RÉSUMÉ
The electroanalytical performance of a new commercial boron-doped diamond disk and a traditional nanocrystalline thin-film electrode were compared for the anodic stripping voltammetric determination of Ag(I). The diamond disk electrode is more flexible than the planar film as the former is compatible with most electrochemical cell designs including those incorporating magnetic stirring. Additionally, mechanical polishing and surface cleaning are simpler to execute. Differential pulse anodic stripping voltammetry (DPASV) was used to detect Ag(I) in standard solutions after optimization of the deposition potential, deposition time and scan rate. The optimized conditions were used to determine the concentration of Ag(I) in a NASA simulated potable water sample and a NIST standard reference solution. The electrochemical results were validated by ICP-OES measurements of the same solutions. The detection figures of merit for the disk electrode were as good or superior to those for the thin-film electrode. Detection limits were ≤5 µg L-1 (S/N = 3) for a 120 s deposition period, and response variabilities were <5% RSD. The polished disk electrode presented a more limited linear dynamic range presumably because of the reduced surface area available for metal phase formation. The concentrations of Ag(I) in the two water samples, as determined by DPASV, were in good agreement with the concentrations determined by ICP-OES.
RÉSUMÉ
The morphology, microstructure, chemistry, electronic properties, and electrochemical behavior of a boron-doped nanocrystalline diamond (BDD) thin film grown on quartz were evaluated. Diamond optically transparent electrodes (OTEs) are useful for transmission spectroelectrochemical measurements, offering excellent stability during anodic and cathodic polarization and exposure to a variety of chemical environments. We report on the characterization of a BDD OTE by atomic force microscopy, optical spectroscopy, Raman spectroscopic mapping, alternating-current Hall effect measurements, X-ray photoelectron spectroscopy, and electrochemical methods. The results reported herein provide the first comprehensive study of the relationship between the physical and chemical structure and electronic properties of a diamond OTE and the electrode's electrochemical activity.
RÉSUMÉ
The electrochemical pretreatment of diamond microelectrodes was investigated for the purpose of learning how an anodic, cathodic or a combined anodic + cathodic polarization affects the charge-transfer kinetics for two surface-sensitive redox systems: ferri/ferrocyanide and serotonin (5-hydroxytryptamine, 5-HT). The pretreatments were performed in 0.5 mol L(-1) H2SO4. The anodic pretreatment was performed galvanically for 30 s at 250 mA cm(-2). The cathodic pretreatment was performed for 180 s at -250 mA cm(-2). The combined pretreatment involved application of the anodic step first followed by the cathodic step. The results clearly demonstrate that the best performance for both redox systems is obtained after the cathodic polarization, which presumably activates the electrode by cleaning the surface and removing site-blocking surface carbon-oxygen functionalities. The cathodic pretreatment was found to be effective at activating a fouled microelectrode in situ. This observation has important implication for the measurement of 5-HT in the bowel.