Comparative electrochemical study of self-assembly of octanethiol from aqueous and aqueous ethanol solutions on a gold electrode

Abstract

The self-assembly of octanethiol (OT) on the surface of a polycrystalline gold electrode in aqueous and aqueous ethanol thiol-containing (1 × 10^–4 М) 0.1 М NaClO₄ solutions was studied. The blocking properties and electrochemical stability of monolayer OT films were studied by chronopotentiometry during OT adsorption under the open circuit conditions (chronoamperometry at a fixed potential) combined with cyclic voltammetry for modified Au/OT electrodes. It was found from the change in the rate of electrochemical reactions in the range of monolayer stability potentials that in aqueous media, compact insulating OT monolayer films formed at a open circuit potential within ~100 s, and the shift of the adsorption potential toward negative values (to–0.6 V) allowed a considerable decrease in the monolayer self-assembly time. The potential shift toward higher negative values (–0.9 V) leads to a removal of OT from the electrode surface during the reductive desorption, with a multipeak current signal recorded on the voltammograms. A transition from aqueous to aqueous ethanol solutions accelerated the formation of an insulating OT monolayer (≈6 s) and led to a change in the shape of the desorption current peak, whose value was almost independent of the ОТ accumulation time and potential.