Among the new hydrogen storage materials, ammonia borane (AB) appears to be the most promising one as it has high hydrogen content, high stability, and being environmentally benign. Dehydrogenation of AB can be achieved via hydrolysis, thermolysis or methanolysis. Methanolysis of AB eliminates some drawbacks of other dehydrogenation reactions of AB. The use of colloidal and supported particles as more active catalyst than their bulky counterparts for the hydrolysis of AB implies that reducing the particle size can cause an increase in the catalytic activity as the fraction of the surface atoms increases by decreasing the particle size. Similarly, transition metal nanoclusters can be utilized as catalyst for the methanolysis of AB as well. For this purpose transition metal nanoclusters need to be stabilized to a certain extent. Actually in the catalytic application of transition metal nanoclusters one of the most important problems is the aggregation of nanoclusters into bulk metal, despite of using the best stabilizers. In this regards, the use of metal nanoclusters as catalysts in systems with confined void spaces such as inside mesoporous and microporous solids appears to be an efficient way of preventing aggregation. In this dissertation we report for the first time the use of intrazeolite rhodium(0) nanoclusters as a catalyst in the methanolysis of ammonia borane. Rhodium(0) nanoclusters could be generated in zeolite-Y by a two-step procedure: (i) incorporation of rhodium(III) cations into the zeolite-Y by ion-exchange, (ii) reduction of rhodium(III) ions within the zeolite cages by sodium borohydride in aqueous solution, followed by filtration and dehydration by heating to 550 &deg / C under 10-4 Torr. Zeolite confined rhodium(0) nanoclusters are stable enough to be isolated as solid materials and characterized by ICP-OES, XRD, SEM, EDX, HRTEM, XPS and N2 adsorption-desorption technique. The zeolite confined rhodium(0) nanoclusters are isolable, bottleable, redispersible and reusable. They are active catalyst in the methanolysis of ammonia-borane even at low temperatures. They provide exceptional catalytic activity with an average value of TOF = 380 h-1 and unprecedented lifetime with 74300 turnovers in the methanolysis of ammonia-borane at 25 &plusmn / 0.1 &deg / C. The work reported here also includes the full experimental details of previously unavailable kinetic data to determine the rate law, and activation parameters (Ea, &amp / #916 / H&amp / #8800 / and &amp / #916 / S&amp / #8800 / ) for the catalytic methanolysis of ammonia-borane.

This research had two main purposes. Firstly it aimed at showing the regulatory framework of both data protection and intellectual property in the European Union and thus making the privacy complications of Digital Rights Managements systems clear in the developed world. This research also aimed at disclosing the complications of employment of DRMs systems in developing countries. To that end Turkey&rsquo / s copyright framework has been reviewed. It was found out that DRMs systems employed in Turkey went beyond the scope of Turkish Copyright Legislation and restricted also legitimate acts which fall within the scope of fair use. DRMs also have hindered development since it restricted availability of educational and cultural works. The review of Turkey&rsquo / s Data Protection regime disclosed that the most important reason behind the non adoption of the draft law was related to the legislators&rsquo / confusion of first pillar and third pillar data protection. It was concluded that Turkey lacked a data protection policy and the lack of such a policy led to the surveillance of the people to such a degree that almost no private space is left for them. The main finding of the research was that Turkey has been one of the best markets for the employment of DRMs with its current copyright regime and lack of data protection rules. The research concluded with proposals of action concerning data protection and DRMs.

Within the broader scope of free movement of persons, free movement of workers is one of the fundamental freedoms guaranteed by the European Union (EU) law. It is one of most significant rights that are granted to the Union citizens and will be enjoyed by Turkish nationals after Turkey&rsquo / s accession the Union. In this regard, this study examines the free movement of Turkish workers in the EU within the framework of Turkey&rsquo / s EU accession process and two recent EU enlargements since 2004. Along with the legal scope of free movement of workers, transitional arrangements applied in two recent enlargements are analyzed as it could provide some foresights about such freedom with respect to Turkey&rsquo / s EU membership.

Transition metal nanoclusters are more active and selective catalysts than their bulk counterparts as the fraction of surface atoms increases with the decreasing particle size. When stabilized in organic or aqueous solutions, they can catalyze many reactions. The catalytic activity of metal nanoclusters depends on the particle size and size distribution. Particle size can be controlled by encapsulating the nanoclusters in the cavities of highly ordered porous materials such as zeolites. In this project, osmium(0) nanoclusters were formed within the void spaces of zeolite. Thus, nanoclusters of certain size were prepared as supported catalyst. Osmium(III) cations were introduced into the cavities of zeolite by ion exchange and were reduced partially or completely to form intrazeolite osmium(0) nanoclusters. The intrazeolite osmium(0) nanocusters were characterized by HRTEM, TEM, EDX, XPS, XRD, ICP-OES spectroscopic methods and N2 adsorption-desorption technique. Intrazeolite osmium(0) nanoclusters were employed as catalyst in the aerobic oxidation of alcohols in organic solution.

Sodium borohydride (NaBH4) offers a simple and safe technology for storage and on demand production of hydrogen being a promising and a feasible method for fuel cell applications. The objectives of the present study are to emphasize the role of sodium borohydride as a part of future hydrogen energy system, to investigate the kinetics of the catalytic hydrolysis reaction of NaBH4 in a batch and flow system with respect to temperature, concentration, catalyst and flow rate for flow reactor by proposing a kinetic model and finally based on kinetic analysis, to design a prototype reactor to meet the hydrogen requirement for a 100W PEM fuel cell and operate it in steady state conditions. To express hydrolysis reaction by a kinetic model, series of batch experiments was performed in a glass flask (30mL) where the following parameters were systematically changed: the solution temperature varied as 20, 30 and 50&deg / C, the NaBH4 concentration changed as 0.17, 0.23 and 0.3M, NaOH concentration varied as 0.27, 1.32 and 2.85M and catalyst amount was changed as 0.048, 0.07 and 0.1g Pt/C (ETEK&reg / ). In the kinetic model catalyst effect proposed within the rate constant. The kinetic model was purposed as: For flow reactor system, in a differential glass reactor (5mL) concentration, catalyst amount, catalyst type and flow rate was systematically analyzed at a constant temperature. For Pt/C catalyst the purposed model was: Also, for intrazeolite Co(0) nanoclusters, as a result of controlled experiments, the rate expression was found as: Based on these data prototype reactor (recycle) with internal volume of 122cm3 and storage volume of 1336 cm3 was designed, manufactured from Delrin&reg / and operated.

Principle of sustainability, as in all areas, is becoming a major issue in urban transportation planning all around the world. Urban transportation political and legal documents are statutory basis of urban transportation plans and projects and developed countries have established urban transportation political and legal documents to ensure that local governments implement plans and projects in line with the sustainability principle. In this thesis, it is intended to analyze the sufficiency of central government&rsquo / s political and legal documents on urban transportation in Turkey in realizing the sustainability of urban transportation plans and projects. For this aim, political and main legal documents of sustainable urban transportation in United States of America (USA) and United Kingdom (UK), which is accepted as one of the leaders in the world about sustainable transportation, are analyzed. Based on this analysis a checklist has been produced, highlighting headings for sustainable urban transportation that should be present in a country&rsquo / s political and legal documents in order to guide and perhaps enforce local governments. Then this checklist has been applied to Turkey to determine strengths and weaknesses of political documents and legislations in Turkey with regards to sustainable urban transportation. A comparative analysis has also been carried out with Turkey, USA and UK under three main headings which are policy documents / guidance papers for local governments, acts and laws / and nation-wide studies. As a result, strengths and weaknesses about political and legal basis of sustainable urban transportation in Turkey have been illustrated and recommendations were made for Turkey to adopt guidance papers and legislations.

This dissertation presents the preparation and characterization of rhodium(0) nanoparticles supported on hydroxyapatite, and investigation of their catalytic activity in hydrogen generation from the hydrolysis of hydrazine-borane and ammonia-borane. Rh+3 ions were impregnated on hydroxyapatite by ion-exchange / then rhodium(0) nanoparticles supported on hydroxyapatite were formed in-situ during the hydrolysis of hydrazine-borane at room temperature. The rhodium(0) nanoparticles supported on hydroxyapatite were isolated as black powders by centrifugation and characterized by ICP-OES, SEM, TEM, EDX, XRD, XPS, and N2 adsorption-desorption spectroscopy. Rhodium(0) nanoparticles supported on hydroxyapatite have a mean particle size of 2.7&plusmn / 0.7 nm. The catalytic activity of rhodium(0) nanoparticles supported on hydroxyapatite was tested separately in the hydrolysis of hydrazine-borane and ammonia-borane. The hydrolysis of hydrazine-borane was started by adding the precatalysts, Rh+3-exchanged hydroxyapatite into the aqueous solution of hydrazine-borane / whereas, the hydrolysis of ammonia-borane was initiated by adding the catalyst rhodium(0) nanoparticles supported on hydroxyapatite which have been isolated from the first run of hydrolysis of hydrazine-borane. Rhodium(0) nanoparticles supported on hydroxyapatite provide a turnover frequency value of 6700 h-1 in the hydrolysis of hydrazine-borane at room temperature. The reuse experiments reveal that these supported nanoparticles are isolable, bottlable, and redispersible in solution. Furthermore, they retain 62 % of their initial activity at the fifth run in the hydrolysis of hydrazine-borane with release of 3 equivalents hydrogen. Activity of rhodium(0) nanoparticles supported on hydroxyapatite is maintained after the redispersion of the sample and 3 equivalents hydrogen generation from the hydrolysis of ammonia-borane confirms the activity of preformed catalyst. Rhodium(0) nanoparticles supported on hydroxyapatite provide a turnover frequency value of 3990 h-1 in the hydrolysis of ammonia-borane at room temperature.

Zugl.: Bonn, Univ., Diss., 2009

L’optimització en enginyeria de processos és un àrea molt estesa que ha anat evolucionant al llarg del temps i ha passat de ser una metodologia d'interès purament acadèmic a una tecnologia que té, i que contínua tenint, gran impacte en la indústria. En aquesta tesi ens hem centrat en el desenvolupament mètodes basats en dues eines típiques d'optimització: programació matemàtica i metaheurístiques. Els objectius d'aquesta tesi són: el primer és desenvolupar una metaheuristica híbrida per a l'optimització del disseny de cadenes de subministrament, d'un sol objectiu (cost o benefici), on tots els paràmetres són coneguts a priori; el segon és desenvolupar un algorisme efectiu per a reducció d'objectius facilitant la resolució de problemes multi-objectiu; i finalment s'han implementat una sèrie de millores en el mètode de la restricció èpsilon per millorar l'eficiència en la resolució de problemes multi-objectiu. Tots els algorismes presentats han estat comparats i avaluats amb els mètodes establerts per la literatura. / La optimización en ingeniería de procesos es un área muy extensa que ha ido evolucionando a lo largo del tiempo y ha pasado de ser una metodología de interés puramente académico a una tecnología que tiene, y que continua teniendo, gran impacto en la industria. En esta tesis nos hemos centrado en el desarrollo de métodos basados en dos herramientas típicas de optimización: programación matemática y metaheurísticas. Los objetivos de esta tesis son: el primero es desarrollar una metaheuristica híbrida para la optimización del diseño de cadenas de suministro, de un solo objetivo (coste o beneficio), donde todos los parámetros son conocidos a priori; el segundo es desarrollar un algoritmo efectivo para la reducción de objetivos facilitando la resolución de problemas multi-objetivo; y finalmente se han implementado una serie de mejoras en el método de la restricción epsilon para mejorar la eficiencia en la resolución de problemas multi-objetivo. Todos los algoritmos presentados han sido comparados y evaluados con los métodos establecidos por la literatura. / Optimization has become a major area in process systems engineering. It has evolved from a methodology of academic interest into a technology that has and continues to make significant impact in industry. In this thesis we have focused on development of tools based on two standard optimization methods: mathematical programming and metaheuristics. The objectives of this thesis are: firstly, the development of a hybrid metaheuristic for optimizing the design of supply chains, single objective (cost or benefit), where all parameters are known previously; secondly, the development of an effective algorithm for objective reduction facilitating the resolution of multi-objective problems; and finally, we improved the epsilon-constraint algorithm in multi-objective optimization. All the algorithms presented have been assessed with the methods established in the literature.

Durante tres años climatológicamente diferentes (2006, 2007 y 2008), se evaluó el impacto de la añada, el vigor de la vid y la heterogeneidad del racimo sobre la composición de la uva y el vino en terruños precoces y tardíos de Cariñena y Garnacha situados en la región mediterránea cálida de la Terra Alta. Para determinar si la maduración del racimo era homogénea, sus partes distales fueron analizadas por separado. Mediante cromatografía, se identificaron los antocianos de la baya y las proantocianidinas de las semillas. El terruño tardío presentó mayor rendimiento y menor concentración de azúcares y antocianos que el precoz. En año cálido (2007), se acumularon más antocianos que en año templado (2008), pero la respuesta de cada variedad fue distinta según el vigor. Los antocianos acilados tendían a concentrarse en las bayas inferiores. En año templado, las semillas presentaron niveles altos de monómeros flavan-3-ol y baja polimerización de procianidinas, mientras que en año cálido los niveles de procianidinas también dependían del vigor. / For three climatically different years (2006, 2007 and 2008), the impact of vintage, vine vigor and bunch heterogeneity was evaluated on grape and wine composition in early and late terroirs of Carignan and Grenache, which were located in the warm Mediterranean region of Terra Alta. To determine the homogeneity of the bunch ripening, top and bottom half of the bunch were analyzed separately. Berry anthocyanins and seed proanthocyanidins were identified by chromatography. The late terroir provided higher yield and lower concentration of sugars and anthocyanins than the early terroir. In warm year (2007), anthocyanins were more concentrated than in temperate year (2008), but the response of each variety differed according to the vigor. Acylated anthocyanins tended to concentrate in the bottom berries. In temperate year, seeds had high levels of monomeric flavan-3-ol and low polymerization of procyanidins, whereas in warm year the procyanidin levels also depended on the vigor.