Remoção de compostos sulfurados e nitrogenados de diesel hidrotratado por adsorção em argila, alumina e sílica-alumina, impregnadas com metais de transição

Na matriz energética brasileira, o óleo diesel tem lugar de destaque, porém ainda é comercializado com teores de compostos sulfurados e nitrogenados considerados altos para as legislações ambientais que entrarão em vigor nos próximos anos. Tradicionalmente, a remoção desses compostos de enxofre de correntes de petróleo é realizada por processos de hidrotratamento (HDT). No entanto, devido as características do diesel brasileiro, se faz necessária maior severidade para atingir as novas especificações dos combustíveis. Isto implica em investimentos e custos operacionais crescentes para atender a demanda que se instala. Neste contexto, a adsorção está sendo estudada para a purificação da corrente de óleo diesel oriunda da etapa de hidrotratamento como polimento final para alcançar as especificações mais exigentes. Sabe-se que os adsorventes comerciais apresentam limitações na remoção destes contaminantes e uma alternativa que tem se mostrado promissora é a incorporação de metais de transição na estrutura do sólido. No presente trabalho foram modificados adsorventes comerciais, tais como aluminas, sílica-aluminas e argilas pela introdução dos elementos níquel, colbalto e molibdênio e testado o desempenho dessas modificações frente à adsorção de compostos sulfurados e nitrogenados presentes em um diesel hidrotratado. Foram feitas caracterizações químicas, físicas, texturais e morfológicas dos sólidos com e sem incorporação de metais de transição na estrutura original. Os experimentos de adsorção foram realizados a 40C. Avaliando todos os sólidos, o adsorvente que mostrou o melhor desempenho na remoção de compostos sulfurados e nitrogenados por massa de adsorvente foi a sílica-alumina sem modificações, que foi capaz de remover em torno de 90% de compostos nitrogenados e 55 % de sulfurados para 2 g de sólido / 10 mL de diesel. Para os materiais modificados, observou-se que a incorporação dos metais de transição ocasionou redução da sua área superficial e do volume total de poros. Desta maneira, os efeitos esperados pelas interações entre o sítios metálicos e os compostos de nitrogênio e enxofre foram reduzidos

Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation

Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CP^iPr₃) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the C_alkyl anchor in three structurally characterized oxidation states. Fe-C_alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C_alkyl interaction. The anionic (CP^iPr₃)FeN₂^- species can be functionalized by a silyl electrophile to generate (CP^iPr₃)Fe-N₂SiR₃. This species also functions as a modest catalyst for the reduction of N₂ to NH₃. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N₂-Fe(μ-SAr)Fe-N₂) across at least three oxidation states (Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N₂ and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N₂-Fe(μ-SAr)Fe-N₂) system undergoes reduction of the bound N₂ to produce NH₃ (~50% yield) and can efficiently catalyze the disproportionation of N₂H₄ to NH₃ and N₂. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiP^NMe₃] and [SiP^iPr₂P^NMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH₃ and N₂H₄). Cation binding is also facilitated in anionic Fe(0)-N₂ complexes. While Fe-N₂ complexes of a related ligand ([SiP^iPr₃]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)₃P)₂Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic C_alkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)₂]^- and [Cu(carbazolide)₃]^- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P₃Fe^II-X complexes supported by tris(phosphine)borate ([PhBP₃Fe^R]^-) and phosphiniminato X-type ligands (-N=PR'₃) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

Structure and properties of amorphous thin film for optical data storage

In this paper the magnetic and magneto-optical properties of amorphous rare earth-transition metal (RE-TM) alloys as well as the magnetic coupling in the multi-layer thin films for high density optical data storage are presented. Using magnetic effect in scanning tunneling microscopy the clusters structure of amorphous RE-TM thin films has been observed and the perpendicular magnetic anisotropy in amorphous RE-TM thin films has been interpreted. Experimental results of quick phase transformation under short pulse laser irradiation of amorphous semiconductor and metallic alloy thin films for phase change optical recording are reported. A step-by-step phase transformation process through metastable states has been observed. The waveform of crystallization propagation in micro-size spot during laser recording in amorphous semiconductor thin films is characterized and quick recording and erasing mechanism for optical data storage with high performance are discussed. The nonlinear optical effects in amorphous alloy thin films have been studied. By photo-thermal effect or third order optical nonlinearity, the optical self-focusing is observed in amorphous mask thin films. The application of amorphous thin films with super-resolution near field structure for high-density optical data storage is performed. (c) 2007 Elsevier B.V. All rights reserved.

Theoretical study on longitudinally pumped Yb3+:Y2O3 lasers

To optimize the performance of longitudinally pumped Yb^(3+):Y2O3 ceramic lasers, cavity parameters such as material length and output coupler transmission at a certain laser output power are calculated numerically using quasi-three-level laser model. The results show great potential of Yb^(3+):Y2O3 ceramics for highly efficient diode-pumped solid-state lasers.

杂质对掺钕磷酸盐激光玻璃光谱性质的影响

综述了过渡金属杂质（Cu，Fe）和稀土杂质（Dy，Pr，Sm，Ce）对掺钕磷酸盐激光玻璃吸收损耗及Nd^3＋荧光猝灭影响的研究状况。

Effect of Fe impurity on the optical loss of Nd-doped phosphate laser glass

The optical loss coefficient at 1053-nm wavelength, influenced by Fe ions in N31-type Nd-doped phosphate laser glass, was determined precisely and analyzed in detail. It is found that the optical loss coefficient per unit of Fe concentration (cm^(-1)/ppmw) increases with Fe concentration in the range of 0---300 ppmw, but it approaches a constant as the Fe concentration is larger than 300 ppmw. Such a concentration effect is due to a shift in the redox equilibrium between Fe3+ and Fe2+ ions in the glass. The effect of oxygen pressure, temperature, and variable valence states of other metal ions in glass samples on the optical loss is also discussed.

高硅氧发光玻璃的制备及其荧光性能

abstract {Silica glass is an attractive host matrix for the emission ions of rare earth and transition metal ions because it has small thermal expansion coefficient, strong thermal resistance, large fracture strength and good chemical durability and so on. However, a major obstacle to using it as the host matrix is a phenomenon of concentration quenching. In this paper, we introduces a novel method to restrain the concentration quenching by using a porous glass with SiO₂ content > 95% (in mass) and prepare intense fluorescence high-SiO₂ glasses and high-SiO₂ laser glass. The porous glass with high-SiO₂ content was impregnated with rare-earth and transition metal ions, and consequently sintered into a compact non-porous glass in reduction or oxidization atmospheres. Various intense fluorescence glasses with high emission yields, a vacuum ultraviolet-excited intensely luminescent glass, high silica glass containing high concentration of Er³⁺ ion, ultrabroad infrared luminescent Bi-doped high silica glass and Nd³⁺-doped silica microchip laser glass were obtained by this method. The porous glass is also favorable for co-impregnating multi-active-ions. It can bring effective energy transferring between various active ions in the glass and increases luminescent intensity and extend range of excitation spectrum. The luminescent active ions-doped high-SiO₂ glasses are potential host materials for high power solid-state lasers and new transparent fluorescence materials.}

Three-photon-excited upconversion luminescence of niobium ions doped silicate glass by a femtosecond laser irradiation

We report on the bluish green upconversion luminescence of niobium ions doped silicate glass by a femtosecond laser irradiation. The dependence of the fluorescence intensity on the pump power density of laser indicates that the conversion of infrared irradiation to visible emission is dominated by three-photon excitation process. We suggest that the charge transfer from O-2-to Nb5+ can efficiently contribute to the bluish green emission. The results indicate that transition metal ions without d electrons play an important role in fields of optics when embedded into silicate glass matrix. (C) 2008 Optical Society of America.

Propriedades luminescentes do SrGa2O4 dopado com íons de Ni2+

O objetivo deste trabalho é a síntese e investigação estrutural e óptica de amostras SrGa2O4 dopados com 1% de íons Ni2+. Estas amostras foram sintetizados por reação do estado sólido convencional, utilizando como materiais de partida de alta pureza Ga2O3, SrCO3 e NiO em quantidades estequiométricas. As amostras foram caracterizadas estruturalmente pelo método de difração de raios - X( XRD ) e as medições de difração mostraram que as amostras têm uma única fase monoclínica. Os padrões de XRD também foram refinados pelo método de Rietveld, que permitiu a determinação dos parâmetros de célula unitária. A Caracterização óptica das amostras puras e dopadas SrGa2O4 foram realizadas as medições a partir de fotoluminescência, de excitação e de absorção fotoacústica, à temperatura ambiente. Os espectros de emissão mostraram três bandas de emissão localizadas em 557 nm, 661 nm e 844 nm e foram identificadas essas bandas, respectivamente, com as seguintes transições eletrônicas :1T2 (1D) → 3A2 (3F), 3T1 (3F)→ 3A2 (3F) e 1T2 (1D) → 3T2 (3F). Os espectros de excitação mostraram seis bandas de absorção associadas às transições electrônicas do nível 3A2 (3F) para o 3T1 (3P) , T1 (3P), 1A1 (1G), 1T2 (1D), 3T1 (3F), 1E (1D) e 1T2, 1E (1G). Medidas de absorção fotoacústica também foram realizados com o fim de verificar as transições ópticas observadas nos espectros de excitação e de identificar novas bandas de absorção óptica. Os resultados demonstraram que os íons de Ni2+ ocupam dois locais octaédricos diferentes na amostra SrGa2O4 dopado. A partir das transições ópticas observadas nos espectros de excitação e fotoacústica, determinou-se o parâmetro de cristal de campo, dq, e parâmetros Racah, B e C. A proporção Dq / B ≈ 1.2 para ambos os locais são típicos para Ni2+ íons inseridos em redes de óxido e em coordenação octaédrica.

Síntese, caracterização e aplicações na desidrogenação oxidativa de propano de materiais tipo hidrotalcita Ni-Mg-Al com diferentes ânions de compensação

Na reação de desidrogenação oxidativa de propano (ODHP), propano reage com oxigênio da superfície de metais de transição para produzir propeno e água, em temperaturas de 300-700C. Porém, o propeno pode facilmente oxidar, formando CO e CO2. Assim, busca-se catalisadores que promovam a seletividade do propeno. Compostos tipo hidrotalcitas estão sendo apontados como catalisadores de grande potencial para a reação. Portanto, o principal objetivo desse trabalho foi sintetizar precursores tipo hidrotalcitas (contendo íons Ni2+, Mg2+ e Al3+ e tereftalato, heptamolibdato e decavanadato como ânions de compensação) para serem testados na reação de desidrogenação oxidativa de propano. Esses precursores foram sintetizados com uma razão Al/(Al+Ni+Mg)=0,5, variando a razão de Ni/Mg. Além disso, realizou-se a troca iônica do tereftalato (TA) por heptamolibdato (Mo7O24) e decavanadato (V10O28). Esses compostos foram calcinados, obtendo-se assim, óxidos mistos de NiMgAl, NiMgAlMo e NiMgAlV que foram testados como catalisadores na reação de ODHP. Para a determinação das propriedades dos catalisadores foram usadas as técnicas de caracterização: DRX, TGA, volumetria de N2, TPR, Raman e FTIR e ICP. Os resultados indicaram que os materiais tipo hidrotalcita foram obtidos com sucesso. No caso dos precursores preparados por troca iônica a cristalinidade foi menor que os da série NiMgAl-TA. Estes mesmos precursores quando calcinados apresentaram áreas muito altas. Nas três séries, os precursores calcinados são constituídos por óxidos mistos como NiO, NiMoO4, Ni2V2O7 cristalinos e espécies de alumínio e magnésio não detectados na DRX. No teste catalítico de ODHP, observou-se que com o aumento da conversão diminuía a seletividade de propeno, para os óxidos mistos que não continham molibdênio. Os catalisadores da série molibdênio foram os que obtiveram melhor desempenho com altas seletividades, mesmo em altas conversões e a série de cujo precursor foi o tereftalato foi a que exibiu maiores conversões, mas com seletividades menores que da série de Mo

Materials science: The ultrasmoothness of diamond-like carbon surfaces

The ultrasmoothness of diamond-like carbon coatings is explained by an atomistic/continuum multiscale model. At the atomic scale, carbon ion impacts induce downhill currents in the top layer of a growing film. At the continuum scale, these currents cause a rapid smoothing of initially rough substrates by erosion of hills into neighboring hollows. The predicted surface evolution is in excellent agreement with atomic force microscopy measurements. This mechanism is general, as shown by similar simulations for amorphous silicon. It explains the recently reported smoothing of multilayers and amorphous transition metal oxide films and underlines the general importance of impact-induced downhill currents for ion deposition, polishing, and nanopattering.

Orthorhombic α-moo 3 coatings with lath-shaped morphology developed by SPPS: Applications to super-capacitors

Electrical double-layer capacitors owe their large capacitance to the formation of a double-layer at the electrode/electrolyte interface of high surface area carbon-based electrode materials. Greater electrical energy storage capacity has been attributed to transition metal oxides/nitrides that undergo fast, reversible redox reactions at the electrode surface (pseudo-capacitive behavior) in addition to forming electrical double-layers. Solution Precursor Plasma Spray (SPPS) has shown promise for depositing porous, high surface area transition metal oxides. This investigation explored the potential of SPPS to fabricate a-MoO 3 coatings with micro-structures suitable for use as super-capacitor electrodes. The effects of number of spray passes, spray distance, solution concentration, flow rate and spray velocity on the chemistry and micro-structure of the a-MoO 3 deposits were examined. DTA/TGA, SEM, XRD, and electrochemical analyses were performed to characterize the coatings. The results demonstrate the importance of post-deposition heating of the deposit by subsequent passes of the plasma on the coating morphology. © ASM International.

Electronic and magnetic properties of Ti(2)O(3), Cr(2)O(3), and Fe(2)O(3) calculated by the screened exchange hybrid density functional.

The electronic and magnetic properties of the transition metal sesqui-oxides Cr(2)O(3), Ti(2)O(3), and Fe(2)O(3) have been calculated using the screened exchange (sX) hybrid density functional. This functional is found to give a band structure, bandgap, and magnetic moment in better agreement with experiment than the local density approximation (LDA) or the LDA+U methods. Ti(2)O(3) is found to be a spin-paired insulator with a bandgap of 0.22 eV in the Ti d orbitals. Cr(2)O(3) in its anti-ferromagnetic phase is an intermediate charge transfer Mott-Hubbard insulator with an indirect bandgap of 3.31 eV. Fe(2)O(3), with anti-ferromagnetic order, is found to be a wide bandgap charge transfer semiconductor with a 2.41 eV gap. Interestingly sX outperforms the HSE functional for the bandgaps of these oxides.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation.

First principles interatomic potential for tungsten based on Gaussian process regression

An accurate description of atomic interactions, such as that provided by first principles quantum mechanics, is fundamental to realistic prediction of the properties that govern plasticity, fracture or crack propagation in metals. However, the computational complexity associated with modern schemes explicitly based on quantum mechanics limits their applications to systems of a few hundreds of atoms at most. This thesis investigates the application of the Gaussian Approximation Potential (GAP) scheme to atomistic modelling of tungsten - a bcc transition metal which exhibits a brittle-to-ductile transition and whose plasticity behaviour is controlled by the properties of $\frac{1}{2} \langle 111 \rangle$ screw dislocations. We apply Gaussian process regression to interpolate the quantum-mechanical (QM) potential energy surface from a set of points in atomic configuration space. Our training data is based on QM information that is computed directly using density functional theory (DFT). To perform the fitting, we represent atomic environments using a set of rotationally, permutationally and reflection invariant parameters which act as the independent variables in our equations of non-parametric, non-linear regression. We develop a protocol for generating GAP models capable of describing lattice defects in metals by building a series of interatomic potentials for tungsten. We then demonstrate that a GAP potential based on a Smooth Overlap of Atomic Positions (SOAP) covariance function provides a description of the $\frac{1}{2} \langle 111 \rangle$ screw dislocation that is in agreement with the DFT model. We use this potential to simulate the mobility of $\frac{1}{2} \langle 111 \rangle$ screw dislocations by computing the Peierls barrier and model dislocation-vacancy interactions to QM accuracy in a system containing more than 100,000 atoms.