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Title: Defect structures in the brannerite-type vanadates. VII. Preparation and study of Zn/sub 1-x/O/sub x/V/sub 2-2x/Mo/sub 2x/O/sub 6/ and Zn/sub 1-x-y/O/sub x/Li/sub y/V/sub 2-2x-y/Mo/sub 2x+y/O/sub 6/ solid solutions

Journal Article · · J. Solid State Chem.; (United States)
OSTI ID:5421389

ZnV/sub 2/O/sub 6/ and LiVMoO/sub 6/, both of monoclinic brannerite-type structure, display miscibility in the whole range of composition and form the solid solution ZnLi = Zn/sub 1-y/Li/sub y/V/sub 2-y/Mo/sub y/O/sub 6/. ZnLi may be treated as a matrix able to incorporate an excess of Mo/sup 6 +/ ions compensated by the equivalent number of cation vacancies O in the Zn/sup 2 +/ sublattice, which results in the formation of ZnLiO = Zn/sub 1-x-y/O/sub x/Li/sub y/V/sub 2-2x-y/Mo/sub 2x+y/O/sub 6/. At y = O, x/sub max/ = 0.15 and the authors deal with ZnO = Zn/sub 1-x/O/sub x/V/sub 2-2x/Mo/sub 2x/O/sub 6/ (which belongs to the ZnV/sub 2/O/sub 6/-MoO/sub 3/ system); at y = 0.25, x/sub max/ approx. = 0.30, and at higher y, x/sub max/ diminishes again. Phase diagrams of ZnV/sub 2/O/sub 6/-MoO/sub 3/ and ZnV/sub 2/O/sub 6/-LiVMoO/sub 6/-MoO/sub 3/ systems are partly resolved on the basis of differential thermal analysis (DTA) and X-ray phase analysis. Lattice parameters of the above-mentioned solid solutions as a function of composition are determined. The MeV/sub 2/O/sub 6/ lattices are amenable to substitution of Mo/sup 6 +/ for V/sup 5 +/ in a quantity exceeding 50%. Dopant ions of various sizes influence the values of lattice parameters. Parameters a and b are dependent on the Mo/V ratio and practically insensitive to the occupation of the original Me/sup 2 +/ site. Parameter c (or c sin ..beta..) is almost sensitive only to the size of Me/sup 2 +//Li/sup +//phi. Cation vacancies behave as ions of a size smaller than the exhausted cations by at least 0.01 A but rather close to 0.06 A.

Research Organization:
Institute of Catalysis and Surface Chemistry, Krakow, Poland
OSTI ID:
5421389
Journal Information:
J. Solid State Chem.; (United States), Vol. 71:2
Country of Publication:
United States
Language:
English