Heterogeneous Catalysis: From Fundamentals to Reaction Engineering

The development of new catalytic processes making efficient use of energy and raw materials with minimal impact on the environment is an extremely challenging task. The principal aim of our research is to improve the scientific basis for the advancement of heterogeneous catalytic processes for fine chemical synthesis and the abatement of pollutants that are detrimental to the environment. This aim is pursued with strongly interdisciplinary research embracing fundamental aspects of surface reactions, catalyst design and reaction engineering. Our research strategy and the current projects are briefly discussed

Space-Resolved Profiling Relevant in Heterogeneous Catalysis

Knowledge of gradients involved in chemical processes, such as heterogeneously catalyzed reactions, on molecular as well as reactor scale is of paramount importance for understanding and optimizing such processes. This review highlights and discusses recent advances in spatially resolved methods for the detection of chemical (structural) and temperature gradients, with particular focus on in situ method

In Situ Monitoring of Heterogeneously Catalyzed Reactions under Supercritical Conditions

A novel high-pressure batch system suitable for in situ monitoring of heterogeneously catalyzed reactions under supercritical conditions is described. The apparatus allows exploration of changes in phase behavior and composition by on-line video imaging as well as on-line sampling and analysis by gas-chromatography using a computer-based approach

Potential of thermal analysis in preparation and characterization of solid catalysis

Supported catalysts contain often only small amounts of active component(s) which renders their characterization difficult, particularly because they usually contain a substantial amount of water. Thermal analysis (TA) coupled with mass spectrometry (MS) offers an interesting potential for characterizing such material, various steps of catalyst preparation as well as crucial properties of fresh and used catalysts can be investigated. Some examples illustrating the versatility of TA-MS in catalysis research, such as solid-state reactions occurring upon exposure of the precursors or catalysts to reducing, oxidizing or inert atmosphere, are presented in this study. The combined use of TA and MS allows in many cases a much more detailed interpretation of the observed phenomena than could be achieved by one of these methods alon

Advances in Infrared Spectroscopy of Catalytic Solid-Liquid Interfaces: The Case of Selective Alcohol Oxidation

Progress in the use of ATR-IR spectroscopy to improve the understanding of liquid-phase heterogeneous catalytic reactions is illustrated using the example of the oxidation of benzyl alcohol over Pd/Al2O3 and Bi-Pd/Al2O3. The in situ studies performed in both batch and continuous reactor cells provide rich information on the reaction pathway and important facets of the mechanism, such as the nature of active Pd sites and the effect of the Bi-promoter. The combination of CO site blocking prior to reaction and isotopic labeling suggests that alcohol dehydrogenation occurs uniformly over Pd nanoparticles, but only selected sites may allow desorption of the product benzaldehyde thus providing the required selectivity. Promotion of Pd/Al2O3 using bismuth produces infrared spectra free of adsorbed CO. This information demonstrates that Bi is deposited on selected adsorption sites (terraces rather than defects) and simultaneously confirms that open terraces favor product decomposition. Experiments performed in the continuous reactor cell using different catalyst film thickness show that reactions can be studied under kinetic or mass transfer limited conditions depending on catalyst film thickness. This allowed to study the alcohol oxidation under conditions of oxygen diffusion limitation, which are preferably applied in praxis in order to prevent catalyst deactivation by over-oxidatio

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 0wt.% to 28wt.% 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 catalyst

Influence of Pt-Ba Proximity on NO x Storage-Reduction Mechanisms: A Space- and Time-Resolved In Situ Infrared Spectroscopic Study

The influence of Pt-Ba proximity on the performance and mechanism of NO x storage-reduction (NSR) was investigated by a comparative study of Pt-Ba/CeO2, Pt/CeO2 and mechanically mixed Pt/CeO2-Ba/CeO2. NO x storage capacity, regeneration activity and selectivity to nitrogen and ammonia during periodic lean (NO+O2)-rich (H2) cycles were evaluated and the chemical gradients along the axial direction of the catalyst beds were monitored by space- and time-resolved in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The presence of Ba and its proximity to Pt greatly influenced the NSR process. In particular, the proximity was crucial to achieve better utilization of bulk Ba components as well as enhancing selectivity to N2. The space-resolved approach is shown to be a powerful tool to understand the impact of the proximity of Pt and Ba constituents on the final NSR performanc

Epoxidation of Allylic Alcohols with TiO2-SiO2: Hydroxy-Assisted Mechanism and Dynamic Structural Changes During Reaction

Epoxidation of allylic alcohols and cyclohexene with TBHP and titania-silica aerogels containing 1 and 5 wt% TiO2 has been studied. For the oxidation of geraniol and cyclohexenol, the regio- and diastereoselectivities and kinetic data indicate an OH-assisted mechanism involving a dative bond between the OH group and the Ti site. This mechanism is disabled in the oxidation of cyclooctenol due to steric hindrance. The moderate regio- and diastereoselectivities of the aerogels, compared with those of TS-1 and the homogeneous model Ti(OSiMe3)4, are attributed to the presence of non-isolated Ti sites and to a "silanol-assisted” mechanism, according to which model the allylic alcohol is anchored to a neighboring SiOH group instead of the Ti-peroxo complex. Kinetic analysis of the initial transient period revealed rapid catalyst restructuring during the first few turnovers. A feasible explanation is the breaking of Si-O-Ti linkages of the carefully predried aerogels by water or TBHP, resulting in active Ti sites with remarkably different catalytic propertie