Room temperature oxidative intercalation with chalcogen hydrides: Two-step method for the formation of alkali-metal chalcogenide arrays within layered perovskites

K. G.Sanjaya Ranmohotti, M. Dariush Montasserasadi, Jonglak Choi, Yuan Yao, Debasish Mohanty, Elisha A. Josepha, Shiva Adireddy, Gabriel Caruntu, John B. Wiley

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7 Scopus citations

Abstract

A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb 2O 7, is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb 2LaNb 2O 7. This compound is then reacted at room-temperature with in situ generated H 2S gas to create RbS layers within the perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) , c = 15.256(1) ; space group P4/mmm) shows the compound to be isostructural with (Rb 2Cl)LaNb 2O 7 where the sulfide resides on a cubic interlayer site surrounded by rubidium ions. The mass increase seen on sulfur intercalation and the refined S site occupation factor (∼0.8) of the product indicate a higher sulfur content than expected for S 2- alone. This combined with the Raman studies, which show evidence for an HS stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfide ion. Intercalation reactions with H 2Se (g) were also carried out and appear to produce an isostructural selenide compound. The utilization of such gaseous hydride reagents could significantly expand multistep topochemistry to a larger number of intercalants.

Original languageEnglish
Pages (from-to)1289-1294
Number of pages6
JournalMaterials Research Bulletin
Volume47
Issue number6
DOIs
StatePublished - Jun 2012

Keywords

  • A. Chalcogénides
  • A. Layered compounds
  • C. X-ray diffraction

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