Structural and Electronic Properties of Lithiated SnO2. A Periodic DFT Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Preparation and properties as positive electrodes of PANI-LiNi0.8Co0.2O2 nanocomposites

PANI-LiNi0.8Co0.2O2 nanocomposite material with improved properties as positive electrode was prepared by a new synthesis method. In a first step, LiNi0.8Co0.2O2 mixed oxide in the form of a fine powder was dispersed in aniline and this suspension was sprayed on the surface of an aqueous solution of HCl and ammonium peroxodisulfate. The resulting PANI-LiNi0.8Co0.2O2 nanocomposite is spontaneously formed by polymerization of the aniline molecules present in the drops together with small particles of the oxide. This method induces the formation of nanocomposites showing a better distribution of the oxide particles in the polymer matrix than that observed in related PANI-LiNi0.8Co0.2O2 microcomposites prepared under ultrasound irradiation to disperse the oxide particles during PANI polymerization. Measurements of electrical conductivity and zeta potential, as well as structural characterization of PANI-LiNi0.8Co0.2O2 nanocomposites, reveal the existence of relatively strong interactions between the conducting polymer and the oxide particles. This feature determines higher values of the electrical conductivity (0.5 S cm(-1)) and of the average operative voltage (3.6 V), as well as of other technological parameters of the nanocomposite when it is used as the positive electrode of rechargeable lithium batteries, in comparison to those of the related microcomposite materials already reported.

Distribution of refractory and volatile elements in CoRoT exoplanet host stars

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Electrochemistry of organometallic compounds. Part II. Oxidations of alkyl and aryl derivatives of bis(salicylaldehyde)ethylenediimine cobalt(III) in dimethylformamide

The influence of the axial organic ligand R on the electrochemical oxidation of the compounds [RCoIII(salen)DMF)], where salen is bis(salicylaldehyde)ethylenediimine, and R CH3, C2H5, n-C3H7, n-C4H9, s-C4H9, i-C4H9, CH2Cl, CF3CH2, c-C6H11CH2, c-C6H11, C6H5, C6H5CH2, p-CH3C6H4CH2, and p-NO2C6H4CH2, was studied by means of cyclic voltametry in dimethylformamide (DMF), 0.2 M in tetraethylammonium perchlorate (TEAP), at 25 and -20°C, with a platinum disc working electrode. The above-mentioned compounds can be classified according to their electrochemical behavior. (a) The complexes with R CH3, C2H5, n-C3H7, n-C4H9, c-C6H11CH2, and C6H5 undergo a reversible one-electron oxidation in the 10-50 V s-1 potential scan range. At slower scan rates, the oxidized product decomposes chemically. At -20°C, this chemical step is slow, and a reversible one-electron electrochemical oxidation is observed. (b) The compounds with R CH2Cl, C6H5CH2, p-CH3C6H4CH2 and p-NO2C6H4CH2 undergo a quasi-reversible one-electron oxidation at room temperaure. At -20°C, the electrochemical process becomes more complex. A following chemical reactions is coupled to the quasi-reversible one-electron transfer. Two reduction peaks are observed. (c) The compounds with R i-C4H9, s-C4H9, and c-C6H11 undergo a reversible one-electron oxidation at -20°C. At room temperature, the irreversible chemical reaction following the electron transfer step is too fast to allow the isolation of the electrochemical step. (d) At -20°C, the derivatives with R C2H5, c-C6H11 CH2 and c-C6H11 are adsorbed at the electrode surface. Evidence indicates that the reagent in these reactions is the pentacoordinated species [RCoIII(salen)]. A linear free-energy relationship between E1/2 (for reversible processes) and the Taft polar parameters o* was obtained with a slope of ρ* = 0.25 ± 0.03. As expected, the benzyl derivatives which present mesomeric effects do not fit this polar correlation. The rated of the electrochemical oxidation is also affected by the nature of the ligand R. For the ligands which are strong electron-withdrawing groups and for the benzyl derivatives, the rate of the electrochemical oxidation of the metal ion decreases at room temperature. At lower temperatures, it is suggested that the oxidation to the CoIV-R species is followed by a chemical reaction in which this complex is partly transformed into a CoIII(R*) species, which is reduced at a much more cathodic potential than the Co(IV) species. © 1979.

Electrochemistry of organometallic compounds. Part III. Oxidations of methyl derivatives of organocobalt(III) complexes with delocalized electronic structure in dimethylformamide

The influence of the equatorial ligand on the electrochemical oxidation of the compounds [H3CCo(chel)B], where chel is bis (dimethylglyoximato), (DH)2; bis(salicylaldehyde)ethylenediimine, salen; bis(salicylaldehyde) o-phenylenediimine, salophen; bis(salicylaldehyde)cyclohexylenediimine, salcn; bis(acetylacetone) ethylenediimine, bae; and where B is pyridine when chel is (DH2), and dimethylformamide (DMF) when chel represents a Schiff base (salen, salcn, salophen and bae), was studied by means of cyclic voltammetry in DMF, 0.2 M in tetraethylammonium perchlorate, between 25 and -25°C, with a platinum disk working electrode. Absorption spectra in the visible and near ultraviolet regions for these compounds in DMF at 25°C were obtained. The complexes exhibit a reversible one-electron oxidation, at -20°C with scan rates >0.5 V s-; chemical reactions following electron transfer are not detected under these conditions. At slower potential or higher temperatures, the oxidized product decomposes chemically in a solvent-assisted (or nucleophile-assisted) reaction, yielding products which are electroactive in the applied potential range. The behavior of the [H3CCo (DH2)py] derivative is better described as a quasi-reversible charge transfer followed by an irreversible chemical reaction. Experimental evidence suggests that in the case of the [H3CCo(bae)] derivative at -20°C, the reactive -species is pentacoordinated and weakly adsorbed at the electrode surface. The value of E 1 2 and the energies of the first two absorption bands in the visible spectra reveal the ability of the studied complexes to donate and to delocalize electronic charge. © 1982.

Electrochemistry of organometallic compounds. Part IV. Oxidations of benzylic derivatives and p-substituted benzylic derivatives of bis(dimethylglyoximato) and bis(salicylaldehyde)o-phenylenediimine cobalt(III) in dimethylformamide

The electrochemical oxidation of some p-substituted benzylic derivatives of Co(III) dimethylglyoximato and Co(III)bis(salicylaldehydc)o-phenylenediimine in dimethylformamide. 0.2 M in tetraethyammonium perchlorate, on a platinum electrode, at several temperatures, is described as an ECE type, the first electrochemical step being a quasi-reversible one-electron charge transfer at room temperature. At temperatures around -20°C, or lower, the influence of the irreversible chemical decomposition of the oxidized species, via a solvent or other nucleophilic-assisted reaction, is negligible. It is suggested that at low temperatures the oxidation to the formally CoIV-R species is followed by an isomerization reaction in which this complex is partially transformed in a CoIII-(R) species or a s π-complex which undergoes an electroreduction at less positive potentials than those corresponding to the reduction of the CoIV-R species. © 1982.

Spectrophotometric study of binary and ternary systems involving metal ions and benzylidenepyruvates: Equilibria in aqueous solutions

The protonation of 4-dimethylaminobenzylidenepyruvate (DMBP) and 2-chloro-4-dimethylaminobenzylidenepyruvate (2-CI-DMBP) and their complex formation with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II) and Al(III) have been studied by potentiometric and spectrophotometric methods at 25 °C and ionic strength 0.500 M, held with sodium perchlorate. The stability order found for 1 :1 complexes of both ligands is Al(III) > Cu(II) > Pb(II) > Ni(II) > Zn(II) > Co(II) > Cd(II) > Mn(II). The stability changes move in the same direction as the pKa of the ligands. The results are compared with literature values reported for metal ion pyruvate systems. Thermodynamic stabilities of ternary complexes formed in Cu(II)-B-L- systems, where B = 2,2′-bipyridyl (bipy), ethylenediamine or glycinate and L = DMBP or 2-CI-DMBP, were also determined. The Cu(bipy)L+ species are more stable than would be expected on purely statistical grounds. The importance of the :t system associated with bipy on the enhanced stability of its mixed ligand complexes is stressed. Analytical applications of the investigated ligands are outlined.

CELULOSE FIBROSA DO BAGACO DA CANA-DE-ACUCAR - AVALIACAO DA ACAO AGLUTINANTE/DESAGREGANTE EM COMPRIMIDOS CONTENDO FARMACO HIDROSSOLUVEL

In this work, a fibrous cellulose obtained from the sugar cane bagasse was analysed about its binder/disintegrating action and about its interference degree in the dissolution rate ('in vitro') of active principles, when incorporated in a compact system that has a water-soluble drug. It was used as reference drug the Lithium Carbonate, considering its solubility in water and it difficulties in the compressibility and flow rate. That cellulose was evaluated in a comparative study, involving another fibrous cellulose generally used in the tablet obtainment (Microcel 3E-200). After the experiment in methodologies of dry granulation and wet granulation, it was concluded that the analysed celluloses presents adequate binder/disintegrating efficience and they are equivalents in these aspect.

Potentiometric study using chemically modified silica gel with pyridinium as membrane for ClO4 - ions

A potentiometric sensor for the perchlorate anion was developed by mixing chemically modified silicagel with pyridinium perchlorate, with an epoxy polymer and graphite. The electrode showed Nernstian response between 1.0 × 10-2 and 1.0 × 10-3M perchlorate concentrations. The electrode showed high selectivity to this ion at solutions pH between 5.5 and 8.0. The presence of IO4 -, NO3 -,Br-, IO3 -, Cl- and SO4 2- ions in the solutions, had only small interference in the electrode response in the range mentioned. © 1995 Springer-Verlag.

Complexation of some trivalent lanthanides, scandium(III) and thorium(IV) by benzylidenepyruvates in aqueous solution

The protonation constants of 4-methylbenzylidenepyruvate (4Me-BP) and 4-isopropylbenzylidenepyruvate (4IP-BP) as well as the stability constants of their binary 1:1 complexes with Cu(II), La(III), Pr(III), Sm(III), Eu(III), Yb(III), Sc(III) and Th(IV) have been determined spectrophotometrically in aqueous solution at 25°C and ionic strength 0.500 M, maintained with sodium perchlorate. For all metal ions considered, the stability changes move in the same direction as the pKa of the ligands. Linear free energy relationships, as applied to oxygen donor substances, suggest the -COCOO- moiety as the metal binding site of the ligands. The results are discussed mainly taking into account that benzylidenepyruvates, besides the α-keto canonical form, may display other forms in aqueous solution with changing pH and the possible occurrence of extra intra-ligand charge polarization, induced by metal ions.

LiNbO3 thin films prepared from a polymeric precursor method

LiNbO3 thin films were prepared from polymeric precursor method by dip coating. The precursor films, deposited on Si(111) substrates, were heat-treated from 400°C to 900°C in order to study the heat treatment influence on the crystallinity and microstructure of the final film. The X-ray diffraction patterns showed, in particular, that these films crystallize at low temperature (450°C) and present no preferential orientation. The scanning electron microscopy studies showed that the film microstructure is strongly influenced by the annealing temperature. © 1997 Trans Tech Publications.

Absorption and fluorescence of Er3+-doped LiYF4: Measurements and simulation

Er3+:LiYF4 single crystal has been studied by absorption and fluorescence spectroscopy in the IR-visible-UV (0-44000 cm-1) region from 4.2 K to room temperature. Polarized spectra were recorded in order to assign numerous Stark levels of electronic transitions mentioned but not attributed before in the related literature and to discuss the irreducible representations (irreps) of the 4I15/2 sublevels. A parametric hamiltonian, including free ion (Eν, α, β, γ, Tλ, ζ, Mk and Pi) and crystal field parameters (B2 0, B4 0, B4 4, B6 0 and B6 4) in an approximate D2d symmetry for the rare earth site in this scheelite type structure, was used to simulate 109 energy positions of the Er ion with a r.m.s. standard deviation of 14.6 cm-1. A comparison with previously published results for Nd3+ in the same matrix is done. © 1998 Elsevier Science S.A.

Structural and surface morphology characterizations of oriented LiNbO3 thin films grown by polymeric precursor method

Polymeric precursor solution was used to deposit LiNbO3 thin films by dip coating on sapphire substrates. The effects of processing variables, such as heat treatment conditions and number of deposited layers, on crystallinity and morphology of the final films were investigated. X-ray diffraction patterns show the oriented growth of the films. The rocking curves, obtained around the (006) LiNbO3 peak, revealed that the shape peak and the FWHM value were influenced by the processing variables. According to these parameters, some films presented very homogeneous dense and smooth surfaces, as shown by the SEM and AFM studies.