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Ferrocene and ferrocenium sites in radiofrequency plasma polymer films on Pt electrodes can be electrochemically oxidized and re-reduced in contact with a variety of electrolyte/solvent systems.When the electrochemical reaction is conducted under near-equilibrium conditions, cyclic voltammetric and chronopotentiometric waveshapes reflect the modulation of ferrocene and ferrocenium site activities by solvent swelling of the film.In water, ferrocene sites exhibit a phase-like (constant) activity during film oxidation, but in acetonitrile ferrocene site activity is proportional to fractional film oxidation.When the film oxidation or reduction is driven by a large potential step (avoiding film ohmic resistance effects), the rate of film reaction is controlled by Fickian diffusion of electrochemical charge through the film.In water, the product of charge diffusion constant and initial concentration of electroactive sites, D1/2C, is 2 X 10-8 mol/cm2 s1/2 for film oxidation and 1.4 X 10-8 mol/cm2 s1/2 for film re-reduction.The difference may be due greater film swelling in the oxidized state.The relationship of charge diffusion rates in redox polymer films on electrodes to their electrocatalytic reactions is discussed.
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Reference：
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion