Direct Access to Oxidation-Resistant Nickel Catalysts through an Organometallic Precursor

The synthesis of nickel catalysts for industrial applications is relatively simple; however, nickel oxidation is usually difficult to avoid, which makes it challenging to optimize catalytic activities, metal loadings, and high-temperature activation steps. A robust, oxidation-resistant and very active nickel catalyst was prepared by controlled decomposition of the organometallic precursor [bis(1,5-cyclooctadiene)nickel(0)], Ni(COD)(2), over silica-coated magnetite (Fe3O4@SiO2). The sample is mostly Ni(0), and surface oxidized species formed after exposure to air are easily reduced in situ during hydrogenation of cyclohexene under mild conditions recovering the initial activity. This unique behavior may benefit several other reactions that are likely to proceed via Ni heterogeneous catalysis.

EFFECTS OF ADDING LANTHANUM TO Ni/ZrO2 CATALYSTS ON ETHANOL STEAM REFORMING

EFFECTS OF ADDING LANTHANUM TO Ni/ZrO2 CATALYSTS ON ETHANOL STEAM REFORMING. The catalytic performance of Ni/ZrO2 catalysts loaded with different lanthanum content for steam reforming of ethanol was investigated. Catalysts were characterized by BET surface area, X-ray diffraction, UV-vis spectroscopy, temperature programmed reduction, and X-ray absorption fine structure techniques. Results showed that lanthanum addition led to an increase in the degree of reduction of both NiO and nickel surface species interacting; with the support, due to the higher dispersion effect. The best catalytic performance at 450 degrees C was found for the Ni/2LZ catalyst, which exhibited an effluent gaseous mixture with the highest H-2 yield.

Ethanol steam reforming over rhodium and cobalt-based catalysts: Effect of the support

The effect of support on the properties of rhodium and cobalt-based catalysts for ethanol steam reforming was studied in this work, by comparing the use of magnesia, alumina and Mg-Al oxide (obtained from hydrotalcite) as supports. It was found that metallic rhodium particles with around 2.4-2.6 nm were formed on all supports, but Mg-Al oxide led to the narrowest particles size distribution; cobalt was supposed to be located on the support, affecting its acidity. Rhodium interacts strongly with the support in the order: alumina> Mg-Al oxide > magnesia. The magnesium-containing catalysts showed low ethene selectivity and high hydrogen selectivity while the alumina-based ones showed high ethene selectivity, assigned to the Lewis sites of alumina. The Mg-Al oxide-supported rhodium and cobalt catalyst was the most promising sample to produce hydrogen by ethanol reforming, showing the highest hydrogen yield, low ethene selectivity and high specific surface area during reaction. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Reforming of a model biogas on Ni and Rh-Ni catalysts: Effect of adding La

Ni catalysts supported on gamma-Al2O3 modified by Rh and La were prepared and evaluated on the reforming of a model biogas. The catalysts were characterized by EDS, XRD, TPR, XANES and surface area estimation (BET). The results showed that in the original Ni catalyst, the Ni interacted strongly with the alumina support, exhibiting high reduction temperatures in TPR tests. In the catalytic tests, the addition of Rh on Ni catalysts improved CH4 conversion but also increased carbon deposition, possible by causing the segregation of Ni species under the reaction conditions. The presence of La on Ni catalysts reduced the carbon deposition by favoring the gasification of carbon species. Addition of synthetic air to the process improved the CH4 conversion and also decreased the carbon formation. The catalysts Ni, Rh-NiLa, and Rh showed good results in the conversion of model sulfur-free biogas, which suggests that they are promising catalysts to be tested in conversion of real biogas. (C) 2012 Elsevier B.V. All rights reserved.

Design of a Dinuclear Nickel(II) Bioinspired Hydrolase to Bind Covalently to Silica Surfaces: Synthesis, Magnetism, and Reactivity Studies

Presented herein is the design of a dinuclear Ni-II synthetic hydrolase [Ni-2(HBPPAMFF)(mu-OAc)(2)(H2O)]-BPh4 (1) (H(2)BPPAMFF = 2-[(N-benzyl-N-2-pyridylmethylamine)]-4-methyl-6-[N-(2-pyridylmethyl)aminomethyl)])-4- methyl-6-formylphenol) to be covalently attached to silica surfaces, while maintaining its catalytic activity. An aldehyde-containing ligand (H(2)BPPAMFF) provides a reactive functional group that can serve as a cross-linking group to bind the complex to an organoalkoxysilane and later to the silica surfaces or directly to amino-modified surfaces. The dinuclear Ni-II complex covalently attached to the silica surfaces was fully characterized by different techniques. The catalytic turnover number (k(cat)) of the immobilized (NiNiII)-Ni-II catalyst in the hydrolysis of 2,4-bis(dinitrophenyl)phosphate is comparable to the homogeneous reaction; however, the catalyst interaction with the support enhanced the substrate to complex association constant, and consequently, the catalytic efficiency (E - k(cat)/K-M) and the supported catalyst can be reused for subsequent diester hydrolysis reactions.

Preparation, structural characterization and catalytic properties of Co/CeO2 catalysts for the steam reforming of ethanol and hydrogen production

In this paper, Co/CeO2 catalysts, with different cobalt contents were prepared by the polymeric precursor method and were evaluated for the steam reforming of ethanol. The catalysts were characterized by N-2 physisorption (BET method), X-ray diffraction (XRD), UV-visible diffuse reflectance, temperature programmed reduction analysis (TPR) and field emission scanning electron microscopy (FEG-SEM). It was observed that the catalytic behavior could be influenced by the experimental conditions and the nature of the catalyst employed. Physical-chemical characterizations revealed that the cobalt content of the catalyst influences the metal-support interaction which results in distinct catalyst performances. The catalyst with the highest cobalt content showed the best performance among the catalysts tested, exhibiting complete ethanol conversion, hydrogen selectivity close to 66% and good stability at a reaction temperature of 600 degrees C. (c) 2012 Elsevier B.V. All rights reserved.

Partial oxidation of methane on NiO-MgO-ZrO2 catalysts

Catalysts containing mixtures of NiO, MgO and ZrO2 were synthesized by the polymerization method. They were characterized by X-ray diffraction (XRD), physisorption of N-2 (BET), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES), and then tested in the partial oxidation of methane (POM) in the presence of air (2CH(4):1O(2)) at 750 degrees C for 6 h. Among the ternary oxides, the catalyst with 40 mol% MgO showed the highest conversion rates in the catalytic processes, but also the highest carbon deposition values (48 mmol h (1)). The greater the amount of NiO-MgO solid solution formed, the higher was the conversion rate of reactants (CH4), peaking at 40 mol% of MgO. Catalysts with lower Ni content on the surface achieved a high rate of CH4 conversion into synthesis gas (H-2 + CO). The formation of more NiO-MgO solid solution seemed to inhibit the deactivation of Ni degrees during reaction. The values of the H-2/CO product ratio were generally found to be slightly lower than stoichiometric. (C) 2012 Elsevier Ltd. All rights reserved.

An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved. (C) 2012 Elsevier B.V. All rights reserved.

Effects of catalyst load in Pt and Pb-based catalysts using formic acid oxidation as a model

In this paper, we discuss the effects of catalyst load with respect to carbon powder for several Pt and Pb-based catalysts, using formic acid as a model molecule. The discussion is based on electrochemical tests, a complete morphological investigation and theoretical calculations. We show that the Pt and Pb-based catalysts presented activity in formic acid oxidation at very low catalyst loads (e.g., 0.5% in respect to the carbon content). Physical characterisations demonstrate that the electrodes are composed of separated phases of Pt and lead distributed in Pt nanometric-sized islands that are heterogeneously dispersed on the carbon support and Pb ultra-small particles homogeneously distributed throughout the entire carbon surface, as demonstrated by the microscopy studies. At high catalyst loads, very large clusters of Pb(x)O(y) could be observed. Electrochemical tests indicated an increase in the apparent resistance of the system (by a factor of 19.7 Omega) when the catalyst load was increased. The effect of lead in the materials was also studied by theoretical calculations (OFT). The main conclusion is that the presence of Pb atoms in the catalyst can improve the adsorption of formic acid in the catalytic system compared with a pure Pt-based catalyst. (C) 2011 Elsevier B.V. All rights reserved.

4-Organochalcogenoyl-1H-1,2,3-triazoles: synthesis and functionalization by a nickel-catalyzed Negishi cross-coupling reaction

A general method for the synthesis of triazoles containing selenium and tellurium was accomplished via a CuCAAC reaction between organic azides and a terminal triple bond, generated by in situ deprotection of the silyl group. The reaction tolerates alkyl and arylazides, with alkyl and aryl substituents directly bonded to the chalcogen atom. The products were readily functionalized by a nickel-catalyzed Negishi cross-coupling reaction, furnishing the aryl-heteroaryl products at the 4-position in good yields. (C) 2012 Elsevier Ltd. All rights reserved.

Coffee is highly tolerant to cadmium, nickel and zinc: Plant and soil nutritional status, metal distribution and bean yield

Sewage sludge has been used to fertilize coffee, increasing the risk of metal contamination in this crop. The aim of this work was to study the effects of Cd, Zn and Ni in adult coffee plants growing under field conditions. Seven-year-old coffee plants growing in the field received one of three;loses of Cd, Zn or Ni: 15,45 and 90 g Cd plant(-1); 35, 105 and 210 g Ni plant(-1); and 100, 300 and 600 g Zn plant(-1), with all three metals in the form of sulphate salts. After three months, we noticed good penetration of the three metals into the soil, especially in the first 50 cm, which is the region where most coffee plant roots are concentrated. Leaf concentrations of K, Ca, Mg, S, B, Cu, Fe and Mn were nor affected. N levels did not change with the application of Ni or Zn but were reduced with either 45 or 90 g Cd plant(-1). Foliar P concentrations decreased with the addition of 45 and 90 g Cd plant(-1) and 600 g Zn plant(-1). Zn levels in leaves were not affected by the application of Cd or Ni. The highest concentrations. of Zn were found in branches (30-230 mg kg(-1)), leaves (7-35 mg kg(-1)) and beam (4-6.5 mg kg(-1)); Ni was found in leaves (4-45 mg kg(-1)), branches (3-18 mg kg(-1)) and beans (1-5 mg kg(-1)); and Cd was found in branches (0-6.2 mg kg(-1)) and beans (0-1.5 mg kg(-1)) but was absent in leaves. The mean yield of two harvests was not affected by Ni, but it decreased at the highest dose of Zn (600 g plant(-1)) and the two higher doses of Cd (45 and 90 g plant(-1)). Plants died when treated with the highest dose of Cd and showed symptoms of toxicity with the highest dose of Zn. Nevertheless, based on the amounts of metal used and the results obtained, we conclude that coffee plants are highly tolerant to the three metals tested. Moreover, even at high doses, there was very little transport to the beans, which is the part consumed by humans. (C) 2011 Elsevier B.V. All rights reserved.

The influence of different co-catalysts in Pt-based ternary and quaternary electro-catalysts on the electro-oxidation of methanol and ethanol in acid media

One of the key objectives in fuel cell technology is to reduce Pt loading by the improvement of its catalytic activity towards alcohol oxidation. Here, a sol-gel based method was used to prepare ternary and quaternary carbon supported nanoparticles by combining Pt-Ru with Mo, Ta, Pb, Rh or Ir, which were used as electro-catalysts for the methanol and ethanol oxidation reactions in acid medium. Structural characterization performed by XRD measurements revealed that crystalline structures with crystallites ranging from 2.8 to 4.1 nm in size and with different alloy degrees were produced. Tantalum and lead deposited as a heterogeneous mixture of oxides with different valences resulting in materials with complex structures. The catalysts activities were evaluated by cyclic voltammetry and by Tafel plots and the results showed that the activity towards methanol oxidation was highly dependent of the alloy degree, while for ethanol the presence of a metal capable to promote the break of C-C bond, such as Rh, was necessary for a good performance. Additionally, the catalysts containing of TaOx or PbOx resulted in the best materials due to different effects: the hi-functional mechanism promoted by TaOx and a better dispersion of the catalysts constituents promoted by PbOx. (C) 2012 Elsevier B.V. All rights reserved.

Steam reforming of ethanol for hydrogen production on Co/CeO²-ZRO² catalysts prepared by polymerization method

Catalysts containing 10%Co supported on CexZr1-xO2 (0 < x < 1) were applied to ethanol steam reforming reactions. The catalysts were characterized by Raman spectroscopy, XANES-H-2 and DRS-UV-Vis. The catalytic tests were conducted at 673, 773 and 873 K, with molar ratios of H2O:ethanol = 3:1. The ethanol conversion and H-2 selectivity were temperature dependent and the association of CeO2 with ZrO2 in the support led to show a low formation of CO, due to the higher mobility of oxygen. (C) 2012 Elsevier B.V. All rights reserved.

Recent Advances in the Development of Magnetically Recoverable Metal Nanoparticle Catalysts

The aim of this Account is to provide an overview of our current research activities on the design and modification of superparamagnetic nanomaterials for application in the field of magnetic separation and catalysis. First, an introduction of magnetism and magnetic separation is done. Then, the synthetic strategies that have been developed for generating superparamagnetic nanoparticles spherically coated by silica and other oxides, with a focus on well characterized systems prepared by methods that generate samples of high quality and easy to scale- up, are discussed. A set of magnetically recoverable catalysts prepared in our research group by the unique combination of superparamagnetic supports and metal nanoparticles is highlighted. This Account is concluded with personal remarks and perspectives on this research field.

Magnetic Barkhausen Noise in Quenched Carburized Nickel-Steels

Two steel sheets, one with 5% Ni and another with 10% Ni, were submitted to carburization and quenching, obtaining a microstructure with martensite and retained austenite. These steels were characterized with magnetic Barkhausen noise (MBN). The Barkhausen signal is distinctively different for the carburized and quenched samples. The carburized and quenched samples present higher coercive field than the annealed samples. X-ray diffraction data indicated that the carburized and quenched samples have high density of dislocations, a consequence of the martensitic transformation.