Metil coenzima M redutase (MCR) e o fator 430 (F430)

This review presents studies on methyl coenzyme M reductase, the biological system Factor 430 (F430) and the use of nickel(II) complexes as structural and functional models. The ability of F430 and nickel(II) macrocycle complexes to mediate the reductive dehalogenation of cyclohexyl halogens and the CH3-S bond cleavage of methyl CoM (by sodium borohydride and some intermediate species) proposed for the catalytic cycle of the biological system F430 was reviewed. The importance of the structure of the nickel complexes and the condition of the catalytic reduction reaction are also discussed.

Síntese e caracterização de perovskitas LaNi(1-x)Co xO3 como precursores de catalisadores para a conversão do metano a gás de síntese pela reforma com CO2

LaNiO3 perovskite was modified by partial substitution of nickel by cobalt in order to increase the stability and resistance to carbon deposition during the methane CO2 reforming. The results showed that a suitable combination of precipitation and calcination steps resulted in oxides with the desired structure and with important properties for application in heterogeneous catalysis. The partial substitution of Ni by Co resulted in lower rates of conversion of both the reactants, but the catalyst stability was highly increased. The LaNi0.3Co0.7O3 catalyst, calcined at 800 ºC, was the most active under the reaction conditions.

Produção de hidrogênio a partir da reforma a vapor de etanol utilizando catalisadores Cu/Ni/gama-Al2o3

Cu/Ni/gamma-Al2O3 catalysts were prepared by an impregnation method with 2.5 or 5% wt of copper and 5 or 15% wt of nickel and applied in ethanol steam reforming. The catalysts were characterized by atomic absorption spectrophotometry, X-ray diffraction, temperature programmed reduction with hydrogen and nitrogen adsorption. The samples showed low crystallinity, with the presence of CuO and NiO, both as crystallites and in dispersed phase, as well as of NiO-Al2O3. The catalytic tests carried out at 400 ºC, with a 3:1 water/ethanol molar ratio, indicated the 5Cu/5Ni/Al2O3 catalyst as the most active for hydrogen production, with a hydrogen yield of 77% and ethanol conversion of 98%.

Recuperação de cádmio de baterias níquel-cádmio via extração seletiva com tributilfosfato (TBP)

This work describes a recovery process of cadmium from spent nickel-cadmium batteries by a new hydrometallurgical route based on the selective extraction in hydrochloric acid medium with tributylphosphate (TBP), alone or dissolved in kerosene. The best results were obtained when TBP concentration was at least 75 vol%. Nickel extraction was negligible under these conditions. It was isolated after processing the rafinate through an anionic ion-exchange column. Final wastes generated are basically sodium chloride solutions, with no turbidity, color or heavy metals present in significant amounts.

Electrooxidación de glifosato sobre electrodos de níquel y cobre

The electrochemical oxidation of glyphosate on an electrode of nickel and on one of copper was studied. With both electrodes electrochemical signals related to the glyphosate concentration were observed. However, the behaviour of the copper electrode was much better than that of the nickel electrode. A calibration curve was obtained of the electrical signal of this electrode as a function of the glyphosate concentration. The detection limit was 30 µM. In the case of nickel, an increase in the oxidation signal, which is related to the glyphosate concentration, was obtained. However, the results were less reproducible and additional information is necessary to propose an interaction mechanism between glyphosate and the electrode.

Rota hidrometalúrgica de recuperação de molibdênio, cobalto, níquel e alumínio de catalisadores gastos de hidrotratamento em meio ácido

This work describes a hydrometallurgical route for processing spent commercial catalysts (CoMo and NiMo/Al2O3). Samples were preoxidized (500 ºC, 5 h) in order to eliminate coke and other volatile species present. The calcined solid was dissolved in concentrated H2SO4 and water (1:1 vol/vol) at 90 ºC; the insoluble matter was separated from the solution. Molybdenum was recovered by solvent extraction using tertiary amines at pH around 1.8. Cobalt (or nickel) was separated by addition of aqueous ammonium oxalate at the above pH. Phosphorus was removed by passing the liquid through a strong anion exchange column. Aluminum was recovered by neutralizing the solution with NaOH. The route presented in this work generates less final aqueous wastes because it is not necessary to use alkaline medium during the metal recovery steps.

Chelating Adsorbents in Purification of Hydrometallurgical Solutions

In this thesis, equilibrium and dynamic sorption properties of weakly basic chelating adsorbents were studied to explain removal of copper, nickel from a concentrated zinc sulfate solution in a hydrometallurgical process. Silica-supported chelating composites containing either branched poly(ethyleneimine) (BPEI) or 2-(aminomethyl)pyridine (AMP) as a functional group were used. The adsorbents are commercially available from Purity Systems Inc, USA as WP-1® and CuWRAM®, respectively. The fundamental interactions between the adsorbents, sulfuric acid and metal sulfates were studied in detail and the results were used to find the best conditions for removal of copper and nickel from an authentic ZnSO4 process solution. In particular, the effect of acid concentration and temperature on the separation efficiency was considered. Both experimental and modeling aspectswere covered in all cases. Metal sorption is considerably affected by the chemical properties of the studied adsorbents and by the separation conditions. In the case of WP-1, acid affinity is so high that column separation of copper, nickel and zinc has to be done using the adsorbent in base-form. On the other hand, the basicity of CuWRAM is significantly lower and protonated adsorbent can be used. Increasing temperature decreases the basicity and the metals affinity of both adsorbents, but the uptake capacities remain practically unchanged. Moreover, increasing temperature substantially enhances intra-particle mass transport and decreases viscosities thus allowing significantly higher feed flow rates in the fixed-bed separation. The copper selectivity of both adsorbents is very high even in the presence of a 250-fold excess of zinc. However, because of the basicity of WP-1, metal precipitation is a serious problem and therefore only CuWRAM is suitable for the practical industrial application. The optimum temperature for copper removal appears to be around 60 oC and an alternative solution purification method is proposed. The Ni/Zn selectivity of both WP-1 and CuWRAM is insufficient for removal of the very small amounts of nickel present in the concentrated ZnSO4 solution.

Alteraciones químicas y fitodisponibilidad de níquel en suelo tratado con lodo albañal

The alteration of soil chemicals and its influence on availability (DTPA extractant method) and phytoavailability (63Ni L-value, isotopic method) of Ni was studied in sewage sludge-amended soil at different pHs. The soil pHs were 4.3, 5.3 and 5.9 and the rates of sewage sludge (SS) 0, 15, 30, 45 and 60 Mg ha-1. The chemical and physicochemical soil characteristics were altered by the SS rate and increased the Ni availability and phytoavailability. The isotopic method (63Ni L-value) was more efficient in predicting the Ni phytoavailability that the Ni-DTPA extractant in soil pHs 5.3 and 5.9.

Estudo da eletrocristalização de Ni e Ni-P sobre ultramicroeletrodo de platina

This work describes a comparative study of the electrocrystallization of Ni and Ni-P on Pt ultramicroelectrodes using chronoamperometric measurements. It was possible to confirm that in all cases a progressive nucleation was the predominant mechanism. Moreover, the application of the Atomistic Theory to the experimental rate of nuclei formation showed that the number of atoms in the critical nucleus was zero, except for Ni-P on Pt at low overpotentials were a value of one was observed. Furthermore, the physical characterisation of the different deposits on Pt by atomic force microscopy allowed observing the coalescence of the hemispherical nuclei of Ni and Ni-P at t max thus confirming the results obtained from the current-time analysis.

Avaliação da composição química de sedimentos do Rio Barigüi na região metropolitana de Curitiba

Sediment samples from the Barigui River in Curitiba, south of Brazil, were evaluated following granulometric composition, organic carbon content, nitrogen, phosphorus and metals such as zinc, lead, chrome, nickel and cadmium. The sediments shown high percentage of phosphorus and nitrogen. Also the elemental organic C:N:P exceed the Redfield ratios possible because the large amount of sewage input into river. The presence of metals is also high, however the metal cadmium has not been found. But the other metals are in greater concentrations and possibly the presence of these metals is given by industrial and domestic sewage.

Hidrogenação eletrocatalítica de substratos orgânicos utilizando eletrodos modificados poliméricos contendo partículas de Ni/Pd e Ni/Pt

Novel modified electrodes bearing dispersed Pd and Pt particles have been prepared from poly (allyl ether of the p-benzenesulfonic acid) films with incorporated nickel particles making use of galvanic displacement reactions. The SEM analysis of the new modified electrodes revealed efficient deposition of Pd but weak up-take of Pt. Electrocatalytic hydrogenation of several classes of organic substrates were carried out using the MEs Ni, Ni/Pd and Ni/Pt. The Ni/Pd ME showed to be the best of them for the hydrogenation of double, triple and carbonyl bonds. The complete hydrogenation of the aromatic rings for the well-adsorbed substrates acetophenone and benzophenone is noteworthy.

Determination of Ni(II) in metal alloys by spectrophotometry UV-Vis using dopasemiquinone

A spectrophotometric method was proposed for Ni(II) determination in alloys using a dopa-semiquinone (L-1) to form [Ni(II)(L1-)3]1-, ε = 9.3 x 10³ L mol-1 cm-1. The optimal conditions for the determination were: wavelength 590 nm, temperature 25 °C, reaction time 45 min and pH 7.5. The Beer's law was obeyed for nickel from 3.33 x 10-5 to 1.78 x 10-4 mol L-1. The method was applied to complex samples, such as inox, nickel-titanium and cobalt-chromium alloys. A study of the potential interferents revealed that Mn was the major interferent. The limit of detection and quantification were 2.88 x 10-5 mol L-1 and 3.06 x 10-5 mol L-1, respectively.

Determinação de metais traço no material particulado em suspensão em Ouro Preto, Minas Gerais

The determination of the airborne particulate matter (PTS) mass and trace metals concentrations were performed in three sites in Ouro Preto, MG, Brazil. It was evaluated 288 samples. The legal limit of annual geometric average (60 µg m-3) to PTS concentrations didn't exceed, but the legal limit for 24 h (240 µg m-3) did in three measurements. Seven metals (Al, Cr, Cu, Fe, Mn, Ni, Pb) analysed by ICP-AES were quantified in 18 samples. Aluminum and iron showed the highest concentrations, indicating the contribution of the soil and of one aluminum plant. The high nickel concentration is probably due to vehicular emissions and industrial combustion processes.

Organização supramolecular da ftalocianina de cobalto(II) e seu efeito na oxidação do aminoácido cisteína

The interest in the chemistry of cobalt (II) tetrasulfonated phthalocyanine (PcTsCo) comes mainly from its macrocycle-ligand structure combined with their special chemical characteristics, such as high solubility, well-defined redox reactions and remarkable optical absorption in the visible region. In this work, we use layer-by-layer technique in order to assemble CoTsPc and poly(allylaminehydrochloride) (PAH) in hybrid supramolecular system. The electronic spectroscopy and cyclic voltammetry techniques were utilized to study PAH/CoTsPc multilayers growth and the cysteine catalytic oxidation. PAH/CoTsPc showed high electrochemical stability and worthwhile to mention is the remarkable influence of supramolecular arrangement on the final redox properties of the system.

Marcadores metálicos como avaliação do impacto crônico de emissões petroquímicas em zona urbana

Nickel and vanadium were tested as tracers of oil refinery emission distribution in populated area of Rio Grande-RS. The anomalies of these elements in surface soil are considered a long-term reflection of the emissions in low atmosphere. The spatial distribution of Ni and V in the soil corresponded to the pattern of local winds. The threshold of 1.5 backgrounds of these metals markedly outlined the area of petrochemical emissions. Anomalies of Ni and V in surface soil have a rather different configuration in comparison with other metal tracers of urban impact: Cd, Cu, Pb and Zn.