Reversible interconversion of a divalent vanadium bronze between δ and β quasi-1D structures

摘要

Charge fluctuations along the quasi-1D frameworks of M _xV _2O _5 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 V _2O _5 framework are accessible. Herein, we demonstrate an unprecedented reversible transformation between double-layered (δ) and tunnel (β) quasi-1D geometries for nanowires of a divalent vanadium bronze, Ca _xV _2O _5 (x ≈ 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 δ → β conversion and the facile diffusion of water molecules within the tunnel geometries for the β → δ reversion.