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The parameters of functions used to predict diffusion-controlled scanning electrochemical microscopy approach curves under positive and negative (hindered diffusion) feedback for sphere-cap tips are reported. These functions were obtained by fitting approach curves simulated with an error-bounded adaptive finite element algorithm. Several geometries corresponding to different sphere-cap dimensions were considered including the effect of the tip insulating sheath. The simulated approach curves were successfully compared with experimental ones obtained with mercury sphere caps electrodeposited onto platinum microdisk electrodes.

Novel pH microsensors were made by electrodepositing mesoporous Pd films onto Pt microdisks, electrochemically loading the films with hydrogen to form the [alpha]+[beta] Pd hydride phase, and then switching to the potentiometric mode to monitor pH. To create a nanostructure, the films were deposited within a molecular template formed by the self-assembly of surfactant molecules, a technique known as true liquid crystal templating. The films retain the micrometer size of the Pt microdisk but offer electroactive areas up to 900 times larger. Optimum hydrogen loading conditions were determined, and the mesoporous Pd microdisks were found to have excellent potentiometric properties. From pH 2 to 12, their potential was Nernstian, highly reproducible, very stable ([+ or -]1.2 mV over 2 h), and without hysteresis. Their response time was better than 1 s. However, the presence of oxygen reduced their lifetime significantly, thereby requiring frequent reloading. These microelectrodes do not require calibration before and after measurements, a procedure normally essential for potentiometric pH microsensors. To our knowledge, these are the first results where nanostructured materials made by the true liquid crystal templating method have been used in the potentiometric mode; moreover, these are the first results demonstrating the application of nanostructured microdisks in the potentiometric mode.

Mesoporous ([H.sub.I]-ePt) platinum microelectrodes electrodeposited from the hexagonal ([H.sub.I]) lyotropic liquid crystalline phase are shown to be excellent amperometric sensors for the detection of hydrogen peroxide over a wide range of concentrations. Good reproducibility, high precision, and accuracy of measurements are demonstrated. Mesoporous microelectrodes retain the high rates of mass transport typical of conventional microelectrodes, and their high real surface area greatly enhances their catalytic activity. This unique combination of properties overcomes the limitations of previous amperometric hydrogen peroxide sensors and yields outstanding qualitative and quantitative results.

A novel combination of an electrochemical quartz crystal microbalance (EQCM) and a scanning electrochemical microscope (SECM) has been built. Unlike conventional EQCMs, the instrument described here allows rapid in situ measurement of the modulus of the quartz crystal's transfer function. Data analysis in the complex plane for the Butterworth-Van Dyke (BVD) equivalent circuit yields the real and the imaginary components R (damping resistance) and X(sub L) (reactive inductance) of the crystal's electroacoustic impedance around its resonant frequency of 10 MHz. The influence of different tip shapes of an approaching microelectrode on the electroacoustic impedance of the quartz crystal was studied and found to be minimal for certain geometries. The capability of the EQCM/SECM instrument was tested in cyclic voltammetric plating/stripping experiments using a copper(I) chloride solution of high concentration in 1 M HCl. Four parameters, X(sub L), R, the substrate, and the tip current, can be recorded simultaneously. Depletion layer effects were observed and could be corrected for to yield accurate current efficiencies for potentiodynamic and potentiostatic copper plating. The amperometric response of the SECM tip positioned closely to the substrate reflects the concentration changes of electroactive ions in the diffusion layer of the substrate electrode.

The steady-state voltammetric behavior for the oxidation of aqueous solutions containing the strong bases sodium and barium hydroxide was studied with gold microelectrodes in the absence and in the presence of different concentrations of supporting electrolyte. A well-defined oxidation wave attributed to the oxidation of hydroxide ions to oxygen was observed in all the solutions investigated, regardless of both the nature of the base and the supporting electrolyte employed. However, in solutions with excess electrolyte, the steady-state limiting current was found to depend on the actual concentration of the supporting electrolyte, as the diffusion coefficient of the electroactive species varies with both the ionic strength and viscosity of the medium. Since the hydroxide ion is a negatively charged species, solutions with low or without supporting electrolyte yielded currents enhanced by migration contributions. Theoretical equations for the dependence of steady-state limiting currents with ionic strength were derived; theoretical and experimental data compared satisfactorily. The usefulness of the oxidation wave of hydroxide ions for analytical applications was shown by examining the dependence of steady-state limiting currents on concentration and pH. At a given ionic strength, the steady-state limiting current is proportional to the concentration of hydroxide ion over the range 0.5-5 mM. Moreover, the pH of the basic solutions can be determined by amperometry in place of potentiometry, with the use of an absolute equation.

A study was conducted to simulate transient and steady-state amperometric tip responses with an alternating direction implicit algorithm using scanning electrochemical microscopy. The shape of the approach curves were analyzed for various electroactive disk to insulator radii ratios. The topographical sensitivity and spatial resolution of the scanning electrochemical microscope were evaluated using simulated results. Findings indicated that the diffusion round the edge of the insulating sheat had a significant effect on the approach curves.