RESUMO
One of the greatest limitations in electrochemical collision/nanoimpact methods is the inability to quantify the size of colliding species due to the uneven current distribution on a disk ultramicroelectrode UME (so-called edge effect). This phenomenon arises since radial diffusion is greater at the edge than the center of the active electrode surface. One method of solving this problem is fabrication of a hemispherical UME. We describe the fabrication of a hemispherical Hg UME on a disk UME by a solution-based electrochemical method, chronocoulometry. The use of hemispherical Hg UME to detect collisions of individual amine-functionalized polystyrene beads removes the "edge effect" and enables simultaneous measurements of the concentration and the size distribution of colloids in suspension. Using finite element simulations, we deduce a quantitative relation between the distribution of current step size and the size distribution of the bead. The frequency of collision measured for a given size of bead is then converted into a concentration (in mol/L) by a quantification of the relative contributions of migration and diffusion for each size of bead. Under our experimental conditions (low concentration of supporting electrolyte), migration dominates the flux of bead. The average size of polystyrene beads of 0.5 and 1 µm radius obtained by electrochemistry and scanning electron microscopy (SEM) differs by only -8% and -9%, respectively. The total concentration of polystyrene beads of 0.5 and 1 µm radius obtained by electrochemistry is found in close agreement (<10% of error) with their nominal concentrations (25 and 100 fM).
