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

Journal of the American Chemical Society
Daniel P ShoemakerMercouri G Kanatzidis

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(2)S(3) and K(2)S(5), which melt between 302 and 206 °C. We present in situ Raman spectroscopy of melts between K(2)S(3) and K(2)S(5) and find strong coupling between n in K(2)S(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(2)S(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...Continue Reading

References

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Jul 25, 2009·Journal of the American Chemical Society·Daniel P ShoemakerRam Seshadri
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Aug 4, 2011·Angewandte Chemie·In ChungMercouri G Kanatzidis

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Citations

Jun 5, 2013·Inorganic Chemistry·Mihai SturzaMercouri G Kanatzidis
Sep 26, 2013·Inorganic Chemistry·Tarun K BeraMercouri G Kanatzidis
Jul 16, 2014·Proceedings of the National Academy of Sciences of the United States of America·Daniel P ShoemakerMercouri G Kanatzidis
Aug 5, 2016·Journal of the American Chemical Society·Andrew J MartinolichJames R Neilson
Mar 10, 2017·Inorganic Chemistry·Mercouri G Kanatzidis
Nov 10, 2016·Chemical Communications : Chem Comm·Saul J MoorhouseDermot O'Hare
Jan 17, 2019·Chemistry : a European Journal·Volodymyr GvozdetskyiJulia V Zaikina
Jul 23, 2013·Chemical Society Reviews·Xiaofeng LiuMarkus Antonietti
Nov 26, 2019·Chemical Communications : Chem Comm·Guangmao LiShilie Pan
Apr 30, 2020·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Dmitri Leo M Cordova, David C Johnson
Jul 21, 2020·Journal of Applied Crystallography·Daniel O'NolanKarena W Chapman
Jun 8, 2021·Chemical Communications : Chem Comm·Jiazheng ZhouShilie Pan
Oct 8, 2019·Journal of the American Chemical Society·Haijie ChenMercouri G Kanatzidis
Apr 12, 2014·Inorganic Chemistry·Saiful M IslamMercouri G Kanatzidis
Aug 20, 2021·Journal of the American Chemical Society·Xiuquan ZhouMercouri G Kanatzidis
Jul 1, 2020·Journal of the American Chemical Society·Dmitri Leo Mesoza CordovaDavid C Johnson
Dec 13, 2018·Journal of the American Chemical Society·Haijie ChenMercouri G Kanatzidis

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