Browsing by Subject "carbon monoxide"
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Item Characterization and Reaction Studies of Silica Supported Platinum and Rhodium Model Catalysts(2012-02-14) Lundwall, Matthew JamesThe physical and catalytic properties of silica supported platinum or rhodium model catalysts are studied under both ultra high vacuum (UHV) and elevated pressure reaction conditions (>1torr). Platinum or rhodium nanoparticles are vapor deposited onto a SiO2/Mo(112) surface and characterized using various surface analytical methods. CO chemisorption is utilized as a surface probe to estimate the concentration of various sites on the nanoparticles through thermal desorption spectroscopy (TDS) and infrared reflection absorption spectroscopy (IRAS) along with microscopy techniques to estimate particle size. The results are compared with hard sphere models of face centered cubic metals described as truncated cubo-octahedron. Results demonstrate the excellent agreement between chemisorption and hard sphere models in estimating the concentration of undercoordinated atoms on the nanoparticle surface. Surfaces are then subjected to high pressure reaction conditions to test the efficacy of utilizing the rate of a chemical reaction to obtain structural information about the surface. The surfaces are translated in-situ to a high pressure reaction cell where both structure insensitive and sensitive reactions are performed. Structure insensitive reactions (e.g. CO oxidation) allow a method to calculate the total active area on a per atom basis for silica supported platinum and rhodium model catalysts under reaction conditions. While structure sensitive reactions allow an estimate of the types of reaction sites, such as step sites (?C7) under reaction conditions (e.g. n-heptane dehydrocyclization). High pressure structure sensitive reactions (e.g. ethylene hydroformylation) are also shown to drastically alter the morphology of the surface by dispersing nanoparticles leading to inhibition of catalytic pathways. Moreover, the relationships between high index single crystals, oxide supported nanoparticles, and high surface area technical catalysts are established. Overall, the results demonstrate the utility of model catalysts in understanding the structure-activity relationships in heterogeneous catalytic reactions and the usefulness of high pressure reactions as an analytical probe of surface morphology.Item Trajectory Simulations of H2O, O3, and CO in the Upper Troposphere and Lower Stratosphere (UTLS)(2014-05-05) Wang, TaoThe purpose of this work is to simulate water vapor (H2O), ozone (O3), and carbon monoxide (CO) in the upper troposphere and lower stratosphere (UTLS) using a domain-filling, forward trajectory model. The influx of H2O to the UTLS is largely determined by the large-scale troposphere-to-stratosphere transport in the tropics, during which air is dehydrated across the cold tropical tropopause. In the domain-filling, forward trajectory model, trajectories are initialized in the upper troposphere, and the circulation is based on reanalysis wind fields. Along the trajectories, winds determine the pathways of parcels and temperature determines the H2O content through an idealized saturation calculation. Compared with the Aura Microwave Limb Sounder (MLS) measurements, this simple advection-condensation strategy yields reasonable results for H2O in the stratosphere in terms of both seasonal variability and vertical structures. The detailed global dehydration patterns are also revealed from this model and it improves our understanding of the H2O and its transport within the UTLS. Besides H2O, ozone (O3) and carbon monoxide (CO) are also important trace gases in the UTLS linked to circulation, transport and climate forcing (for O3). Combined with simple parameterization of chemical production and loss rates from the Whole Atmosphere Community Climate Model (WACCM), we also managed to simulate O3 and CO transport in the UTLS via this trajectory model. The trajectory modeled O3 and CO show good overall agreement with satellite observations from the MLS and the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) in terms of spatial structure and seasonal variability. The trajectory model results also agree well with the Eulerian WACCM simulations. Analysis of the simulated tracers shows that seasonal variations in tropical upwelling exerts strong influence on O3 and CO in the tropical lower stratosphere, and the coupled seasonal cycles provide a useful test of the transport simulations. Interannual variations in the tracers are also closely coupled to changes in upwelling, and the trajectory model can accurately capture and explain observed changes. This demonstrates the importance of variability in tropical upwelling in forcing chemical changes in the tropical UTLS. Trajectory modeling of O3 and CO can provide useful tests for simplified understanding of transport and chemical processes in the UTLS, and provide complementary information to the H2O simulations, which are primarily constrained by tropopause temperatures. This model is easy to use, easy to diagnose, and the Lagrangian perspective makes it exceptionally useful in studying transport processes within the UTLS.