133 research outputs found
Interaction of CO with Surface PdZn Alloys
The adsorption and bonding configuration of CO on clean and Zn-covered Pd(111) surfaces was studied using Low Energy Electron Diffraction (LEED), Temperature Programmed Desorption (TPD) and High Resolution Electron Energy Loss Spectroscopy (HREELS). LEED and TPD results indicate that annealing at 550 K is sufficient to induce reaction between adsorbed Zn atoms and the Pd(111) surface resulting in the formation of an ordered surface PdZn alloy. Carbon monoxide was found to bond more weakly to the Zn/Pd(111) alloy surfaces compared to clean Pd(111). Zn addition was also found to alter the preferred adsorption sites for CO from threefold hollow to atop sites. Similar behavior was observed for supported Pd-Zn/Al2O3 catalysts. The results of this study show that both ensemble and electronic effects play a role in how Zn alters the interactions of CO with the surface
Stability of bimetallic Pd-Zn catalysts for the steam reforming of methanol
ZnO-supported palladium-based catalysts have been shown in recent years to be both active and selective towards the steam reforming of methanol, although they are still considered to be less active than traditional copper-based catalysts. The activity of PdZn catalysts can be significantly improved by supporting them on alumina. Here we show that the Pd/ZnO/Al2O3 catalysts have better long-term stability when compared with commercial Cu/ZnO/Al2O3 catalysts, and that they are also stable under redox cycling. The Pd/ZnO/Al2O3 catalysts can be easily regenerated by oxidation in air at 420 °C followed by re-exposure to reaction conditions at 250 °C, while the Cu/ZnO based catalysts do not recover their activity after oxidation. Reduction at high temperatures (>420 °C) leads to Zn loss from the alloy nanoparticle surface resulting in a reduced catalyst activity. However, even after such extreme treatment, the catalyst activity is regained with time on stream under reaction conditions alone, leading to highly stable catalysts. These findings illustrate that the nanoparticle surface is dynamic and changes drastically depending on the environment, and that elevated reduction temperatures are not necessary to achieve high CO2 selectivity
Eutectic Colony Formation: A Stability Analysis
Experiments have widely shown that a steady-state lamellar eutectic
solidification front is destabilized on a scale much larger than the lamellar
spacing by the rejection of a dilute ternary impurity and forms two-phase cells
commonly referred to as `eutectic colonies'. We extend the stability analysis
of Datye and Langer for a binary eutectic to include the effect of a ternary
impurity. We find that the expressions for the critical onset velocity and
morphological instability wavelength are analogous to those for the classic
Mullins-Sekerka instability of a monophase planar interface, albeit with an
effective surface tension that depends on the geometry of the lamellar
interface and, non-trivially, on interlamellar diffusion. A qualitatively new
aspect of this instability is the occurence of oscillatory modes due to the
interplay between the destabilizing effect of the ternary impurity and the
dynamical feedback of the local change in lamellar spacing on the front motion.
In a transient regime, these modes lead to the formation of large scale
oscillatory microstructures for which there is recent experimental evidence in
a transparent organic system. Moreover, it is shown that the eutectic front
dynamics on a scale larger than the lamellar spacing can be formulated as an
effective monophase interface free boundary problem with a modified
Gibbs-Thomson condition that is coupled to a slow evolution equation for the
lamellar spacing. This formulation provides additional physical insights into
the nature of the instability and a simple means to calculate an approximate
stability spectrum. Finally, we investigate the influence of the ternary
impurity on a short wavelength oscillatory instability that is already present
at off-eutectic compositions in binary eutectics.Comment: 26 pages RevTex, 14 figures (28 EPS files); some minor changes;
references adde
Eutectic colony formation: A phase field study
Eutectic two-phase cells, also known as eutectic colonies, are commonly
observed during the solidification of ternary alloys when the composition is
close to a binary eutectic valley. In analogy with the solidification cells
formed in dilute binary alloys, colony formation is triggered by a
morphological instability of a macroscopically planar eutectic solidification
front due to the rejection by both solid phases of a ternary impurity that
diffuses in the liquid. Here we develop a phase-field model of a binary
eutectic with a dilute ternary impurity and we investigate by dynamical
simulations both the initial linear regime of this instability, and the
subsequent highly nonlinear evolution of the interface that leads to fully
developed two-phase cells with a spacing much larger than the lamellar spacing.
We find a good overall agreement with our recent linear stability analysis [M.
Plapp and A. Karma, Phys. Rev. E 60, 6865 (1999)], which predicts a
destabilization of the front by long-wavelength modes that may be stationary or
oscillatory. A fine comparison, however, reveals that the assumption commonly
attributed to Cahn that lamella grow perpendicular to the envelope of the
solidification front is weakly violated in the phase-field simulations. We show
that, even though weak, this violation has an important quantitative effect on
the stability properties of the eutectic front. We also investigate the
dynamics of fully developed colonies and find that the large-scale envelope of
the composite eutectic front does not converge to a steady state, but exhibits
cell elimination and tip-splitting events up to the largest times simulated.Comment: 18 pages, 18 EPS figures, RevTeX twocolumn, submitted to Phys. Rev.
Barriers for introducing HIV testing among tuberculosis patients in Jogjakarta, Indonesia: a qualitative study
<p>Abstract</p> <p>Background</p> <p>HIV and HIV-TB co-infection are slowly increasing in Indonesia. WHO recommends HIV testing among TB patients as a key response to the dual HIV-TB epidemic. Concerns over potential negative impacts to TB control and lack of operational clarity have hindered progress. We investigated the barriers and opportunities for introducing HIV testing perceived by TB patients and providers in Jogjakarta, Indonesia.</p> <p>Methods</p> <p>We offered Voluntary Counselling and Testing (VCT) to TB patients in parallel to a HIV prevalence survey. We conducted in-depth interviews with 33 TB patients, 3 specialist physicians and 3 disease control managers. We also conducted 4 Focus Group Discussions (FGDs) with nurses. All interviews and FGDs were recorded and data analysis was supported by the QSR N6<sup>® </sup>software.</p> <p>Results</p> <p>Patients' and providers' knowledge regarding HIV was poor. The main barriers perceived by patients were: burden for accessing VCT and fear of knowing the test results. Stigma caused concerns among providers, but did not play much role in patients' attitude towards VCT. The main barriers perceived by providers were communication, patients feeling offended, stigmatization and additional burden.</p> <p>Conclusion</p> <p>Introduction of HIV testing among TB patients in Indonesia should be accompanied by patient and provider education as well as providing conditions for effective communication.</p
Protonation-Induced Microphase Separation in Thin Films of a Polyelectrolyte-Hydrophilic Diblock Copolymer
Block copolymers composed of poly(oligo ethylene glycol methyl ether methacrylate) and poly(2-vinylpyridine) are disordered in the neat state but can be induced to order by protonation of the P2VP block, demonstrating a tunable and responsive method for triggering assembly in thin films. Comparison of protonation with the addition of salts shows that microphase separation is due to selective protonation of the P2VP block. Increasing acid incorporation and increasing 2-vinylpyridine content for P2VP minority copolymers both promote increasingly phase-separated morphologies, consistent with protonation increasing the effective strength of segregation between the two blocks. The self-assembled nanostructures formed after casting from acidic solutions may be tuned based on the amount and type of acid incorporation as well as the annealing treatment applied after casting, where both aqueous and polar organic solvents are shown to be effective. Therefore, POEGMA-b-P2VP is a novel ion-containing block copolymer whose morphologies can be facilely tuned during casting and processing by controlling its exposure to acid.United States. Dept. of Energy. Office of Basic Energy Sciences (Award DE-SC0001088)National Science Foundation (U.S.) (Award CMMI-1246740
Initial Commitment to Pre-Exposure Prophylaxis and Circumcision for HIV Prevention amongst Indian Truck Drivers
Studies of HIV prevention interventions such as pre-exposure prophylaxis (PREP) and circumcision in India are limited. The present study sought to investigate Indian truck-drivers initial commitment to PREP and circumcision utilizing the AIDS Risk Reduction Model. Ninety truck-drivers completed an in-depth qualitative interview and provided a blood sample for HIV and HSV-2 testing. Truck-drivers exhibited low levels of initial commitment towards PREP and even lower for circumcision. However, potential leverage points for increasing commitment were realized in fear of infecting family rather than self, self-perceptions of risk, and for PREP focusing on cultural beliefs towards medication and physicians. Cost was a major barrier to both HIV prevention interventions. Despite these barriers, our findings suggest that the ARRM may be useful in identifying several leverage points that may be used by peers, health care providers and public health field workers to enhance initial commitment to novel HIV prevention interventions in India
Direct Observations of Oxygen-induced Platinum Nanoparticle Ripening Studied by In Situ TEM
This study addresses the sintering mechanism of Pt nanoparticles dispersed on a planar, amorphous Al2O3 support as a model system for a catalyst for automotive exhaust abatement. By means of in situ transmission electron microscopy (TEM), the model catalyst was monitored during the exposure to 10 mbar air at 650 degrees C. Time-resolved image series unequivocally reveal that the sintering of Pt nanoparticles was mediated by an Ostwald ripening process. A statistical analysis of an ensemble of Pt nanoparticles shows that the particle size distributions change shape from an initial Gaussian distribution via a log-normal distribution to a Lifshitz-Slyozov-Wagner (LSW) distribution. Furthermore, the time-dependency of the ensemble-averaged particle size and particle density is determined. A mean field kinetic description captures the main trends in the observed behavior. However, at the individual nanoparticle level, deviations from the model are observed suggesting in part that the local environment influences the atom exchange process
Density functional theory based screening of ternary alkali-transition metal borohydrides: A computational material design project
The dissociation of molecules, even the most simple hydrogen molecule, cannot be described accurately within density functional theory because none of the currently available functionals accounts for strong on-site correlation. This problem led to a discussion of properties that the local Kohn-Sham potential has to satisfy in order to correctly describe strongly correlated systems. We derive an analytic expression for the nontrivial form of the Kohn-Sham potential in between the two fragments for the dissociation of a single bond. We show that the numerical calculations for a one-dimensional two-electron model system indeed approach and reach this limit. It is shown that the functional form of the potential is universal, i.e., independent of the details of the two fragments.We acknowledge funding by the Spanish MEC (Grant No. FIS2007-65702-C02-01), “Grupos Consolidados UPV/EHU del Gobierno Vasco” (Grant No. IT-319-07), and the European Community through e-I3 ETSF project (Grant Agreement No. 211956).Peer reviewe
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