Electrochemical Derivatization of Carbon Surface by Reduction of in Situ Generated Diazonium Cations

Abstract

The derivatization of a glassy carbon electrode surface was achieved by electrochemical reduction of several in situ generated diazonium cations. The diazonium cations were synthesized in the electrochemical cell by reaction of the corresponding amines with NaNO₂ in aqueous HCl. The versatility of the method was demonstrated by using six diazonium cations. This deposition method, which involves simple reagents and does not require the isolation and purification of the diazonium salt, enabled the grafting of covalently bounded layers which exhibited properties very similar to those of layers obtained by the classical derivatization method involving isolated diazonium salt dissolved in acetonitrile or aqueous acid solution. Cyclic voltammetry and electrochemical impedance spectroscopy carried out in aqueous solutions containing electroactive redox probe molecules such as Fe(CN)₆^3-/4- and Ru(NH₃)₆³⁺ confirmed the barrier properties of the deposited layers. The chemical composition of the grafted layers was determined by X-ray photoelectron spectroscopy and surface coverage in the range 3 × 10^-10 to 6 × 10^-10 mol cm^-2 was estimated for films grown in our experimental conditions.