One-dimensional molybdenum thiochlorides and their use in high surface area MoSx chalcogels

Saiful M. Islam, Kota S. Subrahmanyam, Christos D. Malliakas, Mercouri G Kanatzidis

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Abstract

New molybdenum thiochlorides, α-MoSCl3 and β-MoSCl3, have been synthesized by chemical vapor transport. A selenium analog, MoSeCl3, could also be prepared in the same way. The crystal structures consist of infinite chains stabilized by weak van der Waals forces. For the α-phase an infinite chain of 1[Mo2(S2)Cl4Cl4/2] runs along the crystallographic c axis, while for the β-phase 1[Mo2(S2)Cl3Cl6/2] chain passes through the b-axis. MoSeCl3 is isostructural to α-MoSCl3. The formal charge on molybdenum in these thiochlorides have been assigned by X-ray photoelectron spectroscopy (XPS) to be +IV. β-MoSCl3 and already known Mo3S7Cl4 and MoS2Cl3 are weakly paramagnetic. Thermal decomposition of molybdenum thiochlorides leads to MoS2. Red MoS2Cl3 and Mo3S7Cl4 exhibit band gaps of ∼2.07 and ∼2.11 eV, while black α-MoSCl3, β-MoSCl3, and MoSeCl3 exhibit band gaps of ∼1.2, 1.24, and 1.18 eV, respectively. The new thiochlorides can serve as precursors in the synthesis of molybdenum-sulfide gels and aerogels. The MoSx chalcogels have a BET surface area of 353 m2/g and a band gap of 1.5 eV.

Original languageEnglish
Pages (from-to)5151-5160
Number of pages10
JournalChemistry of Materials
Volume26
Issue number17
DOIs
Publication statusPublished - Sep 9 2014

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Molybdenum
Energy gap
Van der Waals forces
Aerogels
Selenium
Pyrolysis
X ray photoelectron spectroscopy
Crystal structure
Gels
Vapors

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

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One-dimensional molybdenum thiochlorides and their use in high surface area MoSx chalcogels. / Islam, Saiful M.; Subrahmanyam, Kota S.; Malliakas, Christos D.; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 26, No. 17, 09.09.2014, p. 5151-5160.

Research output: Contribution to journalArticle

Islam, Saiful M. ; Subrahmanyam, Kota S. ; Malliakas, Christos D. ; Kanatzidis, Mercouri G. / One-dimensional molybdenum thiochlorides and their use in high surface area MoSx chalcogels. In: Chemistry of Materials. 2014 ; Vol. 26, No. 17. pp. 5151-5160.
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