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.

Obtención de láminas delgadas de Y-Ba-Cu-O sobre Si (100)

Se ha utilizado la evaporación secuencial de Cu, Y2O3 y BaF2 para la obtención de láminas delgadas superconductoras de YBa-CuO sobre substratos de Si monocristalino con orientación [100], recubiertos con una lámina barrera de Zr02. Se han estudiado los efectos de la variación de los espesores relativos de las láminas constituyentes y del espesor total de la lámina resultante. Las láminas se han caracterizado mediante medidas de la variación de la resistencia con la temperatura, microscopía electrónoca de barrido, difractometría de rayos X, microson-da electrónica y espectometría de masas de iones secundarios. Las láminas presentan un ligero carácter semiconductor en el estado normal, con temperaturas de inicio de la transición su-perconductora alrededor de 90 K, y resistencia nula, en el mejor de los casos, a 45 K.

Obtenção de filmes espessos de seleneto de cobre sobre carbono vítreo, ouro, titânio e cobre

Copper selenide (berzelianite) films were prepared on the title substrates using the chemical bath deposition technique (CBD). Film composition was determined by energy dispersion of x-rays. The kinetics of film growth is parabolic and film adherence limits the film thickness. On titanium, copper selenide forms islands that do not completely cover the surface, unless the substrate is prepared with a tin oxide layer; film composition also depends on the titanium oxide layer. On vitreous carbon, CBD and mechanical immobilization techniques lead to films with similar resistances for the electron transfer across the film/substrate interface. On gold, composition studies revealed that film composition is always the same if the pH is in the range from 8 to 12, in contrast to films prepared by an ion-ion combination route. On copper, a new procedure for obtaining copper selenide films as thick as 5 µm has been developed.

Electrical and magnetic properties of new compounds of the conductor anion [Ni(dmit)2]- and nitronyl nitroxide magnetic radicals

Three compounds have been synthesized with formulae [3-MeRad][Ni(dmit)2] (1), [4-MeRad][Ni(dmit)2] (2) and [4-PrRad][Ni(dmit)2] (3) where [Ni(dmit)2]- is an anionic pi-radical (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) and [3-MeRad]+ is 3-N-methylpyridinium alpha-nitronyl nitroxide, [4-MeRad]+ is 4-N-methylpyridinium alpha-nitronyl nitroxide and [4-PrRad]+ is 4-N-propylpyridinium alpha-nitronyl nitroxide. The temperature-dependent magnetic susceptibility of 1 revealed that an antiferromagnetic interaction operates between the 3-MeRad+ radical cations with exchange coupling constants of J1 = - 1.72 cm-1 and antiferromagnetism assigned to the spin ladder chains of the Ni(dmit)2 radical anions. Compound 1 exhibits semiconducting behavior and 3 presents capacitor behavior in the temperature range studied (4 - 300 K).

Propriedades e aplicações recentes das ciclodextrinas

Cyclodextrins (CDs) are cyclic oligosaccharides comprised of six or more glucose units connected by alpha-1,4 bonds. They have hydrophobic cavities with a hydrophilic exterior, and are versatile receptors for a variety of substrates. This ability allows them to be applied in many fields, as distinct as supramolecular chemistry, nanotechnology, pharmaceuticals, green chemistry, agrochemicals, analytical chemistry, toiletries, foods, and cosmetics. This review summarizes several aspects related to the physico-chemical properties of CDs and discusses their potential applications illustrated by recent examples. The prospects for their use in several areas are also described.

Active du/dt Filtering for Variable-Speed AC Drives

An oscillating overvoltage has become a common phenomenon at the motor terminal in inverter-fed variable-speed drives. The problem has emerged since modern insulated gate bipolar transistors have become the standard choice as the power switch component in lowvoltage frequency converter drives. Theovervoltage phenomenon is a consequence of the pulse shape of inverter output voltage and impedance mismatches between the inverter, motor cable, and motor. The overvoltages are harmful to the electric motor, and may cause, for instance, insulation failure in the motor. Several methods have been developed to mitigate the problem. However, most of them are based on filtering with lossy passive components, the drawbacks of which are typically their cost and size. In this doctoral dissertation, application of a new active du/dt filtering method based on a low-loss LC circuit and active control to eliminate the motor overvoltages is discussed. The main benefits of the method are the controllability of the output voltage du/dt within certain limits, considerably smaller inductances in the filter circuit resulting in a smaller physical component size, and excellent filtering performance when compared with typical traditional du/dt filtering solutions. Moreover, no additional components are required, since the active control of the filter circuit takes place in the process of the upper-level PWM modulation using the same power switches as the inverter output stage. Further, the active du/dt method will benefit from the development of semiconductor power switch modules, as new technologies and materials emerge, because the method requires additional switching in the output stage of the inverter and generation of narrow voltage pulses. Since additional switching is required in the output stage, additional losses are generated in the inverter as a result of the application of the method. Considerations on the application of the active du/dt filtering method in electric drives are presented together with experimental data in order to verify the potential of the method.

Produção, purificação e aumento da performance de ciclodextrina glicosiltransferases para produção de ciclodextrinas

Biospecific affinity chromatography was used to purify three cyclodextrin glycosyl transferases (CGTases) obtained from microorganisms isolated of soil. The cyclodextrins (CDs) production by CGTases was evaluated using starches from different sources. CDs were measured through the Complexation Theory and by HPLC. CGTase from Bacillus firmus strain 7B showed the best production (30 mmol/L of β-CD and 4.3 mmol/L of γ-CD), and its cultivation conditions were optimized. The maximum enzymatic activity was achieved using lung peptone, soluble starch and agitation speed of 160 rpm. Studied CGTases were shown quite interesting for the industrial production of CDs.

Nanocompósitos semicondutores ZnO/TiO2: testes fotocatalíticos

Titanium dioxide is an efficient photocatalist, being possible to improve its efficiency with better charge separation which occurs when it is coupled with other semiconductors. Nanometric particles of ZnO were used to impregnate TiO2 P25 in order to optimize its photocatalytic properties. ZnO/TiO2 composites were obtained at different proportions and were characterized by X-ray diffraction (XRD), micro-Raman and diffuse reflectance spectroscopies, measurement of surface area (BET) and scanning electron microscopy (SEM). Raman spectroscopy data revealed a change on the TiO2 surface due the presence of ZnO which was observed by an enlargement of TiO2 peaks and a change on the relation rate between anatase and rutile phases of the composites. The photodegradation of azo-dye Drimaren red revealed better efficiency for ZnO/TiO2 3% nanocomposite and for ZnO pure.

Efeitos da adição de átomos de Mn na rede do GaN via métodos de estrutura eletrônica

A computational method to simulate the changes in the electronic structure of Ga1-xMn xN was performed in order to improve the understanding of the indirect contribution of Mn atoms. This periodic quantum-mechanical method is based on density functional theory at B3LYP level. The electronic structures are compared with experimental data of the absorption edge of the GaMnN. It was observed that the indirect influence of Mn through the structural parameters can account for the main part of the band gap variation for materials in the diluted regime (x<0.08), and is still significant for higher compositions (x~0.18).

Aplicação de ciclodextrinas em processos têxteis

Cyclodextrins (CDs) are water soluble cyclic sugars with a hydrophobic nanometric cavity that permits the formation of host/guest inclusion complexes with a large variety of molecules, alternating their physical-chemical properties. In the present review CD research related to the processing of textiles is revised and discussed. CDs may function as encapsulating, dispersing and levelling agents in the dyeing and washing of textiles. Furthermore they may be anchored to polymers and textile fibers in order to impart special properties such as odor reduction, UV protection or for the controlled release of perfumes, aromas, mosquito repellents or substances with therapeutical effects.

O estado da arte da síntese de semicondutores nanocristalinos coloidais

Colloidal semiconductor nanocrystals, also known as quantum dots, have attracted great attention since they have interesting size-dependent properties due to the quantum confinement effect. These nanoparticles are highly luminescent and have potential applications in different technological areas, including biological labeling, light-emitting diodes and photovoltaic devices. The synthetic methods of semiconductor nanocrystals have progressed in the last 30 years, and several protocols were developed to synthesize monodisperse nanocrystals with good optical properties, different compositions and morphologies. This review describes the main methods used to synthesize nanocrystals in the II-VI and III-V systems, and the recent approaches in this field of research.

Precipitação seletiva de tamanhos em nanopartículas semicondutoras coloidais de CdTe e CdSe: um estudo por espectroscopia UV-VIS

The post-preparative size-selective precipitation technique was applied in CdTe and CdSe semiconductor nanocrystals prepared via colloidal route in water. The synthesis of CdTe and CdSe nanoparticles and the effect of the post-preparative size-selective precipitation have been characterized mainly by mean of ultraviolet and visible absorption spectroscopy (UV-Vis). It was demonstrated that the size-selective precipitation are able to isolate particles of different sizes and purify the nanoparticles as well.

Photochemical characteristics of diclofenac and its photodegradation of inclusion complexes with β-cyclodextrins

Diclofenac is one of most frequently detected compounds in the water cycle. In this work, the effect of initial concentration, liquid inclusion complexes with β-Cyclodextrins (β-CDs) on the photodegradation of diclofenac were studied. Six phototransformation products were detected by HPLC chromatograms. UV-absorption spectra of diclofenac and phototransformation products were determined. One of the phototransformation products was identified. The degradation followed pseudo-first-order kinetics. The experiment showed that irradiation of diclofenac in the presence of β-CDs increase photodegradation rate and determined the optimal molar ratio of diclofenac to β-CDs as 1:2. The reduced photohaemolytic activity of diclofenac in the presence of β-CDs may be attributed to the sequestering and stabilizing of the radical intermediates and /or photoproducts by complexation.

Celdas solares fotoelectroquímicas basadas en Bi2WO6

In this study, photoelectrochemical solar cells based on bismuth tungstate electrodes were evaluated. Bi2WO6 was synthesized by a hydrothermal method and characterized by scanning electron microscopy, UV-Vis reflectance spectroscopy, and X-ray powder diffraction. For comparison, solar cells based on TiO2 semiconductor electrodes were evaluated. Photoelectrochemical response of Grätzel-type solar cells based on these semiconductors and their corresponding sensitization with two inexpensive phthalocyanines dyes were determined. Bi2WO6-based solar cells presented higher values of photocurrent and efficiency than those obtained with TiO2 electrodes, even without sensitization. These results portray solar cells based on Bi2WO6 as promising devices for solar energy conversion owing to lower cost of production and ease of acquisition.

Vanadato de bismuto sintetizado por combustão em solução na presença de diferentes combustíveis: síntese, caracterização e estudo da atividade fotocatalítica

In this manuscript, a BiVO4 semiconductor was synthesized by solution combustion synthesis using different fuels (Alanine, Glycine and Urea). Also, the Tween® 80 surfactant was added during synthesis. BiVO4 was characterized by XRD, SEM and diffuse reflectance spectroscopy. Photocatalytic activity was evaluated by the discoloration of methylene blue at 664 nm under UV-visible light irradiation. According to XRD, the monoclinic phase of BiVO4 was obtained for the samples. The smallest particle size and highest k obs value were observed for the BiVO4/alanine sample, which promoted greater demethylation of methylene blue.