Structural and electronic properties of binary and ternary platinum oxides

• Published in: Journal of Physics and Chemistry of Solids Vol. 45; no. 1; pp. 1 - 21
• Main Authors: Schwartz, K.B., Prewitt, C.T.
• Format: Book Review Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 1984; Elsevier
• Subjects: Applied sciences; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Electron states; Exact sciences and technology; Fatigue; Inorganic compounds; Materials science; Mechanical and acoustical properties of condensed matter; Mechanical properties and methods of testing. Rheology. Fracture mechanics. Tribology; Metals, semimetals and alloys; Metals. Metallurgy; Physics; Specific materials; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Water, oxides, hydroxides, peroxides; Platinum oxide; Electronic structure; Electrical conductivity; Review; Atomic arrangement; Crystal structure; Transition metal Compounds; Crystal chemistry; Oxidation number; Platinum Oxides Mixed; Coordination polyhedron; Inorganic compound; Crystalline structure
• ISSN: 0022-3697; 1879-2553
• DOI: 10.1016/0022-3697(84)90096-9

The structural and crystal chemistry of all known binary and ternary platinum oxides are reviewed with emphasis on the types of polyhedral linkage seen and their relationship to electronic properties. Platinum oxides generally fall into two groups: those containing divalent or partially oxidized platinum in planar coordination and those containing fully oxidized tetravalent platinum in octahedral coordination. Highly conducting platinum oxides contain columnar stacks of partially oxidized planar Pt0 4 groups with direct electronic interactions and tend towards chemical non-stoichiometry. The temperature dependence of electrical conductivity in these compounds is related to the dimensionality of the Pt-Pt interaction. Fully oxidized platinum oxides are either semiconductors or insulators, depending on the type of linkage of the octahedral coordination polyhedra and the Pt-Pt distances. The electronic configuration of octahedrally coordinated Pt 4+ (low spin d 6) precludes the possibility of metallic conductivity in these materials. In general, platinum metal is found to be fairly reactive in air at elevated temperatures, particularly in the presence of alkali and alkaline earth metals. Therefore, caution should be taken before assuming platinum containers or thermocouples are inert with respect to reactants during high temperature synthesis reactions in air or oxidizing conditions.