Anodic and Cathodic Platinum Dissolution Processes Involve Different Oxide Species

The degradation of Pt-containing oxygen reduction catalysts for fuel cell applications is strongly linked to the electrochemical surface oxidation and reduction of Pt. Here, we study the surface restructuring and Pt dissolution mechanisms during oxidation/reduction for the case of Pt(100) in 0.1 M HClO₄ by combining operando high-energy surface X-ray diffraction, online mass spectrometry, and density functional theory. Our atomic-scale structural studies reveal that anodic dissolution, detected during oxidation, and cathodic dissolution, observed during the subsequent reduction, are linked to two different oxide phases. Anodic dissolution occurs predominantly during nucleation and growth of the first, stripe-like oxide. Cathodic dissolution is linked to a second, amorphous Pt oxide phase that resembles bulk PtO₂ and starts to grow when the coverage of the stripe-like oxide saturates. In addition, we find the amount of surface restructuring after an oxidation/reduction cycle to be potential-independent after the stripe-like oxide has reached its saturation coverage.     

Investigation of sediment transport at the interface of a porous and a free flow domain

Sediment transport involves fluid flow in two different regions. In the free flow domain, the flow is governed by the viscous Newtonian fluid; sediment only occurs as suspended particles. In the porous domain however, the flow is governed by the pore geometry of the porous skeleton consisting of sedimented grains. In nature, the interface between these two domains is not a no-slip boundary for the free flow. In this study, we quantify how sediment transport is affected by the interaction of the two different flows. We do this by comparing fluid flow in no-slip bounded flow channels to fluid flow in channels containing both a free and a porous domain. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Frequency Domain Methods and Decoupling of Linear Infinite Dimensional Differential Algebraic Systems

We discuss the analysis of linear constant coefficient differential algebraic equations on infinite dimensional Hilbert spaces. We give solution concepts and discuss solvability criteria which are mainly based on Laplace transform. Furthermore, we investigate the decoupling of these systems motivated by the Kronecker normal form for the finite dimensional case. Applications are given by the analysis of mixed systems of ordinary differential, partial differential and differential algebraic equations.     

Comparing adult mathematical literacy with PISA students: results of a pilot study

In Germany, very little empirical data about the mathematical competence of adults is available. The aim of this study is to test the level of mathematical competence in an adult sample. For this purpose, a mathematics test was constructed using the PISA mathematics framework as a guideline. The test consisted of fourteen public items from the mathematics test in PISA 2000. The study was implemented by carrying out house visits (Germany). The sample was comprised of 64 adults (90% women, age: 41 years). The test results were scaled in the metric of PISA 2000. Compared with the average German student competencies in PISA 2000, the average competency in the adult sample was on the same level as the fifteen-year-old comprehensive secondary school student (at a German Gymnasium). Further analysis shows that the mathematics competency level in the adult sample is positively connected to the individual vocational education degree.     

Appropriate problems for learning and for performing—an issue for teacher training

Selecting, modifying or creating appropriate problems for mathematics class has become an activity of increaing importance in the professional development of German mathematics teachers. But rather than asking in general: “What is a good problem?” there should be a stronger emphasis on considering the specific goal of a problem, e.g.: “What are the ingredients that make a problem appropriate for initiating a learning process” or “What are the characteristics that make a problem appropriate for its use in a central test?” We propose a guiding scheme for teachers that turns out to be especially helpful, since the newly introduced orientation on outcome standards a) leads to a critical predominance of test items and b) expects teachers to design adequate problems for specific learning processes (e.g. problem solving, reasoning and modelling activities).     

A structure‐preserving doubling algorithm for Lur'e equations

We introduce a numerical method for the numerical solution of the Lur'e equations, a system of matrix equations that arises, for instance, in linear‐quadratic infinite time horizon optimal control. We focus on small‐scale, dense problems. Via a Cayley transformation, the problem is transformed to the discrete‐time case, and the structural infinite eigenvalues of the associated matrix pencil are deflated. The deflated problem is associated with a symplectic pencil with several Jordan blocks of eigenvalue 1 and even size, which arise from the nontrivial Kronecker chains at infinity of the original problem. For the solution of this modified problem, we use the structure‐preserving doubling algorithm. Implementation issues such as the choice of the parameter γ in the Cayley transform are discussed. The most interesting feature of this method, with respect to the competing approaches, is the absence of arbitrary rank decisions, which may be ill‐posed and numerically troublesome. The numerical examples presented confirm the effectiveness of this method. Copyright © 2015 John Wiley & Sons, Ltd.     

Inductive and Deductive Justification of Knowledge: Flexible Judgments Underneath Stable Beliefs in Teacher Education

Personal epistemological beliefs are considered to play an important role for processes of learning and teaching. However, research on personal epistemology is confronted with theoretical issues as there is conflicting evidence regarding the structure, stability, and context-dependence of epistemological beliefs. We give evidence how theoretical and methodological issues can partly be resolved by distinguishing between relatively stable “epistemological beliefs” and situation-specific “epistemological judgments.” A qualitative content analysis of a series of semistructured interviews (study 1) with pre-service teachers, teachers, and teacher educators as well as a statistical analysis of pre-service teachers’ extensive answers in questionnaires (study 2), both on the topic of “mathematical discovery,” reveal not only beliefs of the participants but also different qualities of judgments. Therefore, in further research both aspects of beliefs should be considered in a more differentiated manner when categorizing belief structures.     

Eigenvalue Asymptotics for Locally Perturbed Second-Order Differential Operators

We consider the appearance of discrete spectrum in spectralgaps of magnetic Schrödinger operators with electric backgroundfield under strong, localised perturbations. We show that forcompactly supported perturbations the asymptotics of the countingfunction of the occurring eigenvalues in the limit of a strongperturbation does not depend on the magnetic field nor on thebackground field.     

Light scattering by large Saharan dust particles: Comparison of modeling and experimental data for two samples

Light scattering by large mineral-dust particles with small-scale surface roughness is investigated by comparing model simulations with laboratory-measured scattering matrices of two distinct dust samples collected from the Sahara desert. The samples have been chosen on the basis of their large effective radii, and the simulations are based on their measured size distributions. Size parameters larger than about 30 are modeled using a modified ray-optics model RODS (Ray optics with diffuse and specular interactions), while smaller particles are simulated with a T-matrix model. RODS allows us to mimic the surface roughness of large dust particles by covering the particle surface by a thin layer of external scatterers with specific single-scattering properties. The Gaussian-random-sphere geometry is used for the shapes of large dust particles. Small particles are modeled as an axial-ratio distribution of spheroids with smooth surfaces. One of the samples consists wholly of large particles and its scattering matrix can be reproduced very well by the RODS model, except for the phase function. The incorporation of wavelength-scale roughness is, however, necessary for good fits. The other sample, consisting of both small and large particles, proves more challenging to match with simulations. The analysis indicates, however, that the difficulties arise at least partially from the small-particle contribution, while RODS results are consistent with the measurements. Further, the results imply that the agreement with measurements would improve if roughness could also be accounted for in the small-particle simulations. Overall, the RODS method seems promising for modeling the optical properties of mineral-dust particles much larger than the wavelength.     

Second class particles as microscopic characteristics in totally asymmetric nearest-neighbor -exclusion processes

We prove laws of large numbers for a second class particle in one-dimensional totally asymmetric -exclusion processes, under hydrodynamic Euler scaling. The assumption required is that initially the ambient particle configuration converges to a limiting profile. The macroscopic trajectories of second class particles are characteristics and shocks of the conservation law of the particle density. The proof uses a variational representation of a second class particle, to overcome the problem of lack of information about invariant distributions. But we cannot rule out the possibility that the flux function of the conservation law may be neither differentiable nor strictly concave. To give a complete picture we discuss the construction, uniqueness, and other properties of the weak solution that the particle density obeys.