Electro-oxidation of carbon monoxide on well-ordered Pt(111)/Sn surface alloys

The electro-oxidation of CO on model platinum-tin alloy catalysts has been studied by ex-situ electrochemical measurements following the preparation of the Pt(111)/Sn(2x2) and Pt(111)/Sn(radical3 x radical3)R30 degrees surfaces. A surface redox couple, which is associated with the adsorption/desorption of hydroxide on the Sn sites, is observed at 0.28 V(RHE)/0.15 V(RHE) in H(2)SO(4) electrolyte on both surfaces. Evidence that it is associated with the adsorption of OH comes from ex-situ photoemission measurements, which indicate that the Sn atoms are in a metallic state at potentials below 0.15 V(RHE) and an oxidized state at potentials above 0.28 V(RHE). Specific adsorption of sulfate anions is not associated with the surface process since there is no evidence from photoemission of sulfate adsorption, and the same surface couple is observed in the HClO(4) electrolyte. CO is adsorbed from solution at 300 K, with saturation coverages of 0.37 +/- 0.05 and 0.2 +/- 0.05 ML, respectively. The adsorbed CO is oxidatively stripped at the potential coincident with the adsorption of hydroxide on the tin sites, viz., 0.28 V(RHE). This strong promotional effect is unambiguously associated with the bifunctional mechanism. The Sn-induced activation of water, and promotion of CO electro-oxidation, is sustained as long as the alloy structure remains intact, in the potential range below 0.5 V(RHE). The results are discussed in the light of the requirements for CO-tolerant platinum-based electrodes in hydrogen fuel cell anode catalysts and catalysts for direct methanol electro-oxidation.     

Evaluation of RBFs for volume data interpolation in CFD

A greedy method for choosing an optimum reduced set of control points is integrated with RBF interpolation and evaluated for the purpose of interpolating large‐volume data sets in CFD. Given a function defined at a set of points, the greedy method selects a small subset of these points that is sufficient to keep the interpolation error at all the remaining points below a chosen bound. This is equivalent to a type of data compression and would have useful storage, post‐processing, and computational applications in CFD. To test the method in terms of both the point selection scheme and the suitability of reduced control point volume interpolation, a trial application of the interpolation to velocity fields in CFD volume meshes is considered. To optimise the point selection process, and attempt to be able to capture multiple length scales, a variable support radius formulation has also been included. Structured and unstructured mesh cases are considered for aerofoils, a wing case and a wing‐body case. For smooth volume functions, the method is shown to work well, producing accurate velocity interpolations using a very small number of the cells in the mesh. For general complex fields including large gradients, the method is still shown to be effective, although large gradients require more interpolation points to be used.Copyright © 2013 John Wiley & Sons, Ltd.     

Kasner-Like Behaviour for Subcritical Einstein-Matter Systems

Confirming previous heuristic analyses à la Belinskii-Khalatnikov-Lifshitz, it is rigorously proven that certain "subcritical" Einstein-matter systems exhibit a monotone, generalized Kasner behaviour in the vicinity of a spacelike singularity. The D-dimensional coupled Einstein-dilaton-p-form system is subcritical if the dilaton couplings of the p-forms belong to some dimension-dependent open neighborhood of zero [1], while pure gravity is subcritical if D S 11 [13]. Our proof relies, like the recent Theorem [15] dealing with the (always subcritical [14]) Einstein-dilaton system, on the use of Fuchsian techniques, which enable one to construct local, analytic solutions to the full set of equations of motion. The solutions constructed are "general" in the sense that they depend on the maximal expected number of free functions.     

Power-Law Inflation in Spacetimes Without Symmetry

We consider models of accelerated cosmological expansion described by the Einstein equations coupled to a nonlinear scalar field with a suitable exponential potential. We show that homogeneous and isotropic solutions are stable under small nonlinear perturbations without any symmetry assumptions. Our proof is based on results on the nonlinear stability of de Sitter spacetime and Kaluza-Klein reduction techniques.     

The curvature problem in general relativity

This essay investigates the relationships among the metric, the connection, the curvature, and the covariant curvature derivatives in general relativity. The extent to which the connection or the curvature together, possibly with certain curvature derivatives, determines the metric is considered, as well as other related problems. Some topological aspects of the problem are included and some applications to holonomy and symmetry groups are given.This article received honorable mention from the Gravity Research Foundation for 1987.     

A Class of Dust-Like Self-Similar Solutions of the Massless Einstein�CVlasov System

In this paper the existence of a class of self-similar solutions of the Einstein–Vlasov system is proved. The initial data for these solutions are not smooth, with their particle density being supported in a submanifold of codimension one. They can be thought of as intermediate between smooth solutions of the Einstein–Vlasov system and dust. The motivation for studying them is to obtain insights into possible violation of weak cosmic censorship by solutions of the Einstein–Vlasov system. By assuming a suitable form of the unknowns it is shown that the existence question can be reduced to that of the existence of a certain type of solution of a four-dimensional system of ordinary differential equations depending on two parameters. This solution starts at a particular point P ₀ and converges to a stationary solution P ₁ as the independent variable tends to infinity. The existence proof is based on a shooting argument and involves relating the dynamics of solutions of the four-dimensional system to that of solutions of certain two- and three-dimensional systems obtained from it by limiting processes. The spacetimes constructed do not constitute a counterexample to cosmic censorship since they are not asymptotically flat. They should be seen as the first step on a possible path towards constructing solutions of importance for understanding the issue of the formation of naked singularities in general relativity.     

Combinatorial approach to the study of particle size effects in electrocatalysis: synthesis of supported gold nanoparticles

A high-throughput method for physical vapor deposition has been applied to the synthesis of libraries of supported gold particles on amorphous substoichiometric TiO(x)() and carbon supports. The TiO(x)() substrate stoichiometry can be varied or kept constant across a supporting sample, and subsequent deposition of particle sizes on supports are controlled through the nucleation and growth process. TEM measurements indicate nucleation and growth of Au particles takes place, with the smallest particles initially observed at 1.4 nm with a maximum density of 5.5 x 10(12) cm(-2) on titania, and 2.6 nm with concomitantly lower density on carbon. The 1.4-nm particles on titania exhibit a binding energy shift in the Au(4f) core level of 0.3 eV from bulk gold, and the shift is approximately 0.1 eV by the time particles grow to a mean size of 2.5 nm. These shifts are associated with final state effects, and the supported gold particles are metallic and appear to be relatively stable in air. When combined with appropriate substrates and screening techniques, this method provides a highly controllable method for the high-throughput synthesis of model supported catalyst.     

Efficient mesh motion using radial basis functions with data reduction algorithms

Mesh motion using radial basis functions has been demonstrated previously by the authors to produce high quality meshes suitable for use within unsteady and aeroelastic CFD codes. In the aeroelastic case the structural mesh may be used as the set of control points governing the deformation, which is efficient since the structural mesh is usually small. However, as a stand alone mesh motion tool, where the surface mesh points control the motion, radial basis functions may be restricted by the size of the surface mesh, as an update of a single volume point depends on all surface points. In this paper a method is presented that allows an arbitrary deformation to be represented to within a desired tolerance by using a significantly reduced set of surface points intelligently identified in a fashion that minimises the error in the interpolated surface. This method may be used on much larger cases and is successfully demonstrated here for a 10⁶ cell mesh, where the initial solve phase cost reduces by a factor of eight with the new scheme and the mesh update by a factor of 55. It has also been shown that the number of surface points required to represent the surface is only geometry dependent (i.e. grid size independent), and so this reduction factor actually increases for larger meshes.     

Quiescent Cosmological Singularities

The most detailed existing proposal for the structure of spacetime singularities originates in the work of Belinskii, Khalatnikov and Lifshitz. We show rigorously the correctness of this proposal in the case of analytic solutions of the Einstein equations coupled to a scalar field or stiff fluid. More specifically, we prove the existence of a family of spacetimes depending on the same number of free functions as the general solution which have the asymptotics suggested by the Belinskii–Khalatnikov–Lifshitz proposal near their singularities. In these spacetimes a neighbourhood of the singularity can be covered by a Gaussian coordinate system in which the singularity is simultaneous and the evolution at different spatial points decouples. Received: 17 January 2000 / Accepted: 27 November 2000