Kinetics of Solid-State Reactions in Heterogeneous Catalysis from Time-Resolved X-Ray Absorption Spectroscopy

The potentials of X-ray absorption spectroscopy (XAS) (quantitative phase composition and average valence together with a short-range order structure analysis) combined with a time-resolution in the second range make time-resolved (TR-) XAS a powerful tool for investigating the reactivity of solids in catalysis and solid-state chemistry. General aspects of TR-XAS investigations are discussed (i.e., instrumentation, data analysis). In addition, some experiments illustrate how the kinetics of solid-state reactions in heterogeneous catalysis can be elucidated from TR-XAS studies.     

Low-voltage terahertz quantum-cascade lasers based on LO-phonon-assisted interminiband transitions

A report is presented on GaAs/(Al,Ga)As terahertz (THz) quantum-cascade lasers (QCLs) based on alternating photon and longitudinal optical (LO) phonon-assisted transitions between quasi-minibands. The design is optimised for low threshold current densities and low operating voltages, resulting in reduced ohmic heating during continuous-wave (CW) operation. The QCLs exhibit lasing over a broad range of frequencies from 2.91 to 3.21 THz. Using single-plasmon waveguides, pulsed operation up to 114 K and CW operation up to 65 K has been achieved.     

The daylighting dashboard – A simulation-based design analysis for daylit spaces

This paper presents a vision of how state-of-the-art computer-based analysis techniques can be effectively used during the design of daylit spaces. Following a review of recent advances in dynamic daylight computation capabilities, climate-based daylighting metrics, occupant behavior and glare analysis, a fully integrated design analysis method is introduced that simultaneously considers annual daylight availability, visual comfort and energy use: Annual daylight glare probability profiles are combined with an occupant behavior model in order to determine annual shading profiles and visual comfort conditions throughout a space. The shading profiles are then used to calculate daylight autonomy plots, energy loads, operational energy costs and green house gas emissions. The paper then shows how simulation results for a sidelit space can be visually presented to simulation non-experts using the concept of a daylighting dashboard. The paper ends with a discussion of how the daylighting dashboard could be practically implemented using technologies that are available today.     

In situ analysis of metal-oxide systems used for selective oxidation catalysis: how essential is chemical complexity?

The mode of operation of selective oxidation reactions is described by a series of chemical rules defining the catalyst and some reaction intermediates. In contrast to catalytic processes over metallic elements, little is known, however, about the atomistic details of selective oxidation. In particular, the participation of the subsurface region of the catalyst in the kinetically relevant elementary steps (Mars–van Krevelen mechanism) is not positively verified. Using in situ X-ray absorption techniques to study binary and ternary molybdenum oxides the present contribution shows that it is possible to tackle some of the problems in selective oxidation by direct experimental observation. The modification of the Mo–O local bonding interaction upon thermal reduction of MoO₃to MoO_3-x is illustrated. This was also found for mixed Mo–V oxides in which the chemical state of the vanadium seemed unaffected by the reaction but the surface Mo:V ratio varied substantially with the gas phase composition. It is further shown that the solid-state phase transformation between reduced and oxidised forms of molybdenum oxides occur so rapidly, that possibly relevant suboxide cannot be identified by ex situ phase analysis. Observation of the time-law of redox transformations showed that lattice oxygen is only available for selective oxidation if the associated solid-state transformation occurs in the kinetic regime of reaction control and not in that of diffusion control.     

Computer-oriented building design: Advances in daylighting and thermal simulation tools

Advanced computer simulation tools for analyzing daylighting features and thermal performance of buildings are improved at the Fraunhofer Institute for Solar Energy Systems. For an analysis of daylighting elements in lighting simulations, new light-deflecting structures and materials have been measured and modeled. In order to study the interaction between lighting and thermal behaviour of rooms, thermal and lighting simulation techniques are linked together. Thus, integrated energy concepts can be evaluated. Programs for handling parallel image generation in a network of high-performance Unix workstations have been developed.     

Physical Validation of Global Illumination Methods: Measurement and Error Analysis

In this paper, we present a physical validation of global illumination algorithms based on measurements from a simple experimental setup. The validation methodology emphasizes tractability and error minimization. To this end, we discuss issues such as the acquisition and accurate simulation of material bidirectional reflection distribution functions (BRDFs) and the light source distribution, as well as error analysis. In addition, we present a nearest‐neighbor resampling technique for BRDFs and a simple method for extracting the light source distribution from digitized high dynamic range (HDR) images. Finally, we compare the measurements to a forward and backward raytracing solution (photon map and RADIANCE, respectively) in a set of case studies.     

Fe-implantation for rear-facet coatings of InP-based quantum cascade lasers

Fe-implantation is used to create a high-resistivity layer at the rear facet of an InP-based quantum cascade laser (lambda = 3.9 mum), subsequently coated with a metallisation of Cr (5 nm) and Au (200 nm). The coatings lead to a 3.7-fold increase of front-facet power and a 20-30% reduction in threshold current density compared to uncoated lasers.