Carbon ring-disk ultramicroelectrodes

Novel ring-disk ultramicroelectrodes (RD-UMEs) with analytical tip diameters as small as 25-30 microns were fabricated. Carbon RD-UMEs were reproducibly prepared by the chemical vapor deposition of alternating concentric layers of silica and carbon on resistively heated 10 microns carbon fibers. High-quality films with excellent adhesion at the interfaces between the carbon and silica layers were shown by electrochemical and scanning electron microscopy measurements. Electrochemical measurements of a solution of 1.0 mM ferrocene with 200 mM LiClO4 in CH3CN were used to characterize the single- and dual-electrode response lf the RD-UME. The electrochemical responses of the ring and the disk are sigmoidal in shape and indicated that radial diffusion is the primary mode of mass transport at each electrode at slow scan rates. Diffusion-controlled generation-collection experiments showed that the concentric dual-electrode configuration exhibits high collection efficiencies at the ring electrode with a 2-5 microns separation between electrodes and a 2-4 microns ring thickness. Close proximity of the ring and disk electrodes led to enhanced detection sensitivity due to back diffusion of regenerated molecules of a reversible redox couple from the collector to the generator electrode.