[Bi{sub 12}O{sub 14}E{sub 12}]{sub n} columns and lone pairs E in Bi{sub 13}Mo{sub 4}VO{sub 34}E{sub 13}: Synthesis, crystal structure, and chemistry of the Bi{sub 2}O{sub 3}-MoO{sub 3}-V{sub 2}O{sub 5} system

Journal Article · Tue Jul 01 04:00:00 EDT 1997 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1006/jssc.1997.7367· OSTI ID:576416

Enjalbert, R; Hasselmann, G; Galy, J ^[1]

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1. Centre d`Elaboration de Materiaux et d`Etudes Structurales, Toulouse (France)

A new phase, Bi{sub 13}Mo{sub 4}VO{sub 34}E{sub 13} (E:Bi(III) lone pair) was found in the Bi{sub 2}O{sub 3}-MoO{sub 3}-V{sub 2}O{sub 5} system and its formula determined via single crystal analysis and confirmed by solid state synthesis. It crystallizes in the monoclinic system, space group P2/c, with cell parameters a = 11.652(7){angstrom}, b = 5.7923(8) {angstrom}, c = 24.420(9){angstrom}, {beta} = 101.38(6){degrees}, and Z = 2. The crystal structure is built up by infinite [Bi{sub 12}O{sub 14}E{sub 12}]{sub n} columns surrounded by 10 (Mo, V)O{sub 4} tetrahedra, situated on layers parallel to (100) and (001), with an extra Bi atom located at the intersection of these {open_quotes}(Mo, V)O{sub 4} layers{close_quotes} in between two tetrahedra.Taking into account the cell dimensions and structural details of Bi{sub 13}Mo{sub 4}VO{sub 34}E{sub 13} which show that a reported phase like Bi{sub 6}Mo{sub 2}O{sub 15} could also be isostructural, a new hypothesis based on the possible replacement of BiO{sub 4} trigonal bipyramid and/or BiO{sub 3}E tetrahedra for MoO{sub 4} tetrahedra strengthens the probability that there is a continuous solid solution in the Bi{sub 2}O{sub 3}-MoO{sub 3} system between the compositions 1.43 Bi{sub 2}O{sub 3}: 1 MoO{sub 3} and 1.75 Bi{sub 2}O{sub 3}: 1 MoO{sub 3}. Synthesis and cell dimensions of various compositions supporting these ideas are given. The domain of existence for such phases can extend in the pseudo-ternary Bi{sub 2}O{sub 3}-MoO{sub 3}-V{sub 2}O{sub 5} system up to the phase Bi{sub 13}Mo{sub 4}VO{sub 34}; this triangular area excludes Bi{sub 26}Mo{sub 10}O{sub 69} and Bi{sub 26}Mo{sub 6}V{sub 4}O{sub 67} compositions.

• OSTI ID: 576416
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 2 Vol. 131; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
BISMUTH OXIDES
CRYSTAL STRUCTURE
LAYERS
MOLYBDENUM OXIDES
PHASE STUDIES
SYNTHESIS
VANADIUM OXIDES