Filmes de óxidos anódicos de nióbio: efeito eletrocrômico e cinética da reação de eletro-intercalação

The aim of this work is to study the electrochromism and the reaction kinetics of lithium electrointercalation in anodic niobium oxide films. The oxide grown in an acid environment by application of an alternating potential shows interference colour (iridescence) and when reduced in lithium perclorate/PC solution, the intercalation of Li+ ions and electrons causes a reversible colour change (electrochromism), characterized here by electrochemical and optical measurements. A model where the reaction kinetics is dominated by diffusion of ionic pairs (Li+, e-) in the oxide film permitted the reproduction of current and absorbance temporal dependence, confirming the relationship between the electrochromic and electrochemical reactions. From the results obtained, a relation was established where the colour change is associated to the reduction of Nb+5 to Nb+4 ions with simultaneous cations injection.

Uso de espectrometria de massas em medidas eletroquímicas - a técnica de DEMS

The combination of cyclic voltammetry and on line mass spectrometry, called differential electrochemical mass spectrometry (DEMS), is already a well established method for on line identification and quantitative detection of the products and intermediates of electrochemical reactions. This article aims to show the principles of the method and how this technique have been used to study electrochemical problems such the electrocatalytic oxidation of organic molecules, as methanol and ethanol, at noble metal electrodes.

Técnicas in situ de baixo custo em eletroquímica: a microbalança a cristal de quartzo

Among in situ techniques, the electrochemical quartz crystal microbalance (EQCM) is a powerful tool for the study of electrochemical reactions that produce mass changes in the electrode/solution interface. This review present some systems in which the EQCM combined with classical electrochemical techniques, gives relevant information for understanding the charge transport process at a molecular level. The aim of this review is to do a brief description of experimental arrangements, with emphasis on some special cares that must be considered by the users. Secondly, some chosen electrochemical systems where the technique was successfully applied are discussed. Finally, a brief analysis of electroacoustic impedance experiments was done in order to show when the Sauerbrey equation can be used.

Eletrocatálise das reações de oxidação de hidrogênio e de redução de oxigênio

This work discusses the electrocatalytic processes taking place in the polymer electrolyte fuel cell electrodes, specifically the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR), because these are clear examples of electrochemical reactions favored by the use of electrocatalysts. Since the gaseous reactants are very little soluble in the electrolyte, the use of special electrodes, named gas diffusion electrodes, is required to promote easy and continuous access of reactant gases to the electrocatalytic sites. Besides this, other important aspects such as the use of spectroscopic techniques and of theoretical models to improve the knowledge of the electrocatalytic systems are shortly discussed.

Platinum Electrodeposition in an Ionic Liquid Analogue. Solvent Stability Monitoring

The use of ionic liquid analogues as solvents has increased in order to substitute the aqueous solvents in some applications in which the side reactions are undesirable. However these solvents prepared from the mixture in the eutectic proportion of species establishing hydrogen bonds are susceptible of electrochemical reactions. The study of platinum deposition on vitreous carbon in an ionic liquid analogue (2 urea: choli ne chloride) is presented; the electrochemical study has permitted to interpret the sequence of the metal deposition process and simultaneously to analyze the behavior of the ionic liquid analogue along the process. Reduction reactions of the solvent relat ed both to the electronation of choline and hydrogen formation have been detected. Different substrata have been used in order to test the possibility and the extent of these reactions depending on the nature of material. The results indicate that the feas ible electrochemical window of the substrate/solvent is highly dependent of the kind of substrate; the negative limit is tied by the massive hydrogen reaction, reaction enhanced by the electrocatalytic character of the substrate.

Espectroscopia de impedância eletroquímica aplicada ao estudo das reações heterogêneas em ânodos dimensionalmente estáveis

This paper discusses different aspects related to the application of electrochemical impedance spectroscopy (EIS) in the study of heterogeneous electrochemical reactions occurring on Dimensionally Stable anodes (DSA®). The most relevant aspects of the semiconductor/electrolyte interface, the application of the EIS classical equivalent circuit approach and the ac porous model in DSA are presented. The paper shows that DSA type electrodes can be consistently investigated by using the ac porous model and an analysis is presented showing the advantage of applying this kind of approach to study heterogeneous reactions on DSA electrodes. Furthermore, some preliminary results on Ti/Ru0,3Ti(0,7-x)Sn x O2 based electrodes are presented to exemplify the use of the ac porous model analysis.

Princípio e utilização da técnica de efeito miragem de concentração

The aim of this work is to present the theoretical and experimental aspects of the mirage effect technique. We are especially interested in the concentration mirage effect, which is a powerful tool in the study of electrochemical reactions that produce ionic movements close to electrodes and to get some fundamental information on mass transport and charge transfer during electrochemical processes. Limitations of this technique are discussed as well as the recent attempts to overcome them.

Evidence of fluoride oxidation for development of the electrochemically-induced crystallization observed in lead oxyfluoroborate glasses

This work reports on a distinct experimental procedure conceived to closely approach the question of development of crystallization in lead oxyfluoroborate glasses in the presence of an electric field. After proposing earlier that this phenomenon should involve occurrence of redox-type electrochemical reactions occurring at the electrodes. it was in fact recently shown that a direct contact of the glasses with both the cathode and anode revealed essential, provided that crystallization did not develop when ions migration to these electrodes became frustrated. The present study demonstrates that. even in Pt,Ag/Glass/YSZ:PbF(2)/Ag,Pt-type electrochemical cells subjected to electric field action, where YSZ:PbF(2) represents composite-like mixtures (formed by Y(2)O(3)-doped ZrO(2) and PbF(2)) placed between the glass and anode. crystallization was observable in given cases. In summary, supported by (micro)structural and electrical characterizations, clear evidence is provided here that, besides Pb(2+) reduction at the cathode, crystallization really involves simultaneous F(-) oxidation at the anode, completing thus the whole redox electrochemical reaction so far postulated. In these cases, F(-) migration to the anode was achievable following PbF(2) percolative-like paths through the YSZ:PbF(2) mixtures. (C) 2010 Elsevier B.V. All rights reserved.

Immobilization of Catalysts of Biological Interest on Porous Oxidized Silicon Surfaces

The present paper deals with the immobilization of redox mediators and proteins onto protected porous silicon surfaces to obtain their direct electrochemical reactions and to retain their bioactivities. This paper shows that MP-11 and viologens are able to establish chemical bonds with 3-aminopropyltriethoxylsilane-modified porous silicon surface. The functionalization of the surfaces have been fully characterized by energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS) to examine the immobilization of these mediators onto the solid surface. Amperometric and open circuit potential measurements have shown the direct electron transfer between glucose oxidase and the electrode in the presence of the viologen mediator covalently linked to the 3-aminopropyltriethoxylsilane (APTES)-modified porous silicon surfaces.

Estudo de reatores eletroquímicos para remoção de Cu2+ , Zn2+, Fenol e BTEX em água produzida

The production of water has become one of the most important wastes in the petroleum industry, specifically in the up stream segment. The treatment of this kind of effluents is complex and normally requires high costs. In this context, the electrochemical treatment emerges as an alternative methodology for treating the wastewaters. It employs electrochemical reactions to increase the capability and efficiency of the traditional chemical treatments for associated produced water. The use of electrochemical reactors can be effective with small changes in traditional treatments, generally not representing a significant additional surface area for new equipments (due to the high cost of square meter on offshore platforms) and also it can use almost the same equipments, in continuous or batch flow, without others high costs investments. Electrochemical treatment causes low environmental impact, because the process uses electrons as reagent and generates small amount of wastes. In this work, it was studied two types of electrochemical reactors: eletroflocculation and eletroflotation, with the aim of removing of Cu2+, Zn2+, phenol and BTEX mixture of produced water. In eletroflocculation, an electrical potential was applied to an aqueous solution containing NaCl. For this, it was used iron electrodes, which promote the dissolution of metal ions, generating Fe2+ and gases which, in appropriate pH, promote also clotting-flocculation reactions, removing Cu2+ and Zn2+. In eletroflotation, a carbon steel cathode and a DSA type anode (Ti/TiO2-RuO2-SnO2) were used in a NaCl solution. It was applied an electrical current, producing strong oxidant agents as Cl2 and HOCl, increasing the degradation rate of BTEX and phenol. Under different flow rates, the Zn2+ was removed by electrodeposition or by ZnOH formation, due the increasing of pH during the reaction. To better understand the electrochemical process, a statistical protocol factor (22) with central point was conducted to analyze the sensitivity of operating parameters on removing Zn2+ by eletroflotation, confirming that the current density affected the process negatively and the flow rate positively. For economical viability of these two electrochemical treatments, the energy consumption was calculated, taking in account the kWh given by ANEEL. The treatment cost obtained were quite attractive in comparison with the current treatments used in Rio Grande do Norte state. In addition, it could still be reduced for the case of using other alternative energy source such as solar, wind or gas generated directly from the Petrochemical Plant or offshore platforms

Espectroscopia de impedância eletroquímica aplicada ao estudo das reações heterogêneas em ânodos dimensionalmente estáveis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrode surface modifications improve cathode hydrogen production and anode capacity in Ni-MH batteries

This paper reports results from electrochemical evaluations of electrodes used as cathodes for a hydrogen evolution reaction and anodes in Ni-MH batteries that had been surface-modified by micro-encapsulation, co-deposition and sol-gel methods. The surface modifications produced actual improvements in the corresponding electrochemical reactions by enhancing the performance and/or the mechanical stability of the electrode material. (c) 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Electronic Perspective on the Electrochemistry of Prussian Blue Films

The derivative of the voltabsommetric scans, together with previous nano-electrogravimetric and X-ray diffraction results, allow different electrochemical processes to be distinguished during the Prussian blue (PB) voltammetric scan. Potassium, proton, and hydrated proton counterions involved in PB electrochemistry are related here to the electrochemical reactions of specific Fe sites. Potassium counterions show two different sites for their insertion: one located in the crystalline framework and another in ferrocyanide vacancies. From the monitoring of electroactive Fe sites, the covalent-exchange model is suggested as one of the first approaches to explain the origin of the PB magnetic ordering observed at room temperature during voltammetric scanning.

Toward pH-controllable bioelectrocatalysis for hydrogen peroxide based on polymer brushes

In the present work, a biosensor was built with smart material based on polymer brushes. The biosensor demonstrated a pH-sensitive on-off property, and it was further used to control or modulate the electrochemical responses of the biosensor. This property could be used to realize pH-controlled electrochemical reaction of hydrogen peroxide and HRP immobilized on polymer brushes. The composite film also showed excellent amperometric i-t response toward hydrogen peroxide in the concentration range of 0-13 μM. In future, this platform might be used for self-regulating targeted diagnostic, drug delivery and biofuel cell based on controllable bioelectrocatalysis. © 2013 Elsevier B.V.

Why silver deposition is so fast: Solving the enigma of metal deposition

A perfect match: Silver deposition is one of the fastest electrochemical reactions, even though the Ag+ ion loses more than 5 eV solvation energy in the process. This phenomenon, an example of the enigma of metal deposition, was investigated by a combination of MD simulations, DFT, and specially developed theory. At the surface, the Ag+ ion experiences a strong interaction with the sp band of silver, which catalyzes the reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.