Optimization of the dispersion of gold and platinum nanoparticles on indium tin oxide for the electrocatalytic oxidation of cysteine and arsenite

Gold and platinum nanoparticles (NPs) were prepared by chemical reduction of the corresponding metal complex bound by ion-exchange to generation-4 poly(amidoamine) dendrimers (PAMAM). Arrays of the NPs on indium tin oxide (ITO) electrodes were formed by adsorbing a monolayer comprising a controlled ratio of NP-PAMAM to PAMAM on ITO that was modified with 3-aminopropyl triethoxysilane; subsequently, the organic components were thermally destroyed. Varying the above-defined ratio resulted in a commensurate change of the density of the NPs on the surface. Using an electrode modified in a solution with a mole fraction of Au-PAMAM (relative to total of Au-PAMAM and PAMAM) of 0.06, which gave NPs separated by 200 nm, the current for the catalytic oxidation of cysteine reached a value that did not increase when more nanoparticles were present. The analogous experiment on the oxidation of AsIII with PtNPs as the catalyst was optimized at a mole fraction of 0.2. Calculations assuming hemispherical diffusion suggested that the diffusion domains during cyclic voltammetry at 5 mV s−1 were less than the distance between the NPs.