Electrical currents resulting from reduction/oxidation processes of tested particles on electrodes modified with metal-containing polymer films

Metal-containing films are considered as systems including a multitude of microelectrodes, the role of which is played by metal clusters distributed in both the film interior and film interfaces. In the case of electrode reactions occurring exclusively on the surface of such metal inclusions and the film thickness significantly exceeding clusters' radii, it is shown that the concentration of species participating in such processes (tested particles, further on) satisfies a diffusion equation complicated with an accompanying electrochemical reaction. By assuming reversibility of the electron transfer processes between polymer fragments, one can arrive at solutions of the derived equation and calculate the corresponding currents resulting from tested particles' reactions. The role of such factors of inclusion of metal clusters into conducting polymer films, as its density and inhomogeneity is discussed in the context of their influence on the measured currents of reduction/oxidation processes of tested particles. Non-stationary effects that might be observed in cycling voltammetry and potential clamp measurements with electrodes modified by metal-containing films are also analyzed. The performed analysis shows that electrochemical properties of the modified electrodes in question practically coincide with those of the electrodes made of the corresponding metals and immersed into the same solutions.