Analytical expressions for the anodic stripping voltammetry of metallic nanoparticles from an electrode are provided. First, for reversible electron transfer, two limits are studied: that of diffusionally independent nanoparticles and the regime where the diffusion layers originating from each particle overlap strongly. Second, an analytical expression for the voltammetric response under conditions of irreversible electron transfer kinetics is also derived. These equations demonstrate how the peak potential for the stripping process is expected to occur at values negative of the formal potential for the redox process in which the surface immobilised nanoparticles are oxidised to the corresponding metal cation in the solution phase. This work is further developed by considering the surface energies of the nanoparticles and its effect on the formal potential for the oxidation. The change in the formal potential is modelled in accordance with the equations provided by Plieth [J. Phys. Chem., 1982, 86, 3166-3170]. The new analytical expressions are used to investigate the stripping of silver nanoparticles from a glassy carbon electrode. The relative invariance of the stripping peak potential at low surface coverages of silver is shown to be directly related to the surface agglomeration of the nanoparticles.

Bubble dynamics, including the formation, growth, and detachment, of single H2 bubbles was studied at a platinum microelectrode during the electrolysis of 1 M H2SO4 electrolyte. The bubbles were visualized through a microscope by a high-speed camera. Electrochemical measurements were conducted in parallel to measure the transient current. The periodic current oscillations, resulting from the periodic formation and detachment of single bubbles, allow the bubble lifetime and size to be predicted from the transient current. A comparison of the bubble volume calculated from the current and from the recorded bubble image shows a gas evolution efficiency increasing continuously with the growth of the bubble until it reaches 100%. Two different substrates, glass and epoxy, were used to embed the Pt wire. While nearly no difference was found with respect to the growth law for the bubble radius, the contact angle differs strongly for the two types of cell. Data provided for the contact point evolution further complete the image of single hydrogen bubble growth. Finally, the velocity field driven by the detached bubble was measured by means of PIV, and the effects of the convection on the subsequent bubble were evaluated.

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Anodic particle coloumetry is used to size silver nanoparticles impacting a carbon microelectrode in a potassium chloride/citrate solution. Besides their size, their agglomeration state in solution is also investigated solely by electrochemical means and subsequent data analysis. Validation of this new approach to nanoparticle agglomeration studies is performed by comparison with the results of a commercially available nanoparticle tracking analysis system, which shows excellent agreement. Moreover, it is demonstrated that the electrochemical technique has the advantage of directly yielding the number of atoms per impacting nanoparticle irrespective of its shape. This is not true for the optical nanoparticle tracking system, which requires a correction for the nonspherical shape of agglomerated nanoparticles to derive reasonable information on the agglomeration state.

Direct current plating, pulse plating, two-pulse plating, and reverse pulse plating were used to produce electrodeposited Co-Cu alloys and Co-Cu/Cu multilayers under galvanostatic control from an electrolyte containing CoSO 4 and CuSO 4 . Atomic force microscopy, X-ray diffraction, and transmission electron microscopy were used to study the sample structure and morphology. Direct current plating resulted in a Co 95 Cu 5 alloy with nearly equal amounts of face-centered cubic ͑fcc͒ and hexagonal close packed phases, while all pulsed current methods yielded multilayers with fcc structure. Giant magnetoresistance ͑GMR͒ behavior was observed in the multilayers with a maximum magnetoresistance ͑MR͒ ratio of about 9% as measured at 8 kOe. The shape of the MR curves and the magnitude of the GMR were very similar, regardless of the sign of the current between the Co deposition pulses. The results of structural studies also confirmed the formation of a multilayer structure for each pulsed electrodeposition mode. The conclusion was that the spontaneous exchange reaction between Co and Cu 2ϩ is responsible for the formation of a pure Cu layer even under reverse pulse plating conditions. The GMR of the multilayer deposits decreased with increasing bilayer number, due to the deterioration of the microstructure as the deposit grew.

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