Nonaqueous synthesis of a new compound: vanadium oxide hydrate V7.2O16*4.2H2O

INOR 391

Igor Djerdj, igor.djerdj@mat.ethz.ch and Markus Niederberger. Department of Materials, ETH Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland
Stoichiometric VO2 exhibits a large reversible change of electric, magnetic and optical properties at around 340 K. This metal-to-insulator transition is accompanied by a structural transition from a rutile to a monoclinic phase. We present a new phase of nonstoichiometric VO2 synthesized by a nonaqueous sol-gel route starting from VOCl3 and benzyl alcohol as a reaction medium. The powder consists of isolated single-crystalline nanorods grown along the [010] direction of tetragonal V7.2O16*4.2H2O with the lattice parameters a = 10.427(2) Å, c = 3.009(1) Å, and space group I4/m (87). Each V cation is coordinated with 6 oxygen atoms forming highly distorted octahedra. The structure possesses channels of about 5 Å in diameter along the c-axis that are large enough for the inclusion of crystal water. Ab initio electron density functional theory calculations revealed that V7.2O16*4.2H2O has a narrow energy gap of 1.16 eV.