Unsupported trimetallic Ni(Co)-Mo-W sulphide catalysts prepared from mixed oxides: characterisation and catalytic tests for simultaneous tetralin HDA and dibenzothiophene HDS reactions

Unsupported A-Mo-W (A = Ni or Co) sulphide catalysts were obtained from mixed oxides containing different W:Mo ratios. An in situ liquid-phase sulphidation of the mixed oxides in a batch reactor was followed by catalytic tests in a liquid-phase reaction (at 613 K and 70 bar), using a mixture of dibenzotiophene (DBT) and tetralin (THN) as the feed. After the catalytic tests, the bulk sulphide catalysts were characterised by nitrogen physical adsorption, XANES/EXAFS, SEM and HR-(S)TEM. The HR-TEM images showed randomly oriented, stacked-layer particles typical of Mo (W) sulphides and an elemental HR-STEM mapping evidenced Mo/W homogeneous distribution in the trimetallic sulphides. The EXAFS results for the trimetallic catalysts are consistent with the presence of nickel or cobalt sulphide domains, and Mo1-xWxS2 solid solutions. The intralayer Mo:W solid solutions were confirmed to be thermodynamically stable with respect to phase separation by DFT calculations, which were also used to aid in the interpretation of the EXAFS results. The effect of the W:Mo ratio on the catalytic properties of the Ni- and Co-containing series was found to be different. For the Ni series, increasing the W content caused an activity increase in THN hydrodearomatization (HDA) relative to DBT hydrodesulphurization (HDS), while it had little influence on the relative contribution of the direct desulphurisation (DDS) route with respect to the previous hydrogenation (HYD) route for DBT HDS. In contrast, for the Co series, the activities and selectivities were essentially insensitive to the W content. Both the Ni and Co series of unsupported sulphides were more selective for the HYD route in DBT HDS than a supported NiMo/Al2O3 catalyst

Green functions for generalized point interactions in 1D: A scattering approach

Recently, general point interactions in one dimension has been used to model a large number of different phenomena in quantum mechanics. Such potentials, however, requires some sort of regularization to lead to meaningful results. The usual ways to do so rely on technicalities which may hide important physical aspects of the problem. In this work we present a new method to calculate the exact Green functions for general point interactions in 1D. Our approach differs from previous ones because it is based only on physical quantities, namely, the scattering coefficients, $R$ and $T$, to construct $G$. Renormalization or particular mathematical prescriptions are not invoked. The simple formulation of the method makes it easy to extend to more general contexts, such as for lattices of $N$ general point interactions; on a line; on a half-line; under periodic boundary conditions; and confined in a box.Comment: Revtex, 9 pages, 3 EPS figures. To be published in PR

Classical limit in terms of symbolic dynamics for the quantum baker's map

We derive a simple closed form for the matrix elements of the quantum baker's map that shows that the map is an approximate shift in a symbolic representation based on discrete phase space. We use this result to give a formal proof that the quantum baker's map approaches a classical Bernoulli shift in the limit of a small effective Plank's constant.Comment: 12 pages, LaTex, typos correcte

A Green's function approach to transmission of massless Dirac fermions in graphene through an array of random scatterers

We consider the transmission of massless Dirac fermions through an array of short range scatterers which are modeled as randomly positioned $\delta$- function like potentials along the x-axis. We particularly discuss the interplay between disorder-induced localization that is the hallmark of a non-relativistic system and two important properties of such massless Dirac fermions, namely, complete transmission at normal incidence and periodic dependence of transmission coefficient on the strength of the barrier that leads to a periodic resonant transmission. This leads to two different types of conductance behavior as a function of the system size at the resonant and the off-resonance strengths of the delta function potential. We explain this behavior of the conductance in terms of the transmission through a pair of such barriers using a Green's function based approach. The method helps to understand such disordered transport in terms of well known optical phenomena such as Fabry Perot resonances.Comment: 22 double spaced single column pages. 15 .eps figure

Alterações na ultra-estrutura de genótipos de soja em resposta ao fornecimento de manganês em solução nutritiva

The deleterious effects of Mn stress on many species have been studied, mainly concerning biochemical, physiological and growth parameters of plants. However, there are few studies relating the anatomical and ultrastructural changes in response to manganese (Mn) nutritional disorders, This study examined the leaf ultrastructure of Mn-inefficient (IAC-15, Santa Rosa) and Mn-efficient (IAC-Foscarin 31) soybean (Glycine max L.) genotypes in response to three rates of Mn (0.5, 2 and 200 µmol L-1) in the nutrient solution. Symptoms of Mn deficiency developed 12 days after transplanting in IAC-15 and Santa Rosa, followed by IAC-Foscarin 31 on the 15th day. Only IAC-15 and Santa Rosa leaves showed symptoms of Mn toxicity. The Mn concentration in leaves ranged from 8.6 (deficiency) to 886.3 mg kg-1 d.w. (toxicity). There were no changes either in stomata length or stomata number per unit of leaf surface. Cytoplasm disorganization was observed in IAC-15 under Mn-excess. In this case, the cytoplasm was amorphous, densely stained and extensively disorganized, with increased vacuolation. Mn effects were not found in mitochondria and nucleus in any of the genotypes tested. Under all Mn concentrations, many lipid globules were observed in the IAC15 chloroplasts. There was an increase in the number of plastids as well as in the size of starch grains within IAC-Foscarin 31 chloroplasts as Mn concentration in the nutrient solution increased. Genotypes had marked differences in the ultrastructure organization, mainly in leaf chloroplasts grown under conditions of both Mn deficiency and toxicity (the most sensitive genotype was IAC-15).Os efeitos negativos provocados tanto pela deficiência quanto pela toxidez de manganês (Mn) no desenvolvimento das plantas têm sido avaliados, considerando-se os aspectos bioquímicos e produtivos da parte aérea, particularmente, onde os sintomas visuais são manifestados. Entretanto, há poucas informações na literatura abordando as alterações anatômicas e de ultra-estrutura, em relação ao suprimento de Mn. Os objetivos do presente estudo foram avaliar os efeitos do fornecimento de três doses de Mn (0,5; 2 e 200 µmol L-1), em solução nutritiva, nas ultra-estruturas de folhas de cultivares de soja Glycine max (L.): Santa Rosa, IAC-15 e IAC-Foscarin 31, contrastantes quanto à aquisição e ao uso do Mn. Os sintomas visuais de deficiência foram observados primeiramente em Santa Rosa e IAC-15 (ineficientes), os únicos a exibirem sintomas de toxidez. As concentrações de Mn nas folhas com sintomas variaram de 8,6 (deficiência) a 886,3 mg kg-1 (toxidez). Não houve alterações no comprimento e no número de estômatos nos limbos foliares. Em condição de toxidez, constatou-se no IAC-15, citoplasma desorganizado, vacuolado em excesso e denso evidenciando alterações nas membranas dos tilacóides. Não ocorreram alterações ultra-estruturais nas mitocôndrias e no núcleo das células dos três genótipos. Constatou-se presença de glóbulos de lipídios nos cloroplastos do cultivar IAC-15, em todas as condições de fornecimento de Mn. Houve aumento no número de plastídeos e grãos de amido, bem como no tamanho destes no IAC-Foscarin 31 com o suprimento de Mn. Os genótipos, tanto na condição de deficiência quanto de excesso, exibiram distintos graus de organização das ultraestruturas, notadamente, os cloroplastos. O IAC-15 exibiu maiores alterações das ultra-estruturas em função das desordens nutricionais em manganês

Optical properties of MgH2 measured in situ in a novel gas cell for ellipsometry/spectrophotometry

The dielectric properties of alpha-MgH2 are investigated in the photon energy range between 1 and 6.5 eV. For this purpose, a novel sample configuration and experimental setup are developed that allow both optical transmission and ellipsometric measurements of a transparent thin film in equilibrium with hydrogen. We show that alpha-MgH2 is a transparent, colour neutral insulator with a band gap of 5.6 +/- 0.1 eV. It has an intrinsic transparency of about 80% over the whole visible spectrum. The dielectric function found in this work confirms very recent band structure calculations using the GW approximation by Alford and Chou [J.A. Alford and M.Y. Chou (unpublished)]. As Pd is used as a cap layer we report also the optical properties of PdHx thin films.Comment: REVTeX4, 15 pages, 12 figures, 5 table