Thermodynamic properties of Pt nanoparticles: Size, shape, support, and adsorbate effects
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The proposed work focuses on the possibility of achieving the reduction in the size of the interfacing filter for the grid connection for a back-to-back modular multilevel converter system with the use of third order LCL filters. To achieve the same attenuation, it is possible to reduce the size of the interfacing filters by the usage of third order filters. However, this kind of filtering comes with the limitation of having sustained oscillations due to lack of damping especially during transient changes. Therefore, in this work, a methodology has been proposed based on the principle of internal model to cater for this unwanted oscillations. The third order system is modeled inside the microcontroller with the damping enabled. The error between the output from the model and the actual are compared and the error is utilized to accomplish the active damping strategy. The proposed architecture is verified via computer simulations based on MATLAB/Simulink domain and various case study results along with their discussion is presented in this paper.
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Lignocellulosic biofuels are promising as sustainable alternative fuels, but lignin inhibits access of enzymes to cellulose, and by-products of lignin degradation can be toxic to cells. The fast growth, high efficiency and specificity of enzymes employed in the anaerobic litter deconstruction carried out by tropical soil bacteria make these organisms useful templates for improving biofuel production. The facultative anaerobe Enterobacter lignolyticus SCF1 was initially cultivated from Cloud Forest soils in the Luquillo Experimental Forest in Puerto Rico, based on anaerobic growth on lignin as sole carbon source. The source of the isolate was tropical forest soils that decompose litter rapidly with low and fluctuating redox potentials, where bacteria using oxygen-independent enzymes likely play an important role in decomposition. We have used transcriptomics and proteomics to examine the observed increased growth of SCF1 grown on media amended with lignin compared to unamended growth. Proteomics suggested accelerated xylose uptake and metabolism under lignin-amended growth, with up-regulation of proteins involved in lignin degradation via the 4-hydroxyphenylacetate degradation pathway, catalase/peroxidase enzymes, and the glutathione biosynthesis and glutathione S-transferase (GST) proteins. We also observed increased production of NADH-quinone oxidoreductase, other electron transport chain proteins, and ATP synthase and ATP-binding cassette (ABC) transporters. This suggested the use of lignin as terminal electron acceptor. We detected significant lignin degradation over time by absorbance, and also used metabolomics to demonstrate moderately significant decreased xylose concentrations as well as increased metabolic products acetate and formate in stationary phase in lignin-amended compared to unamended growth conditions. Our data show the advantages of a multi-omics approach toward providing insights as to how lignin may be used in nature by microorganisms coping with poor carbon availability.
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Model materials consisting of metal nanoparticles loaded onto oxide supports were synthesized, characterized, and investigated in a number of catalytic chemical reactions. By varying the size, shape, and composition of nanoparticle, as well as the material used to support the nanoparticles, it was found that small changes to the catalyst can have enormous changes to the reaction activity and selectivity. Investigation of these carefully synthesized catalysts via in situ characterization, and reaction studies, leads to a deeper understanding of the molecular level parameters that govern catalysis. Through study of the properties of the nanoparticles it was discovered that nanoparticle size and shape have a dominant role in the chemoselective catalysis of furfural over platinum nanoparticles. When vapor phase furfural and hydrogen gas were passed over Pt nanoparticles ranging in size from 1.5 to 7.1 nm, the catalytic selectivity was found to be dominated by the size of the nanoparticle. Large nanoparticles promoted hydrogenation of furfural to furfuryl alcohol, while smaller nanoparticles favored decarbonylation to furan. The same size specific selectivity was found in the hydrogenative reforming (the transformation of hydrocarbons to branched isomers) of C6 hydrocarbons, in which Pt nanoparticle size controls isomerization selectivity. Methylcyclopentane was found to be extremely size dependent at lower temperatures (553 K). It was found that smaller sized nanoparticles favored isomer formation, while larger sizes catalyzed the aromatization reaction more efficiently. n-hexane was found to be much less dependent on particle size, but still showed an increase in isomerization with small particles over larger sized Pt nanoparticles. The composition of PtxRh1-x bimetallic nanoparticles was also studied. These catalysts were characterized under hexane reforming conditions with Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS), in order to find the actual surface atomic composition under real catalytic working conditions. By using AP-XPS and catalytic data in tandem, it was found that an optimum Rh loading occurred when the surface ensemble statistically favored one Rh atom surrounded by Pt atoms. By utilizing different oxide materials for catalytic supports the flow of charge can play a role in the reaction at the surface or interface in a phenomenon known as the strong metal-support interaction (SMSI). When Pt nanoparticles were loaded onto mesoporous supports made of Co3O4, NiO, MnO2, Fe2O3, and CeO2 it was found that their activity for carbon monoxide oxidation was greatly enhanced relative to the support alone or Pt loaded onto inert mesoporous silica. This finding demonstrates that the interface of the metallic Pt nanoparticle and the oxide 2 support is able to produce turnovers that are orders of magnitude higher than the two materials separately. When the same type of experiments were investigated with n-hexane as the reactant and macroporous Al2O3, TiO2, Nb2O5, Ta2O5, and ZrO2 were utilized as supports, it was found that the reaction selectivity was greatly altered depending on the catalytic support material. TiO2, Nb2O5, and Ta2O5 (all of which are strong Lewis acids) were found to be much more selective for isomer production than the standard SiO2 mesoporous silica supported Pt nanoparticle catalyst. Finally, an acidified mesoporous silica material was utilized as the support. This material was synthesized by using AlCl3 to modify the surface of mesoporous silica. This support was found to have no activity for hexane isomerization alone. However, when Pt nanoparticles were supported on the material, the activity and isomer selectivity in hexane reforming was increased several orders of magnitude as compared to the same nanoparticles supported on unmodified mesoporous silica. This dissertation builds on the existing knowledge of known concepts in catalysis science such as structure sensitive reactions, the metal-support interaction, and acid-base chemistry. The results show how small changes in the active sites of a catalyst can create large changes in the catalytic chemistry. This research demonstrates how careful material control, characterization and reaction study can help to elucidate the molecular level components necessary to design efficient catalysts.