, Na{sub 2}O-SrO-B{sub 2}O{sub 3}, are investigated by the powder X-ray diffraction method. Four ternary compounds: NaSrBO{sub 3}, NaSr{sub 4}B{sub 3}O{sub 9}, Na{sub 3}SrB{sub 5}O{sub 10} and NaSrB{sub 5}O{sub 9} were found in it, the two lasts are new. NaSrB{sub 5}O{sub 9} crystallizes in the monoclinic space group P2{sub 1} /c, with the lattice parameters a=6.4963(1) A, b=13.9703(2) A, c=8.0515(1) A, {beta}=106.900(1){sup o}. Na{sub 3}SrB{sub 5}O{sub 9} is also monoclinic, space group C2, a=7.290(1) A, b=13.442(2) A, c=9.792(1) A, {beta}=109.60(1). NaSrB{sub 5}O{sub 9} is isostructural with another pentaborate NaCaB{sub 5}O{sub 9}, and its structure was refined by Rietveld method based on the structural model of NaCaB{sub 5}O{sub 9}. The fundamental building units are [B{sub 5}O{sub 9}]{sup 3-} anionic groups, forming complex thick anionic sheets, extending parallel to the ac plane. The Na and Sr atoms are all eight-coordinated with O atoms, forming trigonal dodecahedra. The [NaO{sub 8}] polyhedra are distributed between the B-O sheets, while the [SrO{sub 8}] polyhedra located in the sheets and connect with each other by edges to form infinite chains along the c-axis. - Graphical abstract: The subsolidus phase relations in the B-rich part of Na{sub 2}O-SrO-B{sub 2}O{sub 3} system has been investigated by powder diffraction. At the same time, two new pentaborates, NaSrB{sub 5}O{sub 9} and Na{sub 3}SrB{sub 5}O{sub 10}, have been successfully synthesized by standard solid-state reaction, and the crystal structure of NaSrB{sub 5}O{sub 9} has been refined by Rietveld method based on the structural model of NaCaB{sub 5}O{sub 9}. It crystallizes in the monoclinic space group P2{sub 1} /c with lattice parameters: a=6.4963(1) A, b=13.9703(2) A, c=8.0515(1) A, {beta}=106.900(1){sup o}. The fundamental building units are [B{sub 5}O{sub 9}]{sup 3-} anionic groups, and structure is composed of separated [BO] sheets, with Na atoms located in between the sheets and Sr atoms surrounded by the [BO] groups.},
doi = {10.1016/j.jssc.2007.02.014},
journal = {Journal of Solid State Chemistry},
number = 4,
volume = 180,
place = {United States},
year = {Sun Apr 15 00:00:00 EDT 2007},
month = {Sun Apr 15 00:00:00 EDT 2007}
}
  • In order to further elucidate the local structure of vanadate glasses, x-ray photoelectron spectroscopy (XPS) and magnetization studies are reported on a series of SrO-vanadate and SrO-borovanadate glasses: [(SrO){sub x}(V{sub 2}O{sub 5}){sub 1-x}], [(SrO){sub 0.5-y}(B{sub 2}O{sub 3}){sub y}(V{sub 2}O{sub 5}){sub 0.5}], and [(SrO){sub 0.2}(B{sub 2}O{sub 3}){sub z}(V{sub 2}O{sub 5}){sub 0.8-z}]. From the analysis of the XPS spectra for the Sr 3p, B 1s, V 2p, and O 1s core levels, several distinct concentration regimes are identified in terms of various structural units being present. Metavanadate chainlike structures of SrV{sub 2}O{sub 6} and individual VO{sub 4} units occur in vanadate glassesmore » with low SrO content x{<=}0.2 with VO{sub 5} polyhedra also appearing at higher SrO content. The SrV{sub 2}O{sub 6} and VO{sub n} polyhedra predominate in the low B{sub 2}O{sub 3} containing SrO-borovanadate glasses as the B substitutes into the V sites of the various VO{sub n} polyhedra and only when the B{sub 2}O{sub 3} concentration exceeds the SrO content do BO{sub n} structures appear. This qualitative picture of three distinct structural groupings for the Sr-vanadate and Sr-borovanadate glasses is consistent with the proposed glass structure based on previous IR and extended x-ray absorption fine structure (EXAFS) studies on these types of vanadate glasses.« less
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  • ((n-C{sub 4}H{sub 9}){sub 4}N){sub 5}Na{sub 3}((1,5-COD)Ir{center dot}P{sub 2}W{sub 15}Nb{sub 3}O{sub 62}), 1, ((n-C{sub 4}H{sub 9}){sub 4}N){sub 5}Na{sub 3}((1,5-COD)Rh{center dot}P{sub 2}W{sub 15}Nb{sub 3}O{sub 62}), and ((n-C{sub 4}H{sub 9}){sub 4}N){sub 4.5}Na{sub 2.5}((C{sub 6}H{sub 6})Ru{center dot}P{sub 2}W{sub 15}Nb{sub 3}O{sub 62}) have been shown to catalyze the oxygenation of cyclohexene with molecular oxygen. The polyoxoanion-supported iridium (I) complex, 1, shows the highest activity of this group with a turnover frequency of 2.9 h{sup {minus}1} at 38{degree}C in CH{sub 2}Cl{sub 2} (540 total turnovers), which is 100-fold greater than its parent iridium compound, ((1,5-COD)IrCl){sub 2}. Additional experiments using H{sub 2}/O{sub 2} mixtures and H{sub 2}O{submore » 2} are also discussed. The apparent rate law for the oxidation of cyclohexene by O{sub 2} by 1 is -d(cyclohexene)/dt = k{sub 2} obsd {center dot} (1){sup 1}(cyclohexene){sup 1}P(O{sub 2}){sup 1{yields}0}. These compounds constitute the first examples of oxygenation catalysis using molecular oxygen and a polyoxoanion-supported transition-metal precatalyst.« less
  • The phase diagram for a portion of the ternary system Ce{sub 2}O{sub 3}-Na{sub 2}O-P{sub 2}O{sub 5} rich in P{sub 2}O{sub 5} has been worked out. The durability of two cerium phosphates, CeP{sub 5}O{sub 14} and CeP{sub 3}O{sub 9}, was investigated and the melting point of CeP{sub 5}O{sub 14} determined (1064{degree}C congruently). Phase diagrams of the two binary systems CeP{sub 3}O{sub 9}CeP{sub 5}O{sub 14} and NaCe(PO{sub 3}){sub 4}-CeP{sub 5}O{sub 14} are presented.
  • A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry withmore » space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610 {sup o}C). -- Graphical abstract: The staking of {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite uranyl molybdate ribbons in the Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] structure. Display Omitted Highlights: {yields} Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 2} a new compound with bidimensional crystal structure, characterized by infinite uranyl molybdate chains. {yields} Crystal structure similar to these of the compounds containing Na, K, Rb. {yields} Molybdenum atoms surrounded by five oxygen atoms to form an original and strongly distorted MoO{sub 5} environment. {yields} The chains arrangement illustrates the key role of the alkaline ionic radius, in the crystal structure distortion for Cs compound.« less