Effect of mechanical coating with Ni and Ni-5% Al on the structure and electrochemical properties of the Mg-50% Ni alloy

The Mg-Ni metastable alloys (with amorphous or nanocrystalline structures) are promising candidates for anode application in nickel-metal hydride rechargeable batteries due to its large hydrogen absorbing capacity, low weight, availability, and relative low price. In spite of these interesting features, improvement on the cycle life performance must be achieved to allow its application in commercial products. In the present paper, the effect of mechanical coating of a Mg-50 at.% Ni alloy with Ni and Ni-5 at.% Al on the structure, powder morphology, and electrochemical properties is investigated. The coating additives, Mg-Ni alloy and resulting nanocomposites (i.e., Mg-Ni alloy + additive) were investigated by means of X-ray diffraction and scanning electron microscopy. The Mg-Ni alloy and nanocomposites were submitted to galvanostatic cycles of charge and discharge to evaluate their electrode performances. The mechanical coating with Ni and Ni-5% Al increased the maximum discharge capacity of the Mg-Ni alloy from of 221 to 257 and 273 mA h g(-1), respectively. Improvement on the cycle life performance was also achieved by mechanical coating.

The electrochemical effect of acid functionalisation of carbon nanotubes to be used in sensors development

The electrochemical behaviour of multi-walled carbon nanotubes was compared with that of glassy carbon, and the differences were investigated by cyclic voltammetry and electrochemical impedance spectroscopy before and after acid pre-treatment. The electrochemical techniques showed that acid functionalisation significantly improves the electrocatalytic properties of carbon nanotubes. These electrocatalytic properties enhance the analytical signal, shift the oxidation peak potential to a less positive value, and the charge-transfers rate increase of both dopamine and K(4)[Fe(CN)(6)]. The functionalisation step and the resulting appearance of edge planes covered with different chemical groups were confirmed by FTIR measurements. Carbon nanotubes after acid pre-treatment are a potentially powerful analytical tool for sensor development. (C) 2010 Elsevier B.V. All rights reserved.

Stabilizing Nonstationary Electrochemical Time Series

Electrochemical systems are ideal working-horses for studying oscillatory dynamics. Experimentally obtained time series, however, are usually associated with a spontaneous drift in some uncontrollable parameter that triggers transitions among different oscillatory patterns, despite the fact that all controllable parameters are kept constant. Herein we present an empirical method to stabilize experimental potential time series. The method consists of applying a negative galvanodynamic sweep to compensate the spontaneous drift and was tested for the oscillatory electro-oxidation of methanol on platinum. For a wide range of applied currents, the base system presents spontaneous transitions from quasi-harmonic to mixed mode oscillations. Temporal patterns were stabilized by galvanodynamic sweeps at different rates. The procedure resulted in a considerable increase in the number of oscillatory cycles from 5 to 20 times, depending on the specific temporal pattern. The spontaneous drift has been associated with uncompensated oscillations, in which the coverage of some adsorbed species are not reestablished after one cycle; i.e., there is a net accumulation and/or depletion of adsorbed species during oscillations. We interpreted the rate of the galvanodynamic sweep in terms of the time scales of the poisoning processes that underlies the uncompensated oscillations and thus the spontaneous slow drift.

Direct Electrochemical Determination of Glyphosate at Copper Phthalocyanine/Multiwalled Carbon Nanotube Film Electrodes

A copper phthalocyanine/multiwalled carbon nanotube film-modified glassy carbon electrode has been used for the determination of the herbicide glyphosate (Gly) at -50 mV vs. SCE by electrochemical oxidation using differential pulse voltamtnetry (DPV). Cyclic voltammetry and electrochemical impedance spectroscopy showed that Gly is adsorbed on the metallic centre of the copper phthalocyanine molecule, with formation of Gly-copper ion complexes. An analytical method was developed using DPV in pH 7.4 phosphate buffer solution, without any pretreatment steps: Gly was determined in the concentration range of 0.83-9.90 mu mol L(-1), with detection limit 12.2 nmol L(-1) (2.02 mu g L(-1))

Structural and electrochemical characteristics of Mg((55-x))Ti(x)Ni((45-y))Pt(y) metal hydride electrodes

In recent years, Mg-Ni-based metastable alloys have been attracting attention due to their large hydrogen sorption capacities, low weight, low cost, and high availability. Despite the large discharge capacity and high activity of these alloys, the accelerated degradation of the discharge capacity after only few cycles of charge and discharge is the main shortcoming against their commercial use in batteries. The addition of alloying elements showed to be an effective way of improving the electrode performance of Mg-Ni-based alloys. In the present work, the effect of Ti and Pt alloying elements on the structure and electrode performance of a binary Mg-Ni alloy was investigated. The XRD and HRTEM revealed that all the investigated alloy compositions had multi-phase nanostructures, with crystallite size in the range of 6 nm. Moreover, the investigated alloying elements demonstrated remarkable improvements of both maximum discharge capacity and cycling life. Simultaneous addition of Ti and Pd demonstrated a synergetic effect on the electrochemical properties of the alloy electrodes. Among the investigated alloys, the best electrochemical performance was obtained for the Mg(51)Ti(4)Ni(43)Pt(2) composition (in at.%), which achieved 448 mAh g(-1) of maximum discharge capacity and retained almost 66% of this capacity after 10 cycles. In contrast, the binary Mg(55)Ni(45) alloy achieved only 248 mAh g(-1) and retained 11% of this capacity after 10 cycles. (C) 2010 Elsevier By. All rights reserved.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

Electrochemical Behaviour of the AA2024 Aluminium Alloy Modified with Self-Assembled Monolayers/Polyaniline Double Films

The electrochemical characteristics of the AA2024 aluminium alloy modified with octadecyltrimethoxysilane (ODTMS) + polyaniline (PANi) and propiltrimethoxysilane (PTMS) + (PANi) were studied in the present work. The results show that the different protective coatings shift the values of corrosion and pit potentials to more positive values making the system nobler and indicate that the double film ODTMS + PANi present the best protection against corrosion characteristics, that is probably due to the two contributions: anodic protection associated with the barrier effect.

Study of a gold electrode modified by trans-[Ru(NH(3))(4)(Ist)SO(4)](+) to produce an electrochemical sensor for nitric oxide

The modification of a gold electrode surface by electropolymerization of trans-[Ru(NH(3))(4)(Ist)SO(4)](+) to produce an electrochemical sensor for nitric oxide was investigated. The influence of dopamine, serotonin and nitrite as interferents for NO detection was also examined using square-wave voltammetry (SWV). The characterization of the modified electrode was carried out by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM) and SERS techniques. The gold electrode was successfully modified by the trans-[Ru(NH(3))(4)(Ist)SO(4)](+) complex ion using cyclic voltammetry. The experiments show that a monolayer of the film is achieved after ten voltammetric cycles, that NO in solution can coordinate to the metal present in the layer, that dopamine, serotonin and nitrite are interferents for the detection of NO, and that the response for the nitrite is much less significant than the responses for dopamine and serotonin. The proposed modified electrode has the potential to be applied as a sensor for NO. (C) 2011 Elsevier Ltd. All rights reserved.

Study of photo-assisted electrochemical degradation of carbaryl at dimensionally stable anodes (DSA (R))

This paper presents the results concerning the degradation of the pesticide carbaryl comparing two methods: electrochemical (EC) and photo-assisted electrochemical (PAEC). The experimental variables of applied current density, electrolyte flow-rate and initial carbaryl concentration were investigated. The results demonstrate that the electrochemical degradation of carbaryl was greatly enhanced when simultaneous UV light was applied. The greatest difference between the PAEC and EC method was apparent when lower current densities were applied. The extent of COD removal was much enhanced for the combined method, independent of the applied current density. It should be noted that the complete removal of carbaryl was achieved with out the need to add NaCl to the reaction mixture, avoiding the risk of chlorinated organic species formation. (C) 2009 Elsevier B.V. All rights reserved.

Electrochemical determination of the antioxidant capacity: The ceric reducing/antioxidant capacity (CRAC) assay

The CRAC assay is a direct electron transfer test of antioxidant capacity for several organic compounds. The ability of eight different compounds in reducing Cc 41 was studied by chronoamperometric measurements of the remaining Ce(3+) species. The following antioxidant classification was observed: tannic acid >> quercetin > rutin > gallic acid approximate to catechin > ascorbic acid > BHA > Trolox. These results agree with others already published and a good correlation (R(2) = 0.937) was found with the classical spectrophotometric FRAP assay. The CRAC assay is simple, fast, free from sample pretreatment and applicable to nontransparent samples.

Photo-assisted electrochemical degradation of the commercial herbicide atrazine

This paper presents a degradation study of the pesticide atrazine using photo-assisted electrochemical methods at a dimensionally stable anode (DSA (R)) of nominal composition Ti/Ru(0.3)Ti(0.7)O(2) in a prototype reactor. The effects of current density, electrolyte flow-rate, as well as the use of different atrazine concentrations are reported. The results indicate that the energy consumption is substantially reduced for the combined photochemical and electrochemical processes when compared to the isolated systems. It is observed that complete atrazine removal is achieved at low current densities when using the combined method, thus reducing the energy required to operate the electrochemical system. The results also include the investigation of the phytotoxicity of the treated solutions.

Photo-assisted electrochemical degradation of real textile wastewater

In the present study, photo-assisted electrochemical degradation of real textile wastewater was performed. Degradation assays were performed at constant current (40 mA cm(-2)) in a combined electro/photochemical flow-cell using a Ti/Ru(0.3)Ti(0.7)O(2) DSA(R) type electrode. The results show that the method is capable of removing color and chemical oxygen demand (COD) from the effluent. Additionally, the effect of initial pH and type of supporting electrolyte (Na(2)SO(4) or NaCl) was investigated. The principal figures of merit used in this study were COD removal and color removal (605 nm). The results show that up to 72% color and up to 59% COD removal in 120 min is possible under the operating conditions employed. Studies of the phytotoxicity of the wastewater before and after the photo-assisted degradation assays are also presented and the results demonstrate that the toxicity of the effluent is dependent on the length of electrolysis time and the treatment procedure employed.

Electrochemical Behavior of Verapamil at Graphite-Polyurethane Composite Electrodes: Determination of Release Profiles in Pharmaceutical Samples

A solid graphite-polyurethane composite electrode has been used to determine release profiles of verapamil, a calcium-channel blocker. The electro-oxidation process was characterized by cyclic voltammetry and electrochemical impedance spectroscopy and showed no adsorption of analyte or oxidation products, unlike at other carbon-based electrodes. Quantification gave linear ranges up to 40molL-1 with cyclic voltammetry and detection limits of 0.7molL-1 by differential pulse and square-wave voltammetry. Commercial product samples were successfully analyzed with results equal to those from spectrophotometry. Because no electrode surface renewal is needed, this electrode material has many advantages.