Carbon-supported platinum-iridium nanowire-shape electrocatalysts containing 20% of metallic loading were synthesized by chemical reduction method using formic acid as a reducing agent and tested towards the oxidation of ethanol in acidic medium. The developed electrocatalysts were synthesized with the following compositions: Pt0.9Ir0.1/C, Pt0.8Ir0.2/C, Pt0.7Ir0.3/C, Pt0.6Ir0.4/C and Pt0.5Ir0.5/C using for comparison the commercial Pt/C Alfa Aesar catalyst. Physico-chemical characterization was performed using X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray fluorescence (XRF, for chemical composition) techniques. All the nanowires present a face-centered cubic crystalline structure of the platinum with modifications in the lattice parameter due to the inclusion of iridium. The XRF analyzes show that the theoretical compositions of the synthesized catalysts are very close to the experimental nominal values. TEM analyses showed the formation of nanowires by the synthesis method used. The electrochemical results on the oxidation of ethanol show that the addition of a second metal to the platinum in the composition of the nanowires increases the catalytic activity of the electrode. The nanowire catalysts with low Ir content (Pt0.9Ir0.1/C, Pt0.8Ir0.2/C, Pt0.7Ir0.3/C) present the best outcomes under the analyzed conditions and are promising for application as anodes in direct ethanol fuel cells.

Demonstra-se, pela primeira vez usando experimentos simples de voltametria cíclica, que a pré-polarização anódica de eletrodos de diamante dopado com boro (DDB) conduz a superfícies parcialmente bloqueadas. Eletrodos de DDB anodicamente pré-polarizados, com diferentes níveis de dopagem de boro, apresentaram respostas de voltametria cíclica sigmoidais para o par redox ferro/ferricianeto a baixas velocidades de varredura (0,5 mV s-1). Por outro lado, quando os mesmos eletrodos são pré-polarizados catodicamente, observaram-se respostas quase-reversíveis e reversíveis na mesma velocidade de varredura, correspondendo a superfícies eletroquimicamente heterogêneas. Assim, as superfícies de DDB podem atuar parcialmente bloqueadas ou com eletroatividade heterogênea, dependendo da polarização, anódica ou catódica, respectivamente.

It is demonstrated, for the first time using simple cyclic voltammetry experiments, that the anodic pre-polarization of boron-doped diamond electrodes (BDD) leads to partially blocked surfaces. Anodically pre-polarized BDD electrodes, with different boron-doping levels, presented sigmoidal cyclic voltammetry profiles to the ferro/ferri-cyanide redox couple under low scan rate (0.5 mV s-1). On the other hand, when the same electrodes are cathodically pre-polarized, quasi-reversible and reversible responses were observed under the same scan rate, corresponding to surfaces with heterogeneous electroactivity. Thus, BDD surfaces can act as partially blocked or with heterogeneous electroactivity, depending on the polarization, anodic or cathodic, respectively.

Fotoeletrodos foram usados para tratar efluentes têxteis sintéticos contaminados com corante azul indantreno. Dois meios de tratamento foram usados (NaCl e Na2SO4) com variações de temperatura, pH, densidade de corrente, concentrações de corante e de cloreto. Um método de Pechini modificado foi aplicado para obter os eletros de Ti/Ru (Ti, Ru, Ti0.5Ru0.5, Ti0.75Ru0.25 e Ti0.25Ru0.75) contendo nanoparticulas de TiO2 anatase e a análise de degradação de cor foi realizada. Caracterizações física (microscopia de força atômica e difratometria de raios X) e eletroquímica (voltametria cíclica) foram feitas. As condições que geraram maior remoção de cor para o sistema apresentado foram NaCl 0,05 mol L-1, 100 mA cm-2, 35 ºC e pH 7, independente da concentração de corante para o eletrodo de Ti0.25Ru0.75.

Photoelectrodes were used to treat synthetic textile wastewater contaminated with indanthrene blue dye. Two media of treatment were used (NaCl and Na2SO4), with variations on temperature, pH, current density, dye and chloride concentration. A modified Pechini method was applied to obtain Ti/Ru-based electrodes (Ti, Ru, Ti0.5Ru0.5, Ti0.75Ru0.25 and Ti0.25Ru0.75) containing anatase TiO2 nanoparticles and a color degradation analysis was done. Physical (atomic force microscopy and X-ray diffractometry) and electrochemical characterizations (cyclic voltammetry) were considered. The condition that yielded highest color removal for the system presented 0.05 mol L-1 NaCl, 100 mA cm-2, 35 °C and pH 7, independent of the dye concentration for the Ti0.25Ru0.75 electrode.

The wastewaters from biodiesel production contain as primarily wastes sodium or potassium soaps, fatty acids, glycerin, alcohol and other contaminants. In general, these waters are chemically unsuitable for release to any water body, so, it is necessary the adoption of techniques for the treatment of this effluent. In this review, electrochemical, biological, physicochemical, and combined treatments reported for the removal of the wastewater containing pollutants come from biodiesel production have been summarized. In addition, the recovery, the reuse, the energy production and the synthesis of new compounds from the organic matter contained in this kind of effluent are also reviewed.

The potentiality of the use of ultrasound radiation in association with a boron-doped diamond electrode was evaluated on the voltammetric determination of the pesticide carbaryl. Improvements in the sensitivity, limit of detection and reproducibility of the measurements were observed due to both, the enhancement of mass transport and the cleaning of the electrode surface provided by ultrasound. Satisfactory recovery levels for carbaryl in pure water (96-98%) and pineapple juice (89-92%) for quiescent and sonovoltammetric methodologies were obtained. These methodologies can be alternative tools for the analyses of pesticides in fruit samples, mainly the insonated condition that improve the analytical performance and dispense intermediary cleanings of the electrode surface.

An analytical method for the determination of the anti-inflammatory drug 5-aminosalicylic acid (5-ASA) in pharmaceutical formulations using square wave voltammetry at pencil graphite electrodes was developed. After the optimization of the experimental conditions, calibration curves were obtained in the linear concentration range from 9.78 × 10-7 to 7.25 × 10-5 mol L-1 resulting in a limit of detection of 2.12 ± 0.05 x 10-8 mol L-1. Statistical tests showed that the concentrations of 5-ASA in commercial tablets and enemas obtained with the proposed voltammetric method agreed with HPLC values at a 95% confidence level.

The beneficial effects of the ultrasound (US) like the cleaning of electrode surface and enhancement of mass transport were evaluated in association with potentiostatic electrolyses for the degradation of pentachlorophenol (PCP) at 3.0 V vs. Ag/AgCl, using a boron-doped diamond (BDD) electrode during 270 minutes. Different decay levels of the PCP spectrum bands in 220, 251 and 321 nm, respectively, were observed after application of ultrasound without electrochemical process (18.1, 17.7 and 19.8 %), silent electrolyses (29.3, 71.6 and 70.8 %), pulsed sonoelectrolysis (31.0, 75.1 and 76.3%) and sonoelectrolyses (39.2, 80.0 and 82.6 %). For silent and sonoelectrolyses processes, cleaning/reactivation of the BDD surface by acetonitrile and/or electrochemical treatment was necessary. The pulsed sonolectrolysis were carried out purposely without cleaning/reactivation of the surface. The results showed greater PCP degradation for insonated studies than those obtained for the silent electrolyses, due to the increase of mass transport, minimization of the electrode fouling and the combined generation of hydroxyl radicals by both ultrasound and the polarized BDD surface. These tools (US and BDD), especially the pulsed sonoelectrolysis, can improve the degradation of pesticides and their metabolites in the environment and enable the use of sonoelectrochemistry for wastewater remediation.

The aim of this review is to present and discuss the applications of ultrasound in electrochemical systems such as in sonoelectroanalysis and sonoelectrolysis for the electrochemical combustion of organic compounds. Initially, theoretical and experimental aspects are discussed, particularly those related to the enhancement of mass transport and the surface cleaning effects. Some results are included to illustrate alternative geometries for the experimental measurements and the working electrodes used in these systems. In the sequence, the available publications are presented and discussed to demonstrate that ultrasound combined with electrochemical techniques is a powerful set-up for the detection of analytes such as metals and/or organic compounds in hostile media and for the effective destruction of toxic organic substances. At the end, a table summarizes the results already published in the literature.

A determinação sonovoltamétrica do 4-nitrofenol foi estudada sobre um eletrodo de diamante dopado com boro. Foram observadas melhorias significativas na sensibilidade analítica devido à limpeza da superfície eletródica e ao aumento no transporte de espécies ao eletrodo proporcionados pelo ultra-som. Desta maneira, para os processos de oxidação e redução, os limites de detecção diminuíram de 11.7 para 3.87 e de 6.38 para 2.57 µg L-1, respectivamente.

The sonovoltammetric determination of 4-nitrophenol was studied on a boron-doped diamond electrode. Significant improvements in the analytical sensibility were observed due to electrode surface cleaning and the enhancement in the transport of species to the electrode surface provided by ultrasound. Thus, for the oxidation and reduction process, the limit of detection diminished from 11.7 to 3.87 and from 6.38 to 2.57 µg L-1, respectively.

This work describes the development of electroanalytical methodologies for the determination of atrazine, ametrine and simazine by square wave voltammetry on a mercury electrode. For pure atrazine and pure ametrine, the detection limits (DL) were 3.7 and 4.3 µg L-1, respectively, while they increased to 4.8 and 6.5 µg L-1 in the presence of 3.0 x 10-6 mol L-1 of the other component (a mathematical deconvolution program was used in the mixture cases). The voltammetric response for simazine could not be separated from that of atrazine and measurements were carried out only in pure simazine solutions (DL: 7.5 µg L-1).

RESUMO Com o objetivo de aprofundar investigações anteriores, foram realizadas modificações superficiais diretas em eletrodos de diamante dopados com boro (DDB), com óxidos metálicos (PtOx, RuO2, IrO2 e PbO2) e com alguns compósitos mistos, utilizando a técnica Sol-Gel. Estes materiais foram estudados por microscopia de força atômica (MFA) e os resultados indicaram a formação de sítios de deposição heterogênea. Técnicas eletroquímicas foram utilizadas para estabelecer a atividade catalítica para a reação de desprendimento de oxigênio (RDO) e para reação de oxidação de etanol em meio ácido utilizando os compósitos de PtOx e PtOx-RuO2. Testou-se ainda a estabilidade de um depósito de PtOx, recoberto por um filme de Nafion®, por meio de operação contínua de longa duração. Estudos de voltametria cíclica comparativa mostraram que a área superficial ativa dos novos materiais mudou consideravelmente com o método de modificação proposto. O eletrodo de IrO2/BDD mostrou o melhor desempenho para a RDO, iniciando o processo de oxidação em ~ 1.4 V vs. HESS, valor este 200 mV menor do que o observado sobre um eletrodo de PtOx/BDD. Foi observada uma pequena perda da atividade do eletrodo de PtOx/BDD (6%) depois de realizada eletrólise de 4 horas, enquanto que 1000 ciclos voltamétricos deixaram a superfície praticamente inalterada. Os estudos realizados mostram que as atividades satisfatórias dos eletrodos preparados pelo método Sol-Gel podem constituir ferramentas interessantes de pesquisa, visando principalmente a utilização destes materiais em aplicações práticas.

Continuing previous investigations, direct surface modifications of boron-doped diamond (BDD) electrodes with metal oxides (PtOx, RuO2, IrO2 and PbO2) and with some mixed composites were carried out by the Sol-Gel technique. The materials were studied by atomic force microscopy (AFM) to determine their surface topologies and by electrochemical techniques to establish the catalytic activity towards the oxygen evolution reaction (OER) and also, for the PtOx and PtOx-RuO2 composites, the ethanol oxidation reactions in acid media. The stability of PtOx coating covered by a Nafion® film was also tested by long-term operation. The AFM results indicated sites of heterogeneous deposition and the electrochemical studies demonstrated that the active surface area changed considerably with the proposed method of modification. The IrO2/BDD electrode showed the best performance to the OER with the onset of the oxidation current at ~1.4 V, a value 200 mV lower than for the PtOx/BDD electrode. The enhanced stability of PtOx/BDD electrodes achieved by the application of a Nafion® film and already reported in acid media was further proved using the ethanol oxidation reaction. Only a small loss of activity (6%) was observed after 4-hours electrolysis while one-thousand voltammetric cycles left the surface practically unchanged. In addition, preliminary studies for the same reaction on PtOx/BDD and PtOx-RuO2/BDD electrodes demonstrated the excellent activity of these mixed Sol-Gel coatings on the BDD surface and the possibility of further investigations for practical applications.