4.7 Article

Reversible Interconversion of a Divalent Vanadium Bronze between δ and β Quasi-1D Structures

Journal

INORGANIC CHEMISTRY
Volume 51, Issue 9, Pages 5264-5269

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ic300191y

Keywords

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Funding

  1. National Science Foundation [DMR 0847169]
  2. Research Corporation for Science Advancement
  3. American Chemical Society [50201DNI10]
  4. Direct For Mathematical & Physical Scien
  5. Division Of Materials Research [0847169] Funding Source: National Science Foundation

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Charge fluctuations along the quasi-1D frameworks of MxV2O5 bronzes have evinced much recent interest owing to the manifestation of colossal metal-insulator transitions and superconductivity. Depending upon the nature of the intercalating cation (M), distinctive geometries of the V2O5 framework are accessible. Herein, we demonstrate an unprecedented reversible transformation between double-layered (delta) and tunnel (beta) quasi-1D geometries for nanowires of a divalent vanadium bronze, CaxV2O5 (x approximate to 0.23), upon annealing-induced dehydration and hydrothermally induced hydration. Such a facile hydration/dehydration-induced interconversion between two prominent quasi-1D structures (accompanied by a change in charge-ordering motifs) has not been observed in the bulk and is posited to result from the ease of propagation of crystallographic slip processes across the confined nanowire widths for the delta -> beta conversion and the facile diffusion of water molecules within the tunnel geometries for the beta -> delta reversion.

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