Abstract

This work confirms formation of surface films of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (H2T(4-NH2Ph)P) in dimethylsulfoxide in the potential range of oxygen electroreduction. Kinetics of variation of faradaic currents and of the interface characteristics are studied at the working electrode potentials of +0.5 V (porphyrin electrooxidation), –0.9 V (oxygen electroreduction), and –1.25 V (coreduction of porphyrin and oxygen). It is shown that the working electrode surface is passivated at the potential of +0.5 V and faradaic currents decrease fast. At the potentials of –0.9 and –1.25 V, the working electrode surface passivation is less pronounced. As shown by analysis of electrode impedance spectra, a film is formed on the electrode surface under electroreduction conditions (–0.9 and –1.25 V), as opposed to electrooxidation conditions (+0.5 V). Charge transport through this film can be characterized by modeling the interface impedance. The kinetics of variation of the interface parameters allow estimating the stage mechanism of film formation and restructuring of the formed layer.

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