Sonically assisted electroanalytical detection of ultratrace arsenic.

A simple portable handheld electrochemical sensor with an integrated sound source for the detection of ultratrace quantities of arsenic using square wave anodic stripping voltammetry is described. The sensor uses low-frequency sound (250 Hz) during the arsenic deposition step to enhance the sensitivity of the arsenic stripping response. It is found that under quiescent (silent) conditions a detection limit of 2.1 x 10(-7) M with a sensitivity of 0.51 M(-1) A is achievable using a 120-s accumulation period, while applying low-frequency sound using a "sonotrode" reduced this detection limit to 3.7 x 10(-9) M with an increased sensitivity of 27.2 M(-1) A. Thus, the low-frequency sonotrode is shown to increase the sensitivity by ca. 50 times while reducing the limit of detection by 2 orders of magnitude. A study of the effect of copper contamination is carried out as well as analysis in real samples; it is found that although as expected copper detrimentally effects the arsenic limit of detection, it does not rise significantly above 10(-8) M levels

The electrochemical reaction mechanism of arsenic deposition on an Au(111) electrode

The cyclic voltammograms and linear sweep voltammograms of arsenic deposited on an Au(1 1 1) electrode were measured in a phosphate buffer (pH 1.0) containing 0.1 mM NaAsO2 under IR compensation mode in order to gain an insight into the mechanism of arsenic deposition and stripping at an Au(1 1 1) surface. The amount of arsenic deposit is determined to be approximately one monolayer by calculating the charge of anodic stripping peak of the linear sweep voltammograms. The rate of deposition decreases as the amount of the deposit increases. The analyses reveal that the electrodeposition of arsenic is a totally irreversible electrode reaction and the exchange current density is 6.3 × 10-7 A cm-2. The Tafel plot analyses indicate that the transfer of the first accepted electron is the rate-determining step. © 2005 Elsevier B.V. All rights reserved

Novel methods for the production of silver microelectrode-arrays: their characterisation by atomic force microscopy and application to the electro-reduction of halothane.

A new method is proposed for the simple preparation of random silver micro and nano-electrode arrays. This employs acoustic streaming directed at a glassy carbon surface to "mechanically" attach particles from a suspension of metal colloidal or other small particles. The particles tend to adhere to the substrate at points of imperfection such as scratches, crevices etc. These arrays are compared with arrays formed by the electro-deposition of silver at a glassy carbon substrate, with the silver being partially stripped off, leaving a stable micro and nanoparticle array on the surface. Both surfaces are characterised using optical and atomic force microscopy. The two types of electrodes are evaluated to their analytical utility via the electrochemical reduction of halothane and their performance compared with that of a silver macroelectrode. A notable increase in sensitivity and peak current is observed

Acoustically fabricated random microelectrode assemblies.

We report the insonation of bismuth, silver, copper and tungsten metal particles suspended in octane in the vicinity of a glassy carbon electrode. AFM and voltammetry reveal that metal particles are immobilised onto the electrode substrate. In the case of bismuth, silver and copper, the possible melting of the metal particles due to the high sonochemical conditions cannot unambiguously be ruled out. However, it is likely that the immobilisation of the metal particles occurs predominantly through mechanical attachment due to the high rates of mass transport, evidenced from the fact that tungsten can be immobilised at a glassy carbon surface which has a melting point (mp 3410 degrees C) outside the likely sonochemical conditions. The immobilised particles are found to be in electrical contact with the glassy carbon electrodes which can then act as random assemblies of microelectrodes. Proof-of-concept for use in electro-analysis is examined for the possible detection of arsenic and cadmium at a silver and bismuth random microelectrode assemblies, respectively. This approach suggests a simple generic methodology for the construction of microelectrode assemblies via abrasive attachment induced by insonation with power ultrasound

Hydrodynamic electrochemistry: design for a high-speed rotating disk electrode.

We report a novel gas-driven high-speed rotating disk electrode (HSRDE). The HSRDE when immersed in an aqueous solution rotates at approximately 650 Hz, generating laminar flow resulting in a diffusion layer, under steady-state conditions, of thickness approximately 2 microm. The use of high-pressure gas to drive the rotator offers significant improvement in electrical noise as compared to conventional mechanically driven devices. The electroanalytical utility of the HSRDE was exemplified by the anodic stripping voltammetry of arsenic(III) at a gold working electrode. The charge under the arsenic stripping peak was found to increase by more than 1 order of magnitude under the enhanced mass transport regime at the HSRDE in comparison to that seen under quiescent conditions

AFM studies of metal deposition: instantaneous nucleation and the growth of cobalt nanoparticles on boron-doped diamond electrodes.

In situ atomic force microscopy (AFM) is used to study the growth of cobalt nuclei on a boron doped diamond electrode under potentiostatic control. The rate of growth of the nuclei at the electrode surface is monitored using AFM as a function of time at different deposition potentials. The nucleation of cobalt nuclei is found to be "instantaneous" and the growth of the nuclei is shown to be kinetically rather than diffusionally controlled over periods of tens and hundreds of seconds. At very short times (<10 seconds) the kinetics of nucleation are apparent

Diffusional protection of electrode surfaces using regular arrays of immobilised droplets: overcoming interferences in electroanalysis.

Regular arrays of ca. micron sized droplets on a gold electrode surface can block diffusion to the electrode surface of one metal ion (which binds with the material in the droplet) whilst having no significant effect on another (which does not), so allowing interference effects in electroanalysis to be eliminated

Nano-electrochemical detection of hydrogen or protons using palladium nanoparticles: distinguishing surface and bulk hydrogen.

The benefits of using nanoparticle-modified electrodes are exemplified through the electrochemical detection of protons and/or hydrogen. It is shown that a palladium-nanoparticle-modified boron-doped diamond allows voltammetric information relating to the relative roles played by the surface and the bulk metal to be obtained for the proton-hydrogen system at palladium surfaces which is not accessible using palladium macroelectrodes or microelectrodes