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Title: Hydrothermal synthesis and crystal structure of a new lithium copper bismuth oxide, LiCuBiO{sub 4}

Abstract

A new lithium copper bismuth oxide, LiCuBiO{sub 4} was prepared by hydrothermal reaction using NaBiO{sub 3}0.1*4H{sub 2}O. The crystal structural model of this compound was refined by using synchrotron X-ray powder diffraction data. This bismuthate has the LiCuSbO{sub 4} related structure with the orthorhombic cell (Space group: Pnma) of a=10.9096(9), b=5.8113(5) and c=5.0073(4) Å, and the final R-factors were R{sub wp}=4.84 and R{sub p}=3.58%. This compound is the first example of a lithium copper bismuthate containing Bi{sup 5+}. An antiferromagnetic ordering of Cu{sup 2+} moment was observed at 6 K. - Graphical abstract: In the crystal structure of LiCuBiO{sub 4} all metal atoms are coordinated octahedrally by six O atoms and LiO{sub 6} and CuO{sub 6} octahedra form the one-dimensional chains by edge-sharing along the b-axis. The LiO{sub 6} and CuO{sub 6} chains form the layer by face-sharing in the bc plane. The Bi atoms are placed in that interlayer and BiO{sub 6} octahedra are edge-sharing with LiO{sub 6} and CuO{sub 6} octahedra. - Highlights: • A new lithium copper bismuth oxide, LiCuBiO{sub 4} is prepared by hydrothermal reaction. • The crystal structure of LiCuBiO{sub 4} is closely related with that of LiCuSbO{sub 4}. • This new compound exhibits anmore » antiferromagnetic ordering of Cu{sup 2+} moment at 6 K.« less

Authors:
 [1];  [1];  [1];  [2];  [1]; ;  [3]; ; ;  [4]
  1. Center for Crystal Science and Technology, University of Yamanashi, Miyamae-cho 7-32, Kofu 400-8511 (Japan)
  2. (Japan)
  3. Laboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku Yokohama, Kanagawa 226-8503 (Japan)
  4. Department of Physical Science, Hiroshima University, 1-3-1 Kagamiyama, Higashihiroshima, Hiroshima 739-8526 (Japan)
Publication Date:
OSTI Identifier:
22658139
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 245; 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; 36 MATERIALS SCIENCE; BISMUTH OXIDES; COPPER IONS; COPPER OXIDES; HYDROTHERMAL SYNTHESIS; LITHIUM COMPOUNDS; ORTHORHOMBIC LATTICES; OXIDATION; SPACE GROUPS; STRUCTURAL MODELS; X-RAY DIFFRACTION

Citation Formats

Kumada, Nobuhiro, E-mail: kumada@yamanashi.ac.jp, Nakamura, Ayumi, Miura, Akira, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo 060-8628, Takei, Takahiro, Azuma, Masaki, Yamamoto, Hajime, Magome, Eisuke, Moriyoshi, Chikako, and Kuroiwa, Yoshihiro. Hydrothermal synthesis and crystal structure of a new lithium copper bismuth oxide, LiCuBiO{sub 4}. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2016.10.003.
Kumada, Nobuhiro, E-mail: kumada@yamanashi.ac.jp, Nakamura, Ayumi, Miura, Akira, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo 060-8628, Takei, Takahiro, Azuma, Masaki, Yamamoto, Hajime, Magome, Eisuke, Moriyoshi, Chikako, & Kuroiwa, Yoshihiro. Hydrothermal synthesis and crystal structure of a new lithium copper bismuth oxide, LiCuBiO{sub 4}. United States. doi:10.1016/J.JSSC.2016.10.003.
Kumada, Nobuhiro, E-mail: kumada@yamanashi.ac.jp, Nakamura, Ayumi, Miura, Akira, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo 060-8628, Takei, Takahiro, Azuma, Masaki, Yamamoto, Hajime, Magome, Eisuke, Moriyoshi, Chikako, and Kuroiwa, Yoshihiro. Sun . "Hydrothermal synthesis and crystal structure of a new lithium copper bismuth oxide, LiCuBiO{sub 4}". United States. doi:10.1016/J.JSSC.2016.10.003.
@article{osti_22658139,
title = {Hydrothermal synthesis and crystal structure of a new lithium copper bismuth oxide, LiCuBiO{sub 4}},
author = {Kumada, Nobuhiro, E-mail: kumada@yamanashi.ac.jp and Nakamura, Ayumi and Miura, Akira and Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo 060-8628 and Takei, Takahiro and Azuma, Masaki and Yamamoto, Hajime and Magome, Eisuke and Moriyoshi, Chikako and Kuroiwa, Yoshihiro},
abstractNote = {A new lithium copper bismuth oxide, LiCuBiO{sub 4} was prepared by hydrothermal reaction using NaBiO{sub 3}0.1*4H{sub 2}O. The crystal structural model of this compound was refined by using synchrotron X-ray powder diffraction data. This bismuthate has the LiCuSbO{sub 4} related structure with the orthorhombic cell (Space group: Pnma) of a=10.9096(9), b=5.8113(5) and c=5.0073(4) Å, and the final R-factors were R{sub wp}=4.84 and R{sub p}=3.58%. This compound is the first example of a lithium copper bismuthate containing Bi{sup 5+}. An antiferromagnetic ordering of Cu{sup 2+} moment was observed at 6 K. - Graphical abstract: In the crystal structure of LiCuBiO{sub 4} all metal atoms are coordinated octahedrally by six O atoms and LiO{sub 6} and CuO{sub 6} octahedra form the one-dimensional chains by edge-sharing along the b-axis. The LiO{sub 6} and CuO{sub 6} chains form the layer by face-sharing in the bc plane. The Bi atoms are placed in that interlayer and BiO{sub 6} octahedra are edge-sharing with LiO{sub 6} and CuO{sub 6} octahedra. - Highlights: • A new lithium copper bismuth oxide, LiCuBiO{sub 4} is prepared by hydrothermal reaction. • The crystal structure of LiCuBiO{sub 4} is closely related with that of LiCuSbO{sub 4}. • This new compound exhibits an antiferromagnetic ordering of Cu{sup 2+} moment at 6 K.},
doi = {10.1016/J.JSSC.2016.10.003},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 245,
place = {United States},
year = {Sun Jan 15 00:00:00 EST 2017},
month = {Sun Jan 15 00:00:00 EST 2017}
}
  • A new uranyl oxyfluoride, [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] has been synthesized by a hydrothermal reaction technique using (C{sub 2}H{sub 5}){sub 4}NBr, UO{sub 2}(OCOCH{sub 3}){sub 2}.2H{sub 2}O, and HF as reagents. The structure of [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] has been determined by a single-crystal X-ray diffraction technique. [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] crystallizes in the monoclinic space group P2{sub 1}/n (No. 14), with a=13.852(3)A, b=15.532(3)A, c=16.481(3)A, {beta}=98.88(3){sup o}, V=3503.4(12)A{sup 3}, and Z=4. [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] reveals amore » novel pseudo-two-dimensional crystal structure that is composed of UO{sub 2}F{sub 5}, UO{sub 3}F{sub 4}, and UO{sub 4}F{sub 3} pentagonal bipyramids. Each uranyl pentagonal bipyramid shares edges and corners through F atoms to form a six-membered ring. The rings are further interconnected to generate infinite strips running along the b-axis. [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] has been further characterized by elemental analysis, bond valence calculations, Infrared and Raman spectroscopy, and thermogravimetric analysis.« less
  • A lithium bismuth phosphate, Li{sub 2}Bi{sub 14.67}(PO{sub 4}){sub 6}O{sub 14}, has been synthesized for the first time by the solid-state method. The crystal structure was determined by single crystal X-ray diffraction at 150 K. Li{sub 2}Bi{sub 14.67}(PO{sub 4}){sub 6}O{sub 14} crystallizes in the monoclinic system C2/c (No. 15), with a = 30.8189(4) A, b = 5.2691(3) A, c = 24.5302(3) A, {beta} 122.84(2){sup o}, V = 3346.81(1) A{sup 3} and Z = 2. The structure along the b axis consists of layers of [Bi{sub 2}O{sub 2}] units as the basic building block. These are separated by isolated PO{sub 4} andmore » LiO{sub 4} tetrahedra. The oxygen co-ordination around two of the phosphorus atoms is disordered. Solid-state {sup 7}Li NMR studies confirm the presence of lithium in the structure. The material shows ionic conductivity of the order of 10{sup -5} S cm{sup -1} at 600 deg. C.« less
  • The first microporous solids incorporating two octahedrally coordinated transition elements, the phosphates (TMA)[sub 2](NH[sub 4])[sub 2][Fe[sub 2]Mo[sub 12]O[sub 30](H[sub 2]PO[sub 4])[sub 6](HOP[sub 4])[sub 2]][center dot]11H[sub 2]O (1) and (TMA)[sub 2]Na[sub 4][Fe[sub 3]Mo[sub 12]O[sub 30](H[sub x]PO[sub 4])[sub 8]][center dot]16H[sub 2]O (2) (TMA = (CH[sub 3])[sub 4]N[sup +]), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction and water absorption isotherms. Phosphate 1 is prepared in 94% yield from Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (NH[sub 4])[sub 2]HPO[sub 4], (TMA)OH, H[sub 3]PO[sub 4], and H[sub 2]O in a mole ratio of 5:1:1:2:7:16:150 at 200[degrees]C for 64 h, while 2 is synthesizedmore » in 62% yield by the reaction of Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (TMA)OH, H[sub 3]PO[sub 4] and H[sub 2]O in a mole ratio of 5:1:1:8:18:250 at 200[degrees]C for 3 days. Orange crystals of 1 are rhombohedral. Both structures are based on Fe[Mo[sub 6]O[sub 15](H[sub x]PO[sub 4])[sub 2]] units which are connected via their phosphate groups to additional Fe[sup 3+] ions to give three-dimensional frameworks. Both compounds display structures that can be rationalized on the basis of regions of hydrophobic and hydrophilic interactions. The interconnected voids and channels in the ferric molybdenum phosphate frameworks are filled with a mixture of charged-compensating cations and water of solvation. Reversible water absorption isotherms indicate that both compounds are microporous with internal void volumes of about 15 and 25 vol % for 1 and 2, respectively. 23 refs., 10 figs., 3 tabs.« less
  • The first organically templated layered structure of scandium sulfate, (H{sub 2}en)Sc{sub 2}(SO{sub 4}){sub 4}.(H{sub 2}O){sub 0.72}, (en=ethylenediamine) was synthesized by a hydrothermal method and characterized by single crystal X-ray diffraction. In the title compound, scandium ions are bridged by sulfate groups with a ratio of 1:2 into a 4{sub 3}{sup 6} layer structure. These layers are parallel packed and separated from each other by ethylenediammonium dications and water molecules. The title compound crystallizes in the monoclinic space group P2/c, with cell parameters a=8.5966(13)A, b=5.1068(8)A, c=18.847(3)A, {beta}=91.210(3){sup o}, V=827.2(2)A{sup 3} and Z=2. Refinement gave R{sub 1}[I>2{sigma}(I)]=0.0354 and wR{sub 2}[I>2{sigma}(I)]=0.0878. Thermogravimetric analysismore » indicates that this material is thermally stable to above 400 deg. C.« less