Heterogeneous rate constants for the anodic oxidation of many inorganic and organic compounds at electrolytically deposited normalbeta‐PbO2 film electrodes in 1.0M HClO4 are increased by doping the oxide with Bi(III). The rate constants at the mixed‐oxide electrode rise sharply for a change from 0 to 10 mole percent (m/o) of Bi(III) in the electrodeposition solution, and reach a mass transport‐limited value for some compounds at 40 m/o Bi(III). Results of kinetic, voltammetric, and spectroscopic studies of these electrodes are described. In addition, the lifetime of Bi(III)‐doped PbO2 film electrodes is discussed as a function of concentration, rotation speed, analyte, and applied voltage.

The electrocatalytic activities were compared for pure and chloride‐doped normalbeta‐PbO2 films on gold and platinum substrates. Rate constants were increased significantly for oxidations of Mn2+, toluene, benzyl alcohol, dimethylsulfoxide and benzaldehyde in acidic media by the incorporation of Cl− into the oxide films. These reactions are concluded to occur by the electrocatalytic transfer of oxygen from H2O to the reaction products. Results of x‐ray diffraction studies indicate the Cl−‐doped PbO2 continues to have the slightly distorted rutile structure of pure normalbeta‐PbO2 . The observed electrocatalytic phenomena is concluded to be the beneficial consequence of surface defects generated when Cl− serves for charge compensation within the surface matrix and, thereby, increases surface sites capable of adsorbing hydroxyl radicals which are transferred in the electrocatalytic O‐transfer reactions.