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Title: Ternary metal-rich sulfide with a layered structure

Abstract

A ternary Nb-Ta-S compound is provided having the atomic formula, Nb.sub.1.72 Ta.sub.3.28 S.sub.2, and exhibiting a layered structure in the sequence S-M3-M2-M1-M2-M3-S wherein S represents sulfur layers and M1, M2, and M3 represent Nb/Ta mixed metal layers. This sequence generates seven sheets stacked along the [001] direction of an approximate body centered cubic crystal structure with relatively weak sulfur-to-sulfur van der Waals type interactions between adjacent sulfur sheets and metal-to-metal bonding within and between adjacent mixed metal sheets.

Inventors:
 [1];  [1]
  1. (Ames, IA)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA; Iowa State University, Ames, IA (US)
OSTI Identifier:
868890
Patent Number(s):
US 5236691
Application Number:
07/666,572
Assignee:
Iowa State University Research Foundation, Inc. (Ames, IA) AMES
DOE Contract Number:
W-7405-ENG-82
Resource Type:
Patent
Country of Publication:
United States
Language:
English
Subject:
ternary; metal-rich; sulfide; layered; structure; nb-ta-s; compound; provided; atomic; formula; nb; 72; 28; exhibiting; sequence; s-m3-m2-m1-m2-m3-s; represents; sulfur; layers; m1; m2; m3; represent; mixed; metal; generates; seven; sheets; stacked; 001; direction; approximate; centered; cubic; crystal; relatively; weak; sulfur-to-sulfur; van; waals; type; interactions; adjacent; metal-to-metal; bonding; layered structure; metal sheets; metal layers; mixed metal; metal layer; metal sheet; crystal structure; relatively weak; ternary metal; centered cubic; metal bond; cubic crystal; /423/

Citation Formats

Franzen, Hugo F., and Yao, Xiaoqiang. Ternary metal-rich sulfide with a layered structure. United States: N. p., 1993. Web.
Franzen, Hugo F., & Yao, Xiaoqiang. Ternary metal-rich sulfide with a layered structure. United States.
Franzen, Hugo F., and Yao, Xiaoqiang. 1993. "Ternary metal-rich sulfide with a layered structure". United States. doi:. https://www.osti.gov/servlets/purl/868890.
@article{osti_868890,
title = {Ternary metal-rich sulfide with a layered structure},
author = {Franzen, Hugo F. and Yao, Xiaoqiang},
abstractNote = {A ternary Nb-Ta-S compound is provided having the atomic formula, Nb.sub.1.72 Ta.sub.3.28 S.sub.2, and exhibiting a layered structure in the sequence S-M3-M2-M1-M2-M3-S wherein S represents sulfur layers and M1, M2, and M3 represent Nb/Ta mixed metal layers. This sequence generates seven sheets stacked along the [001] direction of an approximate body centered cubic crystal structure with relatively weak sulfur-to-sulfur van der Waals type interactions between adjacent sulfur sheets and metal-to-metal bonding within and between adjacent mixed metal sheets.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 1993,
month = 8
}

Patent:

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  • The metal-rich sulfide Ta{sub 6.08}Nb{sub 4.92}S{sub 4} has been prepared by high temperature techniques and characterized by means of X-ray diffraction experiments. It crystallizes in the orthorhombic space group Pnma with four formula units in the cell: a = 3121.00 (54) pm, b = 335.07 (7) pm, and c = 959.18 (19) pm. Its structure is similar to that of niobium-rich sulfides, rather than to that of tantalum-rich sulfides. The metal coordinations are capped distorted cubic prisms and the coordinations of sulfur are capped trigonal prisms.
  • Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf 10Ta 3S 3 was found to crystallize in a new-structure type similar to the knownmore » gamma brasses. This structure is unique in that it is the only reported "stuffed" gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo Kα X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co 2Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.« less
  • Single crystals of a new mutually incommensurate composite crystal with layered structure, (BiS){sub 1.11}NbS{sub 2} were synthesized and the average substructures were studied by the single crystal X-ray diffraction method. The commensurate superlattice reflections along mutually incommensurate directions were observed for the BiS subsystem with the main diffractions of the NbS{sub 2} subsystem. The NbS{sub 2} subsystem with a = 5.7504(9) {angstrom}, b{sub 1} = 3.3306(11) {angstrom}, c = 23.0001(17) {angstrom}, Z = 4, and space group F2mm takes the form of 2H-type NbS{sub 2} sandwiches with Nb atoms trigonal-prismatically coordinated by S atoms. The BiS subsystem with a =more » 5.752(4) {angstrom}, b{sub 2} = 36.156(5) {angstrom}, c = 23.001(5) {angstrom}, Z = 48, and space group F2mm has distorted two-atom-thick double layers with an NaCl-type superstructure. The superstructure has Bi-Bi bonds and non-bonded S-S pairs along mutually incommensurate directions. The periodic length of b{sub 2} is six times as large as those of simple NaCl-type arrangements. The Bi-Bi bonds are located in each half-length of b{sub 2} in the BiS double layers. Each NbS{sub 2} sandwich and BiS double layer stack alternately to form a mutually incommensurate composite crystal with a layered structure. The structural relations among (BiX){sub x}TX{sub 2} (T = Nb, Ta; X = S, Se) type compounds are also discussed.« less
  • A new ternary silver-rich sulfide, BaAg{sub 8}S{sub 5}, was synthesized. This solid-state compound crystallizes in the monoclinic, centrosymmetric space group P{sub 1}/m with a = 7.6720(2) {angstrom}, b = 17.6660(4) {angstrom}, c = 8.9370(2) {angstrom}, {beta} = 107.890(1){degree}, Z = 4, and V = 1152.70(5) {angstrom}{sup 3}. The refinement results are R1 = 0.0490 and wR2 = 0.1136 for 1 > 2{sigma}(I) using 2552 reflections and 137 parameters. As in the binary {alpha}-Ag{sub 2}S and {beta}-Ag{sub 2}S solids, the coordination geometry of both Ag and S is complex. However, if only the bonding of Ag to S is concerned, themore » arrangement is simple. Ag of the first type is connected to two S atoms in both linear and bent fashions. Ag of the second type is coordinated to three S atoms in a pyramidal shape. The structure can be viewed as a three-dimensional network formed by Ag and S atoms with Ba atoms occupying channels parallel to the c axis. Theoretical analysis using the extended Hueckel method indicates that the solid should be a semiconductor.« less
  • Semiempirical electronic structure calculations are utilized to assess the bonding and metal atom arrangement in the recently discovered ternary phosphide ZrNbP, which adopts the Co{sub 2}Si structure type. These same calculations reveal that ZrMoP should form in the Fe{sub 2}P structure type due primarily to metal-metal interactions within each system. Related structural alternatives like the Cu{sub 2}Sb-type and the Ni{sub 2}In-type are also examined for their stability ranges as a function of valence electron concentration (vec). Synthesis and structural characterization of Hf{sub 1.06{minus}}Mo{sub 0.94}P by single-crystal X-ray diffraction are also reported and confirm the prediction of stability of the Fe{submore » 2}P structure type for this vec. Hf{sub 1.06}Mo{sub 0.94}P crystallizes in the space group P62m(No.189); a=6.8954(4) {Angstrom}; c= 3.4164(4) {Angstrom}; Z=3; R=0.024; R{sub w} = 0.027 (I {ge} 3 {sigma}(I)).« less