Desenvolvimento e estudo de nanocatalisadores bimetálicos para catodos de células a combustível

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermoplastic polyesters and Co-polyesters derived from vegetable oil: synthesis and optimization of melt polycondensation for medium and long chain poly(omega-hydroxyfatty acid)s and their ester derivatives

The synthesis of a series of omega-hydroxyfatty acid (omega-OHFA) monomers and their methyl ester derivatives (Me-omega-OHFA) from mono-unsaturated fatty acids and alcohols via ozonolysis-reduction/crossmetathesis reactions is described. Melt polycondensation of the monomers yielded thermoplastic poly(omega-hydroxyfatty acid)s [-(CH2)(n)-COO-](x) with medium (n = 8 and 12) and long (n = 17) repeating monomer units. The omega-OHFAs and Me-omega-OHFAs were all obtained in good yield (>= 80%) and purity (>= 97%) as established by H-1 NMR, Fourier Transform infra-red spectroscopy (FT-IR), mass spectroscopy (ESI-MS) and high performance liquid chromatography (HPLC) analyses. The average molecular size (M-n) and distribution (PDI) of the poly(omega-hydroxyfatty acid)s (P(omega-OHFA)s) and poly(omega-hydroxyfatty ester) s (P(Me-omega-OHFA) s) as determined by GPC varied with organo-metallic Ti(IV) isopropoxide [Ti(OiPr)(4)] polycondensation catalyst amount, reaction time and temperature. An optimization of the polymerization process provided P(omega-OHFA) s and P(Me-omega-OHFA) s with M-n and PDI values desirable for high end applications. Co-polymerization of the long chain (n = 12) and medium chain (n = 8) Me-omega-OHFAs by melt polycondensation yielded poly(omega-hydroxy tridecanoate/omega-hydroxy nonanoate) random co-polyesters (M-n = 11000- 18500 g mol(-1)) with varying molar compositions.

Synthesis and characterization of alpha-nickel (II) hydroxide particles on organic-inorganic matrix and its application in a sensitive electrochemical sensor for vitamin D determination

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

Microwave-assisted hydrothermal synthesis of NiO-Ce1-XEuxO2-δ powders for fuel cell catalytic anodes

CeO2-based materials doped with rare earth (TR +3) can be used as alternative to traditional NiO-YSZ anodes in solid oxide fuel cells as they have higher ionic conductivity and lower ohmic losses compared to YSZ. Moreover, they allow fuel cell operation at lower temperatures (500-800°C). In the anode composition, the concentration of NiO acting as catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, promoting internal reform in the cell. In this work, NiO - Ce1-xEuxO2-δ compounds (x = 0.1, 0.2 and 0.3) have been synthesized by microwave-assisted hydrothermal method. The materials were characterized by TG, XRD, TPR and SEM-FEG techniques. The refinement of data obtained by X-ray diffraction showed the presence of ceria doped with europium crystallized in a cubic phase with fluorite structure, in addition to the presence of NiO. The microwave-assisted hydrothermal method showed significant reduction in the average particle size and good mass control of phase compositions compared to other chemical synthesis techniques.

Asymmetric and Symmetric Triazenido Cyclopalladated Complexes: Synthesis, Structural Analysis and DFT Calculations

The reaction of [Pd{dmba}(l-N3)]2 (dmba = N,N-dimethylbenzylamine) with 1-(2-fluorophenyl)-3-(4- nitrophenyl)triazenido (L1 ) or 1,3-bis(4-nitrophenyl)triazenido (L2 ) anions, in methanol, and subsequent treatment with pyridine (py) allows the preparation of the corresponding cyclopalladated compounds [Pd(dmba)(L1 )(py)] (1) and [Pd(dmba)(L2 )(py)]py (2). The acentric mononuclear entities of (1) and (2) are connected by weak intermolecular non-classical CAHC hydrogen bonds, which results in 2-D arrangements by translation, along the [1 0 0] and [0 01] crystallographic directions, respectively.

Synthesis and characterization of polyarylacetylene for use in the monolithic vitreous carbon processing

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

Synthesis, characterization and thermal behavior of cyclopalladated compounds of the type [Pd{C6H4CH2N(CH3)(2)}(mu-X)](2) (X= Cl, NCO, SCN, CN)

The dimeric compound [Pd(dmba)(μ-Cl)]2 (1) (dmba = N,N-dimethylbenzylamine) reacts with KX, in methanol/acetone, affording the analogous dimeric pseudohalide-bridged species [Pd(dmba)(X)]2 [X = NCO(2), SCN(3), CN(4)]. The compounds were characterized by elemental analysis, infrared spectroscopy, NMR and thermogravimetric analysis. The IR data for 2-4 showed bands typical of coordinated pseudohalide ligands indicating clearly the occurrence of the exchange reaction. Their thermal behavior was investigated and suggested that their thermal stability is influenced by the bridging ligand. The thermal stability decreased in the order [Pd(dmba)(μ-SCN)]2>[Pd(dmba)(μ-Cl)] 2>[Pd(dmba)(;u-NCO)]2>[Pd(dmba)(μ-CN)]2. The X-ray results showed the formation of PdO as final decomposition product. © 1999 Elsevier Science Ltd. All rights reserved.

Structural study of copper oxide supported on a ceria-modified titania catalyst system

A structural study of CuO supported on a CeO2-TiO2 system was undertaken using X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) techniques. The results of XRD revealed the presence of only two phases, TiO2 anatase and CeO2 cerianite. A trend towards smaller TiO2 crystallites was observed when cerium content increased. When the amount of cerium increased, Ti K-edge XANES analysis showed an increasing distortion of Ti sites. The results of Ce LIII-edge EXAFS showed that Ce atoms are coordinated by eight oxygen atoms at 2.32 Å. For the sample containing a small amount of cerium, the EXAFS analysis indicated that the local structure around Ce atoms was highly distorted. The catalysts presented quite different Cu K-edge XANES spectra compared to the spectra of the CuO and Cu2O reference compounds. The Cu-O mean bond length was close to that of the CuO and the Cu atoms in the catalysts are surrounded by approximately four oxygen atoms in their first shell. Copper supported on the ceria-modified titania support catalysts displayed a better performance in the methanol dehydrogenation when compared to copper supported only on titania or on ceria. © 2002 Plenum Publishing Corporation.

Eletro-oxidação de metanol e etanol sobre PtAu/C em meio alcalino

The development of electrocatalysts for the oxidation of methanol and ethanol is very important, because these alcohols may be used in the anode fuel cells which convert chemical energy directly into electrical energy with high efficiency, cleanly and with low noise. Thus, this study reports to the synthesis of nanocatalysts of PtAu supported on carbon by microemulsion method. The physical characterization of these catalysts is performed through the techniques of X-ray diffraction and transmission electron microscopy. The catalytic activity of the prepared materials was studied using conventional electrochemical techniques and also the technique of spectro-electrochemical in situ FTIR, which allows identification of intermediates and products of the reactions. From the x-ray diffraction, it was observed that the thermal treatment applied to catalysts favored incorporation of Au into the crystal lattice of Pt,that is, increased the formation of PtAu alloy. Micrographs indicated particle size about 3 nm to materials not heat treated and 9 nm to materials subjected to thermal treatment (heating at 150 ° C for 1h and 30 min in argon atmosphere). Current density oxidation of methanol on PtAu / C were superior to pure platinum. Spectroscopic results indicated the presence of formate in solution in 50:50 and the composition showed bands for CO2, indicating complete oxidation, in lower potential. During ethanol oxidation on the catalyst PtAu, the main product formed was acetate, product of incomplete oxidation. The good performance for methanol oxidation can be attributed to large amounts of oxygen species adsorbed on the catalyst surface, or an electronic effect.

Niobium pentachloride promoted synthesis of tetrahydropiridines by multicomponent reaction

One-pot multicomponent synthesis of tetrahydropyridine derivatives between aniline derivatives, benzaldehyde and two different β-keto ester (methyl and ethyl acetoacetate) using niobium pentachloride as catalyst under mild conditions, providing good yields.

Estudos experimentais e teórico-computacionais de novos complexos nanozeólitas-enzimas empregados na produção de biocombustíveis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)