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.

Electrospinning atactic polystyrene: a neutron scattering study

Electrospinning is a method used to produce nanoscale to microscale sized polymer fibres. In this study we electrospin 1:1 blends of deuterated and hydrogenated atactic- Polystyrene from N,N-Dimethylformamide for small angle neutron scattering experiments in order to analyse the chain conformation in the electrospun fibres. Small angle neutron scattering was carried out on randomly orientated fibre mats obtained using applied voltages of 10kV-15kV and needle tip to collector distances of 20cm and 30cm. Fibre diameters varied from 3μm – 20μm. Neutron scattering data from fibre samples were compared with bulk samples of the same polymer blend. The scattering data indicates that there are pores and nanovoiding present in the fibres; this was confirmed by scanning electron microscopy. A model that combines the scattering from the pores and the labelled polymer chains was used to extract values for the radius of gyration. The radius of gyration in the fibres is found to vary little with the applied voltage, but varies with the initial solution concentration and fibre diameter. The values for the radius of gyration in the fibres are broadly equivalent to that of the bulk state.

Hydrogen adsorption in a copper ZSM5 zeolite: an inelastic neutron scattering study

Currently microporous oxidic materials including zeolites are attracting interest as potential hydrogen storage materials. Understanding how molecular hydrogen interacts with these materials is important in the rational development of hydrogen storage materials and is also challenging theoretically. In this paper, we present an incoherent inelastic neutron scattering (INS) study of the adsorption of molecular hydrogen and hydrogen deuteride (HD) in a copper substituted ZSM5 zeolite varying the hydrogen dosage and temperature. We have demonstrated how inelastic neutron scattering can help us understand the interaction of H-2 molecules with a binding site in a particular microporous material, Cu ZSM5, and by implication of other similar materials. The H-2 molecule is bound as a single species lying parallel with the surface. As H-2 dosing increases, lateral interactions between the adsorbed H-2 molecules become apparent. With rising temperature of measurement up to 70 K (the limit of our experiments), H-2 molecules remain bound to the surface equivalent to a liquid or solid H-2 phase. The implication is that hydrogen is bound rather strongly in Cu ZSM5. Using the simple model for the anisotropic interaction to calculate the energy levels splitting, we found that the measured rotational constant of the hydrogen molecule is reduced as a consequence of adsorption by the Cu ZSM5. From the decrease in total signal intensity with increasing temperature, we were able to observe the conversion of para-hydrogen into ortho-hydrogen at paramagnetic centres and so determine the fraction of paramagnetic sites occupied by hydrogen molecules, ca. 60%. (c) 2006 Elsevier B.V. All rights reserved.

Dihydrogen in cation-substituted zeolites X - an inelastic neutron scattering study

An inelastic neutron scattering (INS) study of the rotational - vibrational spectrum of dihydrogen sorbed by zeolite X having substituted sodium, calcium and zinc cations is reported. The rotational - vibrational spectrum of H-2 was observed at low energy transfer ( below ca. 25 meV, 202 cm(-1)); the vibration was that of the H-2 molecule against the binding site (H-2 - X, not H - H). The vibration frequency was proportional to the polarising power of the cation (Na+ < Ca2+ < Zn2+). Polarisation of the H-2 molecule dominated the interaction of H-2 with this binding site. The total scattering intensity was proportional to the dihydrogen dose. However the vibrational intensities became constant at ca. 0.3 wt% showing that the H-2 binding sites had saturated. Additional dihydrogen appeared as unbound or weakly bound dihydrogen exhibiting recoil.

Dihydrogen in zeolite CaX: an inelastic neutron scattering study

We report an inelastic neutron scattering (INS) study of the rotational–vibrational spectrum of dihydrogen sorbed by zeolite CaX. In the low energy (<200 cm−1) INS spectrum of adsorbed H2 we observe the rotational–vibrational spectrum of H2, where the vibration is that of the H2 molecule against the binding site (i.e. H2–X, not H–H). We have observed for the first time the vibrational overtones of the hydrogen molecule against the adsorption surface up to sixth order. These vibrations are usually forbidden in INS spectroscopy because of the selection rules imposed by the spin flip event required. In our case we are able to observe such a vibration because the rotational transition J(1 ← 0) convolutes the vibrational spectrum. This paper reports the effect for the first time.

X-ray scattering study of the effect of hydration on the cross-beta structure of amyloid fibrils

We have investigated the effect of sample hydration on the wide-angle X-ray scattering patterns of amyloid fibrils from two different sources, hen egg white lysozyme (HEWL) and an 11-residue peptide taken from the sequence of transthyretin (TTR105-115). Both samples show an inter-strand reflection at 4.7 Å and an inter-sheet reflection which occurs at 8.8 and 10 Å for TTR105-115 and HEWL fibrils, respectively. The positions, widths, and relative intensities of these reflections are conserved in patterns obtained from dried stalks and hydrated samples over a range of fibril concentrations. In 2D scattering patterns obtained from flow-aligned hydrated samples, the inter-strand and inter-sheet reflections showed, respectively, axial and equatorial alignment relative to the fibril axis, characteristic of the cross-β structure. Our results show that the cross-β structure of the fibrils is not a product of the dehydrating conditions typically employed to produce aligned samples, but is conserved in individual fibrils in hydrated samples under dilute conditions comparable to those associated with other biophysical and spectroscopic techniques. This suggests a structure consisting of a stack of two or more sheets whose interfaces are inaccessible to bulk water.

A study by high energy transfer inelastic neutron scattering spectroscopy of the mineral fraction of ox femur bone

We have used high energy transfer (HET) inelastic neutron scattering spectroscopy to measure the vibrational modes in the spectra of hydroxyapatite, bone and brushite to confirm our earlier work that only a fraction of the hydroxyl groups in bone mineral are substituted. The HET spectra are better observed due to the higher scattering cross section of hydrogen compared with the other elements in the calcium phosphate compounds. (C) 2003 Elsevier Science B.V. All rights reserved.

RBF equalizer design using directional evolutionary multi-objective optimization

Whilst radial basis function (RBF) equalizers have been employed to combat the linear and nonlinear distortions in modern communication systems, most of them do not take into account the equalizer's generalization capability. In this paper, it is firstly proposed that the. model's generalization capability can be improved by treating the modelling problem as a multi-objective optimization (MOO) problem, with each objective based on one of several training sets. Then, as a modelling application, a new RBF equalizer learning scheme is introduced based on the directional evolutionary MOO (EMOO). Directional EMOO improves the computational efficiency of conventional EMOO, which has been widely applied in solving MOO problems, by explicitly making use of the directional information. Computer simulation demonstrates that the new scheme can be used to derive RBF equalizers with good performance not only on explaining the training samples but on predicting the unseen samples.

Nonlinear channel equalizer design using directional evolutionary multi-objective optimization

In this paper, a new equalizer learning scheme is introduced based on the algorithm of the directional evolutionary multi-objective optimization (EMOO). Whilst nonlinear channel equalizers such as the radial basis function (RBF) equalizers have been widely studied to combat the linear and nonlinear distortions in the modern communication systems, most of them do not take into account the equalizers' generalization capabilities. In this paper, equalizers are designed aiming at improving their generalization capabilities. It is proposed that this objective can be achieved by treating the equalizer design problem as a multi-objective optimization (MOO) problem, with each objective based on one of several training sets, followed by deriving equalizers with good capabilities of recovering the signals for all the training sets. Conventional EMOO which is widely applied in the MOO problems suffers from disadvantages such as slow convergence speed. Directional EMOO improves the computational efficiency of the conventional EMOO by explicitly making use of the directional information. The new equalizer learning scheme based on the directional EMOO is applied to the RBF equalizer design. Computer simulation demonstrates that the new scheme can be used to derive RBF equalizers with good generalization capabilities, i.e., good performance on predicting the unseen samples.

Multiple-scattering in radar systems: a review

Although extensively studied within the lidar community, the multiple scattering phenomenon has always been considered a rare curiosity by radar meteorologists. Up to few years ago its appearance has only been associated with two- or three-body-scattering features (e.g. hail flares and mirror images) involving highly reflective surfaces. Recent atmospheric research aimed at better understanding of the water cycle and the role played by clouds and precipitation in affecting the Earth's climate has driven the deployment of high frequency radars in space. Examples are the TRMM 13.5 GHz, the CloudSat 94 GHz, the upcoming EarthCARE 94 GHz, and the GPM dual 13-35 GHz radars. These systems are able to detect the vertical distribution of hydrometeors and thus provide crucial feedbacks for radiation and climate studies. The shift towards higher frequencies increases the sensitivity to hydrometeors, improves the spatial resolution and reduces the size and weight of the radar systems. On the other hand, higher frequency radars are affected by stronger extinction, especially in the presence of large precipitating particles (e.g. raindrops or hail particles), which may eventually drive the signal below the minimum detection threshold. In such circumstances the interpretation of the radar equation via the single scattering approximation may be problematic. Errors will be large when the radiation emitted from the radar after interacting more than once with the medium still contributes substantially to the received power. This is the case if the transport mean-free-path becomes comparable with the instrument footprint (determined by the antenna beam-width and the platform altitude). This situation resembles to what has already been experienced in lidar observations, but with a predominance of wide- versus small-angle scattering events. At millimeter wavelengths, hydrometeors diffuse radiation rather isotropically compared to the visible or near infrared region where scattering is predominantly in the forward direction. A complete understanding of radiation transport modeling and data analysis methods under wide-angle multiple scattering conditions is mandatory for a correct interpretation of echoes observed by space-borne millimeter radars. This paper reviews the status of research in this field. Different numerical techniques currently implemented to account for higher order scattering are reviewed and their weaknesses and strengths highlighted. Examples of simulated radar backscattering profiles are provided with particular emphasis given to situations in which the multiple scattering contributions become comparable or overwhelm the single scattering signal. We show evidences of multiple scattering effects from air-borne and from CloudSat observations, i.e. unique signatures which cannot be explained by single scattering theory. Ideas how to identify and tackle the multiple scattering effects are discussed. Finally perspectives and suggestions for future work are outlined. This work represents a reference-guide for studies focused at modeling the radiation transport and at interpreting data from high frequency space-borne radar systems that probe highly opaque scattering media such as thick ice clouds or precipitating clouds.

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases

WThe capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4′-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient α3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.

Modelling bi-directional research: a fresh approach to stakeholder theory

Purpose – While Freeman's stakeholder management approach has attracted much attention from both scholars and practitioners, little empirical work has considered the interconnectedness of organisational perspectives and stakeholder perspectives. The purpose of this paper is to respond to this gap by developing and empirically testing a bi-directional model of organisation/stakeholder relationships. Design/methodology/approach – A conceptual framework is developed that integrates how stakeholders are affected by organisations with how they affect organisations. Quantitative data relating to both sides of the relationship are obtained from 700 customers of a European service organisation and analysed using partial least squares structural equation modelling technique. Findings – The findings provide empirical support for the notion of mutual dependency between organisations and stakeholders as advocated by stakeholder theorists. The results suggest that the way stakeholders relate to organisations is dependent on how organisations relate to stakeholders. Originality/value – The study is original on two fronts: first, it provides a framework and process that can be used by researchers to model bi-directional research with other stakeholder groups and in different contexts. Second, the study presents an example application of bi-directional research by empirically linking organisational and stakeholder expectations in the case of customers of a UK service organisation.

An Exponentially Convergent Nonpolynomial Finite Element Method for Time-Harmonic Scattering from Polygons

In recent years nonpolynomial finite element methods have received increasing attention for the efficient solution of wave problems. As with their close cousin the method of particular solutions, high efficiency comes from using solutions to the Helmholtz equation as basis functions. We present and analyze such a method for the scattering of two-dimensional scalar waves from a polygonal domain that achieves exponential convergence purely by increasing the number of basis functions in each element. Key ingredients are the use of basis functions that capture the singularities at corners and the representation of the scattered field towards infinity by a combination of fundamental solutions. The solution is obtained by minimizing a least-squares functional, which we discretize in such a way that a matrix least-squares problem is obtained. We give computable exponential bounds on the rate of convergence of the least-squares functional that are in very good agreement with the observed numerical convergence. Challenging numerical examples, including a nonconvex polygon with several corner singularities, and a cavity domain, are solved to around 10 digits of accuracy with a few seconds of CPU time. The examples are implemented concisely with MPSpack, a MATLAB toolbox for wave computations with nonpolynomial basis functions, developed by the authors. A code example is included.

A high frequency boundary element method for scattering by convex polygons with impedance boundary conditions

We consider scattering of a time harmonic incident plane wave by a convex polygon with piecewise constant impedance boundary conditions. Standard finite or boundary element methods require the number of degrees of freedom to grow at least linearly with respect to the frequency of the incident wave in order to maintain accuracy. Extending earlier work by Chandler-Wilde and Langdon for the sound soft problem, we propose a novel Galerkin boundary element method, with the approximation space consisting of the products of plane waves with piecewise polynomials supported on a graded mesh with smaller elements closer to the corners of the polygon. Theoretical analysis and numerical results suggest that the number of degrees of freedom required to achieve a prescribed level of accuracy grows only logarithmically with respect to the frequency of the incident wave.