Nonideal electrochemical behavior of biomimetic iron porphyrins: Interfacial potential distribution across multilayer films

The electrochemical behavior of multilayer films formed by iron porphyrins deposited on an edge plane graphite electrode has been examined under anaerobic conditions. In the scan rate interval (1-250 mV/s) where the electrode reaction is reversible, CV diagrams of these films demonstrate substantial deviations from ideality in broadening and separation of the peaks. A model that describes the observed behavior is proposed by taking into account the potential distribution at the electrode/film interface and the concentration dependence of surface activity coefficients. The peak separation is described in terms of the electric double layer that affects the potential difference driving the electrode reaction. The effective potential difference deviates from the applied value due to the potential distribution across the film. The interfacial potential distribution depends on the ionic concentration inside the film. When different ionic concentrations are assumed for oxidation and reduction, different shifts from the applied potential lead to a hysteresis of the peaks. The peak broadening is modeled by using the lattice theory expression for the surface activity coefficients. The model shows that the midpoint potentials of the redox centers depend on the ionic concentration inside the film. At low ionic concentrations, they are remarkably close to the midpoints of the cytochrome c oxidase heme a(3)/Cu-B site.