Probing Passivating Porous Films by Scanning Electrochemical Microscopy

Porous films are ubiquitous in electrochemistry. They frequently form on active electrodes due to the precipitation of insoluble reaction products. They can have beneficial effects, like the protection from electrochemical corrosion, or be of parasitic nature, as in the poisoning of fuel cell air cathodes. The effects of such layers on the electrochemical response of the substrate can be probed by Scanning Electrochemical Microscopy (SECM). Herein, we present modifications to the conventional analytical expressions for SECM microelectrode approach curves, to account for the effects of a porous layer. The modified expressions can be used to fit experimental approach curves and obtain film thickness and porosity parameters. Their performance is demonstrated through comparison to results obtained by finite element modeling, and by fitting experimental approach curves over well-defined filter membranes