Synthesis, characterization, and intercalation of vanadyl phsophate modified with manganese
- Univ. of Pardubice (Czech Republic)
A yellow-brown crystalline solid, stable in air and having a variable composition of [Mn(H{sub 2}O)]{sub x}(VO){sub 1-x}PO{sub 4}{center_dot}2H{sub 2}O (0 {le} x {le} 0.25), has been prepared by the reaction of solid V{sub 2}O{sub 5} with a boiling aqueous solution of H{sub 3}PO{sub 4} and KMnO{sub 4}. The elementary cell of this compound is tetragonal (space symmetry group either P4/n or P4/nmm) with the following parameters for x = 0.25; a = 0.62034 nm, c = 1.3813 nm, V = 0.51359 nm{sup 3}, Z = 4, M{sub r} = 199.44, D{sub calc} = 2.492 g/cm{sup 3}, and D{sub exp} = 2.52 g/cm{sup 3}. The magnetic behavior of this substance indicates the presence of manganese atoms at the oxidation level of III. The paramagnetic centers formed by the Mn{sub III} atoms are not markedly magnetically coupled. The structure of the compound is probably derived from the original layered lattice of vanadyl phosphate hydrate VOPO{sub 4}{center_dot}2H{sub 2}O by replacement of at most one quarter of the vanadyl groups (V{sup V}O){sup 3+} by [Mn{sup III}(H{sub 2}O)]{sup 3+} groups. Upon being heated, the substance forms a monohydrate at first, then the anhydrous salt forms, and finally the water coordinated with manganese atoms escapes. The compound can be intercalated with foreign molecules and ions in the same way as vanadyl phosphate, and the results of intercalation experiments with methanol, ethanol, 1-propanol, 1-butanol, 1-butylamine, 1-octylamine, formic acid, acetic acid, and pyridine, as well as those of oxidation-reduction intercalation with a solution of sodium intercalations are described. The layered complexes formed have been identified by powder X-ray structure analysis, thermogravimetry, differential thermal analysis, and infrared absorption spectroscopy.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 146485
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 2 Vol. 116; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
40 CHEMISTRY
ABSORPTION
ABSORPTION SPECTROSCOPY
ACETIC ACID
ALCOHOLS
AMINES
CHEMICAL PREPARATION
CLATHRATES
DIFFERENTIAL THERMAL ANALYSIS
ETHANOL
FORMIC ACID
MANGANESE COMPOUNDS
METHANOL
OXIDES
PHOSPHATES
PYRIDINE
SORPTIVE PROPERTIES
STOICHIOMETRY
TETRAGONAL LATTICES
THERMAL GRAVIMETRIC ANALYSIS
VALENCE
VANADIUM COMPOUNDS
X-RAY DIFFRACTION