Model catalyst studies of the strong metal-support interaction: Surface structure identified by STM on Pd nanoparticles on TiO2(110)

Model catalysts of Pd nanoparticles and films on TiO2 (I 10) were fabricated by metal vapour deposition (MVD). Molecular beam measurements show that the particles are active for CO adsorption, with a global sticking probability of 0.25, but that they are deactivated by annealing above 600 K, an effect indicative of SMSI. The Pd nanoparticles are single crystals oriented with their (I 11) plane parallel to the surface plane of the titania. Analysis of the surface by atomic resolution STM shows that new structures have formed at the surface of the Pd nanoparticles and films after annealing above 800 K. There are only two structures, a zigzag arrangement and a much more complex "pinwheel" structure. The former has a unit cell containing 7 atoms, and the latter is a bigger unit cell containing 25 atoms. These new structures are due to an overlayer of titania that has appeared on the surface of the Pd nanoparticles after annealing, and it is proposed that the surface layer that causes the SMSI effect is a mixed alloy of Pd and Ti, with only two discrete ratios of atoms: Pd/Ti of 1: 1 (pinwheel) and 1:2 (zigzag). We propose that it is these structures that cause the SMSI effect. (c) 2005 Elsevier Inc. All rights reserved.

Engineering Pt in ceria for a maximum metal-support interaction in catalysis

Conventional supported metal catalysts are metal nanoparticles deposited on high surface area oxide supports with a poorly defined metal−support interface. Typically, the traditionally prepared Pt/ceria catalyzes both methanation (H2/CO to CH4) and water−gas shift (CO/H2O to CO2/H2) reactions. By using simple nanochemistry techniques, we show for the first time that Pt or PtAu metal can be created inside each CeO2 particle with tailored dimensions. The encapsulated metal is shown to interact with the thin CeO2 overlayer in each single particle in an optimum geometry to create a unique interface, giving high activity and excellent selectivity for the water−gas shift reaction, but is totally inert for methanation. Thus, this work clearly demonstrates the significance of nanoengineering of a single catalyst particle by a bottom-up construction approach in modern catalyst design which could enable exploitation of catalyst site differentiation, leading to new catalytic properties.

Surface science studies of strong metal-oxide interactions on model catalysts

The strong metal support interaction (SMSI) was first described in 1978 by Tauster [1-4]. The effect was observed as a severely negative effect on CO and H2 uptake on the catalyst after high temperature calcination under reducing conditions (heating above ~ 700 K) [1,2]. It also had a negative effect on the reaction rate for reactions, such as alkane hydrogenolysis [5,6]. It appeared that the effect occurred for catalysts comprised of reducible supports which were treated at elevated temperature in reducing conditions [2-4]. A classic support which has manifested this behaviour in many studies is TiO2. Over the years following the first discovery of SMSI it has been recognised that the effect is not always negative – for instance for the CO-H2 reaction for which it appears to have a positive effect [5,6]. Further it was noted that hydrogen reduction was not necessary to observe the effect of CO adsorption suppression, it also occurs by vacuum treatment [7], though it should be noted that vacuum treatment at elevated temperature is, in effect, a reducing environment.

4,4 '-Dipyridyl-N,N '-dioxide complexes of metal-thiocyanate/selenocyanate: pi-stacked molecular rods as three-dimensional support for two-dimensional polymeric sheets and intra/interchain S center dot center dot center dot S interaction dependent architecture of the R-2(2)(8) synthon driven assembly of one-dimensional polymeric chains

Three supramolecular complexes of Co(II) using SCN-/SeCN- in combination with 4,4'-dipyridyl-N,N'-dioxide (dpyo), i.e., {[Co(SCN)(2)(dpyo)(2)].(dpyo)}(n) ( 1), {[Co(SCN)(2)(dpyo)(H2O)(2)].(H2O)}(n) ( 2), {[Co(SeCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 3), have been synthesized and characterized by single-crystal X-ray analysis. Complex 1 is a rare example of a dpyo bridged two-dimensional (2D) coordination polymer, and pi-stacked dpyo supramolecular rods are generated by the lattice dpyo, passing through the rhombic grid of stacked layers, resulting in a three-dimensional (3D) superstructure. Complexes 2 and 3 are isomorphous one-dimensional (1D) coordination polymers [-Co-dpyo-Co-] that undergo self-assembly leading to a bilayer architecture derived through an R-2(2)(8) H-bonding synthon between coordinated water and dpyo oxygen. A reinvestigation of coordination polymers [Mn(SCN)(2)(dpyo)( H2O)(MeOH)](n) ( 4) and {[Fe(SCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 5) reported recently by our group [ Manna et al. Indian J. Chem. 2006, 45A, 1813] reveals brick wall topology rather than bilayer architecture is due to the decisive role of S center dot center dot center dot S/Se center dot center dot center dot Se interactions in determining the helical nature in 4 and 5 as compared to zigzag polymeric chains in 2 and 3, although the same R-2(2)(8) synthon is responsible for supramolecular assembly in these complexes.

The assessment of benchmarks executed on bare-metal and using para-virtualization

A full assessment of para-­virtualization is important, because without knowledge about the various overheads, users can not understand whether using virtualization is a good idea or not. In this paper we are very interested in assessing the overheads of running various benchmarks on bare-­‐metal, as well as on para-­‐virtualization. The idea is to see what the overheads of para-­‐ virtualization are, as well as looking at the overheads of turning on monitoring and logging. The knowledge from assessing various benchmarks on these different systems will help a range of users understand the use of virtualization systems. In this paper we assess the overheads of using Xen, VMware, KVM and Citrix, see Table 1. These different virtualization systems are used extensively by cloud-­‐users. We are using various Netlib1 benchmarks, which have been developed by the University of Tennessee at Knoxville (UTK), and Oak Ridge National Laboratory (ORNL). In order to assess these virtualization systems, we run the benchmarks on bare-­‐metal, then on the para-­‐virtualization, and finally we turn on monitoring and logging. The later is important as users are interested in Service Level Agreements (SLAs) used by the Cloud providers, and the use of logging is a means of assessing the services bought and used from commercial providers. In this paper we assess the virtualization systems on three different systems. We use the Thamesblue supercomputer, the Hactar cluster and IBM JS20 blade server (see Table 2), which are all servers available at the University of Reading. A functional virtualization system is multi-­‐layered and is driven by the privileged components. Virtualization systems can host multiple guest operating systems, which run on its own domain, and the system schedules virtual CPUs and memory within each Virtual Machines (VM) to make the best use of the available resources. The guest-­‐operating system schedules each application accordingly. You can deploy virtualization as full virtualization or para-­‐virtualization. Full virtualization provides a total abstraction of the underlying physical system and creates a new virtual system, where the guest operating systems can run. No modifications are needed in the guest OS or application, e.g. the guest OS or application is not aware of the virtualized environment and runs normally. Para-­‐virualization requires user modification of the guest operating systems, which runs on the virtual machines, e.g. these guest operating systems are aware that they are running on a virtual machine, and provide near-­‐native performance. You can deploy both para-­‐virtualization and full virtualization across various virtualized systems. Para-­‐virtualization is an OS-­‐assisted virtualization; where some modifications are made in the guest operating system to enable better performance. In this kind of virtualization, the guest operating system is aware of the fact that it is running on the virtualized hardware and not on the bare hardware. In para-­‐virtualization, the device drivers in the guest operating system coordinate the device drivers of host operating system and reduce the performance overheads. The use of para-­‐virtualization [0] is intended to avoid the bottleneck associated with slow hardware interrupts that exist when full virtualization is employed. It has revealed [0] that para-­‐ virtualization does not impose significant performance overhead in high performance computing, and this in turn this has implications for the use of cloud computing for hosting HPC applications. The “apparent” improvement in virtualization has led us to formulate the hypothesis that certain classes of HPC applications should be able to execute in a cloud environment, with minimal performance degradation. In order to support this hypothesis, first it is necessary to define exactly what is meant by a “class” of application, and secondly it will be necessary to observe application performance, both within a virtual machine and when executing on bare hardware. A further potential complication is associated with the need for Cloud service providers to support Service Level Agreements (SLA), so that system utilisation can be audited.

Hydrogen spillover on carbon-supported metal catalysts studied by inelastic neutron scattering. Surface vibrational states and hydrogen riding modes

Hydrogen spillover on carbon-supported precious metal catalysts has been investigated with inelastic neutron scattering (INS) spectroscopy. The aim, which was fully realized, was to identify spillover hydrogen on the carbon support. The inelastic neutron scattering spectra of Pt/C, Ru/C, and PtRu/C fuel cell catalysts dosed with hydrogen were determined in two sets of experiments: with the catalyst in the neutron beam and, using an annular cell, with carbon in the beam and catalyst pellets at the edge of the cell excluded from the beam. The vibrational modes observed in the INS spectra were assigned with reference to the INS of a polycyclic aromatic hydrocarbon, coronene, taken as a molecular model of a graphite layer, and with the aid of computational modeling. Two forms of spillover hydrogen were identified: H at edge sites of a graphite layer (formed after ambient dissociative chemisorption of H-2), and a weakly bound layer of mobile H atoms (formed by surface diffusion of H atoms after dissociative chernisorption of H-2 at 500 K). The INS spectra exhibited characteristic riding modes of H on carbon and on Pt or Ru. In these riding modes H atoms move in phase with vibrations of the carbon and metal lattices. The lattice modes are amplified by neutron scattering from the H atoms attached to lattice atoms. Uptake of hydrogen, and spillover, was greater for the Ru containing catalysts than for the Pt/C catalyst. The INS experiments have thus directly demonstrated H spillover to the carbon support of these metal catalysts.

Aerogel-coated metal nanoparticle colloids as novel entities for the synthesis of defined supported metal catalysts

Nanometer metal particles of tailored size (3-5 nm) and composition prepared via inverse microemulsion were encapsulated by ultrathin coatings (<2.5 nm) of inorganic porous aerogels covered with surface -OH groups. These composite materials formed metastable colloids in solvent(s), and the organic surfactant molecules were subsequently removed without leading to aggregation (the ethanolic colloid solution was shown to be stable against flocculation for at least weeks). We demonstrate that the totally inorganic-based composite colloids, after the removal of surfactant, can be anchored to conventional solid supports (gamma-alumina, carbons) upon mixing. Application of a high temperature resulted in the formation of strong covalent linkages between the colloids and the support because of the condensation of surface groups at the interface. Detailed characterizations (X-ray diffraction (XRD), pore analysis, transmission electron microscopy (TEM), CO chemisorption) and catalytic testing (butane combustion) showed that there was no significant metal aggregation from the fine metal particles individually coated with porous aerogel oxide. Most of these metal sites on the coated nanoparticles with and without support are fully accessible by small molecules hence giving extremely active metal catalysts. Thus, the product and technology described may be suitable to synthesize these precursor entities of defined metal sizes (as inks) for wash coat/impregnation applications in catalysis. The advantages of developing inorganic nanocomposite chemical precursors are also discussed.

Heathland restoration on former agricultural land: effects of artificial acidification on the availability and uptake of toxic metal cations

Lowland heath is an internationally important habitat type that has greatly declined in abundance throughout Western Europe. In recent years this has led to a growing interest in the restoration of heathland on agricultural land. This generally requires the use of chemical treatments to return soil chemical conditions to those appropriate for the support of heathland ecosystems. However, the potential for negative impacts on the environment due to the potential of these treatments to increase the availability of trace metals via raised soil acidity requires investigation. A large-scale field study investigated the effect of two chemical treatments used in heathland restoration, elemental sulphur and ferrous sulphate, on soil acidity and whether it is possible to predict the effect of the treatments on availability of two potentially toxic cations (Al and Cd) in the soil along with their subsequent accumulation in the shoots of the grass Agrostis capillaris. Results showed that both treatments decreased soil pH, but that only elemental sulphur produced a pH similar to heathland soil. The availability of Al, measured by extraction with 1 M ammonium nitrate, could not be predicted by soil pH, depth in the soil and total Al concentration in the soil. By contrast, availability of Cd could be predicted from these three variables. Concentrations of both Al and Cd in the shoots of A. capillaris showed no significant relationship with the extractable concentration in the soil. Results are discussed in light of the possible environmental impacts of the chemical restoration techniques.