This article reports on the charging behavior of thin films of alkanethiol protected gold nanoparticles, socalled monolayer protected clusters (MPCs), immersed in aqueous solution. We demonstrate that the oxidation of the MPCs is controlled by the transfer of counter-ions across the aqueous/MPC film interface. A model is developed to describe this and its predictions compared with experiment. Langmuir-Schaefer MPC thin films were transferred to a glassy carbon electrode and film charging behavior investigated in a series of aqueous solutions comprised of different base electrolyte anions. The dependence of peak current on film thickness and peak position on anion lipophilicity for MPC oxidative charging can all be accounted for with the ion-transfer limited model. The impact of ion partitioning into the film at equilibrium is also discussed and the effect of the aqueous phase cation is theoretically considered. In addition, the effect of co-transported water with hydrophilic ions transferring into the film on film charging is rationalized
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