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

Abstract

Highlights: ► Topochemical reactions involving intercalation allow construction of metal chalcogenide arrays within perovskite hosts. ► Gaseous chalcogen hydrides serve as effect reactants for intercalation of sulfur and selenium. ► New compounds prepared by a two-step intercalation strategy are presented. -- Abstract: A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb{sub 2}O{sub 7}, is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb{sub 2}LaNb{sub 2}O{sub 7}. This compound is then reacted at room-temperature with in situ generated H{sub 2}S gas to create Rb-S layers within the perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) Å, c = 15.256(1) Å; space group P4/mmm) shows the compound to be isostructural with (Rb{sub 2}Cl)LaNb{sub 2}O{sub 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{sup 2−} alone. This combined with the Raman studies, which show evidence for an H-S stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfidemore » ion. Intercalation reactions with H{sub 2}Se{sub (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.« less

Authors:
; ; ; ; ; ; ;  [1];  [1]
  1. Department of Chemistry and the Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148-2820 (United States)
Publication Date:
OSTI Identifier:
22215093
Resource Type:
Journal Article
Journal Name:
Materials Research Bulletin
Additional Journal Information:
Journal Volume: 47; Journal Issue: 6; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0025-5408
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; HYDRIDES; HYDROGEN SULFIDES; LAYERS; OXIDATION; PEROVSKITE; RUBIDIUM IONS; SELENIUM; SPACE GROUPS; SULFUR; TETRAGONAL LATTICES; X-RAY DIFFRACTION

Citation Formats

Ranmohotti, K.G. Sanjaya, Montasserasadi, M. Dariush, Choi, Jonglak, Yao, Yuan, Mohanty, Debasish, Josepha, Elisha A., Adireddy, Shiva, Caruntu, Gabriel, and Wiley, John B., E-mail: jwiley@uno.edu. Room temperature oxidative intercalation with chalcogen hydrides: Two-step method for the formation of alkali-metal chalcogenide arrays within layered perovskites. United States: N. p., 2012. Web. doi:10.1016/J.MATERRESBULL.2012.03.021.
Ranmohotti, K.G. Sanjaya, Montasserasadi, M. Dariush, Choi, Jonglak, Yao, Yuan, Mohanty, Debasish, Josepha, Elisha A., Adireddy, Shiva, Caruntu, Gabriel, & Wiley, John B., E-mail: jwiley@uno.edu. Room temperature oxidative intercalation with chalcogen hydrides: Two-step method for the formation of alkali-metal chalcogenide arrays within layered perovskites. United States. doi:10.1016/J.MATERRESBULL.2012.03.021.
Ranmohotti, K.G. Sanjaya, Montasserasadi, M. Dariush, Choi, Jonglak, Yao, Yuan, Mohanty, Debasish, Josepha, Elisha A., Adireddy, Shiva, Caruntu, Gabriel, and Wiley, John B., E-mail: jwiley@uno.edu. Fri . "Room temperature oxidative intercalation with chalcogen hydrides: Two-step method for the formation of alkali-metal chalcogenide arrays within layered perovskites". United States. doi:10.1016/J.MATERRESBULL.2012.03.021.
@article{osti_22215093,
title = {Room temperature oxidative intercalation with chalcogen hydrides: Two-step method for the formation of alkali-metal chalcogenide arrays within layered perovskites},
author = {Ranmohotti, K.G. Sanjaya and Montasserasadi, M. Dariush and Choi, Jonglak and Yao, Yuan and Mohanty, Debasish and Josepha, Elisha A. and Adireddy, Shiva and Caruntu, Gabriel and Wiley, John B., E-mail: jwiley@uno.edu},
abstractNote = {Highlights: ► Topochemical reactions involving intercalation allow construction of metal chalcogenide arrays within perovskite hosts. ► Gaseous chalcogen hydrides serve as effect reactants for intercalation of sulfur and selenium. ► New compounds prepared by a two-step intercalation strategy are presented. -- Abstract: A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb{sub 2}O{sub 7}, is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb{sub 2}LaNb{sub 2}O{sub 7}. This compound is then reacted at room-temperature with in situ generated H{sub 2}S gas to create Rb-S layers within the perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) Å, c = 15.256(1) Å; space group P4/mmm) shows the compound to be isostructural with (Rb{sub 2}Cl)LaNb{sub 2}O{sub 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{sup 2−} alone. This combined with the Raman studies, which show evidence for an H-S stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfide ion. Intercalation reactions with H{sub 2}Se{sub (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.},
doi = {10.1016/J.MATERRESBULL.2012.03.021},
journal = {Materials Research Bulletin},
issn = {0025-5408},
number = 6,
volume = 47,
place = {United States},
year = {2012},
month = {6}
}