The application of fluorescence confocal laser scanning microscopy (CLSM) to quantify three-dimensional pH gradients near electrode surfaces is described. The methodology utilizes a trace quantity of a fluorescent dye, fluorescein, in solution, which fluoresces strongly above pH 6.5, to map the pH adjacent to various ultramicroelectrodes undergoing electrochemical processes that lead to pH changes. The experimental fluorescence profiles, determined by CLSM, have been compared to models by solving the underlying mass transport equations, including the effect of natural convection, using the finite element method. The methodology has been validated through studies of the galvanostatic reduction of water at both disk and ring ultramicroelectrodes. The fluorescence profiles were found to be highly sensitive to both the initial bulk solution pH and applied current in a predictable fashion. The potentiostatic reduction of oxygen has been investigated at 25- and 10-microm-diameter platinum electrodes to confirm the effective number of electrons transferred in the reaction. Finally, the application of this methodology to observe defects in microelectrode arrays, particularly those that cannot be seen by optical microscopy, is described.

The use of scanning electrochemical microscopy (SECM) to evaluate the apparent diffusion coefficient, Dapp, of redox-active species in ultrathin Nafion films is described. In this technique, an ultramicroelectrode (UME) tip, positioned close to a film on a macroscopic electrode, is used to oxidize (or reduce) a species in bulk solution, causing the tip-generated oxidant (reductant) to diffuse to the film/solution interface. The oxidation (reduction) of film-confined species regenerates the reductant (oxidant) in solution, leading to feedback to the UME. A numerical model is developed that allows Dapp to be determined. For these studies, ultrathin films of Nafion were prepared using the Langmuir-Schaefer (LS) technique and loaded with an electroactive species, either the ferrocene derivative ferrocenyltrimethylammonium cation, FA+, or tris(2,2'-bipyridyl)ruthenium(II), Ru(bpy)32+. The morphology and the thickness of the Nafion LS films (1.5 +/- 0.2 nm per layer deposited) were evaluated using atomic force microscopy (AFM). For comparison with the SECM measurements, cyclic voltammetry (CV) was employed to evaluate the concentration of electroactive species within the Nafion LS films and to determine Dapp. The latter was found to be essentially invariant with film thickness, but the value for Ru(bpy)32+ was 1 order of magnitude larger than for FA+. CV and SECM measurements yield different values of Dapp, and the underlying reasons are discussed. In general, the Dapp values for these films are considerably smaller than for recast Nafion films, which can be attributed to the compactness of Nafion LS films. Nonetheless, the ultrathin nature of the films leads to fast response times, and we thus expect that these modified electrodes could find applications in sensing, electroanalysis, and electrocatalysis.

Investigations of the kinetics of molecular transfer across the liquid/gas interface and the effect of a molecular monolayer are of considerable interest as a model for certain biological and environmental processes. In this work, a combined scanning electrochemical microscopy (SECM)-Langmuir trough technique has been used to investigate the effect of the chemical character and mechanical compression of molecular monolayers on the rate of oxygen transfer across the air/water (A/W) interface. Specifically, monolayers comprising the fatty alcohol 1-octadecanol and the phospholipid L-R-dipalmitoyl phosphatidic acid were considered. A mercury hemispherical microelectrode probe has been used to measure interfacial kinetics in SECM, and a numerical model has been developed for mass transport in this configuration to allow quantitative analysis of experimental data. The results obtained suggest that, for both monolayers, the oxygen-transfer rate across the interface decreased compared to that across the clean interface, with the blocking effect becoming more pronounced as the surface pressure of the monolayer increased. A simple energy-barrier model was used successfully to interpret the dependence of the rate constant of oxygen transfer on the surface pressure. The experimental data also provide evidence for the effect of the SECM probe on the deformation of the water surface at very close distances to the A/W interface.