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Carbon Monoxide Oxidation on Nanoparticle Catalysts and Gas Phase Reactions of Small Molecules and Volatile Organics with Metal CationsSaoud, Khaled Mohammad Eqab 01 January 2005 (has links)
This dissertation demonstrates the application of a vapor phase method to synthesize supported and unsupported nanoparticle catalysts for CO oxidation. The method is based on the Laser Vaporization/Controlled Condensation (LVCC) technique. The first part of this dissertation presents the vapor phase synthesis and characterization of gold nanoparticles supported on a variety of oxide supports such as CeO2, TiO2, CuO and MgO.The results indicate that Au nanoparticles supported on CeO2 exhibit higher catalytic activity than Au supported on other oxides. The high activity of the Au/CeO2 catalyst is attributed to the strong interaction of Au with CeO2. The results also indicate that 5% Au loading on CeO2 has higher activity than 2% Au or 10% Au. When comparing the catalytic activity of Au/CeO2 prepared by physical (LVCC) and chemical (deposition-precipitation)methods, it was found that the catalytic activity is higher for Au/CeO2 prepared by the deposition-precipitation method.The effect of alloying Au and Cu nanoparticles on the catalytic activity for low temperature CO oxidation was also investigated. The unsupported Au-Cu alloy nanoparticle catalyst exhibits higher catalytic activity than the activities of the individualcomponents and their physical mixtures. The XRD data of Au-Cu alloy taken after the catalysis test indicates the formation of CuO within the bimetallic nanoparticles, whichimproves the catalytic activity of Au-Cu alloy nanoparticle.The second part of this dissertation investigates the gas phase reactions of Au+ and Cu+ with CO, O2 and H2O molecules using the Laser Vaporization ionization, High-Pressure Mass Spectrometry (LVI-HPMS) technique. The gas phase reactions resulting from the interactions of Au+ with CO and O2 molecules are investigated. Although multiple additions of CO and O2 molecules on Au+ have been observed at room temperature, no evidence was found of the production of CO2. This is attributed to the presence of water molecules which effectively replace the oxygen molecules on Au+ at room temperature.Finally, the role of the metal cations Au+ and Cu+ in initiating the gas phase polymerization of butadiene and isoprene vapors was investigated.
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Synthesis and Transformation of AuCu Intermetallic NanoparticlesSinha, Shyam Kanta January 2013 (has links) (PDF)
Investigations on size dependent phase stability and transformations in isolated nanoparticles have gained momentum in recent times. Size dependent phase stability generates size specific particle microstructure which consequently yields size specific functionality. One important prerequisite for conducting studies on nanoparticles is their synthesis. A substantial amount of research effort has therefore been focused on devising methodologies for synthesizing nanoparticles with controlled shapes and sizes. The present thesis deals with both these two aspects: (a) synthesis of nanoparticles and (b) phase transformations in nanoparticles. The system chosen in this study is AuCu intermetallic nanoparticles. The choice of AuCu nanoparticle was due to the fact that the literature contains abundance of structural and thermodynamic data on Au–Cu system which makes it a model system for investigating size dependence of phase transformations. With respect to synthesis, the present thesis provides methodologies for synthesizing alloyed Au–Cu nanoparticles of different sizes, Au–Cu nano-chain network structures and uniform Au–Cu2S hybrid nanoparticles. For every type, results are obtained from a detailed investigation of their formation mechanisms which are also presented in the thesis. With respect to phase transformation, the thesis presents results on the size dependence of fcc to L10 transformation onset in Au–Cu nanoparticles under isothermal annealing conditions.
The present thesis is divided into eight chapters. A summary of results and key conclusions of work presented in each chapter are as follows. The ‘introduction’ chapter (chapter I) describes the organization of the thesis. Chapter II (literature study) presents a review of the research work reported in the literature on the various methodologies used for synthesizing Au–Cu based nanoparticles of different shapes and sizes and on ordering transformation in AuCu nanoparticles. The chapter also presents a brief discussion on the reaction variables that control the process of nucleation and growth of the nanoparticles in solution. Chapter III titled ‘experimental details and instrumentation’ describes the synthesis procedures that were used for producing various nanoparticles in the present work. The chapter also briefly describes the various characterization techniques that were used to investigate the nanoparticles.
The fourth chapter titled ‘synthesis and mechanistic study of different sizes of AuCu nanoparticles’ provides two different methodologies for synthesis, referred as ‘two-stage process’ and ‘two-step process’ that have been used for producing alloyed AuCu nanoparticles of different sizes (5, 7, 10, 14, 17, 25 nm). The ‘two-stage’ process involved sequential reduction of Au and Cu precursors in a one pot synthesis process. Whereas, the ‘two-step’ process involved a two-pot synthesis in which separately synthesized Au nanoparticles were coated with Cu to generate alloyed AuCu nanoparticles. In the two-stage synthesis process it was observed that by changing the total surfactant-to-metal precursor molar ratio, sizes of the alloyed AuCu nanoparticles can be varied. ‘Total surfactants’ here include equal molar amounts of oleic acid and oleylamine surfactants. Interestingly, it was observed that there exists a limitation with respect to the minimum nanoparticle size that can be achieved by using the two-stage process. The minimum AuCu nanoparticle size achieved using the two-stage synthesis process was 14 nm. Mechanism of formation of AuCu nanoparticles in the two-stage synthesis process was investigated to find out the reason for this size limitation and also to determine how the synthesis process can be engineered to synthesize alloyed AuCu nanoparticles with smaller (<14nm) sizes. Studies to evaluate mechanism of synthesis were conducted by investigating phase and size of nanoparticles present in the reaction mixture extracted at various stages of the synthesis process. Their studies revealed that (a) the nanoparticle formation mechanism in the two-stage synthesis process involves initial formation of Au nanoparticles followed by a heterogeneous nucleation and diffusion of Cu atoms into these Au rich seeds to form Au–Cu intermetallic nanoparticles and (b) by increasing the relative molar amount of the oleylamine surfactant, size of the initial Au seed nanoparticles can be further reduced from the minimum size that can be achieved in the case when equal molar amounts of oleylamine and oleic acid surfactants are used. The information obtained from the mechanistic study was then utilized to design the two-step synthesis process. In the two-step process, Au nanoparticles were synthesized in a reaction mixture containing only the oleylamine surfactant. Use of only oleylamine resulted in production of pure Au nanoparticles with sizes that were well below 10 nm. These Au nanoparticles were washed and dispersed in a solution containing Cu precursor. Introduction of a reducing agent into this reaction mixture led to the heterogeneous nucleation of Cu onto the Au seed particles and their subsequent diffusion into them to form alloyed AuCu nanoparticles with sizes of ~5, 7 and 10 nm. The study present in this chapter essentially signified that the surfactants used in the reaction mixture not only prevent nanoparticles from agglomerating in the final dispersion but also control their nucleation and growth and therefore can be used as a tool to tune nanoparticle sizes.
The fifth chapter titled ‘size dependent onset of FCC-to-L10 transformations in AuCu alloy nanoparticles’ illustrates the effect of AuCu nanoparticle size on the onset of ordering under isothermal annealing conditions. Nanoparticles in this study were annealed in-situ in a transmission electron microscope. Samples were prepared by drop drying a highly dilute dispersion of as-synthesized nanoparticles onto an electron transparent TEM grid. Nanoparticles sitting on the TEM grid were well separated from each other to minimize particle sintering during the annealing operation. It was however observed that during the isothermal annealing, particle coarsening due to atomic diffusion was appreciable for 5 nm particles but negligible for 7 and 10 nm particles. Therefore for this study only 7 nm and 10 nm sized particles were considered. Onset of ordering was determined from the time when first sign of the diffraction spot, corresponding to the ordered phase, appears in the selected area electron diffraction pattern from a region containing large number of AuCu nanoparticles. Through a series of isothermal experiments it was observed that the time for onset of ordering increased with decrease in size of the nanoparticles. It is speculated that the delay in onset of ordering may be due to the fact that with a decrease in nanoparticle size the probability of a nanoparticle containing a fluctuation that shall generate a thermodynamically stable nuclei of the ordered phase decreases. A sharp interface between the ordered and the disordered phase inside the particle was also observed which suggested that the ordering transformation in as-synthesized fcc AuCu nanoparticles is a first order transformation.
The sixth chapter titled ‘synthesis and characterization of Au1-xCux–Cu2S hybrid nanostructures: morphology control by reaction engineering’ provides a modified polyol method based synthesis strategy for producing uniform Au–Cu2S hybrid nanoparticles. Detailed compositional and structural characterization revealed that the hybrid nanoparticles are composed of cube shaped Au-rich, Au–Cu solid solution phase and hemispherical shaped Cu2S phase. Interestingly, the hemispherical Cu2S phase was attached to only one facet of the cube shaped phase. A study on the formation mechanism of hybrid nanoparticles was also conducted by characterizing specimens extracted from the reaction mixture at different stages of the synthesis process. The study revealed that the mechanism of formation of hybrid nanoparticles involved initial formation of isolated cube shaped pure Au nanoparticles and Cu–thiolate complex with a sheet morphology. With increase in time at 180°C, the Cu–thiolate complex decomposed and one part of the Cu atoms that were produced from the decomposition were utilized in forming the spherical Cu2S and other part diffused into the Au nanoparticles to form Au–Cu solid solution phase. The chapter also presents a study on the effect of dodecanethiol (DDT) on achieving the hemisphere-on-cube hybrid morphology. In this study it is illustrated that an optimum concentration of dodecanethiol is required both for achieving size and morphological uniformity of the participating phases and for their attachment to form a hybrid nanoparticle.
The seventh chapter titled ‘synthesis of Au–Cu nano-chains network and effect of temperature on morphological evolution’ provides methodology for synthesizing fcc Au– Cu nano-chain network structures using polyvinylprrolidone (PVP) surfactant. It was observed that with increase in the molar amount of PVP in the reaction mixture, morphology of the as-synthesized product gradually changed from isolated nanoparticles to branched nano-chain like. The nano-chains contained twins which indicated an absence of continuous growth and possibility of growth by oriented attachment of initially formed Au–Cu nanoparticles. Both in-situ and ex-situ annealing of the nano-chains led to their decomposition into isolated nanoparticles of varying sizes. Annealing also caused fcc-to¬L10 phase transformation. Investigation of the wave length of perturbation leading to breaking of a nano-chain into particles indicated that the surface energy anisotropy affects the splitting of nano-chain network structure into nano-sized particles.
The thesis ends with a last chapter where we have presented possible future extension of current work.
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