Síntese e fotosensibilização de nanotubos de titanatos

Nesta tese é descrita a preparação de nanotubos de titanatos (TNT) via síntese hidrotérmica alcalina, usando uma nova metodologia que evita a utilização de TiO2 cristalino como precursor. Foi estudada a influência da substituição sódio/protão na estrutura, morfologia e propriedades ópticas dos materiais preparados. Os resultados mostraram que a substituição Na+ → H+ resulta numa redução na distância intercamadas dos TNTs, tendo sido medidos valores entre 1.13±0.03 nm e 0.70±0.02 nm para aquele parâmetro. O comportamento óptico dos TNTs foi estudado na região UV-vis, estimando-se um hiato óptico de energia 3.27±0.03 eV para a amostra com maior teor de sódio enquanto que para a amostra protonada foi determinado um valor de 2.81±0.02 eV. Estes valores mostram que a troca iónica Na+ → H+ teve influência no desvio da banda de absorção dos TNTs para a região do visível próximo. A actividade fotocatalítica dos TNTs na degradação do corante rodamina 6G (R6G) foi posteriormente estudada. Verificou-se que, apesar de a amostra com maior teor de sódio ter sido a que exibiu maior capacidade para adsorver o R6G, foi a amostra protonada que apresentou a actividade catalítica mais elevada na fotodegradação deste corante. Numa segunda fase, e com o objectivo de preparar novos materiais nanoestruturados fotosensíveis, procedeu-se à decoração dos TNTs protonados com semicondutores (SC) nanocristalinos usando um método novo. Para o efeito os TNTs foram decorados com nanocristalites de ZnS, CdS e Bi2S3. Foi estudada a influência do tipo de semicondutor na estrutura, morfologia e propriedades ópticas dos SC/TNTs obtidos. Verificou-se que, para qualquer dos semicondutores usados no processo de decoração, a estrutura dos TNTs é preservada e não ocorre segregação do SC. Verificou-se ainda que a morfologia dos nanocompósitos preparados depende fortemente da natureza do semicondutor. No que respeita ao comportamento óptico destes materiais, foram determinados hiatos ópticos de energia 3.67±0.03 eV, 2.47±0.03 eV e 1.35±0.01 eV para as amostras ZnS/TNT, CdS/TNT e Bi2S3/TNT, respectivamente. Estes resultados mostram que através do processo de decoração de TNTs com semicondutores podem ser preparados materiais nanocompósitos inovadores, com propriedades ópticas novas e/ou pré-definidas numa gama alargada do espectro electromagnético.

Phase growth control in low temperature PLD Co: TiO2 films by pressure

This paper reports on the structural and optical properties of Co-doped TiO2 thin films grown onto (0001)Al2O3 substrates by non-reactive pulsed laser deposition (PLD) using argon as buffer gas. It is shown that by keeping constant the substrate temperature at as low as 310 degrees C and varying only the background gas pressure between 7 Pa and 70 Pa, it is possible to grow either epitaxial rutile or pure anatase thin films, as well as films with a mixture of both polymorphs. The optical band gaps of the films are red shifted in comparison with the values usually reported for undoped TiO2, which is consistent with n-type doping of the TiO2 matrix. Such band gap red shift brings the absorption edge of the Co-doped TiO2 films into the visible region, which might favour their photocatalytic activity. Furthermore, the band gap red shift depends on the films' phase composition, increasing with the increase of the Urbach energy for increasing rutile content. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis and properties of Co-doped titanate nanotubes and their optical sensitization with methylene blue

Agência Financiadora - Fundação para a Ciência e Tecnologia - PTDC/CTM NAN/113021/2009

Properties of tantalum oxynitride thin films produced by magnetron sputtering: the influence of processing parameters

The main purpose of this work is to present and to interpret the change of structure and physical properties of tantalum oxynitride (TaNxOy) thin films, produced by dc reactive magnetron sputtering, by varying the processing parameters. A set of TaNxOy films was prepared by varying the reactive gases flow rate, using a N2/O2 gas mixture with a concentration ratio of 17:3. The different films, obtained by this process, exhibited significant differences. The obtained composition and the interpretation of X-ray diffraction results, shows that, depending on the partial pressure of the reactive gases, the films are: essentially dark grey metallic, when the atomic ratio (N + O)/Ta < 0.1, evidencing a tetragonal β-Ta structure; grey-brownish, when 0.1 < (N + O)/Ta < 1, exhibiting a face-centred cubic (fcc) TaN-like structure; and transparent oxide-type, when (N + O)/Ta > 1, evidencing the existence of Ta2O5, but with an amorphous structure. These transparent films exhibit refractive indexes, in the visible region, always higher than 2.0. The wear resistance of the films is relatively good. The best behaviour was obtained for the films with (N + O)/Ta ≈ 0.5 and (N + O)/Ta ≈ 1.3.

Influence of the Sodium/Proton replacement on the structural, morphological and photocatalytic properties of titanate nanotubes

Titanate nanotubes (TNT) with different sodium contents have been synthesised using a hydrothermal approach and a swift and highly controllable post-washing processes. The influence of the sodium/proton replacement on the structural and morphological characteristics of the prepared materials was analysed. Different optical behaviour was observed depending on the Na+/H+ samples’ content. A band gap energy of 3.27±0.03 eV was estimated for the material with higher sodium content while a value of 2.81±0.02 eV was inferred for the most protonated material, which therefore exhibits an absorption edge in the near visible region. The point of zero charge of the materials was determined and the influence of the sodium content on the adsorption of both cationic and anionic organic dyes was studied. The photocatalytic performance of the TNT samples was evaluated in the rhodamine 6G degradation process. Best photodegradation results were obtained when using the most protonated material as catalyst, although this material has shown the lowest R6G adsorption capability.

Vertex component analysis: a geometric-based approach to unmix hyperspectral data

Hyperspectral remote sensing exploits the electromagnetic scattering patterns of the different materials at specific wavelengths [2, 3]. Hyperspectral sensors have been developed to sample the scattered portion of the electromagnetic spectrum extending from the visible region through the near-infrared and mid-infrared, in hundreds of narrow contiguous bands [4, 5]. The number and variety of potential civilian and military applications of hyperspectral remote sensing is enormous [6, 7]. Very often, the resolution cell corresponding to a single pixel in an image contains several substances (endmembers) [4]. In this situation, the scattered energy is a mixing of the endmember spectra. A challenging task underlying many hyperspectral imagery applications is then decomposing a mixed pixel into a collection of reflectance spectra, called endmember signatures, and the corresponding abundance fractions [8–10]. Depending on the mixing scales at each pixel, the observed mixture is either linear or nonlinear [11, 12]. Linear mixing model holds approximately when the mixing scale is macroscopic [13] and there is negligible interaction among distinct endmembers [3, 14]. If, however, the mixing scale is microscopic (or intimate mixtures) [15, 16] and the incident solar radiation is scattered by the scene through multiple bounces involving several endmembers [17], the linear model is no longer accurate. Linear spectral unmixing has been intensively researched in the last years [9, 10, 12, 18–21]. It considers that a mixed pixel is a linear combination of endmember signatures weighted by the correspondent abundance fractions. Under this model, and assuming that the number of substances and their reflectance spectra are known, hyperspectral unmixing is a linear problem for which many solutions have been proposed (e.g., maximum likelihood estimation [8], spectral signature matching [22], spectral angle mapper [23], subspace projection methods [24,25], and constrained least squares [26]). In most cases, the number of substances and their reflectances are not known and, then, hyperspectral unmixing falls into the class of blind source separation problems [27]. Independent component analysis (ICA) has recently been proposed as a tool to blindly unmix hyperspectral data [28–31]. ICA is based on the assumption of mutually independent sources (abundance fractions), which is not the case of hyperspectral data, since the sum of abundance fractions is constant, implying statistical dependence among them. This dependence compromises ICA applicability to hyperspectral images as shown in Refs. [21, 32]. In fact, ICA finds the endmember signatures by multiplying the spectral vectors with an unmixing matrix, which minimizes the mutual information among sources. If sources are independent, ICA provides the correct unmixing, since the minimum of the mutual information is obtained only when sources are independent. This is no longer true for dependent abundance fractions. Nevertheless, some endmembers may be approximately unmixed. These aspects are addressed in Ref. [33]. Under the linear mixing model, the observations from a scene are in a simplex whose vertices correspond to the endmembers. Several approaches [34–36] have exploited this geometric feature of hyperspectral mixtures [35]. Minimum volume transform (MVT) algorithm [36] determines the simplex of minimum volume containing the data. The method presented in Ref. [37] is also of MVT type but, by introducing the notion of bundles, it takes into account the endmember variability usually present in hyperspectral mixtures. The MVT type approaches are complex from the computational point of view. Usually, these algorithms find in the first place the convex hull defined by the observed data and then fit a minimum volume simplex to it. For example, the gift wrapping algorithm [38] computes the convex hull of n data points in a d-dimensional space with a computational complexity of O(nbd=2cþ1), where bxc is the highest integer lower or equal than x and n is the number of samples. The complexity of the method presented in Ref. [37] is even higher, since the temperature of the simulated annealing algorithm used shall follow a log( ) law [39] to assure convergence (in probability) to the desired solution. Aiming at a lower computational complexity, some algorithms such as the pixel purity index (PPI) [35] and the N-FINDR [40] still find the minimum volume simplex containing the data cloud, but they assume the presence of at least one pure pixel of each endmember in the data. This is a strong requisite that may not hold in some data sets. In any case, these algorithms find the set of most pure pixels in the data. PPI algorithm uses the minimum noise fraction (MNF) [41] as a preprocessing step to reduce dimensionality and to improve the signal-to-noise ratio (SNR). The algorithm then projects every spectral vector onto skewers (large number of random vectors) [35, 42,43]. The points corresponding to extremes, for each skewer direction, are stored. A cumulative account records the number of times each pixel (i.e., a given spectral vector) is found to be an extreme. The pixels with the highest scores are the purest ones. N-FINDR algorithm [40] is based on the fact that in p spectral dimensions, the p-volume defined by a simplex formed by the purest pixels is larger than any other volume defined by any other combination of pixels. This algorithm finds the set of pixels defining the largest volume by inflating a simplex inside the data. ORA SIS [44, 45] is a hyperspectral framework developed by the U.S. Naval Research Laboratory consisting of several algorithms organized in six modules: exemplar selector, adaptative learner, demixer, knowledge base or spectral library, and spatial postrocessor. The first step consists in flat-fielding the spectra. Next, the exemplar selection module is used to select spectral vectors that best represent the smaller convex cone containing the data. The other pixels are rejected when the spectral angle distance (SAD) is less than a given thresh old. The procedure finds the basis for a subspace of a lower dimension using a modified Gram–Schmidt orthogonalizati on. The selected vectors are then projected onto this subspace and a simplex is found by an MV T pro cess. ORA SIS is oriented to real-time target detection from uncrewed air vehicles using hyperspectral data [46]. In this chapter we develop a new algorithm to unmix linear mixtures of endmember spectra. First, the algorithm determines the number of endmembers and the signal subspace using a newly developed concept [47, 48]. Second, the algorithm extracts the most pure pixels present in the data. Unlike other methods, this algorithm is completely automatic and unsupervised. To estimate the number of endmembers and the signal subspace in hyperspectral linear mixtures, the proposed scheme begins by estimating sign al and noise correlation matrices. The latter is based on multiple regression theory. The signal subspace is then identified by selectin g the set of signal eigenvalue s that best represents the data, in the least-square sense [48,49 ], we note, however, that VCA works with projected and with unprojected data. The extraction of the end members exploits two facts: (1) the endmembers are the vertices of a simplex and (2) the affine transformation of a simplex is also a simplex. As PPI and N-FIND R algorithms, VCA also assumes the presence of pure pixels in the data. The algorithm iteratively projects data on to a direction orthogonal to the subspace spanned by the endmembers already determined. The new end member signature corresponds to the extreme of the projection. The algorithm iterates until all end members are exhausted. VCA performs much better than PPI and better than or comparable to N-FI NDR; yet it has a computational complexity between on e and two orders of magnitude lower than N-FINDR. The chapter is structure d as follows. Section 19.2 describes the fundamentals of the proposed method. Section 19.3 and Section 19.4 evaluate the proposed algorithm using simulated and real data, respectively. Section 19.5 presents some concluding remarks.

Light harvesting in solar cells using natural pigments from red fruits adsorbed to mesoporous TiO2

Nature has developed strategies to present us with a wide variety of colours, from the green of leaves to the bright colours seen in flowers. Anthocyanins are between these natural pigments that are responsible for the great diversity of colours seen in flowers and fruits. Anthocyanins have been used to sensitize titanium dioxide (TiO2) in Dye-Sensitized Solar Cells (DSSCs). DSSCs have become one of the most popular research topic in photovoltaic cells due to their low production costs when compared to other alternatives. DSSCs are inspired in what happens in nature during photosynthesis. A primary charge separation is achieved by means of a photoexcited dye capable of performing the electron injection into the conduction band of a wide band-gap semiconductor, usually TiO2. With this work we aimed to synthesize a novel mesoporous TiO2 structure as the semiconductor in order to increase the dye loading. We used natural occurring dyes such as anthocyanins and their synthetic flavylium relatives, as an alternative to the widely used metal complexes of Ru(II) which are expensive and are environmentally unsafe. This offers not only the chance to use safer dyes for DSSCs, but also to take profit of waste biological products, such as wine and olive oil production residues that are heavily loaded with anthocyanin dyes. We also performed a photodegradation study using TiO2 as the catalyst to degrade dye contaminants, such as those from the wine production waste, by photo-irradiation of the system in the visible region of the light spectrum. We were able to succeed in the synthesis of mesoporous TiO2 both powder and thin film, with a high capacity to load a large amount of dye. We proved the concept of photodegradation using TiO2 as catalyst. And finally, we show that wine production waste is a possible dye source to DSSCs application.

Al-doped ZnO ceramic sputtering targets based on nanocrystalline powders produced by emulsion detonation synthesis – deposition and application as a transparent conductive oxide material

Transparent conducting oxides (TCOs) have been largely used in the optoelectronic industry due to their singular combination of low electrical resistivity and high optical transmittance. They are usually deposited by magnetron sputtering systems being applied in several devices, specifically thin film solar cells (TFSCs). Sputtering targets are crucial components of the sputtering process, with many of the sputtered films properties dependent on the targets characteristics. The present thesis focuses on the development of high quality conductive Al-doped ZnO (AZO) ceramic sputtering targets based on nanostructured powders produced by emulsion detonation synthesis method (EDSM), and their application as a TCO. In this sense, the influence of several processing parameters was investigated from the targets raw-materials synthesis to the application of sputtered films in optoelectronic devices. The optimized manufactured AZO targets present a final density above 99 % with controlled grain size, an homogeneous microstructure with a well dispersed ZnAl2O4 spinel phase, and electrical resistivities of ~4 × 10-4 Ωcm independently on the Al-doping level among 0.5 and 2.0 wt. % Al2O3. Sintering conditions proved to have a great influence on the properties of the targets and their performance as a sputtering target. It was demonstrated that both deposition process and final properties of the films are related with the targets characteristics, which in turn depends on the initial powder properties. In parallel, the influence of several deposition parameters in the film´s properties sputtered from these targets was investigated. The sputtered AZO TCOs showed electrical properties at room temperature that are superior to simple oxides and comparable to a reference TCO – indium tin oxide (ITO), namely low electrical resistivity of 5.45 × 10-4 Ωcm, high carrier mobility (29.4 cm2V-1s-1), and high charge carrier concentration (3.97 × 1020 cm-3), and also average transmittance in the visible region > 80 %. These superior properties allowed their successful application in different optoelectronic devices.

Electrochromic devices incorporating biohybrid electrolytes doped with a lithium salt, an ionic liquid or a mixture of both

The sol-gel method was employed in the synthesis of di-urethane cross-linked poly( caprolactone) (PCL(530)/siloxane biohybrid ormolytes incorporating either a mixture of lithium triflate (LiCF3SO3) and the ionic liquid (IL) 1-ethyl-3-methyl imidazolium tetrafluoroborate ([Emim]BF4), or solely with [Emim]BF4 or LiCF3SO3. The ormolyte doped with [Emim]BF4 is thermally more stable and exhibits higher ionic conductivity (4 x 10-4 and 2 x 10-3 S cm-1 at 36 and 98 ºC, respectively) than those containing the LiCF3SO3/[Emim]BF4 mixture or just LiCF3SO3. The three ormolytes were employed in the production of glass/ITO/ormolyte/WO3/ITO/glass electrochromic devices (ECDs) designated as ECD@Y with Y = Li-[Emim]BF4, [Emim]BF4 and Li. The three ECDs displayed fast switching speed (ca. 30 s). ECD@Li-[Emim]BF4 exhibited an electrochromic contrast of 18.4 % and an optical density change of 0.11 in the visible region, the coloration efficiency attained at 555 nm was 159 and 80.2 cm-2 C-1 in the “on” and “off” states, respectively, and the open circuit memory was 48 hours. In the “on” state the CIE 1931 color space coordinates were x = 0.29 and y = 0.30, corresponding to blue color.

Gellan gum-Ionic liquid membranes for electrochromic device application

Biopolymer-based materials have been of particular interest and they are alternatives to synthetic polymers based on the decreasing oil resources. The polymer electrolytes were doped with choline-based IL N,N,Ntrimethyl- N-(2-hydroxyethyl)ammonium bis(trifluoromethylsulfonyl)imide ([N1 1 1 2(OH)][NTf2]), or Er (CF3SO3)3 or both. The polymer electrolytes were employed in the production of glass/ITO/WO3/electrolyte/ CeO2–TiO2/ITO/glass electrochromic devices (ECDs). The lowest onset temperature for the degradation of all the SPEs is at ~130 °C for the Gellan Er (CF3SO3)3 (10:1) this temperature range of stability is wide enough for a material to be applied as an electrolyte/separator component in electrochemical devices. The three ECDs displayed fast switching speed (ca. 15 s). Gellan [N1 1 1 2(OH)][NTf2] Er (CF3SO3)3 (5:1:10) exhibited an electrochromic contrast of 4.2% in the visible region, the coloration efficiency attained at 555 nm was 3.5 and 0.90 cm-2 C-1 in the “colored” and “bleached” states, respectively, and the open circuit memorywas 48 h. Preliminary tests performed with a prototype electrochromic device (ECD) incorporating WO3 as cathodic electrochromic layer, are extremely encouraging.

Flexible organic–inorganic hybrid layer encapsulation for organic opto-electronic devices

In this work we produce and study the flexible organic–inorganic hybrid moisture barrier layers for the protection of air sensitive organic opto-electronic devices. The inorganic amorphous silicon nitride layer (SiNx:H) and the organic PMMA [poly (methyl methacrylate)] layer are deposited alternatingly by using hot wire chemical vapor deposition (HW-CVD) and spin-coating techniques, respectively. The effect of organic–inorganic hybrid interfaces is analyzed for increasing number of interfaces. We produce highly transparent (∼80% in the visible region) hybrid structures. The morphological properties are analysed providing a good basis for understanding the variation of the water vapor transmission rate (WVTR) values. A minimum WVTR of 4.5 × 10−5g/m2day is reported at the ambient atmospheric conditions for 7 organic/inorganic interfaces. The hybrid barriers show superb mechanical flexibility which confirms their high potential for flexible applications.

Organização supramolecular da ftalocianina de cobalto(II) e seu efeito na oxidação do aminoácido cisteína

The interest in the chemistry of cobalt (II) tetrasulfonated phthalocyanine (PcTsCo) comes mainly from its macrocycle-ligand structure combined with their special chemical characteristics, such as high solubility, well-defined redox reactions and remarkable optical absorption in the visible region. In this work, we use layer-by-layer technique in order to assemble CoTsPc and poly(allylaminehydrochloride) (PAH) in hybrid supramolecular system. The electronic spectroscopy and cyclic voltammetry techniques were utilized to study PAH/CoTsPc multilayers growth and the cysteine catalytic oxidation. PAH/CoTsPc showed high electrochemical stability and worthwhile to mention is the remarkable influence of supramolecular arrangement on the final redox properties of the system.

Classificação de biodiesel na região do visível

Classification of biodiesel by oilseed type using pattern recognition techniques is described. The spectra of the samples were performed in the Visible region, requiring noise removal by use of a first derivative by the Savitzky-Golay method, employing a second-order polynomial and a window of 21 points. The characterization of biodiesel was performed using HCA, PCA and SIMCA. For HCA and PCA methods, one can observe the separation of each group of biodiesel in a spectral region of 405-500 nm. SIMCA model was used in a test group composed of 28 spectral measurements and no errors are obtained.

High-Spin and Emissive Molecular Materials: Synthesis and Characterization of New Polynuclear Ni(II) Complexes from the Use of Aromatic Schiff Bases as Bridging Ligands

The employment of the bridging/chelating Schiff bases, N-salicylidene-4-methyl-o-aminophenol (samphH2) and N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in nickel cluster chemistry has afforded eight polynuclear Ni(II) complexes with new structural motifs, interesting magnetic and optical properties, and unexpected organic ligand transformations. In the present thesis, Chapter 1 deals with all the fundamental aspects of polynuclear metal complexes, molecular magnetism and optics, while research results are reported in Chapters 2 and 3. In the first project (Chapter 2), I investigated the coordination chemistry of the organic chelating/bridging ligand, N-salicylidene-4-methyl-o-aminophenol (samphH2). The general NiII/tBuCO2-/samphH2 reaction system afforded two new tetranuclear NiII clusters, namely [Ni4(samph)4(EtOH)4] (1) and [Ni4(samph)4(DMF)2] (2), with different structural motifs. Complex 1 possessed a cubane core while in complex 2 the four NiII ions were located at the four vertices of a defective dicubane. The nature of the organic solvent was found to be of pivotal importance, leading to compounds with the same nuclearity, but different structural topologies and magnetic properties. The second project, the results of which are summarized in Chapter 3, included the systematic study of a new optically-active Schiff base ligand, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in NiII cluster chemistry. Various reactions between NiX2 (X- = inorganic anions) and nacbH2 were performed under basic conditions to yield six new polynuclear NiII complexes, namely (NHEt3)[Ni12(nacb)12(H2O)4](ClO4) (3), (NHEt3)2[Ni5(nacb)4(L)(LH)2(MeOH)] (4), [Ni5(OH)2(nacb)4(DMF)4] (5), [Ni5(OMe)Cl(nacb)4(MeOH)3(MeCN)] (6), (NHEt3)2[Ni6(OH)2(nacb)6(H2O)4] (7), and [Ni6(nacb)6(H2O)3(MeOH)6] (8). The nature of the solvent, the inorganic anion, X-, and the organic base were all found to be of critical importance, leading to products with different structural topologies and nuclearities (i.e., {Ni5}, {Ni6} and {Ni12}). Magnetic studies on all synthesized complexes revealed an overall ferromagnetic behavior for complexes 4 and 8, with the remaining complexes being dominated by antiferromagnetic exchange interactions. In order to assess the optical efficiency of the organic ligand when bound to the metal centers, photoluminescence studies were performed on all synthesized compounds. Complexes 4 and 5 show strong emission in the visible region of the electromagnetic spectrum. Finally, the ligand nacbH2 allowed for some unexpected organic transformations to occur; for instance, the pentanuclear compound 5 comprises both nacb2- groups and a new organic chelate, namely the anion of 5-chloro-2-[(3-hydroxy-4-oxo-1,4-dihydronaphthalen-1-yl)amino]benzoic acid. In the last section of this thesis, an attempt to compare the NiII cluster chemistry of the N-naphthalidene-2-amino-5-chlorobenzoic acid ligand with that of the structurally similar but less bulky, N-salicylidene-2-amino-5-chlorobenzoic acid (sacbH2), was made.

Sol-Gel Nanocrystalline Catalytic Titania Powders and Functional Coatings

In the present work Titania bulk powders and coatings were prepared by subjecting titanium isopropoxide solution to a controlled hydrolysis-condensation process. The powders were characterized using techniques such as FTIR for their chemical interactions, TG-DTA for the thermal decomposition features, XRD for the phase assemblage, BET specific surface area analysis for the textural features. The study discusses the preparation methods and the characterization techniques employed and a detailed discussion on the physico-chemical characterization of the prepared systems. The influence of dopants and leaching on the physico-chemical properties as well as their influence on photo activity is also included. The structural/functional coatings of different Titania compositions includes in this study. Coatings on pre-treated glass surfaces with the best compositions prepared showed 90 % transmittance in the visible region.