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Title: Gas phase contributions to topochemical hydride reduction reactions

Alkali and alkali earth hydrides have been used as solid state reductants recently to yield many interesting new oxygen-deficient transition metal oxides. These reactions have tacitly been assumed to be a solid phase reaction between the reductant and parent oxide. We have conducted a number of experiments with physical separation between the reductant and oxides, and find that in some cases reduction proceeds even when the reagents are physically separated, implying reactions with in-situ generated H{sub 2} and, to a lesser extent, getter mechanisms. Our findings change our understanding of these topochemical reactions, and should enhance the synthesis of additional new oxides and nanostructures. - Graphical abstract: Topochemical reductions with hydrides: Solid state or gas phase reaction? Display Omitted - Highlights: • SrFeO{sub 2} and LaNiO{sub 2} were prepared by topochemical reduction of oxides. • Separating the reducing agent (CaH{sub 2}, Mg metal) from the oxide still results in reduction. • Such topochemical reactions can occur in the gas phase.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [1] ;  [5] ;  [1] ;  [6] ;  [7] ;  [5] ;  [1] ;  [5] ;  [1] ;  [7] ;  [5] ;
  1. Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)
  2. (JST), Kawaguchi, Saitama 332-0012 (Japan)
  3. Institute for Integrated Cell-Material Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)
  4. Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan)
  5. (Japan)
  6. (France)
  7. CREST, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012 (Japan)
Publication Date:
OSTI Identifier:
22274164
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 207; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CALCIUM HYDRIDES; NANOSTRUCTURES; OXIDES; OXYGEN; REAGENTS; REDUCING AGENTS; SOLIDS; SYNTHESIS; TRANSITION ELEMENTS