Asymmetric Hydrogenation of Activated Ketones on Platinum: Relevant and Spectator Species

The heterogeneous enantioselective hydrogenation of activated ketones over chirally modified platinum is reviewed with emphasis on identifying the role of the various species observed in this catalytic system. The past years have witnessed a continuous broadening of the scope of this catalytic system including new reactants and modifiers affording over 97% ee. New reaction pathways have been uncovered and the kinetic and mechanistic studies have been faced with a number of complicating factors caused by spectator species and interactions in solution and on the Pt surface. The previously proposed mechanistic models are critically assessed in the light of these new findings.     

Zur Modellierung von Sauterdurchmesser und Hold-up beim Einsatz eines konischen Turbinenrührers zum Dispergieren gas-flüssig

By comparing the experimental data of the Sauter-mean-diameter d ₃₂ and the hold up ? with models from literature, there are presented equations for d ₃₂ and ? for the used conical turbine in gas-liquid systems. The necessary adjustment of the proportionality constants of the literature equations will be explained on the basis of fluiddynamical phenomena. It can be established by fluid-dynamical results of a former study carried out with laser-doppler-anemometry. Coalescence phenomena are taken into account in the model using an analogy to bubble columns. The analogy to bubble columns turns out to be suitable. Arguments for the necessity of considering the local fluiddynamics in the modelling of dispersions are presented.     

Reactant induced restructuring and corrosion of germanium-palladium catalysts during hydrogenation reactions

An anomalous rate enhancement with increasing conversion has been observed during the liquid phase hydrogenation of nitrobenzene and crotonaldehyde over Ge/Pd/C catalysts at ambient temperature and atmospheric pressure. Inductive coupled plasma atomic emission spectroscopy and electrochemical measurement of the oxidation state of catalysts during reaction revealed that the bimetallic particles were partially oxidized by the reactants, which resulted in Ge-dissolution and increased exposure of Pd on the surface. It is proposed that the surface and bulk composition of Ge/Pd catalysts are a function of their oxidation state. This behaviour is due to the unusually high mobility of Ge in the Pd lattice and to the good solubility of GeO₂ in polar solvents. The influence of hydrogen transport on the corrosion process and the stability of other X/Pd type bimetallic catalysts during liquid phase hydrogenation are also discussed.     

Adsorption mode of ethyl pyruvate on platinum: an in situ XANES study

The adsorption of ethyl pyruvate on Pt(111) has been studied by in situ XANES measurements in the presence and absence of hydrogen. Depending on the hydrogen and ethyl pyruvate pressure, the C and O K‐edge spectra exhibit distinctly different angular dependence. Without hydrogen ethyl pyruvate is oriented preferentially perpendicular to the surface, indicating bonding via the O lone pairs. In the presence of hydrogen the mean orientation is more tilted towards the surface. Likely, ethyl pyruvate also interacts with Pt via its π system under these conditions. The observed angle‐dependent shift of the energy of the π* and σ* resonances indicates the coexistence of differently adsorbed ethyl pyruvate species. The experimental findings demonstrate the importance of the in situ approach for unraveling the adsorption mode of ethyl pyruvate in the enantioselective hydrogenation over cinchona‐alkaloid‐modified Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

In Situ EXAFS Study on the Chemical State of Arsenic Deposited on a NiMoP/Al2O3 Hydrotreating Catalyst

The chemical state of arsenic deposited on a NiMoP/Al₂O₃ hydrotreating catalyst exposed to ppb levels of arsenic over several years in a refinery reactor has been studied by in situ EXAFS. In the as-received As-NiMoP catalyst, arsenic is exclusively coordinated to oxygen atoms. Upon sulfiding the sample in 2%H₂S/2%H₂/96%He, the As atoms become surrounded by approximately two sulfur atoms. No evidence was found for Ni–As bond formation. A possible model for the As local environment is suggested on the basis of combined EXAFS results, STM data and FEFF8.0 simulations (program for ab initio calculations on multiple scattering XAFS and XANES). The FEFF8.0 simulations of the proposed model are in accord with the experimental data measured at the As K edge. In this model, an As atom is located at the edge of a hexagonally truncated Ni-MoS₂ slab and is blocking the active NiMoS site.     

Preparation and characterization of a model system for the study of monolayers and multilayers of vanadia supported on titania

A model system for the study of structural and chemical properties of monolayers and multilayers of vanadium oxide immobilized on titania is presented. Investigation of the planar oxide-oxide interface by XP, UV and IS spectroscopy indicated that vanadium immobilized by a single impregnation step exists as an incomplete heterogeneous layer containing well dispersed V⁴⁺ species. Increase of the vanadia loading by multiple impregnations led to vanadia agglomerates with higher apparent oxidation state of the vanadium. TD spectroscopy with O₂ and CO₂ as probe molecules revealed that the chemical reactivity of the vanadia surface species depends on their structure. The surface containing well-dispersed vanadia species exchanged oxygen more easily and showed pronounced interactions with CO₂.     

Formation and stability of barium aluminate and cerate in NOx storage-reduction catalysts

The formation and stability of BaAl₂O₄ and BaCeO₃ in Pt-Ba/Al₂O₃ and Pt-Ba/CeO₂ based NO_x storage-reduction (NSR) catalysts has been investigated using kinetic measurements, X-ray diffraction, thermal analysis and X-ray absorption spectroscopy. In as-prepared state, the Ba-component in the NSR catalysts was made up of amorphous BaO and BaCO₃. The formation of BaAl₂O₄ started above 850 °C, whereas the formation of BaCeO₃ was already observed at 800 °C and was faster than that of BaAl₂O₄. The stability of BaAl₂O₄ and BaCeO₃ in various liquid and gaseous atmospheres was different. BaAl₂O₄ was rapidly hydrated at room temperature in the presence of water and transformed to Ba(NO₃)₂ and γ-alumina in the presence of HNO₃, whereas BaCeO₃ was decomposed to much lower extent under these conditions. Interestingly, BaCeO₃ was transformed to Ba(NO₃)₂/CeO₂ in the presence of NO₂/H₂O at 300–500 °C. Also, the presence of CO₂ led to decomposition of barium cerate, which has important consequences for the catalyst ageing under NO_x-storage conditions and can be exploited for regeneration of thermally aged NSR-catalysts.     

Role and distribution of different Ba-containing phases in supported Pt–Ba NSR catalysts

Pt–Ba/MeO (where MeO = Al₂O₃, CeO₂, SiO₂ and ZrO₂) NO _x storage-reduction catalysts with Ba-loading varying from 0 wt.% to 28 wt.% were investigated concerning stability of Ba phases and NO _x storage-reduction efficiency. For Pt–Ba/Al₂O₃ three different Ba-containing phases with different thermal stability are distinguished based on their interaction with the support. The relative concentration of these phases varies with the Ba-loading and NO _x storage tests indicated that the BaCO₃ phase decomposing between 400 °C and 800 °C (LT-BaCO₃) is the most efficient Ba containing phase for NO _x storage. Similar investigations of Pt–Ba catalysts supported on CeO₂, SiO₂ and ZrO₂ showed that the relative amount of LT-BaCO₃ phase depends also on the support material. NO _x storage measurements confirmed a correlation between the concentration of LT-BaCO₃ and NO _x storage efficiency. Basicity and textural properties of the support are identified as crucial parameters for efficient NO _x storage catalysts.     

A constant-time dynamic storage allocator for real-time systems

Dynamic memory allocation has been used for decades. However, it has seldom been used in real-time systems since the worst case of spatial and temporal requirements for allocation and deallocation operations is either unbounded or bounded but with a very large bound. In this paper, a new allocator called TLSF (Two Level Segregated Fit) is presented. TLSF is designed and implemented to accommodate real-time constraints. The proposed allocator exhibits time-bounded behaviour, O(1), and maintains a very good execution time. This paper describes in detail the data structures and functions provided by TLSF. We also compare TLSF with a representative set of allocators regarding their temporal cost and fragmentation. Although the paper is mainly focused on timing analysis, a brief study and comparative analysis of fragmentation incurred by the allocators has been also included in order to provide a global view of the behaviour of the allocators. The temporal and spatial results showed that TLSF is also a fast allocator and produces a fragmentation close to that caused by the best existing allocators.