Electrocatalysis of Anodic Oxygen-Transfer Reactions:  Bi3Ru3O11 Electrodes in Acidic Media

• Published in: Chemistry of materials 1997-03, Vol.9 (3), p.715-722
• Main Authors: He, Lin, Anderson, Jeff R, Franzen, Hugo F, Johnson, Dennis C
• Format: Article
• Language: English
• Subjects: Chemistry; Electrochemistry; Electrodes: preparations and properties; Exact sciences and technology; General and physical chemistry; Other electrodes
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/cm960415c

Details are reported for the synthesis and characterization of composite materials prepared from powdered Bi3Ru3O11 and a polymeric adhesive fashioned into disk electrodes. The structure of the synthesized material was found to be that of the cubic KSbO3 type on the basis of single-crystal and powder X-ray diffractometry. The surface morphology of a composite electrode was determined to be quite porous on the basis of micrographs obtained using scanning electron microscopy. Voltammetric data obtained for various anodic reactions at these electrodes were examined for evidence that oxidations can occur with transfer of oxygen to the oxidation products in the potential region corresponding to onset of anodic discharge of H2O. Model reactants include iodide, dimethyl sulfoxide, tetramethylene sulfoxide, and manganese(II). The electronic band structure of Bi3Ru3O11 was calculated; it was concluded that mixing of Ru 4d and O 2p orbitals in an antibonding band at the Fermi level facilitates oxygen transfer.