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Title: Synthesis, structural characterization and properties of SrAl{sub 4−x}Ge{sub x}, BaAl{sub 4−x}Ge{sub x}, and EuAl{sub 4−x}Ge{sub x} (x≈0.3–0.4)—Rare examples of electron-rich phases with the BaAl{sub 4} structure type

Abstract

Three solid solutions with the general formula AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba; 0.32(1)≤x≤0.41(1)) have been synthesized via the aluminum self-flux method, and their crystal structures have been established from powder and single-crystal X-ray diffraction. They are isotypic and crystallize with the well-known BaAl{sub 4} structure type, adopted by the three AEAl{sub 4} end members. In all structures, Ge substitutes Al only at the 4e Wyckoff site. Results from X-rays photoelectron spectroscopy on EuAl{sub 4−x}Ge{sub x} and EuAl{sub 4} indicate that the interactions between the Eu{sup 2+} cations and the polyanionic framework are enhanced in the Ge-doped structure, despite the slightly elevated Fermi level. Magnetic susceptibility measurements confirm the local moment magnetism, expected for the [Xe]4f{sup 7} electronic configuration of Eu{sup 2+} and suggest strong ferromagnetic interactions at cryogenic temperatures. Resistivity data from single-crystalline samples show differences between the title compounds, implying different bonding characteristics despite the close Debye temperatures. A brief discussion on the observed electron count and homogeneity ranges for AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba) is also presented. - Graphical abstract: AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba; 0.32(1)≤x≤0.41(1)), three “electron-rich” phases with BaAl{sub 4} structure type have been synthesized and characterized. Display Omitted - Highlights: • Threemore » BaAl{sub 4}-type ternary aluminum germanides have been synthesized with Eu, Sr and Ba. • Eu, Sr and Ba cations have no apparent influence on the solubility of Ge. • The Ge atoms substitute Al on one of two framework sites, thereby strengthening the interactions between the cations and the polyanionic framework.« less

Authors:
;
Publication Date:
OSTI Identifier:
22274065
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 205; Other Information: Copyright (c) 2013 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; ALUMINIUM; BONDING; CATIONS; CRYSTAL STRUCTURE; DEBYE TEMPERATURE; ELECTRONIC STRUCTURE; EUROPIUM; EUROPIUM IONS; FERMI LEVEL; GERMANIDES; INTERACTIONS; INTERMETALLIC COMPOUNDS; MAGNETIC SUSCEPTIBILITY; MONOCRYSTALS; SOLID SOLUTIONS; SYNTHESIS; X-RAY DIFFRACTION; X-RAY PHOTOELECTRON SPECTROSCOPY

Citation Formats

Zhang, Jiliang, and Bobev, Svilen, E-mail: bobev@udel.edu. Synthesis, structural characterization and properties of SrAl{sub 4−x}Ge{sub x}, BaAl{sub 4−x}Ge{sub x}, and EuAl{sub 4−x}Ge{sub x} (x≈0.3–0.4)—Rare examples of electron-rich phases with the BaAl{sub 4} structure type. United States: N. p., 2013. Web. doi:10.1016/J.JSSC.2013.06.023.
Zhang, Jiliang, & Bobev, Svilen, E-mail: bobev@udel.edu. Synthesis, structural characterization and properties of SrAl{sub 4−x}Ge{sub x}, BaAl{sub 4−x}Ge{sub x}, and EuAl{sub 4−x}Ge{sub x} (x≈0.3–0.4)—Rare examples of electron-rich phases with the BaAl{sub 4} structure type. United States. doi:10.1016/J.JSSC.2013.06.023.
Zhang, Jiliang, and Bobev, Svilen, E-mail: bobev@udel.edu. Sun . "Synthesis, structural characterization and properties of SrAl{sub 4−x}Ge{sub x}, BaAl{sub 4−x}Ge{sub x}, and EuAl{sub 4−x}Ge{sub x} (x≈0.3–0.4)—Rare examples of electron-rich phases with the BaAl{sub 4} structure type". United States. doi:10.1016/J.JSSC.2013.06.023.
@article{osti_22274065,
title = {Synthesis, structural characterization and properties of SrAl{sub 4−x}Ge{sub x}, BaAl{sub 4−x}Ge{sub x}, and EuAl{sub 4−x}Ge{sub x} (x≈0.3–0.4)—Rare examples of electron-rich phases with the BaAl{sub 4} structure type},
author = {Zhang, Jiliang and Bobev, Svilen, E-mail: bobev@udel.edu},
abstractNote = {Three solid solutions with the general formula AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba; 0.32(1)≤x≤0.41(1)) have been synthesized via the aluminum self-flux method, and their crystal structures have been established from powder and single-crystal X-ray diffraction. They are isotypic and crystallize with the well-known BaAl{sub 4} structure type, adopted by the three AEAl{sub 4} end members. In all structures, Ge substitutes Al only at the 4e Wyckoff site. Results from X-rays photoelectron spectroscopy on EuAl{sub 4−x}Ge{sub x} and EuAl{sub 4} indicate that the interactions between the Eu{sup 2+} cations and the polyanionic framework are enhanced in the Ge-doped structure, despite the slightly elevated Fermi level. Magnetic susceptibility measurements confirm the local moment magnetism, expected for the [Xe]4f{sup 7} electronic configuration of Eu{sup 2+} and suggest strong ferromagnetic interactions at cryogenic temperatures. Resistivity data from single-crystalline samples show differences between the title compounds, implying different bonding characteristics despite the close Debye temperatures. A brief discussion on the observed electron count and homogeneity ranges for AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba) is also presented. - Graphical abstract: AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba; 0.32(1)≤x≤0.41(1)), three “electron-rich” phases with BaAl{sub 4} structure type have been synthesized and characterized. Display Omitted - Highlights: • Three BaAl{sub 4}-type ternary aluminum germanides have been synthesized with Eu, Sr and Ba. • Eu, Sr and Ba cations have no apparent influence on the solubility of Ge. • The Ge atoms substitute Al on one of two framework sites, thereby strengthening the interactions between the cations and the polyanionic framework.},
doi = {10.1016/J.JSSC.2013.06.023},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 205,
place = {United States},
year = {Sun Sep 15 00:00:00 EDT 2013},
month = {Sun Sep 15 00:00:00 EDT 2013}
}
  • Solid solutions SrAu{sub x}In{sub 4-x} (0.5{<=}x{<=}1.2) and SrAu{sub x}Sn{sub 4-x} (1.3{<=}x{<=}2.2) have been prepared at 700 deg. C and their structures characterized by powder and single-crystal X-ray diffraction. They adopt the tetragonal BaAl{sub 4}-type structure (space group I4/mmm, Z=2; SrAu{sub 1.1(1)}In{sub 2.9(1)}, a=4.5841(2) A, c=12.3725(5) A; SrAu{sub 1.4(1)}Sn{sub 2.6(1)}, a=4.6447(7) A, c=11.403(2) A), with Au atoms preferentially substituting into the apical over basal sites within the anionic network. The phase width inherent in these solid solutions implies that the BaAl{sub 4}-type structure can be stabilized over a range of valence electron counts (vec), 13.0-11.6 for SrAu{sub x}In{sub 4-x} and 14.1-11.4more » for SrAu{sub x}Sn{sub 4-x}. They represent new examples of electron-poor BaAl{sub 4}-type compounds, which generally have a vec of 14. Band structure calculations confirm that substitution of Au, with its smaller size and fewer number of valence electrons, for In or Sn atoms enables the BaAl{sub 4}-type structure to be stabilized in the parent binaries SrIn{sub 4} and SrSn{sub 4}, which adopt different structure types. - Graphical abstract: BaAl{sub 4}-type structure of solid solutions SrAu{sub x}In{sub 4-x} (0.5{<=}x{<=}1.2) and SrAu{sub x}Sn{sub 4-x} (1.3{<=}x{<=}2.2), with apical sites preferentially occupied by Au atoms.« less
  • The (NH{sub 4})[Fe(AsO{sub 4}){sub 1-x}(PO{sub 4}){sub x}F] (x=0.3, 0.6, 0.8) series of compounds has been synthesized under mild hydrothermal conditions. The compounds crystallize in the orthorhombic Pna2{sub 1} space group, with the unit-cell parameters a=13.1718(1), b=6.5966(6), c=10.797(1) A for x=0.3; a=13.081(1), b=6.5341(6), c=10.713(1) A for x=0.6 and a=13.0329(9), b=6.4994(4), c=10.6702(6) A for x=0.8, with the volumes 938.6(1), 915.7(1) and 903.8(1) A{sup 3}, respectively, with Z=8. Single crystals of (NH{sub 4})[Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.3}F] heated under air atmosphere at 465 deg. C remain as single crystals, changing the composition to Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.3}. This later phase belongs tomore » the orthorhombic Imam space group, with the unit cell parameters a=13.328(2), b=6.5114(5), c=10.703(1) A, V=928.9(2) A{sup 3} and Z=12. The crystal structure of the ammonium phases consists of a KTP three-dimensional framework constructed by chains formed by alternating Fe(2)O{sub 4}F{sub 2} or Fe(1)O{sub 4}F{sub 2} octahedra and As/P(2)O{sub 4} or As/P(1)O{sub 4} tetrahedra, respectively. These octahedra and tetrahedra are linked by a common oxygen vertex. The chains run along the 'a' and 'b' crystallographic axes. The crystal structure of Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.3} is a three-dimensional skeleton derived from that of the precursor, formed from (100) sheets stacked along the [001] direction, and interconnected by chains of alternating Fe(2)O{sub 6} octahedra and As/P(2)O{sub 4} tetrahedra sharing a vertex in the 'a' direction. Transmission electronic microscopy of this compound indicates the existence of unconnected external cavities with a BET surface area of 3.91(3) m{sup 2} g{sup -1}. The diffuse reflectance spectra in the visible region show the forbidden electronic transitions characteristic of the Fe(III) d{sup 5}-high spin cation in slightly distorted octahedral geometry, for all the compounds. The ESR spectra for all the compounds, carried out from room temperature to 4.2 K, remain isotropic with variation in temperature; the g-value is 1.99(1). Magnetic measurements indicate the predominance of antiferromagnetic interactions, with Neel temperatures near to 70.0 and 50.0 K for the ammonium phases and Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.30}, respectively. At low temperatures a spin canting phenomenon for Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.30} is detected. - Graphical abstract: The relationship between the |100| and |010| chains in (NH{sub 4})[Fe(AsO{sub 4}){sub 1-x}(PO{sub 4}){sub x}F] left and the |100| chains and the (001) sheets in Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.3}.« less
  • Reported are the synthesis and the structural characterization of an extended family of rare-earth metal–germanides with a general formula RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Y, Ce–Nd, Sm, Gd–Tm and Lu; x<2). All twelve phases are isotypic, crystallizing with the Mn{sub 5}Si{sub 3} structure type (Pearson index hP16, hexagonal space group P6{sub 3}/mcm); they are the Ca-substituted variants of the corresponding RE{sub 5}Ge{sub 3} binaries. Across the series, despite some small variations in the Ca-uptake, the unit cell volumes decrease monotonically, following the lanthanide contraction. Temperature dependent DC magnetization measurements reveal paramagnetic behavior in the high temperature range, and the obtained effectivemore » moments are consistent with free-ion RE{sup 3+} ground state, as expected from prior studies of the binary RE{sub 5}Ge{sub 3} phases. The onset of magnetic ordering is observed in the low temperature range, and complex magnetic interactions (ferromagnetic/ferrimagnetic) can be inferred, different from the binary phases RE{sub 5}Ge{sub 3}, which are known as antiferromagnetic. In order to understand the role of Ca in the bonding, the electronic structures of the La{sub 5}Ge{sub 3} and the hypothetical compounds La{sub 2}Ca{sub 3}Ge{sub 3} and La{sub 3}Ca{sub 2}Ge{sub 3} with ordered metal atoms are compared and discussed. - Graphical abstract: The family of rare-earth metal–calcium–germanides with the general formula RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Y, Ce–Nd, Sm, Gd–Tm and Lu) crystallize in the hexagonal space group P6{sub 3}/mcm (No. 193, Pearson symbol hP16) with a structure that is a variant of the Mn{sub 5}Si{sub 3} structure type. - Highlights: • The newly synthesized RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Y, Ce–Nd, Sm, Gd–Tm and Lu) constitute an extended family. • The structure is a substitution variant of the hexagonal Mn{sub 5}Si{sub 3} structure type. • Ca-uptake is the highest in the early members, and decreases for the late rare-earth metal analogs. • Experimental and theoretical work suggest limiting solubility range RE{sub ≈3}Ca{sub ≈2}Ge{sub 3}.« less
  • The indicated reactions under arc-melting or high-temperature sintering conditions in Ta containers lead to (1) the apparent Zintl phase La{sub 5}Ge{sub 3}Si{sub 0.75}, stuffed Mn{sub 5}Si{sub 3}-type, P6{sub 3}/mcm from quenching; (2) {alpha}-La{sub 5}Ge{sub 3}Si (Sm{sub 5}Ge{sub 4}-type, Pnma); (3) {beta}-La{sub 5}Ge{sub 3}Si (Zr{sub 5}Si{sub 4}-type, P4{sub 1}2{sub 1}2) at high temperatures; (4) La{sub 5}Ge{sub 3}Tt, Tt=Sn, Pb, phases isotypic with 2); (5) the isotypic La{sub 5}Ge{sub 3}Tr, Tr=Ga, In (Gd{sub 5}Si{sub 4}-type, Pnma). The structures of compounds 3 and 5 (for Tr=Ga) have been refined from single crystal X-ray diffraction data. A general description of the three electron-poorer M{submore » 5}X{sub 4} structure types 2,3,4 (and of Eu{sub 5}As{sub 4}-type (Cmca)) is given in terms of their common building block, an La{sub 9}Tt{sub 6} cubeoctahedra centered about the tightest bound La. Some electronic bonding effects are also generalized with regard to the dominance of extra free electrons beyond simple Zintl expectations.« less
  • The thermal conversion of chemically delithiated layered Li 0.5Ni 1-yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2-yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied in lithium-ion cells. Amore » bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. The study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less