Electrolyte effects on electrochemical properties of osmium complex polymer modified electrodes.

The electrolyte effects on the electrochemical behaviors of osmium complex polymer modified electrodes were investigated by a comparison between two osmium complexes, [Os(bpy)2(PVI)10Cl]Cl (Os-PVI10) and [Os(bpy)2(PVP)10Cl]Cl (Os-PVP10). The electrode process at Os-PVI10 modified electrodes is reaction-controlled, while a diffusion-controlled electrode process exists at Os-PVP10 modified electrodes. Both the cation and anion in supporting electrolytes strongly affect their electrochemical behaviors, such as the redox potential, wave shape and peak current. These phenomena are attributed to a change in the film structure and polymer swelling in various supporting electrolytes. The influence of electrolyte anions on the electrochemical behaviors is related to their hydrophobicity. The electrode process of Os-PVP10 depends on the pH value of solutions, exhibiting different electron transfer mechanisms.