Voltammetric characterization of the self-assembled monolayer (SAM) of octabutylthiophthalocyaninatoiron(II): a potential electrochemical sensor

The fabrication of a self-assembled monolayer (SAM) of 2,3,9,10,16,17,23,24-octa (butylthio)-phthalocyaninatoiron(II) [FePc(SBU)(8)] on gold electrode is described. The integrity of the SAM, with respect to its ability to block certain Faradaic processes, is interrogated using cyclic voltammetric experiments in aqueous solutions. The experiments show that this SAM provide an excellent blocking capability to the Faradaic processes emanating from gold surface oxidation, underpotential deposition (UPD) of copper and redox chemistry of Fe(NH4)(SO4)(2) in HClO4. It is revealed by cyclic voltammetry that an ill-defined reversible couple of the SAM of FePc(SBu)(8) can be greatly improved by a simple repetitive cycling of the modified electrode in a DMF solution containing TBAP within a short space of time (ca. 2 min). This 'activation' process provides good information concerning the surface coverage and orientation of the monolayer. The reversible redox wave shows a potential shift of about -57 mV per pH in the pH range of 2-9. A preliminary investigation indicates that FePc(SBu)(8)-SAM modified gold electrode shows electrocatalytic activity toward the oxidation Of L-cysteine in acidic medium. The monolayer is stable and easily reproducible. However, due to its susceptibility to destruction via oxidative and reductive desorptions, its potential application as an electrochemical sensor would be much better in acidic and neutral than alkaline environments. (C) 2002 Elsevier Science Ltd. All rights reserved.