Electrocatalysis at Microelectrodes: Geometrical Considerations

The influence of the shape of individual electrocatalytically active, axisymmetric particles supported on an inactive substrate, on the current associated with heterogeneous redox reactions involving solution-phase species has been examined theoretically. In agreement with previous work, the diffusion-limited currents, for a disk and supported truncated spheres of the same area including a full sphere are very similar (within ca. 10%). Large enhancements in the predicted values of i(lim) were found, however, for spheroids of the prolate type, as the aspect ratio was increased. Analyses of arrays of electrocatalytically active disks embedded in a planar inactive support in the presence of a diffusion boundary layer of well-defined thickness, for example, a rotating disk electrode, revealed that values of i(lim) very close to those expected for fully catalytic surfaces could be achieved for disk coverages on the order of 1%. Similar conclusions were made for corresponding arrays of small disks embedded in microdisks or spherical inactive supports in quiescent media. This effect might explain observations made for iron porphyrins adsorbed on graphite surfaces in aqueous electrolytes, for which the experimentally determined onset for oxygen reduction is found to be at potentials well ahead of the onset of the voltammetric wave associated with the conversion of the inactive (ferric) to the active (ferrous) form of the macrocycle.