Abstract
The mechanism for the formation of monolayers of on gold and platinum microelectrodes has been investigated by monitoring the time evolution of the surface coverage. The monolayers were formed in 2:1 solution containing between 10 and 100 μM of the complex. The voltammetric response of these films corresponding to the redox reaction is nearly ideal. Cyclic voltammetry was used to determine the surface coverage vs. time profile following transfer of the modified electrode into aqueous perchlorate electrolyte. Monolayer formation occurs on the tens of minutes time scale and follows a second order rate law for both gold and platinum electrodes. For gold, the rate constant is for bulk concentrations between 10 and 100 μM. In contrast, more complex behavior is observed on platinum with multilayers being formed where exceeds approximately 20 μM. The apparent rate constants for binding to platinum are at least a factor of 2 smaller than for gold. For both electrode materials, desorption follows first order rate kinetics indicating that the adsorbates do not interact strongly with one another. The time constants for desorption are comparable with those found for adsorption. The first order desorption rate constants are and for modified gold and platinum electrodes, respectively. © 2000 The Electrochemical Society. All rights reserved.
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