WC-CoCr coatings sprayed by high velocity oxygen-fuel (HVOF) flame on AA7050 aluminum alloy: electrochemical behavior in 3.5% NaCl solution

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

The Extent on the Nanoscale of Pt-Skin Effects on Oxygen Reduction and Its Influence on Fuel Cell Power

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

Well-Alloyed PtFe/C Nanocatalysts of Controlled Composition and Same Particle Size: Oxygen Reduction and Methanol Tolerance

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

Evaluation of the photoelectrocatalytic method for oxidizing chloride and simultaneous removal of microcystin toxins in surface waters

The production of chlorine was investigated in the photoelectrocatalytic oxidation of a chloride-containing solution using a TiO(2) thin-film electrode biased at current density from 5 to 50 mA cm(-2) and illuminated by UV light. Such parameters as chloride concentrations from 0.001 to 0.10 mol L(-1), pH 2-12, and interfering salts were varied in this study in order to determine their effect on this oxidation process. At an optimum condition this photoelectrocatalytic method can produce active chlorine at levels compatible to water disinfections processes using a chloride concentration higher than 0.010 mol L(-1) at a pH of 4 and a current density of 30 mA cm(-2). The method was successfully applied to treat surface water collected from a Brazilian river. After 150 min of photoelectrocatalytic oxidation, we obtained a 90% reduction in total organic carbon removal, a 100% removal of turbidity, a 93% decrease in colour and a chemical oxygen demand (COD) removal of around 96% (N=3). The proposed technology based on photoelectrocatalytic oxidation was also tested in treating 250 mL of a solution containing 0.05 mol L(-1) NaCl and 50 mu g L(-1) of Microcystin aeruginosa. The bacteria is completely removed after 5 min of photoelectrocatalysis following an initial rate constant removal of -0.260 min(-1), suggesting that the present method could be considered as a promising alternative to chlorine-based disinfections. (C) 2008 Elsevier Ltd. All rights reserved.

Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

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

Alkene epoxidation with iodosylbenzene catalysed by polyionic manganese porphyrins electrostatically bound to counter-charged supports

Manganese(III) complexes of tetra-anionic and tetra-cationic porphyrins have been immobilised on counter-charged, surface-modified silica supports and on organic ion-exchange resins. The reactions of these supported manganese(III) porphyrin systems and analogous uncharged homogeneous systems have been examined using cyclooctene and (E)- and (Z)-4- methylpent-2-ene epoxidations, with iodosylbenzene (PhIO) as the oxygen donor.Comparisons using the manganese porphyrin systems as catalysts for the epoxidation of cyclooctene in acetonitrile reveal that, in low turnover reactions (maximum 136 turnovers), they all give an essentially quantitative yield of epoxide although the heterogeneous reactions are significantly slower than the homogeneous analogues. In large scale repeat-use experiments, however, the supported catalysts are clearly superior, giving markedly better yields.The epoxidations of (E)- and (Z)-4- methylpent-2-ene with all the catalysts show a very high stereoretention, with the (Z)-alkene reacting faster than the (E)-isomer. The sterically hindered manganese(III) 5,10,15,20-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphyrin (MnTDCSPP) shows the highest selectivity for the (Z)-isomer; by contrast the supported manganese(III) 5,10,15,20-tetrakis[2,3,5,6-tetrafluoro-4-(trimethylammonio)phenyl]porphyrin on Dowex (MnTF(4)TMAPP-Dowex) reacts with the two alkenes at effectively the same rate.The mechanism of the epoxidations and the influence of the porphyrin ligand and support on the substrate selectivity are discussed.

Electrically detected and conventional magnetic resonance investigation of surface and bulk states in polyaniline thin films

Electrically detected magnetic resonance (EDMR) and electron paramagnetic resonance (EPR) were used to investigate emeraldine base polyaniline films. The magnetic susceptibility presented a Curie (localized spins)-Pauli (delocalized spins) transition at 240 K, when we also observed a transition in the dependence of the g factor with temperature (T). Peak-to-peak linewidth decreases with increasing temperature, reflecting that motional narrowing limits the hyperfine and dipolar broadening in this polymer. EDMR spectra could only be observed above 250 K in accordance to EPR results. Surface and bulk transport could be separated and their analysis reflected the effect of magnetic interaction with oxygen. (c) 2007 American Institute of Physics.

A theoretical analysis on electronic structure of the (110) surface of TiO2-SnO2 mixed oxide

Mixed oxide compounds, such as TiO2-SnO2 system are widely used as gas sensors and should also provide varistor properties modifying the TiO2 surface. Therefore, a theoretical investigation has been carried out characterizing the effect of SnO2 on TiO2 addition on the electronic structure by means of ab initio SCF-LCAO calculations using all electrons. In order to take into account the finite size of the cluster, we have used the point charge model for the (TiO2)(15) cluster to study the effect on electronic structure of doping the TiO2 (110) Surface. The contracted basis set for titanium (4322/42/3), oxygen (33/3) and tin (43333/4333/43) atoms were used. The charge distributions, dipole moments, and density of states of doping TiO2 and vacancy formation are reported and analysed. (C) 2003 Elsevier B.V. All rights reserved.

Evaporative water loss and oxygen uptake in two casque-headed tree frogs, Aparasphenodon brunoi and Corythomantis greeningi (Anura, Hylidae)

Evaporative water loss (EWL) and oxygen uptake ((V) over dot o(2)) was measured in two species of tree frogs with cranial co-ossification, Aparasphenodon brunoi and Corythomantis greeningi. Both species use their head to seal the entrance of bromeliads, tree holes or rocky crevices used as shelters. EWL was significantly reduced in sheltered individuals of both species as compared with those exposed nude to desiccation. EWL per unit area through the head surface was significantly lower than the body skin for A. brunoi but not for C., greeningi. EWL per unit surface area through C. greeningi body skin was about 50% that of A. brunoi, indicating a less permeable skin in the former species. The relationship between cranial coossification and EWL is discussed. ((V) over dot o(2)) in A. brunoi was comparable with other anurans of similar size, whereas in C. greeningi, it was lower than predicted from body mass. Moreover, ((V) over dot o(2)), in C. greeningi showed less sensitivity to temperature increase than in A. brunoi. C. greeningi occurs in a drier environment than A. brunoi, and this appears to be reflected in their EWL and ((V) over dot o(2)) characteristics. (C) 1997 Elsevier B.V.

Electrosynthesis of binuclear ruthenium complexes from [RuCl3(dppb)(L)] precursors [L = pyridine, 4-methylpyridine or dimethyl sulfoxide; dppb=1,4-bis(diphenylphosphino)butane]

Electrolysis has been examined as a method of synthesis for [(L)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] complexes, where dppb = 1,4-bis(diphenylphosphino)butane and L = pyridine (py), 4-methylpyridine (4-pic) or dimethyl sulfoxide (DMSO), by using [RuCl3(dppb)(L)] as precursors. The products of the electrolysis were characterized by P-31-{H-1} NMR, cyclic voltammetry and near infrared spectroscopy. The presence of the [Ru2Cl5(dppb)(2)] complex in the electrochemical cell suggests a mechanism by which the starting original species from the bulk solution reacts with the reduced form [RuCl2(dppb)(L)] generated at the surface of the electrode. The crystal structure of the precursor mer-[RuCl3(dppb)(4-pic)] was determined by X-ray diffraction.

Synthesis, spectroscopic characterization and X-ray crystallographic studies of trans-[PtCl2(PEt3)(PySOR)] complexes, where PySOR=(2-methylsulphinyl)-pyridine and (2-n-propylsulphinyl)pyridine

Alkylsulphinylpyridine ligands containing three potential donor centres: N, S and O atoms and two complexes of general formula trans-[PtCl2(PEt3)PySOR)] (R = Me and Pr-n) were prepared and characterized by elemental analysis, i.r. spectroscopy, H-1- and P-31-n.m.r. and X-ray crystallography. The ambidentate ligands act in both situations as monodentate ligands, bonded to the metal exclusively through the nitrogen atom. The crystal structures revealed the occurrence of discrete molecules and, in both complexes, the Pt atoms are coordinated in square planar arrangements by two chloride ions, in a trans configuration, by the pyridine nitrogen atom, and by the phosphine P atom. The oxygen atoms do not take part in the complexation scheme.

Structural and surface properties of thermally prepared Ti/RhxTi(1-x)Oy electrodes: I - influence of preparation parameters

Electrodes of RhxTi(1-x) O-y nominal composition were prepared by thermal decomposition of the chloride or nitrate precursor salts dissolved in strongly acidic medium and applied by brush to both sides of a Tidegrees support. A systematic study of the influence of calcination temperature and time as well as oxygen flux was conducted. The coatings were characterised by SEM, EDAX, XRD, open circuit potential measurements and cyclic voltammetry (CV). Visible-ultraviolet spectrophotometry was employed to identify the chemical form of the precursor in solution while thermogravimetric analysis (TGA) was used to assess the decomposition temperature ranges. Optimisation of the coating preparation parameters showed coatings obtained from [Rh(H2O)(6)](NO3)(3) precursor dissolved in HNO3 1:2 (v/v) and fired at 430 degreesC for 2 h in a 5 1 min (-1) oxygen stream-furnished stable electrodes having the highest electrochemically active surface area. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

A NOVEL SYNTHETIC ROUTE FOR SUPPORTING RUTHENIUM COMPLEXES ON FUNCTIONALIZED SILICA-GEL

The immobilization of the ruthenium moiety Ru(NH3)4SO3 by reaction of trans-[Ru(NH3)4SO2(H2O)]2+ with silica gel functionalized with 3-(1-imidazolyl)propyl groups is reported. A 60% surface coverage was obtained in the proportion of the resulting material [=Si(CH2)3imN-Ru(NH3)4SO3]. The anchored Ru(II) complex was characterized and its reactivity investigated. Derivatives of CO, pyrazine, and isonicotinamide have been prepared and characterized by electronic and vibrational spectroscopies, as well as by chemical means. The [=Si(CH2)3imN-Ru(NH3)4SO4]Cl, obtained through oxidation of the corresponding ruthenium(II) sulfite species, has been characterized and the aquo and the oxalate derivative have been synthesized.

Synthesis and properties of branched polyethylene/high-density polyethylene blends using a homogeneous binary catalyst system composed of early and late transition metal complexes

Branched polyethylene/high-density polyethylene blends (BPE/HDPE) with a wide range of molecular weights, melt flow indexes (MFI), and intrinsic viscosity were prepared using the homogeneous binary catalyst system composed by Ni(alpha-diimine)Cl-2 (1) (alpha-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {Tp(Ms*)} TiCl3 (2) (Tp(Ms*)=hydridobis(3-mesitylpyrazol-1-yl)(5-mesityl-pyrazol-1-yl)) activated with MAO and/or TIBA in hexane at two different polymerization temperatures (30 and 55 degreesC) and by varying the nickel loading molar fraction (x(Ni)). At all Temperatures, a non-linear correlation between the x(Ni) and the productivity was observed, suggesting the occurrence of a synergistic effect between the nickel and the titanium catalyst precursors, which is more pronounced at 55 degreesC. The molecular weight of the BPE/HDPE blends considerably decreases with increasing Al/M molar ratio. The melt flow indexes (MFI) and intrinsic viscosities (eta) are strongly affected by x(Ni), but the melting temperatures are nearly constant, 132 +/- 3 degreesC. Dynamic mechanical thermal analysis (DMTA) shows the formation of different polymeric materials where the stiffness vanes according, to the x(Ni) and temperature used in the polymerization reaction. The surface morphology of the BPE/HDPE blends studied by scanning electron microscopy (SEM) revealed a low miscibility between the PE phases resulting in the formation of a sandwich structure after etching with o-xylene.

The influence of oxygen in the photoexpansion of GaGeS glasses

Irreversible photoexpansion and photobleaching effect has been observed in amorphous Ga10Ge25S65 glass when its surface was exposed to light with energy greater than the band gap, 3.52 eV. The magnitude of the expansion of GaGeS glasses depends on the exposure conditions. Extended X-ray absorption fine structure (EXAFS) spectroscopy and Rutherford backscattering spectrometry (RBS) have been used to identify the chemical nature of the glass samples before and after illumination. The quantitative analysis of the EXAFS data leads to a two-shell model of 0.5 oxygen atoms at 2.01 Angstrom and 3.6 sulfur atoms at a 2.20 Angstrom. RBS technique demonstrated that chemical composition of the glass surface after irradiation is oxygen rich. The existence of Ge-O bonds in the glass after illumination was also confirmed by infrared measurements. (C) 2002 Elsevier B.V. B.V. All rights reserved.