A comprehensive study on carbon dioxide reforming of methane over Ni/gamma-Al2O3 catalysts

Carbon dioxide reforming of methane into syngas over Ni/gamma-Al2O3 catalysts was systematically studied. Effects of reaction parameters on catalytic activity and carbon deposition over Ni/gamma-Al2O3 catalysts were investigated. It is found that reduced NiA1204, metal nickel, and active species of carbon deposited were the active sites for this reaction. Carbon deposition on Ni/gamma Al2O3 varied depending on the nickel loading and reaction temperature and is the major cause of catalyst deactivation. Higher nickel loading produced more coke on the catalysts, resulting in rapid deactivation and plugging of the reactor. At 5 wt % Ni/gamma-Al2O3 catalyst exhibited high activity and much lesser magnitude of deactivation in 140 h. Characterization of carbon deposits on the catalyst surface revealed that there are two kinds of carbon species (oxidized and -C-C-) formed during the reaction and they showed different reactivities toward hydrogenation and oxidation. Kinetic studies showed that the activation energy for CO production in this reaction amounted to 80 kJ/mol and the rate of CO production could be described by a Langmuir-Hinshelwood model.

A comparative study of N2O conversion to N-2 over Co/AC and Cu/AC catalysts

Catalytic conversion of N2O to N-2 over Cu- and Co-impregnated activated carbon catalysts (Cu/AC and Co/AC) was investigated. Catalytic activity measurements were carried out in a fixed-bed flow reactor at atmospheric pressure. The catalysts were characterized by N-2 adsorption, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). This study aimed to provide insights into the following aspects: the metal dispersion, changes in pore structure, influence of catalyst loading on reaction, and reaction mechanism. Increasing loading of Co or Cu led to decreasing dispersion, but 20 wt % loading was an upper limit for optimal activities in both cases, with too high loading causing sintering of metal. Co exhibited a relatively better dispersion than Cu. Impregnation of metal led to a large decrease in surface area and pore volume, especially for 30 wt % of loading. 20 wt % of loading has proved to be the optimum for both Cu and Co, which shows the highest activity. Both N2O-Co/AC and -Cu/AC reactions are based upon a redox mechanism, but the former is limited by the oxygen transfer from catalysts to carbon, while N2O chemisorption on the surface of Cu catalyst controls the latter. The removal of oxygen from cobalt promotes the activity of Co/AC, but it is beneficial for Cu/AC to keep plenty of oxygen to maintain the intermediate oxidation of copper-Cu1+. The different nature of the two catalysts and their catalytic reaction mechanisms are closely related to their different electronegativities.

Electrochemistry of macrocyclic cobalt(III/II) hexaamines: Electrocatalytic hydrogen evolution in aqueous solution

The macrocyclic cobalt hexaamines [Co(trans-diammac)](3+) and [Co(cis-diammac)](3+) (diammac = 6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine) are capable of reducing the overpotential for hydrogen evolution on a mercury cathode in aqueous solution. Protons are reduced in a catalytic process involving reoxidation of the Co-II species to its parent Co-III complex. The cycle is robust at neutral pH with no decomposition of catalyst. The stability of the [Co(trans-diammac)](2+) and [Co(cis-diammac)](2+) complexes depends on the pH of the solution and the coordinating properties of the supporting electrolyte. Electrochemical studies indicate that the adsorbed Co-II complex on the surface of mercury is the active catalyst for the reduction of protons to dihydrogen.

Thylakoid membrane architecture

Confocal scanning laser microscopic observations were made on live chloroplasts in intact cells and on mechanically isolated, intact chloroplasts. Chlorophyll fluorescence was imaged to observe thylakoid membrane architecture. C-3 plant species studied included Spinacia oleracea L., Spathiphyllum sp. Schott, cv. 'Mauna Loa', and Pisum sativum L. C-4 plants were also investigated: Saccharum officinarum L., Sorghum bicolor L. Moench, Zea mays L. and Panicum miliaceum L. Some Spinacia chloroplasts were treated with 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) to enhance or sodium dithionite (SD) to reduce the photosystem II fluorescence signal. Confocal microscopy images of C-3 chloroplasts differed from electron microscopy pictures because they showed discrete spots of bright fluorescence with black regions between them. There was no evidence of fluorescence from stroma thylakoids. The thylakoid membrane system at times appeared to be string-like, with brightly fluorescing grana lined up like beads. C-4 bundle sheath chloroplasts were imaged from three different types of C-4 plants. Saccharum and Sorghum bundle sheath chloroplasts showed homogeneous fluorescence and were much dimmer than mesophyll chloroplasts. Zea had rudimentary grana, and dim, homogeneous intergrana fluorescence was visualised. Panicum contained thylakoids similar in appearance and string-like arrangement to mesophyll chloroplasts. Isolated Pisum chloroplasts, treated with a drop of 5 mM MgCl2 showed a thylakoid membrane system which appeared to be unravelling. Spongy mesophyll chloroplasts of Spinacia treated with 5 mM sodium dithionite showed a granal thylakoid system with distinct regions of no fluorescence. A time-series experiment provided evidence of dynamic membrane rearrangements over a period of half an hour.

Asymmetric MRI magnet design using a hybrid numerical method

This paper describes a hybrid numerical method for the design of asymmetric magnetic resonance imaging magnet systems. The problem is formulated as a field synthesis and the desired current density on the surface of a cylinder is first calculated by solving a Fredholm equation of the first kind. Nonlinear optimization methods are then invoked to fit practical magnet coils to the desired current density. The field calculations are performed using a semi-analytical method. A new type of asymmetric magnet is proposed in this work. The asymmetric MRI magnet allows the diameter spherical imaging volume to be positioned close to one end of the magnet. The main advantages of making the magnet asymmetric include the potential to reduce the perception of claustrophobia for the patient, better access to the patient by attending physicians, and the potential for reduced peripheral nerve stimulation due to the gradient coil configuration. The results highlight that the method can be used to obtain an asymmetric MRI magnet structure and a very homogeneous magnetic field over the central imaging volume in clinical systems of approximately 1.2 m in length. Unshielded designs are the focus of this work. This method is flexible and may be applied to magnets of other geometries. (C) 1999 Academic Press.

Effects of acid treatments of carbon on N2O and NO reduction by carbon-supported copper catalysts

The influences of HCl, HNO3 and HF treatments of carbon on N2O and NO reduction with 20 wt% Cu-loaded activated carbon were studied. The order of activity in both N2O and NO is as follows: Cu20/AC-HNO3>Cu20/AC>Cu20/AC-HF>Cu20/AC-HCl. The same sequence was also observed for the amount of CO2 evolved during TPD experiments of supports acid for the catalyst dispersion. On the other hand, N2O exhibited a higher reaction rate than NO and a higher sensitivity to acid treatments, and the presence of gas-phase O-2 had opposite effects in N2O and NO reduction. The key role of carbon surface chemistry is examined to rationalize these findings and the relevant mechanistic and practical implications are discussed. The effects of oxygen surface groups on the pore structure of supports and catalysts are also analyzed, (C) 2000 Elsevier Science Ltd. All rights reserved.

A hybrid, inverse approach to the design of magnetic resonance imaging magnets

This paper describes a hybrid numerical method of an inverse approach to the design of compact magnetic resonance imaging magnets. The problem is formulated as a field synthesis and the desired current density on the surface of a cylinder is first calculated by solving a Fredholm equation of the first, kind. Nonlinear optimization methods are then invoked to fit practical magnet coils to the desired current density. The field calculations are performed using a semi-analytical method. The emphasis of this work is on the optimal design of short MRI magnets. Details of the hybrid numerical model are presented, and the model is used to investigate compact, symmetric MRI magnets as well as asymmetric magnets. The results highlight that the method can be used to obtain a compact MRI magnet structure and a very homogeneous magnetic field over the central imaging volume in clinical systems of approximately 1 m in length, significantly shorter than current designs. Viable asymmetric magnet designs, in which the edge of the homogeneous region is very close to one end of the magnet system are also presented. Unshielded designs are the focus of this work. This method is flexible and may be applied to magnets of other geometries. (C) 2000 American Association of Physicists in Medicine. [S0094-2405(00)00303-5].

Grazers and diggers: Exploitation competition and coexistence among foragers with different feeding strategies on a single resource

A mathematical model is presented that describes a system where two consumer species compete exploitatively for a single renewable resource. The resource is distributed in a patchy but homogeneous environment; that is, all patches are intrinsically identical. The two consumer species are referred to as diggers and grazers, where diggers deplete the resource within a patch to lower densities than grazers. We show that the two distinct feeding strategies can produce a heterogeneous resource distribution that enables their coexistence. Coexistence requires that grazers must either move faster than diggers between patches or convert the resources to population growth much more efficiently than diggers. The model shows that the functional form of resource renewal within a patch is also important for coexistence. These results contrast with theory that considers exploitation competition for a single resource when the resource is assumed to be well mixed throughout the system.

Habitat structure and egg distributions in the processionary caterpillar Ochrogaster lunifer: lessons for conservation and pest management

1. The spatial and temporal distribution of eggs laid by herbivorous insects is a crucial component of herbivore population stability, as it influences overall mortality within the population. Thus an ecologist studying populations of an endangered butterfly can do little to increase its numbers through habitat management without knowledge of its egg-laying patterns across individual host-plants under different habitat management regimes. At the other end of the spectrum, a knowledge of egg-laying behaviour can do much to control pest outbreaks by disrupting egg distributions that lead to rapid population growth. 2. The distribution of egg batches of the processionary caterpillar Ochrogaster lunifer on acacia trees was monitored in 21 habitats during 2 years in coastal Australia. The presence of egg batches on acacias was affected by host-tree 'quality' (tree size and foliar chemistry that led to increased caterpillar survival) and host-tree 'apparency' (the amount of vegetation surrounding host-trees). 3. In open homogeneous habitats, more egg batches were laid on high-quality trees, increasing potential population growth. In diverse mixed-species habitats, more egg batches were laid on low-quality highly apparent trees, reducing population growth and so reducing the potential for unstable population dynamics. The aggregation of batches on small apparent trees in diverse habitats led to outbreaks on these trees year after year, even when population levels were low, while site-wide outbreaks were rare. 4. These results predict that diverse habitats with mixed plant species should increase insect aggregation and increase population stability. In contrast, in open disturbed habitats or in regular plantations, where egg batches are more evenly distributed across high-quality hosts, populations should be more unstable, with site-wide outbreaks and extinctions being more common. 5. Mixed planting should be used on habitat regeneration sites to increase the population stability of immigrating or reintroduced insect species. Mixed planting also increases the diversity of resources, leading to higher herbivore species richness. With regard to the conservation of single species, different practices of habitat management will need to be employed depending on whether a project is concerned with methods of rapidly increasing the abundance of an endangered insect or concerned with the maintenance of a stable, established insect population that is perhaps endemic to an area. Suggestions for habitat management in these different cases are discussed. 6. Finally, intercropping can be highly effective in reducing pest outbreaks, although the economic gains of reduced pest attack may be outweighed by reduced crop yields in mixed-crop systems.

Novel silica gel supported TiO2 photocatalyst synthesized by CVD method

TiO2 in anatase crystal phase is a very effective catalyst in the photocatalytic oxidation of organic compounds in water. To improve the recovery rate of TiO2 photocatalysts, which in most cases are in fine powder form, the chemical vapor deposition (CVD) method was used to load TiO2 onto a bigger particle support, silica gel. The amount of titania coating was found to depend strongly on the synthesis parameters of carrier gas flow rate and coating time. XPS and nitrogen ads/desorption results showed that most of the TiO2 particles generated from CVD were distributed on the external surface of the support and the coating was stable. The photocatalytic activities of TiO2/silica gel with different amounts of titania were evaluated for the oxidation of phenol aqueous solution and compared with that of Degussa P25. The optimum titania loading rate was found around 6 wt % of the TiO2 bulk concentration. Although the activity of the best TiO2/silica gel sample was still lower than that of P25, the synthesized TiO2/silica gel catalyst can be easily separated from the treated water and was found to maintain its TiO2 content and catalytic activity.

Water wave-driven seepage in marine sediments

The action of water waves moving over a porous seabed drives a seepage flux into and out of the marine sediments. The volume of fluid exchange per wave cycle may affect the rate of contaminant transport in the sediments. In this paper, the dynamic response of the seabed to ocean waves is treated analytically on the basis of pore-elastic theory applied to a porous seabed. The seabed is modelled as a semi-infinite, isotropic, homogeneous material. Most previous investigations on the wave-seabed interaction problem have assumed quasi-static conditions within the seabed, although dynamic behaviour often occurs in natural environments. Furthermore, wave pressures used in the previous approaches were obtained from conventional ocean wave theories: which are based on the assumption of an impermeable rigid seabed. By introducing a complex wave number, we derive a new wave dispersion equation, which includes the seabed characteristics (such as soil permeability, shear modulus, etc.). Based on the new closed-form analytical solution, the relative differences of the wave-induced seabed response under dynamic and quasi-static conditions are examined. The effects of wave and soil parameters on the seepage flux per wave cycle are also discussed in detail. (C) 2000 Elsevier Science Ltd. All rights reserved.

Porous clays and pillared clays-based catalysts. Part 2: A review of the catalytic and molecular sieve applications

Metal oxide pillared clay (PILC) possesses several interesting properties, such as large surface area, high pore volume and tunable pore size (from micropore to mesopore), high thermal stability, strong surface acidity and catalytic active substrates/metal oxide pillars. These unique characteristics make PILC an attractive material in catalytic reactions. It can be made either as catalyst support or directly used as catalyst. This paper is a continuous work from Kloprogge's review (J.T. Kloprogge, J. Porous Mater. 5, 5 1998) on the synthesis and properties of smectites and related PILCs and will focus on the diverse applications of clay pillared with different types of metal oxides in the heterogeneous catalysis area and adsorption area. The relation between the performance of the PILC and its physico-chemical features will be addressed.

A method for the design of MRI radiofrequency coils based on triangular and pulse basis functions

This paper presents a numerical technique for the design of an RF coil for asymmetric magnetic resonance imaging (MRI) systems. The formulation is based on an inverse approach where the cylindrical surface currents are expressed in terms of a combination of sub-domain basis functions: triangular and pulse functions. With the homogeneous transverse magnetic field specified in a spherical region, a functional method is applied to obtain the unknown current coefficients. The current distribution is then transformed to a conductor pattern by use of a stream function technique. Preliminary MR images acquired using a prototype RF coil are presented and validate the design method. (C) 2002 Elsevier Science B.V. All rights reserved.

Finite element modelling of reactive fluids mixing and mineralization in pore-fluid saturated hydrothermal/sedimentary basins

We present the finite element simulations of reactive mineral carrying fluids mixing and mineralization in pore-fluid saturated hydrothermal/sedimentary basins. In particular we explore the mixing of reactive sulfide and sulfate fluids and the relevant patterns of mineralization for Load, zinc and iron minerals in the regime of temperature-gradient-driven convective flow. Since the mineralization and ore body formation may last quite a long period of time in a hydrothermal basin, it is commonly assumed that, in the geochemistry, the solutions of minerals are in an equilibrium state or near an equilibrium state. Therefore, the mineralization rate of a particular kind of mineral can be expressed as the product of the pore-fluid velocity and the equilibrium concentration of this particular kind of mineral Using the present mineralization rate of a mineral, the potential of the modern mineralization theory is illustrated by means of finite element studies related to reactive mineral-carrying fluids mixing problems in materially homogeneous and inhomogeneous porous rock basins.

On the theory of mixing-frequency electron spin-echo envelope modulation spectroscopy

It has recently been stated that the parametrization of the time variables in the one-dimensional (I-D) mixing-frequency electron spin-echo envelope modulation (MIF-ESEEM) experiment is incorrect and hence the wrong frequencies for correlated nuclear transitions are predicted. This paper is a direct response to such a claim, its purpose being to show that the parametrization in land 2-D MIF-ESEEM experiments possesses the same form as that used in other 4-pulse incrementation schemes and predicts the same correlation frequencies. We show that the parametrization represents a shearing transformation of the 2-D time-domain and relate the resulting frequency domain spectrum to the HYSCORE spectrum in terms of a skew-projection. It is emphasized that the parametrization of the time-domain variables may be chosen arbitrarily and affects neither the computation of the correct nuclear frequencies nor the resulting resolution. The usefulness or otherwise of the MIF parameters \gamma\ > 1 is addressed, together with the validity of the original claims of the authors with respect to resolution enhancement in cases of purely homogeneous and inhomogeneous broadening. Numerical simulations are provided to illustrate the main points.