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Title: Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}

Abstract

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, and its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity .more » Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.« less

Authors:
;  [1];  [2];  [3];  [3];  [4]; ;  [1]
  1. Université de Tunis El Manar, Laboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Campus Universitaire, 2092 Manar II, Tunis (Tunisia)
  2. Université Grenoble Alpes, Laboratoire d’Electrochimie et de Physicochimie des Matériaux et des Interfaces LEPMI, F-38000 Grenoble (France)
  3. Bragg Institute, Australian Nuclear Science and Technology Organisation (ANSTO), New Illawarra Road, Lucas Heights, New South Wales 2234 (Australia)
  4. (Australia)
Publication Date:
OSTI Identifier:
22584138
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 239; 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; ARSENATES; CATIONS; CERAMICS; COBALT OXIDES; ELECTRON SCANNING; IONIC CONDUCTIVITY; MHZ RANGE; MICROSTRUCTURE; MOLECULAR DYNAMICS METHOD; MONOCLINIC LATTICES; MONOCRYSTALS; SCANNING ELECTRON MICROSCOPY; SODIUM; SOLIDS; SPACE GROUPS; SPECTROSCOPY; SYNTHESIS; X RADIATION; X-RAY DIFFRACTION

Citation Formats

Ben Smida, Youssef, Marzouki, Riadh, Georges, Samuel, Kutteh, Ramzi, Avdeev, Maxim, School of Chemistry, University of Sydney, Sydney, New South Wales 2006, Guesmi, Abderrahmen, and Zid, Mohamed Faouzi. Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.04.005.
Ben Smida, Youssef, Marzouki, Riadh, Georges, Samuel, Kutteh, Ramzi, Avdeev, Maxim, School of Chemistry, University of Sydney, Sydney, New South Wales 2006, Guesmi, Abderrahmen, & Zid, Mohamed Faouzi. Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}. United States. doi:10.1016/J.JSSC.2016.04.005.
Ben Smida, Youssef, Marzouki, Riadh, Georges, Samuel, Kutteh, Ramzi, Avdeev, Maxim, School of Chemistry, University of Sydney, Sydney, New South Wales 2006, Guesmi, Abderrahmen, and Zid, Mohamed Faouzi. 2016. "Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}". United States. doi:10.1016/J.JSSC.2016.04.005.
@article{osti_22584138,
title = {Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}},
author = {Ben Smida, Youssef and Marzouki, Riadh and Georges, Samuel and Kutteh, Ramzi and Avdeev, Maxim and School of Chemistry, University of Sydney, Sydney, New South Wales 2006 and Guesmi, Abderrahmen and Zid, Mohamed Faouzi},
abstractNote = {A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, and its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.},
doi = {10.1016/J.JSSC.2016.04.005},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 239,
place = {United States},
year = 2016,
month = 7
}
  • A new sodium arsenate with layer structure has been synthesized and its crystal structure solved and refined by single-crystal X-ray diffraction. The crystal is trigonal, space group P3-bar m1, a=11.199(3)A, c=5.411(2)A, V=587.80(3)A{sup 3}, Z=1; the refinement converged to R=0.0282 and wR=0.0751 for 590 reflections with (I)>2sigma(I). The structural model gives the formula Na{sub 7}As{sub 11}O{sub 32}, which would be non-neutral; besides, the structural model is not validated by the charge distribution (CD) analysis, which gives an unsatisfactory agreement on the computed charges of the cations. The CD analysis suggest incomplete (5/6) occupation of the O5 site, which leads to themore » deficiency of an oxygen atom per unit cell and to formula Na{sub 7}As{sub 11}O{sub 31}: this new structural model corresponds to a neutral compound, is validated by the CD analysis, and results in better displacement parameters for O5 than its non neutral counterpart. The (001) anionic layers are built up from corner and edge sharing of As1 and As2 distorted octahedra and As3 distorted tetrahedra, the sodium cations playing the role of interlayer cations. The effects of the oxygen deficiency on the crystal structure are discussed.« less
  • The title compound sodium dicobalt triarsenate NaCo{sub 2}As{sub 3}O{sub 10} has been synthesized by solid state reaction. Crystal structure and electrical properties were studied by X-ray diffraction and complex impedance spectroscopy, respectively. The obtained structural model is supported by charge-distribution (CHARDI) analysis and bond-valence-sum (BVS) validations tools. The structure (triclinic, P−1, a=6.800 (8) Å, b=7.816 (9) Å, c=8.718 (3) Å, α=108.03 (2)°, β=108.48 (3)°, γ=100.11 (2)°) can be described as a three-dimensional framework resulted from corner-connection between cobalt metallic chains running along [−110] and As{sub 3}O{sub 10} groups; the negative charge is balanced by Na{sup +} ions which house themore » two tunnels parallel to a and b axes. Ball milling was used as mechanical means to reduce the particles sizes of the synthesized powder. At the optimal sintering temperature of 650 °C, 85% of the relative density was obtained. The conductivity measurements show that NaCo{sub 2}As{sub 3}O{sub 10} is a cationic conductor with an activation energy of 0.48 eV and a conductivity of σ=1.2×10{sup −5} S cm{sup −1} at 310 °C. The BVS model is extended to simulate the ionic migration pathways of alkali cations in the anionic framework. - Graphical abstract: 1D pathways link Na atoms along the a-axis with bond valence mismatch |ΔV(Na)|=0.64 v.u. - Highlights: • A new single crystal NaCo{sub 2}As{sub 3}O{sub 10} was grown by solid state reaction and its structure determined by single-crystal X-ray diffraction. • The purity of the powder sample was verified by Rietveld refinement. • The CIS measurements were optimized and the obtained spectra were fitted by electrical equivalent circuits. • The conduction pathways for Na{sup +} cations are simulated by means of the bond valence sum model.« less
  • A sodium gadolinium phosphate crystal, Na{sub 3}GdP{sub 2}O{sub 8}, has been synthesized by a high-temperature solution reaction, and it exhibits a new structural family of the alkali-metal-rare-earth phosphate system. Although many compounds with formula M{sub 3}LnP{sub 2}O{sub 8} have been reported, but they were shown to be orthorhombic [R. Salmon, C. Parent, M. Vlasse, G. LeFlem, Mater. Res. Bull. 13 (1978) 439] rather than monoclinic as shown in this paper. Single-crystal X-ray diffraction analysis shows the structure to be monoclinic with space group C2/c and the cell parameters: a=27.55 (25), b=5.312 (4), c=13.935(11) A, {beta}=91.30(1){sup o}, and V=2038.80 A{sup 3},more » Z=4. Its structure features a three-dimensional GdP{sub 2}O{sub 8}{sup 3-} anionic framework with two different types of interesting tunnels at where Na atoms are located by different manners. The framework is constructed by Gd polyhedra and isolated PO{sub 4} tetrahedra. It is different from the structure of K{sub 3}NdP{sub 2}O{sub 8} [R. Salmon, C. Parent, M. Vlasse, G. LeFlem, Mater. Res. Bull. 13 (1978) 439] with space group P2{sub 1}/m that shows only one type of tunnel. The emission spectrum and the absorption spectrum of the compound have been investigated. Additionally, the calculations of band structure, density of states, dielectric constants, and refractive indexes have been also performed with the density functional theory method. The obtained results tend to support the experimental data. - Graphical abstract: Projection of the structure of Na{sub 3}GdP{sub 2}O{sub 8} with a unit cell edge along the b-axis. The Na-O bonds are omitted for clarity.« less
  • A 3:2 salt (BPDT-TTF)/sub 3/(InI/sub 4/)/sub 2/ was obtained by electrocrystallization and its structure was determined by single-crystal x-ray diffraction (triclinic, space group /bar P/1, a = 7.403 (2) /angstrom/, b = 9.170 (2) /angstrom/, c = 25.883 (7) /angstrom/, /alpha/ = 89.29 (2)/degree/, /beta/ = 96.34 (2)/degree/, /gamma/ = 92.83 (2)/degree/, V = 1774.2 (8) /angstrom//sup 3/, Z = 1). Analysis of the C/double bond/C and C/emdash/S bond lengths in the PT (i.e., BPDT-TTF) molecules suggest that this salt consists of donor molecules PT in two different oxidation states (i.e., BPDT-TTF/sup +/ and BPDT-TTF/sup 0.5+/). This oxidation assignment ismore » consistent with the authors ESR measurements and band electronic structure calculations. The (BPDT-TTF)/sub 3/(InI/sub 4/)/sub 2/ salt is a semiconductor at room temperature and below, which can be rationalized in terms of electron localization in the stacks of BPDT-TTF/sup +/ cations and the electronic instability associated with the well-nested Fermi surface for the layers of (BPDT-TTF)/sub 2//sup +/ dimers. Preliminary x-ray diffraction experiments indicate that (BPDT-TTF)/sub 3/(T1I/sub 4/)/sub 2/ is isostructural with (BPDT-TTF)/sub 3/(InI/sub 4/)/sub 2/. 28 refs., 7 figs., 3 tabs.« less
  • A novel sodium lead pentaborate, NaPbB{sub 5}O{sub 9}, has been successfully synthesized by standard solid-state reaction. The single-crystal X-ray structural analysis showed that NaPbB{sub 5}O{sub 9} crystallizes in the monoclinic space group P2{sub 1}/c with a=6.5324(10) A, b=13.0234(2) A, c=8.5838(10) A, {beta}=104.971(10){sup o}, and Z=4. The crystal structure is composed of double ring [B{sub 5}O{sub 9}]{sup 3-} units, [PbO{sub 7}] and [NaO{sub 7}] polyhedra. [B{sub 5}O{sub 9}]{sup 3-} groups connect with each other forming two-dimensional infinite {sub {infinity}}[B{sub 5}O{sub 9}]{sup 3-} layers, while [PbO{sub 7}] and [NaO{sub 7}] polyhedra are located between the layers. [PbO{sub 7}] polyhedra linked together viamore » corner-sharing O atom forming novel infinite {sub {infinity}}[PbO{sub 6}] chains along the c axis. The thermal behavior, IR spectrum and the optical diffuse reflectance spectrum of NaPbB{sub 5}O{sub 9} were reported. -- Graphical abstract: A new phase, NaPbB{sub 5}O{sub 9}, has been discovered in the ternary M{sub 2}O-PbO-B{sub 2}O{sub 3} (M=alkali-metal) system. The crystal structure consists of a novel infinite {sub {infinity}}[PbO{sub 6}] chains. Display Omitted Research highlights: NaPbB{sub 5}O{sub 9} is the first borate discovered in the ternary M{sub 2}O-PbO-B{sub 2}O{sub 3} (M=alkali-metal) system. NaPbB{sub 5}O{sub 9} crystal structure includes a two-dimensional infinite {sub {infinity}}[B{sub 5}O{sub 9}]{sup 3-} layers and a novel one-dimensional infinite {sub {infinity}}[PbO{sub 6}] chains. [PbO{sub 7}] polyhedron has a highly asymmetric bonding configuration.« less