No description available.

Perchlorate is known to adversely affect the thyroid gland functions including iodide take up, thus perchlorate should be removed from drinking water. Bituminous coal-based activated carbon (AC) has been used for perchlorate removal in past years. Virgin carbon and carbon modified by oxidation with HNO3, NaOH and H2O2 were examined in this study for their ability to remove perchlorate by reduction or adsorption mechanisms. Surface functional groups formed on the modified AC (MAC) were examined with diffuse reflectance infrared spectrometry. Inhibition of perchlorate removal onto MAC by various anions ( - Cl , - 3 NO , and - 2 4 SO ) and solution pH (4.5, 7.2 and 10.5) were examined to characterize the MACs before an electrochemical reaction was performed. Surface functional groups were increased by oxidation. Groups that were found on the carbon include, but are not limited to lactone, quinine, carboxylate, and nitrogenoxygen groups. The effect of pH on removal of perchlorate by MAC was greatly affected by the change in the zero point charge (ZPC) induced on the carbon by modification. Virgin carbon also experienced difficulty in removing perchlorate when solution pH was above the ZPC. Anion inhibition varied with the modification process. - 3 NO inhibited perchlorate removal only by the virgin carbon. The other anions showed no major effects on the removal efficiency of perchlorate by the carbons. Electrochemical processes did not show favorable results in removal of perchlorate. The dominant mechanism of perchlorate removal during desorption tests was adsorption onto the carbon surfaces via ion exchange.

In recent years, the need for high performance power sources has increased dramatically with the proliferation of ultra-compact electronic systems for mobile communication, man-portable and versatile military equipment, and electric vehicles. Volume- and mass- based power density are two of the most important performance metrics for portable power sources, including hydrogen generating fuel reforming systems (onboard) for hydrogen fuel cells. Two innovative multifunctional reactor concepts, CO2/H2 Active Membrane Piston (CHAMP) and Direct Droplet Impingement Reactor (DDIR), are combined for the purpose of hydrogen generating fuel reforming system (onboard) for fuel cells. In CHAMP-DDIR, a liquid fuel mixture is pulse-injected onto the heated catalyst surface for rapid flash volatilization and on-the-spot reaction, and a hydrogen selective membrane is collocated with the catalyst to reduce the diffusion distance for hydrogen transport from the reaction zone to the separation site. CHAMP-DDIR allows dynamic variation of the reactor volume to optimally control the residence time and reactor conditions, such as pressure and temperature, thus improving both the reaction and separation processes. A comprehensive CHAMP-DDIR model, which couples key physical processes including 1) catalytic chemical reactions, 2) hydrogen separation/permeation at membrane, 3) liquid fuel evaporation, and 4) heat and mass transport, has been developed to investigate the behavior of this novel reactor system, aiming at maximizing the volumetric power density of hydrogen generation from methanol/water liquid fuel. The relationships between system design parameters and the rate-limiting process(es), i.e., reaction, permeation, and transport, which govern reactor output, have identified. Experimental characterization of the prototype reactor has been performed for laboratory demonstration of the concept and model validation. Both model predictions and experiments successfully demonstrate the unique practical performance improvements of CHAMP-DDIR through combining time-modulated fuel introduction and the active change of reactor volume/pressure. This work has led to a number of fundamental insights and development of engineering guidelines for design and operation of CHAMP-DDIR class of reactors, which can be extended to a broad range of fuels and diverse practical applications.

No description available.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14639号 / 工博第3107号 / 新制||工||1462(附属図書館) / 26991 / UT51-2009-D351 / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 榊 茂好, 教授 田中 庸裕, 教授 村上 正浩 / 学位規則第4条第1項該当

<p>In recent years, first principles periodic Density Functional Theory (DFT) calculation</p><p>has been used to investigate heterogeneous catalytic reactions and examine catalyst</p><p>structures as well as adsorption properties in a variety of systems. The increasing</p><p>contribution to give detailed understanding of elementary reaction mechanism is critical to</p><p>provide fundamental insights into the catalyst design. It is a link to the fundamental</p><p>knowledge and a bridge to the practical application. DFT calculations is also a powerful</p><p>tool to predict and yield promising catalysts which is time- and cost-saving in the practical</p><p>end.</p><p>Because of the recent boom in natural shale gas deposit, there is an increasing interest</p><p>in developing more efficient ways to transform light alkanes into desired and high-value</p><p>chemicals, such as propylene. Propylene is a valuable raw material in the petrochemical</p><p>application to make value-added commodities, such as plastics, paints, and fibers, etc. The</p><p>conventional cracking, steam cracking (SC) and fluid catalytic cracking (FCC), could not</p><p>meet the growing demand of propylene. Thus, it has motivated extensive research of</p><p>production technologies. On the other hand, the abundance of light alkanes extracted from</p><p>the shale gas makes on-purpose production an appealing method which is economically</p><p>competitive. Non-oxidative dehydrogenation of propane (PDH) is a one of ways to make</p><p>up the supply and solve the issue.</p><p>xiii</p><p>According to the current research and industrial work, platinum (Pt) shows promising</p><p>performance for the PDH. However, it suffered from some major drawbacks, such as</p><p>thermodynamic limitation, rapid deactivation leading to poor catalytic performance and</p><p>frequent regeneration. In addition, it is a relatively high cost noble metal. Consequently,</p><p>many efforts have been devoted to the enhancement of the catalytic performance. It was</p><p>found that the stability and the selectivity of Pt-based catalysts can be improved via</p><p>modifying its properties with transition metals as promoters.</p><p>In this thesis, DFT calculations were performed for propane dehydrogenation over</p><p>two different catalyst systems, bimetallic platinum-zinc alloy and monometallic platinum</p><p>catalysts. The work provides insights into the catalyst crystal structures, the adsorption</p><p>characteristics of diverse adsorbates as well as the energy profiles regarding to the</p><p>selectivity of the propane dehydrogenation. Bulk calculation signifies a stable tetragonal</p><p>configuration of the PtZn catalyst which is in accordance with the experimental result. The</p><p>thermodynamic stability regarding to the stability of bulk and surface alloys are studied</p><p>with the consideration of physical constrains. We have identified the thermodynamic</p><p>stability of several PtZn low-index surface facets, (101), (110), (001), (100) flat surfaces</p><p>and stepped surface (111), at certain chemical potential environmental conditions through</p><p>the surface energy phase diagram. Stoichiometric and symmetric (101) slab is</p><p>thermodynamically stable under the region of high Pt chemical potential, and the offstoichiometric</p><p>and symmetric (100 Zn-rich) slab under the low Pt chemical potential.</p><p>In this work, PtZn(101) is used as a model surface to demonstrate the effect on the</p><p>catalytic performance with zinc promotion of platinum. In comparison with Pt(111) surface,</p><p>an elimination of 3-fold Pt hollow site on PtZn(101) is of important and it leads to the</p><p>xiv</p><p>change of binding site preferences. The divalent groups (1-propenyl, 2-propenyl) change</p><p>from Pt top site on PtZn(101) to 3-fold site on Pt(111), which is because of the lack of Pt</p><p>3-fold site on alloyed surface. As for propylene, it changes from di-σ site on PtZn to 𝜋 site</p><p>on Pt. The surface reaction intermediates are found to bond more weakly on PtZn(101)</p><p>than on the Pt surface. Especially, the binding energy of propylene reduces from -1.09 to -</p><p>0.16 eV. The weaker binding strength facilitates the activity of propylene on alloyed</p><p>surfaces.</p><p>Through a complete and classic reaction network analysis, the introduction of Zn</p><p>shows an increase in the endothermicity and the energy barrier of each elementary reaction</p><p>on the alloy surface. With the consideration of entropy for kinetic under real experimental</p><p>condition, the alloying of Zn is found to lower the energy barrier for the propylene product</p><p>desorption and increases that for propylene dehydrogenation. Meanwhile, the competition</p><p>between desired C-H and undesired C-C cleavages is investigated. It is found that the</p><p>cleavage of C-H is energetically favorable than that of C-C. These positive factors</p><p>potentially lead to a high selectivity toward propylene production on PtZn(101).</p><p>Subsequently, Microkinetic modeling is performed to estimate kinetic parameters</p><p>including the reaction order, rate-determining step to build a possible reaction mechanism.</p><p>Finally, conclusions brought out about the comparison between bimetallic and</p><p>monometallic catalyst, and suggestions for future work are presented.</p>

2-Aminopyrrole-3-carboxylate derivatives are important starting materials for biologically active compounds like pyrrolotriazole, pyrrolotriazine so their synthese has great importance in the synthetic organic chemistry. There are only two methods for the synthesis of 2-aminopyrrole-3-carboxylates in the literature. Therefore, there is a great need for the design and development of a new method for the synthesis of 2-aminopyrrole-3-carboxylates. In this work, 2-aminopyrrole-3-carboxylate derivatives were synthesized starting from cyano acetic acid ethyl ester with a new method. In the first step, cyanoacetic acid ethyl ester was alkylated with bromo acetone in the presence of NaH. Then, obtained gamma-ketoester was reacted with primary amines in the presence of catalytic amount of zincpechlorate (Zn(ClO4)2). As a result, 2-aminopyrrole-3-carboxylate derivatives were obtained. Cyanoacetic acid ethyl ester was also alkylated with various bromo acetophenone derivatives in the presence of DBU (1,8-Diazabicycloundec-7-ene). As a result of these reactions, different gamma-ketoesters were obtained. The reaction of these gamma-ketoesters with primary amines in the presence of catalytic amount of Zn(ClO4)2 concluded with 2-aminopyrrole-3-carboxylate derivatives.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22663号 / 工博第4747号 / 新制||工||1742(附属図書館) / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 杉野目 道紀, 教授 村上 正浩, 教授 大江 浩一 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

Observing and studying how life forms behave, i.e., their movement, adaptability, and so on, have enabled human beings to develop new technologies or optimize existing ones. One of the more noticeable phenomena in Nature is morphogenesis. Morphogenetic processes exist in different stages of biological development, from cellular division to tissue and organ formation. It is easy to observe shape development during mophogenesis due to emerging imaging techniques. However, it is hard to understand this process due to its complex organization, and the morphogenetic responses can be induced by a variety of chemicals or mechanical stresses and are subject to the stochastic fluctuation of the environment, making it even more difficult to acquire a fundamental understanding. It is natural to think of mimicking the complex biological process using simplified synthetic approaches. Endowing synthetic protocells with the ability to control their shape and motion autonomously would enable them to perform more like a biological system, but with less complexity. Creating synthetic morphogenesis would potentially further our understanding in biological morphogenetic processes. Moreover, we can borrow some of the morphogenetic functions in engineered materials to achieve a variety of applications, including artificial tissues, self-healing materials, controlled drug delivery, manipulation of soft robots, among others. In this dissertation, we used a synthetic cellular system controlled by a reaction regulated network that imitates the genetic control as a minimal model to understand the potential mechanisms of morphogenesis. Different simulation methods were used depending on the length scales of interest in each problem. We studied the following aspects of the minimal model system: (a) catalytic reaction induced local morphological control of amphiphilic diblock copolymer vesicles; (b) non-equilibrium control over the self-assembled structures of amphiphilic surfactants; and (c) diffusiophoretic/self-diffusiophoretic motion of colloidal particles in response to the concentration gradient field. The results obtained in this thesis work will provide a valuable road-map to guide future experiments.