Electrografting of carbon surfaces with aliphatic chains and its effect on the rectification of ferrocene as redox probe in solution.

The mediated oxidation of acetate and octanoate ions in acetonitrile was used to covalently modify carbon surfaces with films bearing saturated aliphatic chains of different length. Film thickness increases proportionally with the length of the aliphatic chain within the carboxylate precursor. The thickest film was obtained from octanoate oxidation and allowed observing a rectification phenomenon when ferrocene is used as redox probe in acetonitrile solution. This effect increases with the bulky and hydrophobic nature of the supporting electrolyte cations; n -Hx 4 N + > n -Bu 4 N + > Me 4 N + . The combination of the bulky and hydrophobic properties of the supporting electrolyte ions as well as the hydrophobic properties of the electrografted films is determining of the rectification of ferrocene in cyclic voltammetry experiments. This phenomenon was simulated through a CEC mechanism in solution, where the mass transport inside the film channels was emulated through single chemical equilibria.