Au on (111) and (110) surfaces of CeO2: A density-functional theory study

The atomic structures of gold supported on (111) and (110) surfaces of CeO2 have been studied using density-functional theory calculations. A single Au atom is placed on three adsorption sites on the surfaces; the stoichiometric surfaces, an oxygen vacancy and a Ce-vacancy. It is found that (i) the Au adsorption energies are in the following order: E-ad(Ce-vacancy) > E-ad(O-vacancy) > E-ad(stoichiometric surface); and (ii) the Au atom adsorption on the Ce-vacancy activates O atoms nearby. One 0 atom is less stable than that in O-2 in the gas phase and another O atom is much easier to remove compared to that of the stoichiometric surfaces. These results suggest that the Au adsorption on Ce-vacancies not only creates an O-vacancy but also activates an O atom nearby. This provides a piece of direct evidence that Au adsorption on a Ce-vacancy may be responsible for some unique catalytic properties of Au/CeO2. (C) 2008 Elsevier B.V. All rights reserved.

The dissociation of molecularly adsorbed CO and CN over the 4d transition metals: A universal relationship between the reaction barriers and the reaction enthalpies

Density functional theory calculations are used to study the stability of molecularly adsorbed CO and CN over transition metal surfaces. The minimum energy reaction pathways, corresponding reaction barriers (E-a), and reaction enthalpies (Delta H) for the dissociation of CO and CN to atomic products over the 4d transition metals from Zr to Pd have been determined. CO is found to be the more stable adsorbate on the right hand side of the period (from Tc onwards), whereas CN is the more stable surface species on the early metals (Zr, Nb and Mo). A single linear relationship is found to exist that correlates the barriers of both reactions with their respective reaction enthalpies. (c) 2006 Elsevier B.V. All rights reserved.

CO dissociation and O removal on Co(0001): a density functional theory study

CO dissociation and O removal (water formation) are two important processes in the Fischer-Tropsch synthesis. In this study, both processes are studied on the flat and stepped Co(0 0 0 1) using density functional theory. It is found that (i) it is difficult for CO to dissociate on the flat Co(0 0 0 1) due to the high barrier of 1.04 eV relative to the CO molecule in the gas phase; (ii) the stepped Co(0 0 0 1) is much more favoured for CO dissociation; (iii) the first step in water formation, O + H --> OH, is unlikely to occur on the flat Co(0 0 0 1) due to the high barrier of 1.72 eV, however, this reaction can become feasible on steps where the barrier is reduced to 0.73 eV; and (iv) the barrier in the second step, OH + H --> H2O, on steps is higher than that on the flat surface. (C) 2004 Elsevier B.V. All rights reserved.

Chitosan nanoparticle as protein delivery carrier - Systematic examination of fabrication conditions for efficient loading and release

Chitosan nanoparticles fabricated via different preparation protocols have been in recent years widely studied as carriers for therapeutic proteins and genes with varying degree of effectiveness and drawbacks. This work seeks to further explore the polyionic coacervation fabrication process, and associated processing conditions under which protein encapsulation and subsequent release can be systematically and predictably manipulated so as to obtain desired effectiveness. BSA was used as a model protein which was encapsulated by either incorporation or incubation method, using the polyanion tripolyphosphate (TPP) as the coacervation crosslink agent to form chitosan-BSA-TPP nanoparticles. The BSA-loaded chitosan-TPP nanoparticles were characterized for particle size, morphology, zeta potential, BSA encapsulation efficiency, and subsequent release kinetics, which were found predominantly dependent on the factors of chitosan molecular weight, chitosan concentration, BSA loading concentration, and chitosan/TPP mass ratio. The BSA loaded nanoparticles prepared under varying conditions were in the size range of 200-580 nm, and exhibit a high positive zeta potential. Detailed sequential time frame TEM imaging of morphological change of the BSA loaded particles showed a swelling and particle degradation process. Initial burst released due to surface protein desorption and diffusion from sublayers did not relate directly to change of particle size and shape, which was eminently apparent only after 6 h. It is also notable that later stage particle degradation and disintegration did not yield a substantial follow-on release, as the remaining protein molecules, with adaptable 3-D conformation, could be tightly bound and entangled with the cationic chitosan chains. In general, this study demonstrated that the polyionic coacervation process for fabricating protein loaded chitosan nanoparticles offers simple preparation conditions and a clear processing window for manipulation of physiochemical properties of the nanoparticles (e.g., size and surface charge), which can be conditioned to exert control over protein encapsulation efficiency and subsequent release profile. The weakness of the chitosan nanoparticle system lies typically with difficulties in controlling initial burst effect in releasing large quantities of protein molecules. (C) 2007 Elsevier B.V. All rights reserved.

PLS modelling and fault detection on the Tennessee Eastman benchmark

This paper describes the application of multivariate regression techniques to the Tennessee Eastman benchmark process for modelling and fault detection. Two methods are applied : linear partial least squares, and a nonlinear variant of this procedure using a radial basis function inner relation. The performance of the RBF networks is enhanced through the use of a recently developed training algorithm which uses quasi-Newton optimization to ensure an efficient and parsimonious network; details of this algorithm can be found in this paper. The PLS and PLS/RBF methods are then used to create on-line inferential models of delayed process measurements. As these measurements relate to the final product composition, these models suggest that on-line statistical quality control analysis should be possible for this plant. The generation of `soft sensors' for these measurements has the further effect of introducing a redundant element into the system, redundancy which can then be used to generate a fault detection and isolation scheme for these sensors. This is achieved by arranging the sensors and models in a manner comparable to the dedicated estimator scheme of Clarke et al. 1975, IEEE Trans. Pero. Elect. Sys., AES-14R, 465-473. The effectiveness of this scheme is demonstrated on a series of simulated sensor and process faults, with full detection and isolation shown to be possible for sensor malfunctions, and detection feasible in the case of process faults. Suggestions for enhancing the diagnostic capacity in the latter case are covered towards the end of the paper.

Metamaterial made of paired planar conductors: Particle resonances, phenomena and properties

The properties and characteristics of a recently proposed anisotropic metamaterial based upon layered arrays of tightly coupled pairs of "dogbone" shaped stripe conductors have been explored in detail. It has been found that a metamaterial composed of such stacked layers exhibits artificial magnetism and may support backward wave propagation. The equivalent network models of the constitutive conductor pairs arranged in the periodic array have been devised and applied to the identification of the specific types of resonances, and to the analysis of their contribution into the effective dielectric and magnetic properties of the artificial medium. The proposed "dogbone" configuration of conductor pairs has the advantage of being entirely realizable and assemblable in planar technology. It also appears more prospective than simple cut-wire or metal-plate pairs because the additional geometrical parameters provide an efficient control of separation between the electric and magnetic resonances that, in turn, makes it possible to obtain a fairly broadband left-handed behaviour of the structure at low frequencies.

Numerical simulation of the charge balance and temperature evolution in an electron beam ion trap

A computer code has been developed to simulate and study the evolution of ion charge states inside the trap region of an electron beam ion trap. In addition to atomic physics phenomena previously included in similar codes such as electron impact ionization, radiative recombination, and charge exchange, several aspects of the relevant physics such as dielectronic recombination, ionization heating, and ion cloud expansion have been included for the first time in the model. The code was developed using object oriented concepts with database support, making it readable, accurate, and well organized. The simulation results show a good agreement with various experiments, and give useful information for selection of operating conditions and experiment design.

Positronium formation from valence and inner shells in noble gas atoms

When recent experimental positronium (Ps) formation cross sections in noble gases have been compared with the most up-to date theoretical studies, the agreement is qualitative, but not quantitative. In this paper we re-examine this process and show that at low energies Ps formation must be treated non-perturbatively. We also look at Ps formation with inner shell electrons.

Barrier height variations and interface properties of PtSi/Si structures

To study some of the interfacial properties of PtSi/Si diodes, Schottky structures were fabricated on (100) crystalline silicon substrates by conventional thermal evaporation of Pt on Si followed by annealing at different temperatures (from 400 degrees C to 700 degrees C) to form PtSi. The PtSi/n-Si diodes, all yielded Schottky barrier (SB) heights that are remarkably temperature dependent. The temperature range (20-290 K) over which the I-V characteristics were measured in the present study is broader with a much lower limit (20 K), than what is usually reported in literature. These variations in the barrier height are adequately interpreted by introducing spatial inhomogeneity into the barrier potential with a Gaussian distribution having a mean barrier of 0.76 eV and a standard deviation of 30 meV. Multi-frequency capacitance-voltage measurements suggest that the barrier is primarily controlled by the properties of the silicide-silicon interface. The forward C-V characteristics, in particular, show small peaks at low frequencies that can be ascribed to interface states rather than to a series resistance effect.

Light emission from gold and silver thin films in a scanning tunneling microscope: role of contamination and interpretation of grain structure in photon maps

Scanning tunnelling microscope (STM) tip-induced light emission from Au and Ag has been studied. Thin film samples similar to100nm thick were prepared by thermal evaporation at 0.5nm/s onto a room-temperature glass substrate to produce grains of 20-50nm in lateral dimension at the surface. Light emission from the samples in the STM was quasi-simultaneously recorded with the topography, at 1.8V tip bias and 3-40nA current, alternating pixel by pixel at the same bias. Typically, a surface scan range of 150 nm x 150 nm was surveyed. Au, W and PtIr tips were used.