Metodologia para o crescimento de esferas monocristalinas de metais nobres

This paper describes in detail a technique employed to grow quasi-spherical single crystals of noble metals for electrochemical applications, using platinum as an example. The metal beads were formed by melting the extremity of a wire in an oxygen / butane flame. X-ray techniques were used to check the crystallization and to determine the orientation of the crystals. Treatment with a pure hydrogen flame followed by a cooling procedure in a hydrogen / argon atmosphere were used for conditioning the well-defined platinum single crystal surfaces. Finally, electrochemical characterization of the Pt(111), Pt(110) and Pt(100) surfaces was done in diluted sulfuric acid solution in the hydrogen adsorption / desorption potential region.

Preparação de LiNbO3 e LiNbO3:Eu3+ pelo método dos precursores poliméricos

The ferroelectric compound LiNbO3 was prepared by the polymeric precursors method in the polycrystalline form containing different concentrations of Eu3+. The compounds were characterized by X-ray diffraction, vibrational and electronic spectroscopy. Electronic spectroscopy was shown to be sensitive to small concentrations of contaminating phases allowing a good control of the compound purity. The presence of Eu3+ ions leads to the formation of the LiNb3O8 phase in the range of 500 to 800 °C. Above this temperature range LiNbO3 and tetragonal (T') EuNbO4 were obtained.

Bastões de grafite reciclados de baterias comuns e seu uso como eletrodo modificado em hidrogenação eletrocatalítica de alguns substratos orgânicos

This paper presents some results on the employ of recycled graphite electrode obtained from used common 1.5 V batteries in the preparation of modified electrode and the electrocatalytical hydrogenation of benzaldehyde and of n-valeraldehyde. This inexpensive and easy to obtain electrode was prepared by coating it with a 1:1 mixed film of poly-(allylfenil ether): poly-[allyl p-(2-ethylammonium) benzene ether] and introduction of dispersed platinum particles by ion exchange and reduction of PtCl4-2. Electroreduction of H+ from aqueous H2SO4 using the proposed electrode hydrogenated the substrates in a way comparable with that of vitreous carbon electrode.

Construção e aplicação de eletrodo de aço inoxidável UNS S31254 como eletrodo indicador em titulações condutimétricas

UNS S31254 SS electrodes have been built to substitute platinum in conductimetric titrations. The electrodes were tested in both acid-basic titration (chloridric acid and sodium hydroxide) and precipitation titration (sodium chloride and argentum nitrate as titrant). The practical application was exemplified from conductimetric tritations of HF ¾ HNO3 mixtures used in metalurgical industry to passivate stainless steels. The results were compared with those obtained using commercial platinum electrodes. The equivalent volumes obtained were comparable within 3% experimental error. Its application depends on the nature of electrolyte. These results have shown that stainless steel, less expensive than platinum (about three order of magnitude), can substitute platinum electrodes in routine analyses and didactic laboratories.

Recuperação de metais de catalisadores mássicos e monometálicos

This work presents a study on the dissolution of some commercial monometallic and non-supported deactivated catalysts in HF + H2O2 mixtures (and, eventually, other media) under mild experimental conditions, after a previous oxidation step. The samples were neither crushed nor grinded. The best experimental conditions were dependent on the nature of the support and of the active phase. For example, the Pt/Al2O3 catalyst was dissolved in about 10 minutes, without agitation and heating; however, dissolution of the Pd/Al2O3, Ni/Al2O3, Ni/SiO2, Cu/Al2O3 and V2O5 samples required a temperature of 60 ºC and an agitation of 400 rpm. A careful addition of a NaOH solution allowed a quantitative precipitation of aluminium as criolite (Na3AlF6) or precipitation of Si as Na2SiF6; NaF was obtained as a by-product. As expected, processing of Pd/C, V2O5 and CuO.Cr2O3 samples was relatively simple. Metals recovery from catalysts reached a quantitative level in all samples studied; it is particularly interesting that platinum and palladium could be easily recovered in a single step process, thus separing them from aluminium.

Hidrogenação eletrocatalítica de substratos orgânicos: estudo da eficiência dos metais nobres níquel, paládio e platina usando eletrodos modificados

Nickel, palladium and platinum micro-crystals were dispersed in films covering a vitreous carbon plate electrode by ion exchange followed by electroreduction of their ions. These modified electrodes were used in the electrocatalytic hydrogenation of several substrates of different classes and their efficiency is reported. A comparison among them was performed based on the structural characteristics of the metals. A modified electrode containing platinum showed to be more efficient than a palladium modified electrode and the one of nickel was the less efficient.

Métodos de preparação de nanopartículas metálicas suportadas em carbono de alta área superficial, como eletrocatalisadores em células a combustível com membrana trocadora de prótons

Fuel cells are attracting much interest as efficient and clean energy conversion devices. The main components of low temperature fuel cells are the electrocatalysts used to promote the anodic and cathodic reactions, which are based on platinum and platinum alloys. These electrocatalysts are normally prepared in the form of metal nanoparticles supported on a conductive material, usually high surface area carbon, to improve catalyst utilization and reduce cost. This work presents and comments some methods used presently to produce these electrocatalysts. The performances of the produced electrocatalysts are compared to that of state-of-the-art commercial E-TEK electrocatalysts.

Influência do material e volume do porta-amostra na determinação termogravimétrica do teor de cinzas em mel

The results suggest that the two variables studied are significant and that they may be independently optimized. The material of the sample holder interferes with the incineration process only due to the amount of heat transfered. The sample holder volume aids diffusion of the atmosphere to the honey sample, minimizing the foaming effect. According to the results, for the thermogravimetric analysis of ash content in honey, sample holders of platinum or alumina of 150 µL are indicated.

Síntese e caracterização de novos complexos de platina (II) com ligantes derivados do furano e nitrofurano

Platinum (II) complexes, for example, cisplatin and carboplatin, have been used as chemotherapeutic agents for the treatment of various types of cancer. Several other complexes of this metallic ion are also under clinical evaluation. This work describes the synthesis of five new platinum (II) complexes having furan and 5-nitrofuran derivatives and chloride as ligands. The compounds were characterized by NMR, IR and elemental analysis.

Filmes de nanodiamantes para aplicações em sistemas eletroquímicos e tecnologia aeroespacial

The goal of this work is to show the use of undoped nanodiamond films as a new material for electrochemical and aerospace applications. Correlation between the applications and physico-chemical features of nano and conventional CVD polycrystalline diamond films are presented. An important and innovative application of these nanodiamonds is organic electrosynthesis, including pharmaceutical and water disinfection products, as well as electroanalytical applications, for example, development of biosensors for detection of glucose, glutamate and dopamine. In aeronautics and space developments, these nanodiamonds could be used as electrodes in rechargable batteries and in tribological investigations.

Síntese e reatividade de complexos platina-trifenilestibina: uma revisão bibliográfica

This article deals with synthesis and reactivity of complexes with triphenylstibine (SbPh3) as the ligand. A comparative study of analogous complexes of triphenylphosphine (PPh3) and triphenylarsine (AsPh3) with platinum in the oxidation states zero, two and four is included. The bibliographic revision includes publications since 1936, when the first Pt(II) complex with triphenylstibine was described.

Síntese e caracterização de um novo complexo de platina (IV) a partir de seu análogo de platina (II) utilizando iodo molecular como agente oxidante: uma rota sintética interessante para obtenção de novos complexos de platina

In an attempt to reduce toxicity and widen the spectrum of activity of cisplatin and its analogues, much attention has been focused on designing new platinum complexes. This work reports the synthesis and characterization of novel compounds of the platinum (II) and platinum (IV) containing 2-furoic hydrazide acid and iodide as ligands. Although the prepared compounds do not present the classical structure of biologically active platinum analogues, they could be potentially active or useful as precursors to prepare antitumor platinum complexes. The reported compounds were characterized by ¹H NMR, 13C NMR, 195Pt NMR, IR and elemental analyses.

Propriedades estruturais e microestruturais de manganitas dopadas com cobre

We report a structural study on polycrystalline La0.86Sr0.14Mn1-y Cu yO3+delta samples (y = 0, 0.05, 0.10, 0.15, 0.20) using refinement of powder X-ray diffraction data and analysis of scanning electron microscopy images. It is found that the structure remains rhombohedral through the whole series, with a decrease in the average Mn-Mn bond distances, slight variations in Mn-O-Mn angle and reduction in the unit cell volume with increasing Cu amounts. The values of Mn-Mn distances suggest compact structures with d within ±1%. Scanning electron microscopy images reveal homogeneous microstructure in all samples, besides a trend for smaller grains and larger porosity with increasing Cu content.

Influência de M/C (M = Mo, Cu, Fe e W) incorporado à camada difusora do eletrodo de difusão de gás frente à reação de oxidação de hidrogênio na presença de CO

The performance of proton exchange membrane fuel cells (PEMFC) with Pt-based anodes is drastically lowered when CO-containing hydrogen is used to feed the system, because of the strong adsorption of CO on platinum. In the present work the effects of the presence of a conversion layer of CO to CO2 composed by several M/C materials (where M = Mo, Cu, Fe and W) in gas diffusion anodes formed by Pt catalysts were investigated. The diffusion layers formed by Mo/C e W/C show good CO-tolerance, and this was attributed to the CO removal by parallel occurrence of the water-gas shift reaction and the so-called bifunctional mechanism.

Dinâmica complexa no sistema bromato/hipofosfito/acetona/manganês e ferroína

New chemical systems have been recently designed for the study of complex phenomena such as oscillatory dynamics in the temporal domain and spatiotemporal pattern formation. Systems derived from oscillators based on the chemistry of bromate are the most extensively studied, with the celebrated Belousov-Zhabotinsky (BZ) reaction being the most popular example. Problems such as the formation of bubbles (CO2) and solid precipitate in the course of the reaction and the occurrence of simply short-lived oscillations under batch conditions are very common and, in some cases, compromise the use of some of these systems. It is investigated in this paper the dynamic behavior of the bromate/hypophosphite/acetone/dual catalyst system, which has been sugested as an interesting alternative to circumvent those inconvenients. In this work, manganese and ferroin are employed as catalysts and the complete system (BrO3-/H2PO2-/acetone/Mn(II)-ferroin) is studied under batch conditions. Temporal symmetry breaking was studied in a reactor under agitation by means of simultaneous records of the potential changes of platinum and Ag/AgBr electrodes, both measured versus a reversible hydrogen electrode. Additionally, spatio-temporal formation of target patterns and spiral waves were obtained when the oscillating mixture was placed in a quasi two-dimensional reactor.