CeO2-promoted Ni/activated carbon catalysts for the water–gas shift (WGS) reaction

The low temperature water–gas shift (WGS) reaction has been studied over carbon-supported nickel catalysts promoted by ceria. To this end, cerium oxide has been dispersed (at different loadings: 10, 20, 30 and 40 wt.%) on the activated carbon surface with the aim of obtaining small ceria particles and a highly available surface area. Furthermore, carbon- and ceria-supported nickel catalysts have also been studied as references. A combination of N2 adsorption analysis, powder X-ray diffraction, temperature-programmed reduction with H2, X-ray photoelectron spectroscopy and TEM analysis were used to characterize the Ni–CeO2 interactions and the CeO2 dispersion over the activated carbon support. Catalysts were tested in the low temperature WGS reaction with two different feed gas mixtures: the idealized one (with only CO and H2O) and a slightly harder one (with CO, CO2, H2, and H2O). The obtained results show that there is a clear effect of the ceria loading on the catalytic activity. In both cases, catalysts with 20 and 10 wt.% CeO2 were the most active materials at low temperature. On the other hand, Ni/C shows a lower activity, this assessing the determinant role of ceria in this reaction. Methane, a product of side reactions, was observed in very low amounts, when CO2 and H2 were included in the WGS feed. Nevertheless, our data indicate that the methanation process is mainly due to CO2, and no CO consumption via methanation takes place at the relevant WGS temperatures. Finally, a stability test was carried out, obtaining CO conversions greater than 40% after 150 h of reaction.

Nanoparticles of tungsten as low-cost monometallic catalyst for selective hydrogenation of 3-hexyne

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

Stability of Cs-Ionsiv in Portland cement blends for radioactive waste disposal

The suitability of Portland cement blends for encapsulation of Cs-Ionsiv in a monolithic wasteform was investigated. No evidence of reaction or dissolution of the Cs-Ionsiv in the cementitious environment was found by scanning electron microscopy and X-ray diffraction. However, a small fraction (≤1.6 wt%) of the Cs inventory was released from the encapsulated Ionsiv during leaching experiments carried out on hydrated samples. Cs release was enhanced by exchange of K and Na present in the cementitious pore water. Cement systems lower in K and Na, such as slag based blends, showed lower Cs release than the fly ash based analogues. © 2010 Materials Research Society.

Studies of interfacial effects between mercury and steel /

"Work performed under Contract No. AT-(40-1)-1310."

Heat stress, heat strain, and productivity in Washington State tree fruit harvesters

Thesis (Master's)--University of Washington, 2016-06

Determination of binding constants by affinity chromatography

This review summarizes developments in the use of affinity chromatography to characterize biospecific interactions in terms of reaction stoichiometry and equilibrium constant. In that regard, the biospecificity incorporated into the design of the experiment ensures applicability of the method regardless of the sizes of the reacting solutes. By the adoption of different experimental strategies (column chromatography, simple partition equilibrium, solid-phase immunoassay and biosensor technology protocols) quantitatiative affinity chromatography can be used to characterize interactions governed by an extremely broad range of binding affinities. In addition, the link between ligand-binding studies and quantitative affinity chromatography is illustrated by means of partition equilibrium studies of glycolytic enzyme interactions with muscle myofibrils. an exercise which emphasizes that the same theoretical expressions apply to naturally occurring examples of affinity chromatography in the cellular environment. (C) 2004 Elsevier B.V. All rights reserved.

Study of hexane adsorption in nanoporous MCM-41 silica

We study here the adsorption of hexane on nanoporous MCM-41 silica at 303, 313, and 323 K, for various pore diameters between 2.40 and 4.24 nm. Adsorption equilibria, measured thermogravimetrically, show that all the isotherms, that are somewhat akin to those of type V, exhibit remarkably sharp capillary adsorption phase transition steps and are reversible. The position of the phase transition step gradually shifts from low to high relative pressure with an increase in the temperature as well as the pore sizes. The isosteric heats of adsorption derived from the equilibrium information using the Clapeyron equation reveal a gradual decrease with increasing adsorbed amount because of the surface heterogeneity but approach a constant value near the phase transition. A decrease in the pore size results in an increase in the isosteric heat of adsorption because of the increased dispersion forces. A simple strategy, based on the Broekhoff and De Boer adsorption theory, successfully interprets the hexane adsorption isotherms for the different pore size MCM-41 samples. The parameters of an empirical expression, used to represent the potential of interaction between the adsorbate and adsorbent, are obtained by fitting the monolayer region prior to capillary condensation and the experimental phase transition simultaneously, for some pore sizes. Subsequently, the parameters are used to predict the adsorption isotherm on other pore size samples, which showed good agreement with experimental data.

Impact of potential models on adsorption of linear molecules on carbon black

In this paper, we investigate the effects of potential models on the description of equilibria of linear molecules (ethylene and ethane) adsorption on graphitized thermal carbon black. GCMC simulation is used as a tool to give adsorption isotherms, isosteric heat of adsorption and the microscopic configurations of these molecules. At the heart of the GCMC are the potential models, describing fluid-fluid interaction and solid-fluid interaction. Here we studied the two potential models recently proposed in the literature, the UA-TraPPE and AUA4. Their impact in the description of adsorption behavior of pure components will be discussed. Mixtures of these components with nitrogen and argon are also studied. Nitrogen is modeled a two-site plus discrete charges while argon as a spherical particle. GCMC simulation is also used for generating simulation mixture isotherms. It is found that co-operation between species occurs when the surface is fractionally covered while competition is important when surface is fully loaded.

Determination of thermal and optical parameters of melanins by photopyroelectric spectroscopy

Photopyroelectric spectroscopy (PPE) was used to study the thermal and optical properties of melanins. The photopyroelectric intensity signal and its phase were independently measured as a function of wavelength and chopping frequency for a given wavelength in the saturation part of the PPE spectrum. Equations for both the intensity and the phase of the PPE signal were used to fit the experimental results. From these fits we obtained for the first time, with great accuracy, the thermal diffusivity coefficient, the thermal conductivity, and the specific heat of the samples, as well as a value for the condensed phase optical gap, which we found to be 1.70 eV. (c) 2005 American Institute of Physics.

Kinetics of reduction of FeO from slag by graphite and coal chars

The rates of reduction of FeO from iron-saturated FeO-CaO-Al2O3-SiO2 slags by graphite, coke, bituminous coal and anthracitic coal chars at temperatures in the range 1 673-1873 K have been measured using a sessile drop technique. The extents of reaction were determined using EPMA analysis of quenched samples, and on line gas analysis using a quadrupole mass spectrometer. The reaction rates have been shown to be dependent critically on carbon type. For the reaction geometry used in this investigation the reduction rates of graphite and coke are observed to be faster than with coal chars. This unexpected finding is shown to be associated with differences in the dominant chemical and mass transfer mechanisms occurring at the reaction interface. High reaction rates are observed to occur with the formation of liquid Fe-C alloy product and the associated gasification of carbon from the alloy. The rates of reduction by coal chars are determined principally by the chemical reaction at the carbon/gas interface and slag phase mass transfer.

Features of nitrogen adsorption on nonporous carbon and silica surfaces in the framework of classical density functional theory

Equilibrium adsorption data of nitrogen on a series of nongraphitized carbon blacks and nonporous silica at 77 K were analyzed by means of classical density functional theory to determine the solid-fluid potential. The behavior of this potential profile at large distance is particularly considered. The analysis of nitrogen adsorption isotherms seems to indicate that the adsorption in the first molecular layer is localized and controlled mainly by short-range forces due to the surface roughness, crystalline defects, and functional groups. At distances larger than approximately 1.3-1.5 molecular diameters, the adsorption is nonlocalized and appears as a thickening of the adsorbed film with increasing bulk pressure in a relatively weak adsorption potential field. It has been found that the asymptotic decay of the potential obeys the power law with the exponent being -3 for carbon blacks and -4 for silica surface, which signifies that in the latter case the adsorption potential is mainly exerted by surface oxygen atoms. In all cases, the absolute value of the solid-fluid potential is much smaller than that predicted by the Lennard-Jones pair potential with commonly used solid-fluid molecular parameters. The effect of surface heterogeneity on the heat of adsorption is also discussed.

Effect of adsorption deformation on thermodynamic characteristics of a fluid in slit pores at sub-critical conditions

Solvation. pressure due to adsorption of fluids in porous materials is the cause of elastic deformation of an adsorbent, which is accessible to direct experimental measurements. Such a deformation contributes to the Helmholtz free energy of the whole adsorbent-adsorbate system due to accumulation of compression or tension energy by the solid. It means that in the general case the solid has to be considered as not solely a source of the external potential field for the fluid confined in the pore volume, but also as thermodynamically nonmert component of the solid-fluid system. We present analysis of nitrogen adsorption isotherms and heat of adsorption in slit graphitic pores accounting for the adsorption deformation by means of nonlocal density functional theory. (c) 2006 Elsevier Ltd. All rights reserved.

Influence of adsorbate interaction on transport in confined spaces

This article provides a review of the recent theory of transport in nanopores developed in the author's laboratory. In particular the influence of fluid-solid interactions on the transport coefficient is examined, showing that such interactions reduce the value of the coefficient by almost an order of magnitude in comparison to the Knudsen theory for non-interacting systems. The activation energy and potential energy barriers for diffusion in smooth pores with a one-dimensional potential energy profile are also discussed, indicating the inadequacy of the commonly used assumption of proportionality between the activation energy and heat of adsorption or the minimum pore potential energy. A further feature affected by fluid-solid interactions is the nature of the reflection of fluid molecules colliding with a pore wall surface, varying from being nearly specular - such as in carbon nanotubes - to nearly diffuse for amorphous solids. Diffuse reflection leads to momentum loss and reduced transport coefficients. However, fluid-solid interactions do not affect the transport coefficient in the single-file diffusion regime when the surface reflection is diffuse, and the transport coefficient in this case is largely independent of the adsorbed density.

Structural evolution in a hydrothermal reaction between Nb2O5 and NaOH solution: From Nb2O5 grains to microporous Na2Nb2O6 center dot(2)/3H2O fibers and NaNbO3 cubes

Niobium pentoxide reacts actively with concentrate NaOH solution under hydrothermal conditions at as low as 120 degrees C. The reaction ruptures the corner-sharing of NbO7 decahedra and NbO6 octahedra in the reactant Nb2O5, yielding various niobates, and the structure and composition of the niobates depend on the reaction temperature and time. The morphological evolution of the solid products in the reaction at 180 degrees C is monitored via SEM: the fine Nb2O5 powder aggregates first to irregular bars, and then niobate fibers with an aspect ratio of hundreds form. The fibers are microporous molecular sieve with a monoclinic lattice, Na2Nb2O6 center dot(2)/3H2O. The fibers are a metastable intermediate of this reaction, and they completely convert to the final product NaNbO3 Cubes in the prolonged reaction of 1 h. This study demonstrates that by carefully optimizing the reaction condition, we can selectively fabricate niobate structures of high purity, including the delicate microporous fibers, through a direct reaction between concentrated NaOH solution and Nb2O5. This synthesis route is simple and suitable for the large-scale production of the fibers. The reaction first yields poorly crystallized niobates consisting of edge-sharing NbO6 octahedra, and then the microporous fibers crystallize and grow by assembling NbO6 octahedra or clusters of NbO6 octahedra and NaO6 units. Thus, the selection of the fibril or cubic product is achieved by control of reaction kinetics. Finally, niobates with different structures exhibit remarkable differences in light absorption and photoluminescence properties. Therefore, this study is of importance for developing new functional materials by the wet-chemistry process.

Temperature and the respiratory properties of whole blood in two reptiles, Pogona barbata and Emydura signata

We investigated the capacity of two reptiles, an agamid lizard Pogona barbata and a chelid turtle Emydura signata, to compensate for the effects of temperature by making changes in their whole blood respiratory properties. This was accomplished by measuring the P-50 (at 10, 20 and 30 degrees C), hematocrit (Hct), haemoglobin concentration ([Hb]) and mean cell haemoglobin concentration (MCHC) in field acclimatised and laboratory acclimated individuals. The acute effect of temperature on P50 in P barbata, expressed as heat of oxygenation (Delta H), ranged from -16.8 +/- 1.84 to -28.5 +/- 2.73 kJ/mole. P-50 of field acclimatised P barbata increased significantly from early spring to summer at the test temperatures of 20 degrees C (43.1 +/- 1.2 to 48.8 +/- 2.1 mmHg) and 30 degrees C (54.7 +/- 1.2 to 65.2 +/- 2.3 mmHg), but showed no acclimation under laboratory conditions. For E. signata, Delta H ranged from -31.1 +/- 6.32 to -48.2 +/- 3.59 kJ/mole. Field acclimatisation and laboratory acclimation of P-50 did not occur. However, in E. signata, there was a significant increase in [Hb] and MCHC from early spring to summer in turtles collected from the wild (1.0 +/- 0.1 to 1.7 +/- 0.2 mmol/L and 4.0 +/- 0.3 to 6.7 +/- 0.7 mmol/L, respectively). (C) 2005 Published by Elsevier Inc.