Current Search: catalysis (x)
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Title
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Model Nanocatalysts with Tunable Reactivity: Tailoring the Structure and Surface Chemistry of Nanomaterials for Energy and Alternative Fuels Catalysis.
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Creator
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Mistry, Hemma, Roldan Cuenya, Beatriz, Chow, Lee, Stolbov, Sergey, Zhai, Lei, University of Central Florida
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Abstract / Description
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One of the most pressing challenges of our time is meeting growing global energy demands while limiting human impact on the environment. To meet this challenge, new catalysts are needed to enable carbon neutral energy production processes and low cost synthesis of alternative fuels. In order to design new catalysts for such processes, fundamental understanding is needed on how the structural and chemical properties of nanostructured materials influences their surface chemistry. In this...
Show moreOne of the most pressing challenges of our time is meeting growing global energy demands while limiting human impact on the environment. To meet this challenge, new catalysts are needed to enable carbon neutral energy production processes and low cost synthesis of alternative fuels. In order to design new catalysts for such processes, fundamental understanding is needed on how the structural and chemical properties of nanostructured materials influences their surface chemistry. In this dissertation, I explore how the properties of nanoparticles, such as particle size, shape, composition, and chemical state, can be used to tune their reactivity. For this work, model nanoparticles were synthesized with well-defined structural and chemical properties, and a variety of surface science approaches were used for catalyst characterization. In particular, emphasis was placed on understanding the changes which may occur in the catalyst structure and chemical state during a reaction using advanced in situ techniques and correlating these changes to reactivity. After exploring how nanostructuring the catalyst surface can be used to tune reactivity and how dynamic changes can occur to nanocatalysts in reactive environments, these general principles are applied to a model reaction, the electroreduction of carbon dioxide, which is a promising process for synthesizing valuable products using renewable energy while consuming waste carbon dioxide. I explore the mechanisms behind how catalyst particle size, composition, and oxidation state can be used to improve activity and tune selectivity towards different carbon dioxide reduction products. Such fundamental mechanistic insights are critically needed to design efficient catalysts for this reaction.
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Date Issued
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2016
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Identifier
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CFE0006482, ucf:51440
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0006482
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Title
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Size, Shape, Composition and Chemical state effects in nanocatalysis.
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Creator
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Ahmadi, Mahdi, Roldan Cuenya, Beatriz, Rahman, Talat, Kara, Abdelkader, Coffey, Kevin, University of Central Florida
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Abstract / Description
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The field of nanocatalysis has gained significant attention in the last decades due to the numerous industrial applications of nanosized catalysts. Size, shape, structure, and composition of the nanoparticles (NPs) are the parameters that can affect the reactivity, selectivity and stability of nanocatalysts. Therefore, understanding how these parameters affect the catalytic properties of these systems is required in order to engineer them with a given desired performance. It is also important...
Show moreThe field of nanocatalysis has gained significant attention in the last decades due to the numerous industrial applications of nanosized catalysts. Size, shape, structure, and composition of the nanoparticles (NPs) are the parameters that can affect the reactivity, selectivity and stability of nanocatalysts. Therefore, understanding how these parameters affect the catalytic properties of these systems is required in order to engineer them with a given desired performance. It is also important to gain insight into the structural evolution of the NP catalysts under different reaction conditions to design catalysts with long durability under reaction condition. In this dissertation a synergistic combination of in situ, ex situ and operando state-of-the art techniques have allowed me to explore a variety of parameters and phenomena relevant to nanocatalysts by systematically tuning the NP size, chemical state, composition and chemical environment.
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Date Issued
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2016
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Identifier
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CFE0006243, ucf:51084
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0006243
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Title
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Cerium oxide Nanoparticles: Their Phosphatase Activity and its Control.
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Creator
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Dhall, Atul, Self, William, Seal, Sudipta, Zervos, Antonis, University of Central Florida
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Abstract / Description
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Cerium oxide nanoparticles are established scavengers of reactive oxygen and nitrogen species. They have many potential biomedical applications that depend on their physicochemical properties and mode of preparation. Recent studies have found these nanoparticles possess phosphatase mimetic activity. Studying such catalytic activities will qualify their biomedical applications and render information on their bioavailability and potential toxicity.Two oxidation states of cerium exist in these...
Show moreCerium oxide nanoparticles are established scavengers of reactive oxygen and nitrogen species. They have many potential biomedical applications that depend on their physicochemical properties and mode of preparation. Recent studies have found these nanoparticles possess phosphatase mimetic activity. Studying such catalytic activities will qualify their biomedical applications and render information on their bioavailability and potential toxicity.Two oxidation states of cerium exist in these nanoparticles (3+ or 4+). It is hypothesized that the oxidation state of cerium in the nanoparticles determines the amount of adsorbed water on the crystal lattices. This in turn governs their activity as phosphatases. Nanoparticles with higher levels of cerium in the 4+ state exhibit phosphatase activity while those with higher levels of cerium in the 3+ state do not. This phosphatase activity may be controlled with the addition of inhibitory anions. It is hypothesized that anions with structures similar to phosphate can inhibit phosphatase activity by leading to the production of complexes on the surface of cerium oxide nanoparticles.Substrates that were used to test this activity include para-nitrophenyl phosphate (pNPP), 4-methylumbelliferyl phosphate (MUP) and adenosine triphosphate (ATP). To highlight the role of adsorbed water, we also performed experiments on pNPP with methanol as a solvent. The activity was measured by absorbance (pNPP and ATP) or fluorescence (MUP) and reported as nmol of phosphate/min. In some cases this rate was calculated through coupled reactions or by measuring the rate of formation of other colored products formed along with the release of phosphate such as pNP (para-nitrophenol).The phosphatase activity increased as the amount of adsorbed water increased implying that the abundance of adsorbed water makes the surface of 4+ ceria nanoparticles more active. Phosphatase activity for all the substrates exhibited Michaelis-Menten kinetics. Although the phosphatase activity of these nanoparticles is slow (turnover rate) as compared to real biological phosphatases, it can be used as a model catalytic activity to follow other catalytic activities that are associated with nanoparticles that have an abundance of cerium in the 4+ state, such as catalase activity. These results also provide information on the nature of the active sites involved in the catalytic activities associated with these nanoparticles.We identified three inhibitors, tungstate, molybdate and arsenate, which decreased the phosphatase activity of these nanoparticles in a dose dependent manner. Vmax, Km and Ki values were determined by varying substrate concentrations in the presence and absence of inhibitors. A partial mixed inhibition model was fit for each of these inhibitors.Summary: Phosphatase activity of cerium oxide nanoparticles with higher levels of cerium in the 4+ oxidation state was used as a model catalytic activity to study the nature of the active sites involved in catalysis. The study of inhibitors can reveal more information as to the surface binding of substrates in catalysis.
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Date Issued
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2014
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Identifier
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CFE0005603, ucf:50261
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0005603
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Title
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Computational Approach to the Problems of Electro- and Photo-Catalysis.
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Creator
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Zuluaga, Sebastian, Stolbov, Sergey, Schelling, Patrick, Roldan Cuenya, Beatriz, Masunov, Artem, University of Central Florida
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Abstract / Description
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The main objective of this work is to gain basis for rational design of catalysts used in fuel cells for conversion of chemical energy stored in hydrogen molecules into electric energy, as well as photo-catalysts used for hydrogen production from water under solar irradiation. This objective is achieved by applying the first principles computational approach to reveal relationship among compositions of materials under consideration, their electronic structure and catalytic activity. A major...
Show moreThe main objective of this work is to gain basis for rational design of catalysts used in fuel cells for conversion of chemical energy stored in hydrogen molecules into electric energy, as well as photo-catalysts used for hydrogen production from water under solar irradiation. This objective is achieved by applying the first principles computational approach to reveal relationship among compositions of materials under consideration, their electronic structure and catalytic activity. A major part of the work is focused on electro-catalysts for hydrogen fuel cells. Platinum (Pt) is widely used in the electrodes of fuel cells due to its good catalytic properties. However, Pt is an expensive and scarce element, its catalytic activity is not optimal and also it suffers from CO poisoning at anode. Therefore the search for new catalytic materials is needed for large scale implementation of fuel cells. The main direction of search of more efficient electro-catalysts is based in the design in which an active element monoatomic layer (AE) is deposited on a metal substrate (MS) made of a cost-effective material. Two goals are achieved by doing this: on the one hand, the cost of the catalytic system is reduced by reducing the amount of the AE in the system and on the other hand the catalytic properties of the AE can be tuned through its interactions with the MS. In the first part of this work the Pd-based alloys and layered structures have been studied as promising electro-catalysts for the ORR on the fuel cell cathodes, more precisely Pd-Co alloys and Pd/M/Pd (M=Co,Fe). There exists a robust model linking the activity of a surface toward ORR to computable thermodynamic properties of the system and further to the binding energies of the ORR intermediates on the catalyst surface. A more challenging task is to find how to tune these binding energies through modification of the surface electronic structure that can be achieved by varying the surface composition and/or morphology. To resolve this challenge, the electronic structure, binding energies of intermediates and the ORR free energies have been calculated within the density functional theory (DFT) approximation. The results presented in this work show that in contrast to the widely accepted notion, the strain exerted by a substrate on AE hardly affects the surface activity toward ORR, while the hybridization of the electronic states of the AE-and MS-electronic states is the key factor controlling the catalytic properties of these systems. Next it is shown that the catalytic activity of the promising anode electrocatalysts, such as Pt/M, M=Au, Ru and Pd, is also determined by the AE-MS hybridization with a minor effect of the strain. Furthermore, we have shown that, if AE is weakly bound to the substrate (as it is for Pt/Au), surface reconstruction occurs. This leads to the breaking of the relation between the electronic structure of the clean surface and the reactivity of the sytem. Other kind of promising ORR catalysts is designed in the form of Ru nanoparticles modified by chalcogens. In this work, I present the results obtained for small Ru clusters and flat Ru facets modified with chalcogens (S, Se and Te). The O and OH binding energies are chosen as descriptors of the ORR. The results on the two systems are compared, concluding that large clusters with relative large flat facets have higher catalytic activity due to the absence of low coordinated and thus high reactive Ru atoms. Regarding the problem of the hydrogen production via photo-catalytic splitting of water, one of the challenges is tuning the band gap of the photo-anodes to optimal levels. Graphitic carbon nitride (g-C3N4) is a promising material to be used as a photo-anode, however, a reduction of the band gap width by rational doping of the material would improve the efficiency significantly. This issue is addressed in the last chapter of this work. Two problems are considered: a) the stability of the doped system and b) the band gap width. To address the first problem the ab-initio thermodynamics approach has been used, finding that the substitution of C and N with the doping agent (B, C, N, O, Si and P) is thermodynamically preferred over the interstitial addition of dopant to the g-C3N4 structure. However, due to high kinetic energy barriers for the detachment of C and N atoms, involved in the substitution doping, the interstitial addition found to be kinetically more favorable. Since the density functional theory fails to reproduce the band gap of semiconductors correctly, the GW approximation was used to study the band gap of the system. The results indicate that the g-C3N4 system maintain its semiconductor character if doped with B, O and P under certain conditions, while reducing the band gap.
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Date Issued
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2013
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Identifier
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CFE0005288, ucf:50546
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0005288
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Title
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DENSITY-FUNCTIONAL THEORY APPLIED TO PROBLEMS IN CATALYSIS AND ELECTROCHEMISTRY.
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Creator
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Kumar, Santosh, Schelling, Patrick, University of Central Florida
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Abstract / Description
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We study the structure and energetics of water molecules adsorbed at ceria (111) surfaces below one monolayer coverage using density-functional theory. The results of this study provide a theoretical framework for interpreting recent experimental results on the redox properties of water at ceria (111) surfaces. In particular, we have computed the structure and energetics of various absorption geometries at stoichiometric ceria (111) surface. In contrast to experiment results, we do not find a...
Show moreWe study the structure and energetics of water molecules adsorbed at ceria (111) surfaces below one monolayer coverage using density-functional theory. The results of this study provide a theoretical framework for interpreting recent experimental results on the redox properties of water at ceria (111) surfaces. In particular, we have computed the structure and energetics of various absorption geometries at stoichiometric ceria (111) surface. In contrast to experiment results, we do not find a strong coverage dependence of the adsorption energy. For the case of reduced surface, our results show that it may not be energetically favorable for water to oxidize oxygen vacancy site at the surface. Instead, oxygen vacancies tend to result in water more strongly binding to the surface. The result of this attractive water-vacancy interaction is that the apparent concentration of oxygen vacancies at the surface is enhanced in the presence of water. Finally, we discuss this problem with reference to recent experimental and theoretical studies of vacancy clustering at the (111) ceria surface. We also describe the simulation results for the structure and dynamics of liquid water using the SIESTA electronic structure approach. We find that the structure of water depends strongly on the particular basis set used. Applying a systematic approach to varying the basis set, we find that the basis set which results in good agreement with experimental binding energies for isolated water dimers also provides a reasonable description of the radial distribution functions of liquid water. We show that the structure of liquid water varies in a systematic fashion with the choice of basis set. Comparable to many other first-principle studies of liquid water using gradient-corrected density functionals, the liquid is found to be somewhat overstructured. The possibility of further improvements through a better choice of the basis set is discussed. We find that while improvements are likely to be possible, application to large-scale systems will require use of a computational algorithm whose computational cost scales linearly with system size. Finally, we study the molecular and atomic adsorption of oxygen on the gold nano-clusters. We show multiple stable and metastable structures for atomically and molecularly adsorbed oxygen to the gold cluster. We plan to predict the reaction pathway and calculate activation energy barrier for desorption of molecular oxygen from the atomically adsorbed gold cluster which is very important for any catalytic reaction occurring using gold nanoparticles.
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Date Issued
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2006
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Identifier
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CFE0001211, ucf:46938
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0001211
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Title
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IN-SITU GAS PHASE CATALYTIC PROPERTIES OF METAL NANOPARTICLES.
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Creator
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Ono, Luis, Roldan Cuenya, Beatriz, University of Central Florida
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Abstract / Description
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Recent advances in surface science technology have opened new opportunities for atomic scale studies in the field of nanoparticle (NP) catalysis. The 2007 Nobel Prize of Chemistry awarded to Prof. G. Ertl, a pioneer in introducing surface science techniques to the field of heterogeneous catalysis, shows the importance of the field and revealed some of the fundamental processes of how chemical reactions take place at extended surfaces. However, after several decades of intense research,...
Show moreRecent advances in surface science technology have opened new opportunities for atomic scale studies in the field of nanoparticle (NP) catalysis. The 2007 Nobel Prize of Chemistry awarded to Prof. G. Ertl, a pioneer in introducing surface science techniques to the field of heterogeneous catalysis, shows the importance of the field and revealed some of the fundamental processes of how chemical reactions take place at extended surfaces. However, after several decades of intense research, fundamental understanding on the factors that dominate the activity, selectivity, and stability (life-time) of nanoscale catalysts are still not well understood. This dissertation aims to explore the basic processes taking place in NP catalyzed chemical reactions by systematically changing their size, shape, oxide support, and composition, one factor at a time. Low temperature oxidation of CO over gold NPs supported on different metal oxides and carbides (SiO2, TiO2, TiC, etc.) has been used as a model reaction. The fabrication of nanocatalysts with a narrow size and shape distribution is essential for the microscopic understanding of reaction kinetics on complex catalyst systems ("real-world" systems). Our NP synthesis tools are based on self-assembly techniques such as diblock-copolymer encapsulation and nanosphere lithography. The morphological, electronic and chemical properties of these nanocatalysts have been investigated by atomic force microscopy (AFM), scanning tunneling microscopy (STM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and temperature-programmed desorption (TPD). Chapter 1 describes briefly the basic principles of the instrumentation used within this experimental dissertation. Since most of the state-of-art surface science characterization tools provide ensemble-averaged information, catalyst samples with well defined morphology and structure must be available to be able to extract meaningful information on how size and shape affect the physical and chemical properties of these structures. In chapter 2, the inverse-micelle encapsulation and nanosphere lithography methods used in this dissertation for synthesizing uniformly arranged and narrow size- and shape-selected spherical and triangular NPs are described. Chapter 3 describes morphological changes on individual Au NPs supported on SiO2 as function of the annealing temperature and gaseous environment. In addition, NP mobility is monitored. Chapter 4 explores size-effects on the electronic and catalytic properties of size-selected Au NPs supported on a transition metal carbide, TiC. The effect of interparticle interactions on the reactivity and stability (catalyst lifetime) of Au NPs deposited on TiC is discussed in chapter 5. Size and support effects on the formation and thermal stability of Au2O3, PtO and PtO2 on Au and Pt NPs supported on SiO2, TiO2 and ZrO2 is investigated in chapter 6. Emphasis is given to gaining insight into the role of the NP/support interface and that played by oxygen vacancies on the stability of the above metal oxides. Chapter 7 reports on the formation, thermal stability, and vibrational properties of mono- and bimetallic AuxFe1-x (x = 1, 0.8, 0.5, 0.2, 0) NPs supported on TiO2(110). At the end of the thesis, a brief summary describes the main highlights of this 5-year research program.
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Date Issued
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2009
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Identifier
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CFE0002940, ucf:47962
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0002940
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Title
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TUNING THE PROPERTIES OF NANOMATERIALS AS FUNCTION OF SURFACE AND ENVIRONMENT.
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Creator
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Karakoti, Ajay, Seal, Sudipta, University of Central Florida
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Abstract / Description
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Nanotechnology has shaped the research and development in various disciplines of science and technology by redefining the interdisciplinary research. It has put the materials science at the forefront of technology by allowing the researchers to engineer materials with properties ranging from electronics to biomedical by using materials as diverse as ceramics to just plain carbon. These exceptional properties are achieved by minimizing the dimension of particles in such smaller domains that...
Show moreNanotechnology has shaped the research and development in various disciplines of science and technology by redefining the interdisciplinary research. It has put the materials science at the forefront of technology by allowing the researchers to engineer materials with properties ranging from electronics to biomedical by using materials as diverse as ceramics to just plain carbon. These exceptional properties are achieved by minimizing the dimension of particles in such smaller domains that the boundary between the individual atoms, ions or cluster of particles is very small. This results in a change in conventional properties of particles from continuum physics to quantum physics and hence the properties of nanoparticles can be tuned based upon their size, shape and dimensionality. One of the most apparent changes upon decreasing the particle size is the increase in surface area to volume ratio. Thus nanoparticles possess greater tendency to interact with the environment in which they are present and similarly the environment can affect the properties of nanomaterials. The environment here is described as the immediate solid, liquid or gaseous material in immediate contact with the external surface of the nanoparticles. In order to control the physico-chemical properties of nanoparticles it is important to control the surface characteristics of nanoparticles and its immediate environment. The current thesis emphasizes the role of tuning the surface of nanoparticles and/or the environment around the nanoparticles to control their properties. The current approach in literature uses nanoparticles as a platform that can be used for a myriad of applications by just changing the surface species which can tune the properties of nanoparticles. Such surface modification can provide nanomaterials with hydrophilic, hydrophobic, biocompatible, sensing, fluorescence and/or electron transfer properties. The current thesis demonstrates the interaction between nanoparticles and the environment by changing the surface characteristics of nanomaterials through the use of oxide nanoparticles as examples. The first part of the thesis discusses the synthesis, modification and properties of cerium oxide nanoparticles (CNPs), a versatile material used in wide range of applications from catalysis to glass polishing, for their potential use in biomedical applications as a function of medium. The thesis starts by projecting the effect of environment on the properties of nanomaterials wherein it is shown that simple medium, such as, water can influence the optical properties of nanoparticles. It was shown that the strong polarizing effect of water on the non-bonding f electrons can cause a blue shift in the optical properties of CNPs as a function of increase in trivalent oxidation state of cerium in CNPs. This phenomenon, contradictory to existing literature in solid state where a red shift is observed upon increasing the trivalent oxidation state of cerium in CNPs, is purely attributed to the medium-inflicted change in properties of nanoparticles. This concept is built upon in the first half of thesis by increasing the colloidal stability of nanoparticles by surface and/or medium modification. It is shown that the narrow range of pH in which the colloidal CNPs are stable can be extended by changing the medium from water to polyhydroxy compounds such as glucose and dextran. The synthesis was designed specially to avoid the traditional precipitation and re-dispersion strategy of synthesis of nanoparticles to preserve the surface activity. The complex forming ability of cerium with polysaccharides was employed to synthesize the CNPs in a one step process and the pH stability of the NPs was extended between 2.0 to 9.5. The difference in the complexing ability of the monomer - glucose and its anhydro glucose polymer - dextran is reflected in the ability of cerium to form super-agglomerates with the monomer while anhydro gluco polymer forms extremely disperse 3-5 nm nanoparticles through steric modification. It is shown that the antioxidant activity of nanoparticles remain unchanged by surface modification by demonstrating the cycling of the oxidation state of cerium in CNPs, with time, through hydrogen peroxide mediated transition of oxidation states of cerium. It is demonstrated that the polymeric coatings, generally considered as passive surface coatings, can also play an active role in tuning the properties of nanomaterials and increasing their biocompatibility as well as bio-catalytic activity. It is demonstrated that the antioxidant activity of CNPs can be increased as a function of polyethylene glycol (PEG) while the biocompatibility is unaltered due to the biocompatible nature of PEG. The antioxidant activity of CNPs involves an electron transfer (ET) from the CNPs to the reactive oxygen species or vice versa. This heterogeneous ET system is further complicated by the presence of surface adsorbed species. Interfacial charge/electron transfer (ET) between a particle and adsorbed (or covalently bonded) molecule presents significant complexity as it involves a solid state electron transfer over long distance. Unlike a free ion, in solid state, the conducting electrons can be temporarily trapped by the coupling lattice sites. Adsorption/attachment of surface species to nanoparticle can disturb the electronic levels by further polarizing the electron cloud thereby localizing the electron and facilitating the charge transfer. Such an interfacial electron transfer between NPs and adsorbed organic species can be compared to the single electron transfer carried by organometallic systems with a metal ion core modified with electron delocalizing porphyrin ligands. It is demonstrated that in this PEGyltaed CNPs system, the PEG essentially forms a complex with CNPs in the presence of hydrogen peroxide to facilitate this electron transfer process. The superoxide dismutase (SOD) and catalase mimetic ability of CNPs is described and special emphasis is given to its biocompatibility. The second half of the thesis emphasizes the role of synthesis and surface modification in influencing the catalytic performance of cerium oxide modified titanium dioxide catalysts for decomposition of methanol. Noble metals supported on oxide nanoparticles have been an area of active research in catalysis. It is demonstrated that the modification of surface of the oxide nanoparticles by noble metals is a function of the synthesis process. By keeping the size of the nanoparticles constant, it was demonstrated that the differences in the oxidation state of noble metals can lead to change in the activity of noble metals. This contribution adds to the already existing controversy in the open literature about the role of the oxidation state of platinum in catalysis. The core level shifts in the binding energy of the 4f electrons of platinum was used as a guide to the gauge the oxidation state. Results from an in-house built catalytic reactor coupled to mass spectrometer and in-situ diffuse reflectance infra-red spectroscopy are used to quantify the catalytic performance and identify the mechanism of reaction as well as products of methanol decomposition.
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Date Issued
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2010
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Identifier
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CFE0003189, ucf:48590
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0003189
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Title
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INVESTIGATION OF NANOCERIA-MODIFIED PLATINUM-GOLD COMPOSITE ELECTRODES FOR THE ELECTROCHEMICAL REDUCTION OF OXYGEN IN ALKALINE MEDIA.
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Creator
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Hegishte, Rahul, Diaz, Diego, University of Central Florida
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Abstract / Description
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Platinum-gold and nanoceria-modified platinum-gold electrodes were prepared on a platinum surface via electrochemical reduction of solutions of platinum and gold salts in the dispersion of nanoceria. The molar ratios of Pt and Au were varied in both PtAu and PtAu/CeO2 electrodes while the total concentration of the metals was maintained at 2 x 10-3M and the concentration of nanoceria was maintained constant at 5 x 10-3M. The electrodes were characterized by their cyclic voltammetry curves in...
Show morePlatinum-gold and nanoceria-modified platinum-gold electrodes were prepared on a platinum surface via electrochemical reduction of solutions of platinum and gold salts in the dispersion of nanoceria. The molar ratios of Pt and Au were varied in both PtAu and PtAu/CeO2 electrodes while the total concentration of the metals was maintained at 2 x 10-3M and the concentration of nanoceria was maintained constant at 5 x 10-3M. The electrodes were characterized by their cyclic voltammetry curves in 0.5M sulfuric acid solution. The electrochemically active area of the electrodes was determined using the copper underpotential deposition method. The linear sweep voltammograms of the PtAu and PtAu/CeO2 electrodes were plotted from -1V to 0V vs. Ag/AgCl, 3M KCl reference electrode using the rotating disk electrodes for the rotation speeds from 200 to 3600rpm in an oxygen saturated 0.1M sodium hydroxide solution. The values of the kinetic controlled current density were determined from the rotating disk voltammetry. The values of the limiting current density for each rotation speed were used to plot the Koutecky-Levich plots for the electrodes. The rate constants were obtained from the Koutecky-Levich plots for each composition of the electrode. The values of kinetic current density and the rate constants indicated that the addition of Au enhances the ORR rates in both the PtAu and the PtAu/CeO2 electrodes. The values of the kinetic current densities of the PtAu/CeO2 were lower than that of the PtAu electrodes owing to the poor electrical conductivity of ceria. The Koutecky-Levich plots for the PtAu and the PtAu/CeO2 electrodes are linear for the four-electron reduction of oxygen in the alkaline media, which indicates that the overall reaction follows the first order kinetics. The electron transfer rate constants obtained from the Koutecky-Levich plots for the PtAu and the PtAu/CeO2 electrodes both were found to increase in values with the addition of Au. The Tafel plots were plotted for the PtAu and PtAu/CeO2 electrodes and the values of Tafel slopes were found to be in a small range for lower amounts of Au which indicated that the ORR rates were enhanced in lower amounts of Au. The values of Tafel slopes were found to be much higher for the ceria-modified PtAu electrodes as compared to the PtAu electrodes, which indicate the lower rates of ORR after the modification with ceria. Also, the ORR rates for the electrodes with smaller amounts of Au in PtAu/CeO2 were higher than those in the larger amounts of Au.
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Date Issued
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2011
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Identifier
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CFE0003639, ucf:48860
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0003639
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Title
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Nitrogen-Containing Materials for Mechanochemical Synthesis, Luminescence Analysis, and Heterogeneous Catalysis.
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Creator
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Nash, David, Zhai, Lei, Hampton, Michael, Harper, James, Rex, Matthew, Blair, Richard, University of Central Florida
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Abstract / Description
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Various inorganic nitrogen-containing materials have been exploited for their different properties. Several nitride materials are commercially attractive due to their mechanical properties making them suitable for ceramic industries and wide bandgaps fitting for use as semiconductor and insulator materials, as well as optoelectronics. Nitride materials can exhibit versatility in applications such as the use of gallium nitride to make blue LEDs, nitrides of titanium and silicon being utilized...
Show moreVarious inorganic nitrogen-containing materials have been exploited for their different properties. Several nitride materials are commercially attractive due to their mechanical properties making them suitable for ceramic industries and wide bandgaps fitting for use as semiconductor and insulator materials, as well as optoelectronics. Nitride materials can exhibit versatility in applications such as the use of gallium nitride to make blue LEDs, nitrides of titanium and silicon being utilized as medical implants for their chemical inertness and hardness, and the heavy use of boron nitride as a solid lubricant in the cosmetic industry. Amines have been used as nitrogen-containing organic ligands in organometallic complexes that exhibit phenomenal photophysical properties. These complexes have been heavily studied for potential applications in optoelectronics and chemical sensing. This dissertation will focus on two nitrogen-containing materials that have yet to be explored for the potential applications to be discussed. The first is hexagonal-boron nitride (h-BN), which was previously mentioned to have a substantial use in the cosmetic industry, giving products such as lipstick, foundation, and blush their slick feeling. Computational models have shown the possibility of altered electronic properties of defect sites in the h-BN sheets. These defect sites will be explored experimentally to determine any catalytic activity. Specifically, the hydrogenation reaction using defect-laden hexagonal-boron nitride will be investigated. Successful catalysis would add to the short list of non-metal catalyst, and provide an alternative catalyst that costs significantly less than the traditional metal catalysts commonly used in commercial industries. The second of the two nitrogen-containing materials is a class of metal complexes based on organometallic clusters of copper(I) iodide. Copper(I) iodide clusters formed with amine ligands have been studied for around four decades and the photophysics behind their photoluminescent properties are well understood. Much of the work has been done for use as a potential emissive material in the optoelectronics field. They have also been studied for applications in the sensing of environmental compounds. Here, research will display its use as a novel sensor for narcotic substances. This forensic application will be further explored to develop and eventually commercialize a complete field drug testing system for law enforcement and crime lab use, with the goal to equip law enforcement personnel with a presumptive drug testing method that is accurate, easy-to-use, safe, adaptable, and affordable. This system will consist of a narcotic drug-indicating test strip, a handheld fluorescence spectrometer manufactured in-house using relatively inexpensive parts, and a mobile app that will leverage photoemission data of the tested drug samples collected by multiple crime labs to provide the ability for sample-to-reference data matching. Law enforcement users would have the ability to rapidly identify an unknown substance by applying it to a test strip, testing it using the spectrometer, and capturing an image of the resulting photoemission and analyzing the spectral profile in search of a match with the support of a cloud database.
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Date Issued
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2017
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Identifier
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CFE0007129, ucf:52297
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0007129
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Title
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SYNTHESIS, STRUCTURE, AND CATALYTIC PROPERTIES OF SIZE-SELECTED PLATINUM NANOPARTICLES.
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Creator
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Mostafa, Simon, Roldan Cuenya, Beatriz, University of Central Florida
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Abstract / Description
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The use of heterogeneous catalysis is well established in chemical synthesis, energy, and environmental engineering applications. Supported Pt nanoparticles have been widely reported to act as catalysts in a vast number of chemical reactions. In this report, the performance of Pt/ZrO2 nanocatalyst for the decomposition of methanol, ethanol, 2-propanol, and 2-butanol is investigated. The potential of each alcohol for the production of H2 and other relevant products in the presence of a...
Show moreThe use of heterogeneous catalysis is well established in chemical synthesis, energy, and environmental engineering applications. Supported Pt nanoparticles have been widely reported to act as catalysts in a vast number of chemical reactions. In this report, the performance of Pt/ZrO2 nanocatalyst for the decomposition of methanol, ethanol, 2-propanol, and 2-butanol is investigated. The potential of each alcohol for the production of H2 and other relevant products in the presence of a catalyst is studied. All the alcohols studied show some decomposition activity below 200ðC which increased with increasing temperature. In all cases, high selectivity towards H2 formation is observed. With the exception of methanol, all alcohol conversion reactions lead to catalyst deactivation at high temperatures (T >250ðC for 2-propanol and 2-butanol, T >325ðC for ethanol) due to carbon poisoning. However, long-term catalyst deactivation can be avoided by optimizing reaction conditions such as operating temperature. In addition, the performance of Pt/γ-Al2O3 is evaluated in the oxidation of 2-propanol. Pt nanoclusters of similar size (~1 nm diameter) but different structure (shape) were found to display distinctively different catalytic properties. All the systems studied achieve high conversion (~ 90%) below 100ðC. However, flatter particles display a lower reaction onset temperature, demonstrating superior catalytic performance. Acetone, CO2, and water are generated as products indicating that both partial and complete oxidation are taking place. A number of techniques including AFM, XPS, TEM, HAADF-TEM, XAFS as well as packed-bed reactor experiments were used for sample characterization and evaluation of catalytic performance.
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Date Issued
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2010
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Identifier
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CFE0003081, ucf:48319
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0003081
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Title
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Predictive Modeling of Functional Materials for Catalytic and Sensor Applications.
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Creator
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Rawal, Takat, Rahman, Talat, Chang, Zenghu, Leuenberger, Michael, Zou, Shengli, University of Central Florida
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Abstract / Description
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The research conducted in my dissertation focuses on theoretical and computational studies of the electronic and geometrical structures, and the catalytic and optical properties of functional materials in the form of nano-structures, extended surfaces, two-dimensional systems and hybrid structures. The fundamental aspect of my research is to predict nanomaterial properties through ab-initio calculations using methods such as quantum mechanical density functional theory (DFT) and kinetic Monte...
Show moreThe research conducted in my dissertation focuses on theoretical and computational studies of the electronic and geometrical structures, and the catalytic and optical properties of functional materials in the form of nano-structures, extended surfaces, two-dimensional systems and hybrid structures. The fundamental aspect of my research is to predict nanomaterial properties through ab-initio calculations using methods such as quantum mechanical density functional theory (DFT) and kinetic Monte Carlo simulation, which help rationalize experimental observations, and ultimately lead to the rational design of materials for the electronic and energy-related applications. Focusing on the popular single-layer MoS2, I first show how its hybrid structure with 29-atom transition metal nanoparticles (M29 where M=Cu, Ag, and Au) can lead to composite catalysts suitable for oxidation reactions. Interestingly, the effect is found to be most pronounced for Au29 when MoS2 is defect-laden (S vacancy row). Second, I show that defect-laden MoS2 can be functionalized either by deposited Au nanoparticles or when supported on Cu(111) to serve as a cost-effective catalyst for methanol synthesis via CO hydrogenation reactions. The charge transfer and electronic structural changes in these sub systems lead to the presence of 'frontier' states near the Fermi level, making the systems catalytically active. Next, in the emerging area of single metal atom catalysis, I provide rationale for the viability of single Pd sites stabilized on ZnO(101 ?0) as the active sites for methanol partial oxidation, an important reaction for the production of H2. We trace its excellent activity to the modified electronic structure of the single Pd site as well as neighboring Zn cationic sites. With the DFT-calculated activation energy barriers for a large set of reactions, we perform ab-initio kMC simulations to determine the selectivity of the products (CO2 and H2). These findings offer an opportunity for maximizing the efficiency of precious metal atoms, and optimizing their activity and selectivity (for desired products). In related work on extended surfaces while trying to explain the Scanning Tunneling Microscopy images observed by our experimental collaborators, I discovered a new mechanism involved in the process of Ag vacancy formation on Ag(110), in the presence of O atoms which leads to the reconstruction and eventually oxidation of the Ag surface. In a similar vein, I was able to propose a mechanism for the orange photoluminescence (PL), observed by our experimental collaborators, of a coupled system of benzylpiperazine (BZP) molecule and iodine on a copper surface. Our results show that the adsorbed BZP and iodine play complimentary roles in producing the PL in the visible range. Upon photo-excitation of the BZP-I/CuI(111) system, excited electrons are transferred into the conduction band (CB) of CuI, and holes are trapped by the adatoms. The relaxation of holes into BZP HOMO is facilitated by its realignment. Relaxed holes subsequently recombine with excited electrons in the CB of the CuI film, thus producing a luminescence peak at ~2.1 eV. These results can be useful for forensic applications in detecting illicit substances.
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Date Issued
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2017
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Identifier
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CFE0006783, ucf:51813
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0006783
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Title
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Catalytically Enhanced Heterogeneous Combustion of methane.
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Creator
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Terracciano, Anthony, Orlovskaya, Nina, Vasu Sumathi, Subith, Chow, Louis, Kassab, Alain, University of Central Florida
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Abstract / Description
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Heterogeneous combustion is an advanced internal combustion technique, which enables heat recuperation within the flame by utilizing a highly porous ceramic media as a regenerator. Heat released within the gas phase convectively transfers to the solid media. This heat within the solid media then travels towards the inlet, enabling reactant preheating. Such heat redistribution enables stable burning of both ultra-lean fuel/air mixtures, forming a more diffuse flame through the combustion...
Show moreHeterogeneous combustion is an advanced internal combustion technique, which enables heat recuperation within the flame by utilizing a highly porous ceramic media as a regenerator. Heat released within the gas phase convectively transfers to the solid media. This heat within the solid media then travels towards the inlet, enabling reactant preheating. Such heat redistribution enables stable burning of both ultra-lean fuel/air mixtures, forming a more diffuse flame through the combustion chamber, and results in reduced pollutant formation. To further enhance heterogeneous combustion, the ceramic media can be coated with catalytically active materials, which facilitates surface based chemical reactions that could occur in parallel with gas phase reactions.Within this work, a flow stabilized heterogeneous combustor was designed and developed consisting of a reactant delivery nozzle, combustion chamber, and external instrumentation. The reactant delivery nozzle enables the combustor to operate on mixtures of air, liquid fuel, and gaseous fuel. Although this combustor has high fuel flexibility, only gaseous methane was used within the presented experiments. Within the reactant delivery nozzle, reactants flow through a tube mixer, and a homogeneous gaseous mixture is delivered to the combustion chamber. ?-alumina (?-Al2O3), magnesia stabilized zirconia (MgO-ZrO2), or silicon carbide (SiC) was used as the material for the porous media. Measurement techniques which were incorporated in the combustor include an array of axially mounted thermocouples, an external microphone, an external CCD camera, and a gas chromatograph with thermal conductivity detector which enable temperature measurements, acoustic spectroscopy, characterization of thermal radiative emissions, and composition analysis of exhaust gasses, respectively. Before evaluation of the various solid media in the combustion chamber the substrates and catalysts were characterized using X-ray diffraction, X-ray fluorescence, scanning electron microscopy and energy dispersive spectroscopy. MgO-ZrO2 porous media was found to outperform both ?-Al2O3 and SiC matrices, as it was established that higher temperatures for a given equivalence ratio were achieved when the flame was contained within a MgO-ZrO2 matrix. This was explained by the presence of oxygen vacancies within the MgO doped ZrO2 fluorite lattice which facilitated catalytic reactions. Several catalyst compositions were evaluated to promote combustion within a MgO-ZrO2 matrix even further.Catalysts such as: Pd enhanced WC, ZrB2, Ce0.80Gd0.20O1.90, LaCoO3, La0.80Ca0.20CoO3, La0.75Sr0.25Fe0.95Ru0.05O3, and La0.75Sr0.25Cr0.95Ru0.05O3; were evaluated under lean fuel/air mixtures. LaCoO3 outperformed all other catalysts, by enabling the highest temperatures within the combustion chamber, followed by Ce0.80Gd0.20O1.90. Both LaCoO3 and Ce0.80Gd0.20O1.90 enabled a flame to exist at ?=0.45(&)#177;0.02, however LaCoO3 caused the flame to be much more stable. Furthermore, it was discovered that the coating of MgO-ZrO2 with LaCoO3 significantly enhanced the total emissive power of the combustion chamber. In this work as acoustic spectroscopy was used to characterize heterogeneous combustion for the first time. It was found that there is a dependence of acoustic emission n the equivalence ratio and flame position regardless of media and catalyst combination. It was also found that when different catalysts were used, the acoustic tones produced during combustion at fixed reactant flow rates were distinct
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Date Issued
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2016
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Identifier
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CFE0006508, ucf:51364
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Format
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Document (PDF)
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PURL
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http://purl.flvc.org/ucf/fd/CFE0006508