Understanding fluxes as media for directed synthesis: In situ local structure of molten potassium polysulfides

Daniel P. Shoemaker, Duck Young Chung, J. F. Mitchell, Travis H. Bray, L. Soderholm, Peter J. Chupas, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Rational exploratory synthesis of new materials requires routes to discover novel phases and systematic methods to tailor their structures and properties. Synthetic reactions in molten fluxes have proven to be an excellent route to new inorganic materials because they promote diffusion and can serve as an additional reactant, but little is known about the mechanisms of compound formation, crystal precipitation, or behavior of fluxes themselves at conditions relevant to synthesis. In this study we examine the properties of a salt flux system that has proven extremely fertile for growth of new materials: the potassium polysulfides spanning K 2S 3 and K 2S 5, which melt between 302 and 206 °C. We present in situ Raman spectroscopy of melts between K 2S 3 and K 2S 5 and find strong coupling between n in K 2S n and the molten local structure, implying that the S n 2- chains in the crystalline state are mirrored in the melt. In any reactive flux system, K 2S n included, a signature of changing species in the melt implies that their evolution during a reaction can be characterized and eventually controlled for selective formation of compounds. We use in situ X-ray total scattering to obtain the pair distribution function of molten K 2S 5 and model the length of Sn 2- chains in the melt using reverse Monte Carlo simulations. Combining in situ Raman and total scattering provides a path to understanding the behavior of reactive media and should be broadly applied for more informed, targeted synthesis of compounds in a wide variety of inorganic fluxes.

Original languageEnglish
Pages (from-to)9456-9463
Number of pages8
JournalJournal of the American Chemical Society
Volume134
Issue number22
DOIs
Publication statusPublished - Jun 6 2012

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Polysulfides
Raman Spectrum Analysis
Potassium
Molten materials
Fluxes
Salts
X-Rays
Scattering
Growth
Distribution functions
Raman spectroscopy
polysulfide
Crystalline materials
X rays
Crystals

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Understanding fluxes as media for directed synthesis : In situ local structure of molten potassium polysulfides. / Shoemaker, Daniel P.; Chung, Duck Young; Mitchell, J. F.; Bray, Travis H.; Soderholm, L.; Chupas, Peter J.; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 134, No. 22, 06.06.2012, p. 9456-9463.

Research output: Contribution to journalArticle

Shoemaker, Daniel P. ; Chung, Duck Young ; Mitchell, J. F. ; Bray, Travis H. ; Soderholm, L. ; Chupas, Peter J. ; Kanatzidis, Mercouri G. / Understanding fluxes as media for directed synthesis : In situ local structure of molten potassium polysulfides. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 22. pp. 9456-9463.
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