Francisco Céspedes | PubMed Health

PubMed2004

Carbon composite microelectrodes: charge percolation and electroanalytical performance.

Microelectrodes based on two different epoxy-graphite composites (Araldite-M/HY5162 and Araldite-PY302-2/HY943) that are compatible with organic solvents have been developed and characterized. The variation in the bulk conductivity with graphite particle loading is described by percolation theory and indicates that the particles interact strongly with one another. The percolation threshold is 52% v/v loading of graphite, and this composite exhibits a bulk conductivity of 15 S m(-1). Microdisk electrodes of 25-microm diameter were produced by first etching a microcavity at the tip of a platinum microelectrode, which was then packed with a composite containing 60% v/v graphite so as to optimize both electrical conductivity and the electrode stability in acetonitrile and methanol solutions. Solution phase voltammetry of ferrocene is nearly ideal, and the responses are dominated by radial diffusion (slow scan rates) and semi-infinite linear diffusion (fast scan rates). The microelectrodes display high signal-to-noise ratios, good sensitivity, and low detection limits. The response times given by the product of the resistance, R, and capacitance, C, are 7.5 x 10(-4) and 1.4 x 10(-1) s for the Araldite M and PY302-2 composites, respectively. Although these response times are significantly slower than those associated with microelectrodes based on carbon fibers or metal wires, they are sufficient for time-resolved electroanalytical applications. The long response times arise from the large composite resistances, 3.1 x 10(11) and 8.3 x 10(11) Omega cm(-2) for Araldite M and PY302-2, respectively. Voltammetry of ferrocene in the absence of deliberately added supporting electrolyte is also reported. Significantly, indistinguishable slopes and intercepts for a calibration curve of peak current vs ferrocene concentration where 2 < [ferrocene] < 50 microM are obtained in the presence and absence of supporting electrolyte.

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PubMed2002

Carbon composite electrodes: surface and electrochemical properties.

Electrodes based on particulate carbon-epoxy or silicone composites have been formed and characterised using electrochemical methods, scanning electron microscopy and scanning electrochemical microscopy. These composites are rigid, exhibit high electrical conductivity and are stable in organic solvents for prolonged periods. The bulk resistance of the Araldite-M and Araldite-CW2215 based electrodes is low, 130+/-12 and 185+/-15 ohms, respectively. In contrast, the bulk resistance of the silicone based electrodes is 1480+/-112 ohms. The uncompensated resistance of electrochemical cells where the composites act as working electrodes is significantly larger than that expected on the basis of solution resistance alone, i.e., up to 7.5 kohms in the case of the silicone composites. These results are interpreted in terms of the presence of pores within the composite material. The response times of the composite electrodes to changes in the applied potential is between 3.1 and 7.2 ms which, although almost an order of magnitude longer than a comparable glassy carbon electrode, is sufficiently rapid to give useful voltammetric data for scan rates of several V s(-1). Close to ideal reversible cyclic voltammetry is observed for ferrocene under semi-infinite diffusion control for scan rates between 0.01 and 0.1 V s(-1) at the Araldite composites. In contrast, the large resistance associated with the silicone based materials causes quasi-reversible responses to be observed over this range of scan rate. Scan rate dependent cyclic voltammetry and time resolved chronoamperometry responses observed for ferrocene in solution are consistent with those expected for a random array of microelectrodes. Scanning electron microscopy and scanning electrochemical microscopy has been used to image the shape, size and electrochemical activity of the electroactive zones. In the case of Araldite-M, the quality of the electrode surface has been probed by comparing the rate of heterogeneous electron transfer at a composite microelectrode with that found for a carbon fibre electrode. The standard heterogeneous electron transfer rate constant, k degrees , is 6.0+/-0.1 x 10(-3) cm s(-1) for the composite compared to 1.5+/-0.1 x 10(-1) cm s(-1) for the carbon fibre electrode. While the smaller rate constant found for the composite suggests a less pristine surface, k degrees is sufficiently large to support reversible, electron transfer under typical electroanalytical conditions. These fundamental measurements will underpin the development of enzyme based biosensors for use in organic solvents.

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