A new metastable three-dimensional bismuth sulfide with large tunnels: Synthesis, structural characterization, ion-exchange properties, and reactivity of KBi3S5

Timothy J. McCarthy, Troy A. Tanzer, Mercouri G Kanatzidis

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Abstract

The new ternary bismuth sulfide KBi3S5 forms from the reaction of Bi in a K2Sx flux at 300°C (94% yield). The compound crystallizes in the orthorhombic space group Pnma (no. 62) with a = 17.013(5) Å, b = 4.076(2) Å, c = 17.365(4) Å, V = 1204(2) Å3, and Z = 4 (final R/Rw = 5.1/6.7%), data with Fo2 > 3σ(Fo2) 782, no. of variable; 59, 2θmax = 50°. The compound contains an open framework composed of edge-sharing BiS6 octahedra to form large tunnels which are occupied by K+ ions fractionally distributed over two sites. The S⋯S distances across the channel range from 9.45-14.02 Å. KBi3S5 is a semiconductor with a band-gap of 1.21 eV. It undergoes a structural change upon heating at 520°C. KBi3S5 exhibits topotactic ion-exchange with RbCl to give β-RbBi3S5 at 350-380°C. Ion-exchange with aqueous HCl in air forms an oxidized, metastable bismuth sulfide which undergoes endothermic decomposition to Bi2S3 at ∼140°C.

Original languageEnglish
Pages (from-to)1294-1301
Number of pages8
JournalJournal of the American Chemical Society
Volume117
Issue number4
Publication statusPublished - Feb 1 1995

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Ion Exchange
Bismuth
Ion exchange
Tunnels
Semiconductors
Heating
Energy gap
Air
Ions
Semiconductor materials
Fluxes
Decomposition
Sulfides
bismuth sulfide

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "A new metastable three-dimensional bismuth sulfide with large tunnels: Synthesis, structural characterization, ion-exchange properties, and reactivity of KBi3S5",
abstract = "The new ternary bismuth sulfide KBi3S5 forms from the reaction of Bi in a K2Sx flux at 300°C (94{\%} yield). The compound crystallizes in the orthorhombic space group Pnma (no. 62) with a = 17.013(5) {\AA}, b = 4.076(2) {\AA}, c = 17.365(4) {\AA}, V = 1204(2) {\AA}3, and Z = 4 (final R/Rw = 5.1/6.7{\%}), data with Fo2 > 3σ(Fo2) 782, no. of variable; 59, 2θmax = 50°. The compound contains an open framework composed of edge-sharing BiS6 octahedra to form large tunnels which are occupied by K+ ions fractionally distributed over two sites. The S⋯S distances across the channel range from 9.45-14.02 {\AA}. KBi3S5 is a semiconductor with a band-gap of 1.21 eV. It undergoes a structural change upon heating at 520°C. KBi3S5 exhibits topotactic ion-exchange with RbCl to give β-RbBi3S5 at 350-380°C. Ion-exchange with aqueous HCl in air forms an oxidized, metastable bismuth sulfide which undergoes endothermic decomposition to Bi2S3 at ∼140°C.",
author = "McCarthy, {Timothy J.} and Tanzer, {Troy A.} and Kanatzidis, {Mercouri G}",
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N2 - The new ternary bismuth sulfide KBi3S5 forms from the reaction of Bi in a K2Sx flux at 300°C (94% yield). The compound crystallizes in the orthorhombic space group Pnma (no. 62) with a = 17.013(5) Å, b = 4.076(2) Å, c = 17.365(4) Å, V = 1204(2) Å3, and Z = 4 (final R/Rw = 5.1/6.7%), data with Fo2 > 3σ(Fo2) 782, no. of variable; 59, 2θmax = 50°. The compound contains an open framework composed of edge-sharing BiS6 octahedra to form large tunnels which are occupied by K+ ions fractionally distributed over two sites. The S⋯S distances across the channel range from 9.45-14.02 Å. KBi3S5 is a semiconductor with a band-gap of 1.21 eV. It undergoes a structural change upon heating at 520°C. KBi3S5 exhibits topotactic ion-exchange with RbCl to give β-RbBi3S5 at 350-380°C. Ion-exchange with aqueous HCl in air forms an oxidized, metastable bismuth sulfide which undergoes endothermic decomposition to Bi2S3 at ∼140°C.

AB - The new ternary bismuth sulfide KBi3S5 forms from the reaction of Bi in a K2Sx flux at 300°C (94% yield). The compound crystallizes in the orthorhombic space group Pnma (no. 62) with a = 17.013(5) Å, b = 4.076(2) Å, c = 17.365(4) Å, V = 1204(2) Å3, and Z = 4 (final R/Rw = 5.1/6.7%), data with Fo2 > 3σ(Fo2) 782, no. of variable; 59, 2θmax = 50°. The compound contains an open framework composed of edge-sharing BiS6 octahedra to form large tunnels which are occupied by K+ ions fractionally distributed over two sites. The S⋯S distances across the channel range from 9.45-14.02 Å. KBi3S5 is a semiconductor with a band-gap of 1.21 eV. It undergoes a structural change upon heating at 520°C. KBi3S5 exhibits topotactic ion-exchange with RbCl to give β-RbBi3S5 at 350-380°C. Ion-exchange with aqueous HCl in air forms an oxidized, metastable bismuth sulfide which undergoes endothermic decomposition to Bi2S3 at ∼140°C.

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