Electrochemical Oxidative Formation and Reductive Desorption of a Self-Assembled Monolayer of Decanethiol on a Au(111) Surface in KOH Ethanol Solution.

Electrochemical oxidative adsorption and reductive desorption of a self-assembled monolayer (SAM) of decanethiol on a Au(111) single crystal electrode were examined in 0.1 M KOH ethanol solution containing various concentrations of decanethiol ranging from 1 muM to 1 mM. Anodic and cathodic current peaks corresponding to the adsorption and desorption of decanethiol, respectively, were observed in cyclic voltammograms of a Au(111) single crystal electrode obtained in 0.1 M KOH ethanol solution containing more than 10 muM of decanethiol. Positions of both peaks depended on the concentration of decanethiol, and they shifted negatively by ca. 0.057 V/decade with increase in decanethiol concentration. This result confirms that the adsorption and desorption of decanethiol is a one-electron process. The reductive charge, which consists of desorption charge and capacitive charge, increased when the sweep rate was decreased and the decanethiol concentration was increased and reached the saturated value of 103 (+/-5%) muC cm-2, which corresponds to the reductive charge of thiol SAM of full coverage with a ( radical3 x radical3)R30 degrees structure. Potentiostatic SAM formation was also investigated by holding the potential at +0.1 V. The reductive charge, i.e., the coverage of the SAM, increased with time and reached the saturated value of 103 (+/-5%) muC cm-2, corresponding to full coverage, after holding the potential at +0.1 V for a certain period of time. The time when the amount of adsorbed thiolate reached full coverage depended on the concentration of decanethiol. The higher the concentration was, the faster full coverage was reached. The desorption peak shifted negatively as the holding time at +0.1 V was increased even after the adsorbed amount had reached full coverage. These results suggest that the ordering of decanethiol SAMs requires a much longer time than the time required for full coverage adsorption. The position of the reductive desorption peak was independent of the thiol concentration if the electrode was kept at +0.1 V for long enough so that a highly ordered SAM was formed. The cathodic peak shifted negatively as the sweep rate was increased, showing that reductive desorption of the SAM was rather slow. The rate constant for the reductive desorption was determined from the potential dependent peak shift to be 0.24 s-1, which is in good agreement with the value obtained for a SAM prepared without potential control, indicating that the quality of the electrochemically prepared SAM is as good as that of the SAM prepared nonelectrochemically.