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Emmanuel Maisonhaute

Publications and source records attributed to Emmanuel Maisonhaute.

6 recordsLinked to original sources

Zeptomole voltammetric detection and electron-transfer rate measurements using platinum electrodes of nanometer dimensions.

The characterization of quasi-hemispherical Pt electrodes of nanometer dimensions (radius 2-150 nm), prepared by electrophoretic coating of etched Pt wires with poly-(acrylic acid), is described. The goals of these experiments are to estimate the accuracy of using steady-state voltammetric limiting currents (i(lim)) in determining the true electrode area and to develop new electrochemical methods for rapidly screening individual electrodes for non-ideal geometries. Electrochemical active areas were determined by measuring the electrical charge (Q) associated with oxidation of adsorbed bis(2,2'-bipyridine)chloro(4,4'-trimethylenedipyridine)osmium(II) in fast-scan voltammetric measurements (scan rate 1000 V/s). Voltammetric peaks corresponding to oxidation of as few as approximately 7000 molecules (approximately 11 zmol) at individual electrodes are reported, allowing precise measurement of electrode areas as small as approximately 10(-10) cm2. A plot of i(lim) (for a soluble redox species) versus Q1/2 (for an adsorbed redox species), constructed from i(lim)-Q1/2 data pairs obtained as a function of the electrode radius, is shown to be linear if the electrode geometry is independent of electrode radius; departure of experimental values from the straight-line plot is a diagnostic indicator of a nonideal electrode geometry. The results indicate that approximately 50% of the electrodes prepared by the electrophoretic polymer-coating procedure are quasi-hemispherical, the remaining being recessed slightly below the polymer coating. The heterogeneous electron-transfer rate constant for the oxidation of the ferrocenylmethyltrimethylammonium cation in H2O/ 0.2 M KCl was also determined from steady-state voltammetry using the method of Mirkin and Bard and found to be 4.(8) +/- 3.(2) cm/s with alpha = 0.6(4) +/- 0.1(5).

Journal Article↗

Microelectrode study of single cavitational bubbles induced by 500 kHz ultrasound.

Insight is gained into about the processes governing cavitational activity and acoustic streaming induced by high frequency (500 kHz) ultrasound by the use of microelectrodes with short time resolution electrochemical equipment to allow monitoring of the activity of single cavitating bubbles. Current transients are interpreted as showing the flux of solution towards the electrode surface due to microstreaming. In order to explain the current amplitude, a simplified model is produced. Important parameters such as bubble size and shape on the surface as well as the boundary layer thickness for microstreaming are taken into account. This model leads to the amplitude of the oscillations of the cavitating bubble. Introducing realistic bubble sizes, this amplitude is found to be in the order of 1 micron. The conclusions arising from this work allow a further interpretation of previous observations at millimeter scale electrodes.

Journal Article↗

Surface acoustic cavitation understood via nanosecond electrochemistry. Part III: Shear stress in ultrasonic cleaning.

Acoustic cavitation is extensively used for cleaning purposes. However, little is known about the fundamental aspects of the cleaning process. Our previous electrochemical data suggested that acoustic bubbles were oscillating at a distance of only a few tens of nanometers above the surface [J. Phys. Chem. B 105 (2001) 12,087; E. Maisonhaute, B.A. Brookes, R.G. Compton, J. Phys. Chem. B 106 (2002) 3166-3172]. The flow velocities resulting from the bubble collapse lead to important drag and shear forces on the surface, responsible for cleaning and/or eroding the latter. We review here the forces acting on an adsorbed particle located on the surface, and develop arguments to explain why small adsorbates are harder to remove by sonication. Then, experimental results on particle desorption and surface effects brought about by ultrasound are presented and shown to agree with our theoretical predictions.

Adsorption↗