A prominent goal of scientists is to develop products and processes to meet the ever-growing needs of society. Today's needs include products that are economical, specialized, and made through processes with minimal impact on the environment. One such product that serves an important and widespread need is poly(bisphenol A carbonate) for its physical properties and ease of synthesis and processing. However, this polymer does not meet the growing need of being environmentally benign as production involves carcinogenic, chlorinated solvents and toxic monomers that can leach out from the polymer product. An answer to this new demand is the development of a different process for the production of polycarbonate plastics utilizing carbon dioxide and epoxides. Carbon dioxide is an attractive monomer that is cheap and nontoxic, and its utilization signifies an important contribution to counteract global greenhouse emissions. The stability of carbon dioxide has posed a significant and complex challenge towards its utilization. Epoxides are attractive since they are synthesized from a wide variety of olefins, both naturally occurring and those derived from petroleum. The exploration of catalysts to facilitate the coupling of epoxides to carbon dioxide to afford polycarbonates has been under investigation in the Darensbourg lab for fifteen years, and has lead to the development of several successful systems such as zinc bisphenoxides and chromium salens. This dissertation focuses on the development of another successful catalyst system, chromium tetramethyltetraazaannulene, and further elucidation of the mechanism by which polycarbonates are formed. Herein, aspects of the copolymerization process using this system will be discussed in detail, such as cocatalyst and pressure dependence, catalyst derivatization, and kinetic and mechanistic investigations. The end result of these investigations is the development of the most active chromium-based catalyst for the copolymerization of cyclohexene oxide and carbon dioxide and a better understanding of how the copolymer product is produced.

This study was to investigate the effect on conversion, deactivation of long-term, selectivity of product, and kinetics in deep oxidation of toluene over copper catalyst. The copper catalyst is supported on honeycomb of ceramic monolith (400 cell/inch2). The operation parameters in heterogeneous reactor were performed as follows: 1000 ppm initial concentration of toluene, temperature of reaction in ranging from 200 ¢J to 400 ¢J, 15 % of oxygen concentration, and 4000 hr-1 of space velocity. In the selection of catalyst, we decided to use 20% Cu catalyst for its high conversion, high selectivity and low cost in oxidation of toluene. The conversion of toluene in catalytic reaction was increased with the increasing both of reaction temperature and influent concentration of oxygen, and decreased with the going up of initial concentration of toluene and of space velocity. In the catalyst stability of long-term test, Cu catalysts had a good stability after 7 days reaction in heterogeneous reactor. The tests such as BET, SEM and EA were also determined to verify the stability from surface of catalyst. The kinetics of heterogeneous reactor over Cu catalyst supported on ceramic honeycomb in oxidation of toluene was found that a pseudo-first order could be described by both Power-rate law and Mars-Van Krevelen model. The apparent reaction order and activated energy were obtained in this work.

This experiment is composed of three parts: Gas sampling and analysis by Regenerative Thermal Oxidizer in the factory ¡Afabrication and screening of catalyst, and a discussion about efficiency of Catalytic Oxidation toluene by varied factors. Regarding gas sampling in the factory, we found that the transformation rate of VOCs by Regenerative Thermal Oxidizer(RTO) at operation temperature 982¢J into tolueneis 94.7%, into 2-butanone is 96.5%, into isopropyl alcohol is 95%. Among the three, toluene showed the lowest transformation rate. Regarding catalyst sampling and research, we found that metal catalyst by immersion method(immersion method) ( weight ratio of Cu:Co¡BCu¡GMn and Mn¡GCo is 1¡G1¡BPure Cu¡BPure Co and Pure Mn)and metal load(metal /molecular sieve) is 5%¡B10%. Among the twelve metal catalysts, we figured out 10% metal C-Co(1:1) is the best catalyst concerning transformation rate. Regarding the operation factors, the experiment showed¡G(1)the more the concentration of toluene¡Athe more the temporary inhibition¡Aand therefore, the transformation rate went down¡A(2)The more the speed of inhalation¡Athe time the air stayed still decreased, and a obvious decrease of transformation rate can be seen(3)the increase of oxygen concentration showed a positive effect toward transformation rate.(4)When at a higher reaction temperature, for the above mentioned three factors, the influence upon transformation rate became less. In addition, for the cost evaluation, the 10% metal Cu-Co(weight rate 1:1) catalyst we chose in our experiment is 92.79 Taiwanese Dollars for one batch of 120g and the catalyst per gram is 0.77 Taiwanese Dollars.

Abstract Ammonia (NH3) is one of valuable chemicals which is commonly used in manufacturing the fertilizer, synthetic fiber, synthetic plastics, and dynamites, and is used in the factories such as papermaking, textile mill, camera and electrical. NH3 is also a typical pollutant which is found to be emitted from industrial processes, agriculture areas and livestock farm. It causes burn damage due to the corrosion and has a long-term impact on human bronchus. This study was to investigate the performance and kinetics in oxidation of ammonia by using a method of selective catalytic oxidation (denoted by SCO) over a series catalysts of Cu/Ce . The major parameters were performed at the following conditions: initial concentration NH3 of influent in ranging from 500 ppm to 1000 ppm, temperatures ranging from 150¢J to 500¢J, oxygen content in inlet stream in ranging from 4¢Hto 20¢Hand humidity in ranging from 1¢Hto 20¢H(or an absolute humidity of 607 ppm-12136 ppm). In the first stage experiments, the purpose was to select a best catalyst, which had the great activity and highest selectivity on nitrogen. The catalysts used in this work were prepared into three types in the following: Cu/La/Ce (molar ratio: 8/1/1, 7/1/2, 7/2/1, 6/1/3, 6/2/2 and 6/3/1), Cu/La (molar ratio: 6/4, 7/3, 8/2 and 9/1) and Cu/Ce (molar ratio: 6/4, 7/3, 8/2 and 9/1); total numbers of catalysts were 14. Test results showed the molar ratio 6:4 of Cu/Ce catalyst was found to have the best activity and selectivity to convert NH3 in this work. The second stage experiments were carried to investigate the effect of parameters on conversion of NH3 over a Cu/Ce catalyst of molar ratio 6:4. The conversion of NH3 in process of SCO increased with operation conditions such as the going up of temperature, and the increasing both of oxygen content and of residence time. The lower conversion of NH3 was achieved by an increasing on initial concentration of NH3, space velocity and humidity. The third stage experiments were conducted to investigate the effect of operation period on deactivation of NH3 over the above catalyst. At constant initial concentration of NH3, oxygen content and space velocity for 30 hr continuously, we found Cu/Ce catalyst had an excellent stability in conversion of NH3. Further tests by XRD, SEM and EA were determined. The kinetics of SCO over a Cu/Ce catalyst of molar ratio 6:4 in oxidation of NH3, using differential method, was found that a pseudo-first order reaction could be described by Mars-Van Krevelend model. An equation of destruction efficiency in terms of NH3 was obtained, and a good fitting was got between the predicted and the experimental values.

The main object of this study is to explore the possibility of using metallocene catalyst and reagent toe preparation syndiotactic polystyrene (sPS) framework connected with different polymer segments. Despite its enhanced thermal stability, the stereo-regular sPS generally has poor miscibility with other conventional polymers, which substantially limits its use in commerce. Therefore, chemical modifications on sPS were attempted in this study to hopefully introduce polar chain segments into the olefinic sPS chains and to possibly vary its properties and so, its miscibility with other polymers. Here, a novel metallocene catalyst prepared from (

Abstract Ammonia is one of valuable chemicals which are commonly used in various industrial factors. It is also a typical pollutant, and has a long-term impact on human health for toxicity characteristics. This study was to investigate the performance, product selectivity and kinetics in oxidation of ammonia solution in WAO process over Cu/ACF catalyst. The operation parameters in continuous WAO process were performed as follows: initial concentration of ammonia in ranging from 200 ppm to 1000 ppm, pH at 12, velocity of influent at below 3.0 ml/min, temperature ranging from 443K to 463K and pressure at 3.0 MPa. In the experiments of catalyst selection, we decided to use 5% Cu/ACF catalyst for its high conversion and selectivity in oxidation of ammonia. A conversion of 95.42% in oxidation of ammonia was achieved under 463K and the product selectivity of N2 was raised from 53% to 85%. We found that Cu/ACF and ACF catalysts both had the good conversion and selectivity in oxidation of ammonia in WAO process. In the long-term test of catalyst stability, Cu/ACF had a bad stability after 48 hours reaction in WAO process. The tests such as XRD, SEM and EA were also determined. The kinetics of WAO over Cu/ACF catalyst in oxidation of ammonia using Power-Rate Law was presented. The apparent reaction order and activated energy were obtained.

Abstract The purpose of this study was to investigate the removal performance in oxidation of ammonia solution, synthesized concentration in range of 200 mg/l -1000 mg/l, in continuous WAO process over Cu/La/Ce catalyst. The operation parameters in WAO process were performed as follows: reaction temperature, influent velocity, initial concentration of ammonia and oxygen pressure. During the first stage WAO test, ammonia conversion only reached to 40.1% under the conditions performed as follows: initial concentration of ammonia in 400 mg/l, 12 of pH, 453 K of temperature, 3.0 MPa of total pressure and 3.0 ml/min of influent velocity. In the second stage experiments conducted by 453 K, pH 12, 3.0MPa and 400 mg/l, the ammonia conversion was above 86.2% over catalyst in WAO process. In addition, the conversion of ammonia were found to be 89%, 82.6%, 81.6% and 79.3% when the initial concentration were regulated in 200, 400, 800 and 1000 mg/l respectively; 91.4% conversion of ammonia could be obtained when temperature was raised at 473 K. The tests such as XRD, SEM, EDS, ICP-MS and EA were also determined. The kinetics of WAO over Cu/La/Ce catalyst in oxidation of ammonia solutions using Power-Rate Law was presented to calculate the apparent reaction order and activated energy.

This study was to investigate the effect on the conversion, long-term test, product selectivity and kinetics in oxidation of ammonia over copper catalyst supported on slag powder. The operation parameters in heterogeneous reactor were performed as follows: 1000 ppm initial concentration of ammonia, temperature of reaction in ranging from 100 ¢J to 500 ¢J, 10 % of oxygen concentration, and 80000hr-1 of space velocity. In the experiments of catalyst selection, we decided to use 15% Cu catalyst for its high conversion and selectivity in oxidation of ammonia. The conversion of ammonia in catalytic reaction increased with the increasing both of reaction temperature and influent concentration of oxygen but decreased with the going up of initial concentration of ammonia and of space velocity. In the long-term test of catalyst stability, Cu catalyst had a good stability after 48 hours reaction in heterogeneous reactor. The tests such as XRD, SEM and EA were also determined. The kinetics of heterogeneous reactor over Cu catalyst supported on slag powder in oxidation of ammonia was found that a pseudo-first order could be described by Mars-Van Krevelend model. The apparent reaction order and activated energy were obtained.

This dissertation is focused on understanding heterogeneous metal catalysts supported on oxides using a model catalyst system of SiO2 thin film supported metal nano-clusters. The primary technique applied to this study is scanning tunneling microscopy (STM). The most important constituent of this model catalyst system is the SiO2 thin film, as it must be thin and homogeneous enough to apply electron or ion based surface science techniques as well as STM. Ultra-thin SiO2 films were successfully synthesized on a Mo(112) single crystal. The electronic and geometric structure of the SiO2 thin film was investigated by STM combined with LEED, Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The relationship between defects on the SiO2 thin film and the nucleation and growth of metal nano-clusters was also investigated. By monitoring morphology changes during thermal annealing, it was found that the metal-support interaction is strongly dependent on the type of metal as well as on the defect density of the SiO2 thin film. Especially, it was found that oxygen vacancies and Si impurities play an important role in the formation of Pd-silicide. By substituting Ti atoms into the SiO2 thin film network, an atomically mixed TiO2-SiO2 thin film was synthesized. Furthermore, these Ti atoms play a role as heterogeneous defects, resulting in the creation of nucleation sites for Au nano-clusters. A marked increase in Au cluster density due to Ti defects was observed in STM. A TiO2-SiO2 thin film consisting of atomic Ti as well as TiOx islands was also synthesized by using higher amounts of Ti (17 %). More importantly, this oxide surface was found to have sinter resistant properties for Au nano-clusters, which are desirable in order to make highly active Au nano-clusters more stable under reaction conditions.

Before studying to increase the catalyst utilization is one way to improve the performance of a fuel cell. But because it wastes a lot of time on making the hydrophobic pillared micro structures (HMPS) process. So this study aims to develop a fast and effective manufacturing method in order to increase the reaction surface area and catalyst utilization. The experiment has used the metal mesh stamping method to make the specific structure so as to increase the reaction surface area. The size of the metal mesh was the line path 35£gm, and the net square 70£gm*70£gm. The pressure was 300kg/cm2 and 500kg/cm2 that made the stamping structure in order to increase the reaction surface area. When the reaction surface area nearly increased 27 %, the performance also nearly increased 27 %; And when the reaction surface area nearly increased 36 %, the performance also nearly increased 36 %. So the increment of its performance nearly accorded with the increment of the reaction surface area. This method has saved a lot of time in the production process. Furthermore, the catalyst loading of cathode is halved in this experiment, the performance of fuel cell have no obviously decreased or reduced by half. As a result, the utilization of catalyst is raised.