Nanoparticles can display four unique advantages over macroelectrodes when used for electroanalysis: enhancement of mass transport, catalysis, high effective surface area and control over electrode microenvironment. Therefore, much work has been carried out into their formation, characterisation and employment for the detection of many electroactive species. This paper aims to give an overview of the investigations carried out in this field. Particular attention is paid to examples of the advantages and disadvantages nanoparticles show when compared to macroelectrodes and the advantages of one nanoparticle modification over another. Most work has been carried out using gold, silver and platinum metals. However, iron, nickel and copper are also reviewed with some examples of other metals such as iridium, ruthenium, cobalt, chromium and palladium. Some bimetallic nanoparticle modifications are also mentioned because they can cause unique catalysis through the mixing of the properties of both metals.

Electrochemical detection of hydrogen peroxide using an edge-plane pyrolytic-graphite electrode (EPPG), a glassy carbon (GC) electrode, and a silver nanoparticle-modified GC electrode is reported. It is shown, in phosphate buffer (0.05 mol L(-1), pH 7.4), that hydrogen peroxide cannot be detected directly on either the EPPG or GC electrodes. However, reduction can be facilitated by modification of the glassy-carbon surface with nanosized silver assemblies. The optimum conditions for modification of the GC electrode with silver nanoparticles were found to be deposition for 1 min at -0.5 V vs. Ag from 5 mmol L(-1) AgNO3/0.1 mol L(-1) TBAP/MeCN, followed by stripping for 2 min at +0.5 V vs. Ag in the same solution. A wave, due to the reduction of hydrogen peroxide on the silver nanoparticles is observed at -0.68 V vs. SCE. The limit of detection for this modified nanosilver electrode was 2.0 x 10(-6) mol L(-1) for hydrogen peroxide in phosphate buffer (0.05 mol L(-1), pH 7.4) with a sensitivity which is five times higher than that observed at a silver macro-electrode. Also observed is a shoulder on the voltammetric wave corresponding to the reduction of oxygen, which is produced by silver-catalysed chemical decomposition of hydrogen peroxide to water and oxygen then oxygen reduction at the surface of the glassy-carbon electrode.

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The electrochemical oxidation of Cr(III) to Cr(VI) species was examined in aqueous solution. The responses of boron doped diamond, glassy carbon and gold electrodes were probed towards the oxidation of trivalent chromium over a wide pH range (1.0-13.0). High quality voltammetric profiles were found to appear only at a gold electrode and in solutions of pH greater than 12. It was found that the oxidation reaction proceeds via a multi-step mechanism, where the first electron transfer is electrochemically irreversible and rate-determining, followed by two fast electron transfers. DIGISIM was successfully utilized to model the experimentally obtained data. The oxidation was additionally found to involve OH À ions, at potentials where these are adsorbed at the gold electrode surface. AFM measurements were carried out to complement these findings.