Effects of metal catalysts on CO2 gasification reactivity of biomass char

The effects of five metal catalysts (K, Na, Ca, Mg, and Fe) on CO2 gasification reactivity of fir char were studied using thermal gravimetric analysis. The degree of carbonization, crystal structure and morphology of char samples was characterized by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The CO2 gasification reactivity of fir char was improved through the addition of metal catalysts, in the order K>Na>Ca>Fe>Mg. XRD analysis indicated that Na and Ca improved the formation of crystal structure, and that Mg enhanced the degree of carbon structure ordering. SEM analysis showed that spotted activation centers were distributed on the surface of char samples impregnated with catalysts. Moreover, a loose flake structure was observed on the surface of both K-char and Na-char. Finally, the kinetic parameters of CO2 gasification of char samples were calculated mathematically.

Efeito da pressão na obtenção e nas propriedades óticas e sensoras de filmes finos à base de 'SN''O IND. 2' com a adição de 'ZNO'

Pós-graduação em Química - IQ

The modification of structural and optical properties of nano- and submicron ZnO powders by variation of solvothermal syntheses conditions

Nano- (30-60 nm) and submicron (100-350 nm) ZnO particles were synthesized using solvothermal method at 200 degrees C from an ethanolic solution of zinc acetate dihydrate, applying different reaction conditions, i.e., pH value of precursor and time of the reaction. The X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), UV-vis diffuse reflectance (DR), Raman spectroscopy, and photoluminescence (PL) spectroscopy have been employed for characterization of synthesized ZnO powders. It was shown that the structural, morphological, and optical properties are largely determined by reaction conditions during solvothermal synthesis. The particle crystallinity improves with the decrease of pH value and/or the increase of time of the reaction. The Raman and PL spectra analyses indicate that the oxygen interstitials are dominant intrinsic defects in solvothermally synthesized ZnO powders. It was observed that concentration of defects in wurtzite ZnO crystal lattices slightly changes with the variation of pH value of the precursor and time of the solvothermal reaction. The correlation between structural ordering and defect structure of particles and corresponding growth processes was discussed.

Glasslike ordering and spatial inhomogeneity of magnetic structure in Ba3FeRu2O9: Role of Fe/Ru site disorder

Several doped 6H hexagonal ruthenates, having the general formula Ba3MRu2O9, have been studied over a significant period of time to understand the unusual magnetism of ruthenium metal. However, among them, the M = Fe compound appears different since it is observed that unlike others, the 3d Fe ions and 4d Ru ions can easily exchange their crystallographic positions, and as a result many possible magnetic interactions become realizable. The present study involving several experimental methods on this compound establishes that the magnetic structure of Ba3FeRu2O9 is indeed very different from all other 6H ruthenates. Local structural study reveals that the possible Fe/Ru site disorder further extends to create local chemical inhomogeneity, affecting the high-temperature magnetism of this material. There is a gradual decrease of Fe-57 Mossbauer spectral intensity with decreasing temperature (below 100 K), which reveals that there is a large spread in the magnetic ordering temperatures, corresponding to many spatially inhomogeneous regions. However, finally at about 25 K, the whole compound is found to take up a global glasslike magnetic ordering.

InAs/ln(0.52)Al(0.48)As quantum wire structure with the specific layer-ordering orientation on InP(001)

Quantum wires were formed in the 6-period InAs/In0.52Al0.48As structure on InP(0 0 1) grown by molecular beam epitaxy. The structure was characterized with transmission electron microscopy. It was found that the lateral periodic compositional modulation in the QWR array was in the [1 (1) over bar 0] direction and layer-ordered along the specific orientation deviating from the [0 0 1] growth direction by about 30 degrees. This deviating angle is consistent with the calculation of the distribution of elastic distortion around quantum wires in the structure using the finite element technique. (C) 1999 Elsevier Science B.V. All rights reserved.

Magnetic structure and orbital ordering in tetragonal and monoclinic KCrF3 from first-principles calculations

KCrF3 has been systematically investigated by using the full-potential linearized augmented plane wave plus local orbital method within the generalized gradient approximation and the local spin density approximation plus the on-site Coulomb repulsion approach. The total energies for ferromagnetic and three different antiferromagnetic configurations are calculated in the high-temperature tetragonal and low-temperature monoclinic phases, respectively.

X‑ray crystal structure of rac-[Ru(phen)2dppz]2+ with d(ATGCAT)2 shows enantiomer orientations and water ordering

We report an atomic resolution X-ray crystal structure containing both enantiomers of rac-[Ru(phen)2dppz]2+ with the d-(ATGCAT)2 DNA duplex (phen = phenanthroline; dppz = dipyridophenazine). The first example of any enantiomeric pair crystallized with a DNA duplex shows different orientations of the Λ and Δ binding sites, separated by a clearly defined structured water monolayer. Job plots show that the same species is present in solution. Each enantiomer is bound at a TG/CA step and shows intercalation from the minor groove. One water molecule is directly located on one phenazine N atom in the Δ-enantiomer only.

Diversity and Equitability Ordering Profiles Applied to the Study of Forest Structure

Diversity and Equitability Ordering Profiles Applied to the Study of Forest Structure

Average structure of an An (sub 48) plagioclase from the Hogarth Ranges

The average structure (CI) of a volcanic plagioclase megacryst with composition Ano, from the Hogarth Ranges, Australia, has been determined using three-dimensional, singlecrystal neutron and X-ray diffraction data. Least squaresr efinements, incorporating anisotropic thermal motion of all atoms and an extinction correction, resulted in weighted R factors (based on intensities) of 0.076 and 0.056, respectively, for the neutron and X-ray data. Very weak e reflections could be detected in long-exposure X-ray and electron diffraction photographs of this crystal, but the refined average structure is believed to be unaffected by the presence of such a weak superstructure. The ratio of the scattering power of Na to that of Ca is different for X ray and neutron radiation, and this radiation-dependence of scattering power has been used to determine the distribution of Na and Ca over a split-atom M site (two sites designated M' and M") in this Ano, plagioclase. Relative peak-height ratios M'/M", revealed in difference Fourier sections calculated from neutron and X-ray data, formed the basis for the cation-distribution analysis. As neutron and X-ray data sets were directly compared in this analysis, it was important that systematic bias between refined neutron and X-ray positional parameters could be demonstrated to be absent. In summary, with an M-site model constrained only by the electron-microprobedetermined bulk composition of the crystal, the following values were obtained for the M-site occupanciesN: ar, : 0.29(7),N ar. : 0.23(7),C ar, : 0.15(4),a nd Car" : 0.33(4). These results indicate that restrictive assumptions about M sites, on which previous plagioclase refinements have been based, are not applicable to this Ano, and possibly not to the entire compositional range. T-site ordering determined by (T-O) bond-length variation-t,o : 0.51(l), trm = t2o = t2m = 0.32(l)-is weak, as might be expectedf rom the volcanic origin of this megacryst.

Pore structure characterization of North American shale gas reservoirs using USANS/SANS, gas adsorption, and mercury intrusion

Small-angle and ultra-small-angle neutron scattering (SANS and USANS), low-pressure adsorption (N2 and CO2), and high-pressure mercury intrusion measurements were performed on a suite of North American shale reservoir samples providing the first ever comparison of all these techniques for characterizing the complex pore structure of shales. The techniques were used to gain insight into the nature of the pore structure including pore geometry, pore size distribution and accessible versus inaccessible porosity. Reservoir samples for analysis were taken from currently-active shale gas plays including the Barnett, Marcellus, Haynesville, Eagle Ford, Woodford, Muskwa, and Duvernay shales. Low-pressure adsorption revealed strong differences in BET surface area and pore volumes for the sample suite, consistent with variability in composition of the samples. The combination of CO2 and N2 adsorption data allowed pore size distributions to be created for micro–meso–macroporosity up to a limit of �1000 Å. Pore size distributions are either uni- or multi-modal. The adsorption-derived pore size distributions for some samples are inconsistent with mercury intrusion data, likely owing to a combination of grain compression during high-pressure intrusion, and the fact that mercury intrusion yields information about pore throat rather than pore body distributions. SANS/USANS scattering data indicate a fractal geometry (power-law scattering) for a wide range of pore sizes and provide evidence that nanometer-scale spatial ordering occurs in lower mesopore–micropore range for some samples, which may be associated with inter-layer spacing in clay minerals. SANS/USANS pore radius distributions were converted to pore volume distributions for direct comparison with adsorption data. For the overlap region between the two methods, the agreement is quite good. Accessible porosity in the pore size (radius) range 5 nm–10 lm was determined for a Barnett shale sample using the contrast matching method with pressurized deuterated methane fluid. The results demonstrate that accessible porosity is pore-size dependent.

Solute induced liquid crystalline behaviour of a quaternary ammonium salt and its application to structure determination

A new liquid crystalline phase, induced by the addition of small amounts of a non-mesogenic solute (such as dimethyl sulphoxide or methyl iodide) to a quaternary ammonium salt, N-methyl-N,N,N-trioctadecylammonium iodide (MTAI), has been detected by NMR and optical microscopic studies. In some cases, there is a coexistence of nematic and smectic phases. Information on the ordering of the phases in the magnetic field of the spectrometer has been derived from NMR spectra of a dissolved molecule, C-13-enriched methyl iodide. The low order parameter of the pure thermotropic nematic phase of the salt provides first-order spectra of the dissolved oriented molecules. Analyses of spectra of cis,cis-mucononitrile exemplifies the utility of the MTAI nematic phase in the determination of structural parameters of the solute.

Supramolecular ordering in oligothiophene−fullerene monolayers

Scanning tunneling microscopy (STM) of monolayers comprising oligothiophene and fullerene molecular semiconductors reveals details of their molecular-scale phase separation and ordering with potential implications for the design of organic electronic devices, in particular future bulk heterojunction solar cells. Prochiral terthienobenzenetricarboxylic acid (TTBTA) self-assembles at the solution/graphite interface into either a porous chicken wire network linked by dimeric hydrogen bonding associations of COOH groups (R22(8)) or a close-packed network linked in a novel hexameric hydrogen bonding motif (R66(24)). Analysis of high-resolution STM images shows that the chicken wire phase is racemically mixed, whereas the close-packed phase is enantiomerically pure. The cavities of the chicken wire structure can efficiently host C60 molecules, which form ordered domains with either one, two, or three fullerenes per cavity. The observed monodisperse filling and long-range co-alignment of fullerenes is described in terms of a combination of an electrostatic effect and the commensurability between the graphite and molecular network, which leads to differentiation of otherwise identical adsorption sites in the pores.

Fluorite and Mixed-Metal Kagome-Related Topologies in Metal-Organic Framework Compounds: Synthesis, Structure, and Properties

Two new three-dimensional metal-organic frameworks (MOFs) [Mn-2(mu(3)-OH)(H2O)(2)(BTC)]-2 H2O, I, and [NaMn(BTC)], II (BTC=1,2,4-benzenetricarboxylate = trimellitate) were synthesized and their structures determined by single-crystal X-ray diffraction (XRD). In I, the Mn-4 cluster, [Mn-4(mu(5)-OH)(2)(H2O)(4)O-12], is connected with eight trimellitate anions and each trimellitate anion connects to four different Mn-4 clusters, resulting in a fluorite-like structure. In II, the Mn2O8 dimer is connected with two Na+ ions through carboxylate oxygen to form mixed-metal distorted Kagome-related two-dimensional -M-O-M- layers, which are pillared by the trimellitate anions forming the three-dimensional structure. The extra-framework water molecules in I are reversibly adsorbed and are also corroborated by powder XRD studies. The formation of octameric water clusters involving free and coordinated water molecules appears to be new. Interesting magnetic behavior has been observed for both compounds. Electron spin resonance (ESR) studies indicate a broadening of the signal below the ordering temperature and appear to support the findings of the magnetic studies.

On the functional ordering of biomembranes : Implications for drug binding

Cells are packed with membrane structures, defining the inside and outside, and the different subcellular compartments. These membranes consisting mainly of phospholipids have a variety of functions in addition to providing a permeability barrier for various compounds. These functions involve cellular signaling, where lipids can act as second messengers, or direct regulation of membrane associating proteins. The first part of this study focuses on relating some of the physicochemical properties of membrane lipids to the association of drug compounds to membranes. A fluorescence based method is described allowing for determination of the membrane association of drugs. This method was subsequently applied to a novel drug, siramesine, previously shown to have anti-cancer activity. Siramesine was found to associate with anionic lipids. Especially interesting is its strong affinity for a second messenger lipid phosphatidic acid. This is the first example of a small molecule drug compound specifically interacting with a cellular lipid. Phosphatidic acid in cells is required for the activation of many signaling pathways mediating growth and proliferation. This provides an intriguing possibility for a simple molecular mechanism of the observed anti-cancer activity of siramesine. In the second part the thermal behavior and self assembly of charged and uncharged membrane assemblies was studied. Strong inter-lamellar co-operativity was observed for multilamellar DPPC vesicles using fluorescence techniques together with calorimetry. The commonly used membrane models, large unilamellar vesicles (LUV) and multilamellar vesicles (MLV) were found to possess different biophysical properties as interlamellar interactions of MLVs drive segregation of a pyrene labeled lipid analogue into clusters. The effect of a counter-ion lattice on the self assembly of a cationic gemini surfactant was studied. The presence of NaCl strongly influenced the thermal phase behavior of M-1 vesicles, causing formation of giant vesicles upon exceeding a phase transition temperature, followed by a subsequent transition into a more homogenous dispersion. Understanding the underlying biophysical aspects of cellular membranes is of fundamental importance as the complex picture of the structure and function of cells is evolving. Many of the cellular reactions take place on membranes and membranes are known to regulate the activity of many peripheral and intergral membrane associating proteins. From the point of view of drug design and gene technology, membranes can provide an interesting target for future development of drugs, but also a vehicle sensitive for environmental changes allowing for encapsulating drugs and targeting them to the desired site of action.

Self Assembly and Electronic Structure of ZnO Nanocrystals

In this paper, we report the synthesis and self assembly of various sizes of ZnO nanocrystals. While the crystal structure and the quantum confinement of nanocrystals were mainly characterized using XRD and UV absorption spectra, the self assembly and long range ordering were studied using scanning tunneling microscopy after spin casting the nanocrystal film on the highly oriented pyrolytic graphite surface. We observe self assembly of these nanocrystals over large areas making them ideal candidates for various potential applications. Further, the electronic structure of the individual dots is obtained from the current-voltage characteristics of the dots using scanning tunneling spectroscopy and compared with the density of states obtained from the tight binding calculations. We observe an excellent agreement with the experimentally obtained local density of states and the theoretically calculated density of states.