Caracterização de superfícies nano-estruturadas de interesse catalítico

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Física Laboratorial, Ensino e História da Física

Remoção do fenol em solução aquosa por adsorção em carvão activado

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção de grau de Mestre em Engenharia Química e Bioquímica

The solvation and electrochemical behaviour of Copper acetylacetonate complexes in ionic liquids

The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)(2) (1) and [Cu(HFacac)(2)(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)(2)] show higher g(z) values and lower hyperfine coupling constants, A(z), in ionic liquids than in organic solvents, in agreement with longer Cu-O bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)(2)(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF(4) and bmimNTf(2) ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf(2) than in bmimBF(4) ionic liquid. (C) 2013 Elsevier B.V. All rights reserved.

Fabrication of the three-dimensional dendritic Ni-Co films by electrodeposition on stainless steel substrates

Co-deposition of nickel and cobalt was carried out on austenitic stainless steel (AISI 304) substrates by imposing a square waveform current in the cathodic region. The innovative procedure applied in this work allows creating a stable, fully developed, and open porous three-dimensional (3D) dendritic structure, which can be used as electrode for redox supercapacitors. This study investigates in detail the influence of the applied current density on the morphology, mass, and chemical composition of the deposited Ni-Co films and the resulting 3D porous network dendritic structure. The morphology and the physicochemical composition were studied by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (W). The electrochemical behavior of the materials was evaluated by cyclic voltammetry (CV). The results highlight the mechanism involved in the coelectrodeposition process and how the lower limit current density tailors the film composition and morphology, as well as its electrochemical activity.

Avaliação da eficácia de tratamentos convencionais e aplicações alternativas para prevenir a biodeterioração em património cultural

Dissertação de Mestrado em Conservação e Restauro.Área de especialização: Pedra

Redox-active cytotoxic diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes: Reduction behaviour and theoretical interpretation

Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

Synthesis of titanate nanostructures using amorphous precursor material and their adsorption/photocatalytic properties

This article reports on a new and swift hydrothermal chemical route to prepare titanate nanostructures (TNS) avoiding the use of crystalline TiO2 as starting material. The synthesis approach uses a commercial solution of TiCl3 as titanium source to prepare an amorphous precursor, circumventing the use of hazardous chemical compounds. The influence of the reaction temperature and dwell autoclave time on the structure and morphology of the synthesised materials was studied. Homogeneous titanate nanotubes with a high length/diameter aspect ratio were synthesised at 160 degrees C and 24 h. A band gap of 3.06 +/- 0.03 eV was determined for the TNS samples prepared in these experimental conditions. This value is red shifted by 0.14 eV compared to the band gap value usually reported for the TiO2 anatase. Moreover, such samples show better adsorption capacity and photocatalytic performance on the dye rhodamine 6G (R6G) photodegradation process than TiO2 nanoparticles. A 98% reduction of the R6G concentration was achieved after 45 min of irradiation of a 10 ppm dye aqueous solution and 1 g L-1 of TNS catalyst.

Caracterização do crescimento de filmes ultra-finos e nano-estruturas em superfícies

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Física, especialidade de Engenharia de Superfícies, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Characterisation and electrochemical behaviour of electrodeposited Cu-Fe foams applied as pseudocapacitor electrodes

Copper iron (Cu-Fe) 3D porous foams for supercapacitor electrodes were electrodeposited in the cathodic regime, on stainless steel current collectors, using hydrogen bubbling dynamic template. The foams were prepared at different current densities and deposition times. The foams were submitted to thermal conditioning at temperatures of 150 and 250 degrees C. The morphology, composition and structure of the formed films were studied by SEM, EDS and XRD, respectively. The electrochemical behaviour was studied by cyclic voltammetry, electrochemical impedance spectroscopy and chronopotentiometry. The morphology of the 3D Cu-Fe foams is sensitive to the electrodeposition current and time. The increase of the current density produces a denser, larger and more ramified dendritic structure. Thermal conditioning at high temperature induces a coarser grain structure and the formation of copper oxides, which affect the electrochemical behaviour. The electrochemical response reveals the presence of various redox peaks assigned to the oxidation and reduction of Cu and Fe oxides and hydroxides in the foams. The specific capacitance of the 3D Cu Fe foams was significantly enhanced by thermal conditioning at 150 degrees C. The highest specific capacitance values attained 297 Fg(-1) which are much above the ones typically observed for single Cu or Fe Oxides and hydroxides. These values highlight a synergistic behaviour resulting from the combination of Cu and Fe in the form of nanostructured metallic foams. Moreover, the capacitance retention observed in an 8000 charge/discharge cycling test was above 66%, stating the good performance of these materials and its enhanced electrochemical response as supercapacitor negative electrodes. (C) 2014 Elsevier B.V. All rights reserved.

Electrochemical response of 70Co-30Ni highly branched 3D-dendritic structures for charge storage electrodes

A 70Co-30Ni dendritic alloy was produced on stainless steel by pulse electrodeposition in the cathodic domain, and oxidized by potential cycling. X-ray diffraction (XRD) identified the presence of two phases and scanning electron microscopy (SEM) evidenced an open 3D highly branched dendritic morphology. After potential cycling in 1 M KOH, SEM and X-ray photoelectron spectroscopy (XPS) revealed, respectively, the presence of thin nanoplates, composed of Co and Ni oxi-hydroxides and hydroxides over the original dendritic film. Cyclic voltammetry tests showd the presence of redox peaks assigned to the oxidation and reduction of Ni and Co centres in the surface film. Charge/discharge measurements revealed capacity values of 121 mAh g(1) at 1 mA cm(2). The capacity retention under 8000 cycles was above 70%, stating the good reversibility of these redox materials and its suitability to be used as charge storage electrodes. Electrochemical impedance spectroscopy (EIS) spectra, taken under different applied bias, showed that the capacitance increased when the electrode was fully oxidized and decreased when the electrode was reduced, reflecting different states-of-charge of the electrode. (C) 2015 Elsevier Ltd. All rights reserved.

Influence of the substrate on structure and magnetic properties of Co-N thin films

Cubic cobalt nitride films were grown onto different single crystalline substrates Al2O3 (0 0 0 1) and (1 1 View the MathML source 0), MgO (1 0 0) and (1 1 0) and TiO2 (1 0 0) and (1 1 0). The films display low atomic densities compared with the bulk material, are ferromagnetic and have metallic electrical conductivity. X-ray diffraction and X-ray absorption fine structure confirm the cubic structure of the films and with RBS results indicate that samples are not homogeneous at the microscopic scale, coexisting Co4+xN nitride with nitrogen rich regions. The magnetization of the films decreases with increase of the nitrogen content, variation that is shown to be due to the decrease of the cobalt density, and not to a decrease of the magnetic moment per cobalt ion. The films are crystalline with a nitrogen deficient stoichiometry and epitaxial with orientation determined by the substrate.

Estudo do comportamento de nanopartículas de dióxido de titânio em diferentes suspensões

Dissertação efectuada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em engenharia de Materiais

Paracoccidioides cerebriformis Moore, 1935. MYCOLOGIC AND IMMUNOCHEMICAL STUDY

The present study concern on mycologic and immunochemical data obtained from two samples of a fungus considered as belonging to the species Paracoccidioides cerebriformis described by Moore in 1935, and maintained since then on Sabouraud’s agar in the mycology collection of the Instituto de Medicina Tropical de São Paulo. After 60 years, the samples exhibited the same characteristics described by Moore (1935). However, experimental lesions did not resulted in guinea-pigs inoculated intratesticularly. The dominant antigen in Paracoccidioides brasiliensis, 43 kDa glicoprotein (gp43), could not be demonstrated by SDS PAGE and Western blotting. Immunoelectrophoresis did not demonstrated the E arch of cathodic migration using a policlonal anti gp43 serum. According to these findings, it is concluded that the fungus described by Moore (1935) as P. cerebriformis does not belong to the genus Paracoccidioides. Paracoccidioidomycosis should therefore be considered as resulting from infection by a single species, Paracoccidioides brasiliensis (Splendore, 1912) as asserted by Almeida (1930). Further studies, through molecular biology methods, could identify the mentioned fungus

Fotocatálise solar para tratamento de águas de captação

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Química e Bioquímica

Estudo electroquímico de compostos naturais e semicondutores com possível utilização em células foto voltaicas

As células foto voltaicas orgânicas ou células de Gräetzel (depois do seu descobridor) são aparelhos para a colecta de energia solar que utilizam um semicondutor inorgânico e uma molécula orgânica. Dita molécula orgânica é capaz de excitar-se na presença de radiação electromagnética e ceder esta energia através da doação de electrões a este semicondutor. Embora estas estruturas e o seu processo de fabrico sejam relativamente pouco onerosas, o aproveitamento da energia solar é ainda muito baixo. Para além desta deficiência, os corantes sintéticos sofrem de “bleaching” ou então são reduzidos ou oxidados facilmente quando não conseguem transferir a energia que foi absorvida ou quando é difícil voltar ao estado original por dificuldades no completamento de circulação de electrões. Neste trabalho pretende-se então estudar o comportamento de moléculas e misturas complexas de moléculas com capacidade para serem excitadas pela luz solar. Como a dita xcitação promove a transferência de um electrão, este processo será seguido pela técnica de Voltametria cíclica. Como substâncias absorventes de luz utilizaremos compostos naturais (principalmente flavonóides) puros, ou então na forma de complexos naturais extraídos de algumas plantas. Estas misturas de corantes serão extractos aquosos (infusões) de casca de laranja e limão assim como extractos de folhas de cerejeira, com o objectivo de proporcionar lternativas aos flavonóides utilizados neste estudo. A caracterização voltamétrica desta célula é feita em diferentes formas de iluminação. Sobre a célula assim formada faz-se incidir rimeiro luz de lâmpadas fluorescentes, depois luz ultra violeta e por fim sem qualquer tipo de luz incidente. Na base do fabrico da variante mais clássica destas células está o semicondutor óxido de itânio (TiO2), por ser uma substância muito comum e barata e com propriedades semicondutoras notáveis. Uma forma comum de melhorar a eficiência deste material é introduzir dopantes com o intuito de melhorar a eficiência do processo de transferência electrónica. Um segundo objectivo deste trabalho é o estudo de sistemas semicondutor/molécula foto activa. Semicondutores como ZnO, TiO2 e TiO2 dopado serão então estudados. O gels de TiO2 ou o TiO2 dopado serão depositados sobre lâminas de vidro comum, nas quais foi anteriormente depositado uma película de alumínio que serve de condutor (eléctrodo egativo). Uma outra variante será a utilização de óxido de zinco, um semicondutor de baixo custo que por sua vez vai ser depositado em lâminas de alumínio comercial. A nossa célula foto electroquímica será então formada por moléculas de corante, uma lâmina e um semicondutor (que funcionará como eléctrodo de trabalho), com ou sem electrólito/catalizador (solução de iodo/iodeto), e eléctrodos de referência de Ag/AgCl, e outro auxiliar de grafite. Um outro objectivo é fazer um pequeno estudo sobre influencia do catalisador I2/etilenodiamina no comportamento electroquímico da célula, de forma a poder utilizar o solvente (etilenodiamina) com menor volatilidade do que a água, que é empregada no par I2/I3.m A importância deste facto prende-se com a limitada vida destas células quando o electrólito/solvente é evaporado pelas altas temperaturas da radiação incidente.