As zeólitas são amplamente utilizadas pela indústria em diferentes processos. Nos processos relacionados à conversão térmica do carvão, as zeólitas encontram aplicação, por exemplo, como suporte de catalisadores para a Síntese de Fischer-Tropsch, ou mesmo como adsorventes de efluentes líquidos ou de gases poluentes. No entanto, a microporosidade da zeólita limita a difusão dos produtos e dos reagentes ocasionando um transporte de massa lento e um longo tempo de residência, aumentando a possibilidade de reações secundárias, formação de coque e desativação do catalisador. Uma das maneiras de superar essas limitações é a introdução de um sistema secundário de poros, através da reestruturação da rede cristalina com modeladores de estruturas ou ataques químicos básicos e ácidos nas zeólitas de modo a formar materiais hierárquicos ou mesoporosos. Neste trabalho, foram investigadas três rotas para promover a mesoporosidade em zeólitas do tipo Y. Primeiramente foi realizada a síntese da zeólita hierárquica através da modificação com líquidos iônicos. O segundo método empregado foi o processo de dessilicação, utilizando hidróxido de sódio como base e, por último, a desaluminação com ácido oxálico. As zeólitas mesoporosas foram caracterizadas através de análises de área específica (BET), distribuição de tamanho de poros (BJH), difração de raios X (DRX) e redução à temperatura programada (TPR-H2). Dentre os métodos adotados, os resultados para DRX e BET mostraram que o tratamento de dessilicação destruiu a cristalinidade da zeólita, acarretando no abandono dessa rota de investigação. A síntese com líquido iônico se mostrou eficiente para a formação de mesoporos e, conforme a distribuição de tamanho de poros, seu sistema apresentou-se ordenado de maneira hierarquizada. A desaluminação não danificou a estrutura da zeólita, porém foi obtido um aumento pouco expressivo em seu número de mesoporos. A reação de esterificação foi utilizada, como modelo, para avaliar o efeito dos mesoporos sobre a atividade catalítica da reação. A reação de esterificação ocorreu a 70°C por 1 h, utilizando ácido acético e álcoois com diferentes tamanhos de moléculas. Em comparação à zeólita de partida (CBV720 - Zeolyst), a criação da mesoporosidade na zeólita através dos líquidos iônicos resultou em um aumentou na conversão de ácido acético para os álcoois etílico (em 17,65%), isopropílico (em 8,42%) e isobutílico (em 2%). Para a zeólita mesoporosa sintetizada por desaluminação, houve um acréscimo de 10,93% e 2,11% na conversão para os álcoois etílico e isopropílico, respectivamente. Os resultados mostraram que a presença de mesoporosidade influenciou positivamente o desempenho das zeólitas Y na reação modelo de esterificação, mostrando-se um excelente mecanismo a ser aplicado para facilitar o transporte de massa nos poros da zeólita, especialmente para a síntese feita com o emprego de líquidos iônicos. / Zeolites are widely used by industry in different processes. In processes related to the thermal conversion of coal, the zeolites find application, for example, as catalyst support for the Fischer-Tropsch Synthesis, or even as adsorbents of liquid effluents or pollutant gases. However, the small pore diameter of the zeolite limits the diffusion of the products and the reactants causing slow mass transport and a long residence time that increase the possibility of secondary reactions, coke formation and catalyst deactivation. One of the ways to overcome these limitations is the introduction of a secondary pore system by restructuring the crystal lattice with structural modellers or basic chemical and acidic attacks on zeolites to form hierarchical or mesoporous materials. In this work, three routes were investigated to promote mesoporosity in Y type zeolites. First, the hierarchical zeolite was synthesized through the modification with ionic liquids. The second method used was the desilication process, using sodium hydroxide as the base and, finally, the desalumination method with oxalic acid. The mesoporous zeolites were characterized by specific surface area analysis (BET), pore size distribution (BJH), X-ray diffraction (XRD) and temperature programmed reduction (TPR-H2). Among the methods adopted, the results for XRD and BET showed that the desilication treatment destroyed the crystallinity of the zeolite, leading to the abandonment of this research route. The synthesis with ionic liquid was efficient for the formation of mesopores and, according to the pore size distribution, its system was hierarchically ordered. The desalumination did not damage the zeolite structure, but a small increase in its number of mesopores was noted. The esterification reaction was used to evaluate the effect of mesopores on the catalytic activityof the reaction. The esterification reaction occurred at 70°C for 1 h using acetic acid and alcohols with different sizes of molecules. Compared to the starting zeolite (CBV720 - Zeolyst), the creation of mesoporosity in the zeolite through the ionic liquids resulted in an increase in the conversion of acetic acid for the reaction conducted with ethyl (17.65%), isopropyl (8.42%) and isobutyl alcohols (2%). For the mesoporous zeolite synthesized by desalumination, there was an increase of 10.93% and 2.11% in the conversion to the ethyl and isopropyl alcohols, respectively. The results showed that the presence of mesoporosity positively influenced the performance of the zeolites Y in the esterification model reaction, showing an excellent mechanism to be applied to facilitate the mass transport in the zeolite pores, especially for the synthesis made with the use of ionic liquids.

Heat transfer fluids are materials responsible for heat distribution, transfer and storage. Their significance is undeniable - many technological processes cannot be carried out without using heat transfer materials (for example due to overheating). These are usually mixtures of many compounds, for example glycols, silicones or water. Today's technologies constantly require more efficient, environmentally- and economically-friendly solutions for heat transfer applications. It is necessary to know the full physicochemical characteristics to design a new heat transfer fluid (mainly density, heat capacity, viscosity and thermal conductivity). Nanofluids (mixture of a basefluid and nanoparticles) were proposed as a solution for many industrial issues due to their enhanced thermophysical properties (i.e. thermal conductivity) than pure liquids. Moreover, these enhancements exhibit unusual features which make this group of materials interesting from molecular and industrial point of view. Ionic liquids, task specific materials with tuneable properties were repeatedly recommended as heat transfer fluids due to their specific properties (mainly low vapour pressure, wide liquidus range, or non-flammability) caused by the ionic structure. A very interesting material can be obtained by mixing ionic liquids and nanoparticles where specific properties of ionic liquids are preserved, and thermophysical properties are enhanced due to nanoparticles dispersion. In this work, we investigated ionic liquid - based nanofluids from the experimental and theoretical point of view, including imidazolium-, pyrrolidinium- and phosphonium-based ionic liquids with several different anions, and multiwalled carbon nanotubes, graphite, boron nitride and mesoporous carbon as nanoparticles, and also in mixtures with water. As a final result, we assessed the molecular recognition of the thermophysical properties enhancements in ionanofluids, developed the predictive models for physical properties, compared all investigated systems to commercial heat transfer fluids. The project was supported by King Faisal University (Saudi Arabia) through a research fund from the International Cooperation and Knowledge Exchange Administration department at KFU. Cytec are thanked for the generous donation of the trihexyl(tetradecyl)phosphonium chloride sample.

In our research Hyper-Rayleigh scattering (HRS) is employed as an effective, simple investigation technique to study solutions of small molecules, pure liquids, nano-adsorbing systems and metal colloids. A set of apparatus has been built with good spectral resolution and high sensitivity to successfully measure characteristics of intensity and polarization properties of HRS. It was found that the consistency was different for pure liquid and solutions of small molecules when comparing experimental measurements of depolarized ratios and polarization patterns with theoretical expectations. This is due to the presence of both incoherent and coherent contributions to HRS in pure liquids, of which the origin of the coherent contribution is different for different pure liquids. In our results, pure liquid nitrobenzene was found to have strong coherent contribution to HRS caused by intermolecular interactions. Three different chemical compounds were used to mix with nitrobenzene to break the strong orientational correlations between molecules. Comparison between the results show different behaviors in the effectiveness in eliminating the coherent HRS signals, and the effectiveness was correlated to the molecular structures. Theory of second harmonic scattering from surface has been expanded as leading order contributions containing nonlocal electric dipole mode and local quadrupole mode, which can be exhibited in our experimental study of polarization patterns. Polarization patterns from polystyrene particles of different sizes adsorbed with different species of dyes were measured to investigate and compare with theoretical expectations. For small-size adsorbing system, measurements of polarization patterns were basically consistent with theory. However, for adsorbing system of polystyrene particles with a size of 900 nm, the polarization patterns showed discrepancies when comparing with theory, which indicated that higher order multipoles are needed in the theory. Silver and gold colloids were employed as the subject of investigation for measuring the polarization patterns of HRS. The results were found to be consistent when comparing with their extinction spectra and TEM images. We have managed to measure polarization patterns of HRS originated from surface of non-spherical colloids and the results showed that the origin of HRS can be qualitatively understood, although a more elaborated theory is needed to describe the data. / by Chen, Ji = 由有機液體以及金屬膠體產生的非線性光散射的研究 / 陳佶. / Source: Dissertation Abstracts International, Volume: 70-09, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 117-118). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307. / by Chen, Ji = You you ji ye ti yi ji jin shu jiao ti chan sheng de fei xian xing guang san she de yan jiu / Chen Ji.

Ionic liquids are organic salts with room temperature melting points. Their unique physicochemical properties make them popular choices in the fields of tribology, energy storage and production, and extractions. Previous studies show that IL’s interfacial volume, extending some nanometers from an adjacent surface, is characterized by the self-assembly of IL molecules into ordered structures. This ordering imparts unique properties which often govern the properties of ILs and affect their application in the aforementioned areas. This thesis describes research conducted to understand the behaviors and interactions of ILs at interfaces, along with investigations of bulk IL structures and transitions in the presence of water. The findings reported will help the scientific community by giving insight into the physical and chemical processes surrounding IL behavior, allowing ILs’ physicochemical properties to be more accurately tailored, via judicious synthesis, to a desired application. Major findings of this work show that the ordered interfacial region may extend up to two orders of magnitude further from the interface than previously thought. Specifically, this thesis shows several examples of reversible IL self-assembly into long-range ordered films that extend up to ~ 2 μm from a surface. This is approximately twelve times the thickness of interfacial region previously reported. Temperature controlled studies on the bulk structure of an IL at its phase transition temperatures aid in understanding the structural arrangement of molecules in the bulk fluid as a function of temperature. Spectroscopic analyses of these bulk studies and the above interfacial systems showed no similarities, indicating that the self-assembled interfacial structures are, in fact, unique. Being hygroscopic in nature, water is the most common impurity found in ILs. Water can affect IL intermolecular forces and the resulting structures in bulk fluids as well as at the interface. One of the chapter of this thesis describes these interactions, and the variably hydrated IL structures for two classes of ILs via spectroscopic and electrochemical techniques. The outcomes of this thesis will aid the community in understanding interfacial and bulk structures of ILs, as well as influences of temperature and water on these structures. The description of extended IL structures provides valuable insights into new design principles for truly task-specific ILs.

Doctor of Philosophy (PhD) / The glass-transition traverses continuously from liquid to solid behaviour, yet the role of structure in this large and gradual dynamic transition is poorly understood. This thesis presents a theoretical study of the relationship between structure and dynamics in two-dimensional glass-forming alloys, and provides new tools and real-space insight into the relationship at a microscopic level. The work is divided into two parts. Part I is concerned with the role of structure in the appearance of spatially heterogeneous dynamics in a supercooled glass-forming liquid. The isoconfigurational ensemble method is introduced as a general tool for analysing the effect that a configuration has on the subsequent particle motion, and the dynamic propensity is presented as the aspect of structural relaxation that can be directly related to microscopic variations in the structure. As the temperature is reduced, the spatial distribution of dynamic propensity becomes increasingly heterogeneous. This provides the first direct evidence that the development of spatially heterogeneous dynamics in a fragile glass-former is related to spatial variations in the structure. The individual particle motion also changes from Gaussian to non- Gaussian as the temperature is reduced, i.e. the configuration expresses its character more and more intermittently. The ability of several common measures of structure and a measure of structural ‘looseness’ to predict the spatial distribution of dynamic propensity are then tested. While the local coordination environment, local potential energy, and local free volume show some correlation with propensity, they are unable to predict its spatial variation. Simple coarse-graining does not help either. These results cast doubt on the microscopic basis of theories of the glass transition that are based purely on concepts of free volume or local potential energy. In sharp contrast, a dynamic measure of structural ‘looseness’ - an isoconfigurational single-particle Debye-Waller (DW) factor - is able to predict the spatial distribution of propensity in the supercooled liquid. This provides the first microscopic evidence for previous correlations found between short- and long-time dynamics in supercooled liquids. The spatial distribution of the DW factor changes rapidly in the supercooled liquid and suggests a picture of structural relaxation that is inconsistent with simple defect diffusion. Overall, the work presented in Part I provides a real-space description of the transition from structure-independent to structure-dependent dynamics, that is complementary to the configuration-space description provided by the energy landscape picture of the glass transition. In Part II, an investigation is presented into the effect of varying the interparticle potential on the phase behaviour of the binary soft-disc model. This represents a different approach to studying the role of structure in glass-formation, and suggests many interesting directions for future work. The structural and dynamic properties of six different systems are characterised, and some comparisons are made between them. A wide range of alloy-like structures are formed, including substitutionally ordered crystals, amorphous solids, and multiphase materials. Approximate phase diagrams show that glass-formation generally occurs between competing higher symmetry structures. This work identifies two new glass-forming systems with effective chemical ordering and substantially different short- and medium-range structure compared to the glassformer studied in Part I. These represent ideal candidates for extending the study presented in Part I. There also appears to be a close connection between quasicrystal and glass-formation in 2D via random-tiling like structures. This may help explain the experimental observation that quasicrystals sometimes vitrify on heating. The alignment of asymmetric unit cells is found to be the rate-limiting step in the crystal nucleation and growth of a substitutionally ordered crystal, and another system shows amorphous-crystal coexistence and appears highly stable to complete phase separation. The generality of these results and their implications for theoretical descriptions of the glass transition are also discussed.

This thesis focuses on liquid redox electrolytes in dye-sensitized solar cells (DSCs). A liquid redox electrolyte, as one of the key constituents in DSCs, typically consists of a redox mediator, additives and a solvent. This thesis work concerns all these three aspects of liquid electrolytes, aiming through fundamental insights to enhance the photovoltaic performances of liquid DSCs. Initial attention has been paid to the iodine concentration effects in ionic liquid (IL)-based electrolytes. It has been revealed that the higher iodine concentration required in IL-based electrolytes can be attributed to both triiodide mobility associated with the high viscosity of the IL, and chemical availability of triiodide. The concept of incompletely solvated ionic liquids (ISILs) has been introduced as a new type of electrolyte solvent for DSCs. It has been found that the photovoltaic performance of ISIL-based electrolytes can even rival that of organic solvent-based electrolytes. And most strikingly, ISIL-based electrolytes provide highly stable DSC devices under light-soaking conditions, as a result of the substantially lower vapor pressure of the ISIL system. A significant synergistic effect has been observed when both guanidinium thiocyanate and N-methylbenzimidazole are employed together in an IL-based electrolyte, exhibiting an optimal overall conversion efficiency. Tetrathiafulvalene (TTF) has been investigated as an organic iodine-free redox couple in electrolytes for DSCs. An unexpected worse performance has been observed for the TTF system, albeit it possesses a particularly attractive positive redox potential. An organic, iodine-free thiolate/disulfide system has also been adopted as a redox couple in electrolytes for organic DSCs. An impressive efficiency of 6.0% has successfully been achieved by using this thiolate/disulfide redox couple in combination with a poly (3, 4-ethylenedioxythiophene) (PEDOT) counter electrode material under full sunlight illumination (AM 1.5G, 100 mW/cm2). Such high efficiency can even rival that of its counterpart DSC using a state-of-the-art iodine-based electrolyte in the systems studied.The cation effects of lithium, sodium and guanidinium ions in liquid electrolytes for DSCs have been scrutinized. The selection of the type of cations has been found to exert quite different impacts on the conduction band edge (CB) of the TiO2 and also on the electron recombination kinetics, therefore resulting in different photovoltaic behavior. / QC 20120124

Computer simulations play a profound and fundamental role inmodern theoretical physics, chemistry and materials science. Tounderstand the complex physics of metally liquids, metals,quasicrystals and metally glasses a working model imposing thelocal and global order is needed. Experiments and theory havepredicted the local order in liquid metals to beicosahedral. The current work has been done using molecular dynamicscomputer simulations of a monatomic system using a simplepair-potential for the interactions. Two new pair-potentialshas been developed, the Zetterling-1(Z1) and Zetterling-2(Z2)potentials. They are specifically modeled to impose icosahedralorder. The basis for the development of the potentials was theold Dzugutov potential which is known to freeze into adodecagonal quasicrystal. The new Zetterling potentials have alonger interaction range and a narrower first minimum. The morenarrow first minimum will enhance the local icosahedralordering and the longer interaction range was introduced toincorporate a second maximum in the potential mimicing theFriedel oscillations found in metallic systems. These Friedeloscillations are due to the singularity which arises at theFermi surface due to the screening of the positive charge bythe electron gas. Five papers are included in the study. The first two papersare studies of icosahedral clustering in the liquid andsupercooled liquid. The simulations in Paper I was done usingthe old Dzugutov potential while the new potentials were usedin Paper II using both molecular dynamics and the Basin Hoppingalgorithm presented in Chapter 5. Paper III considers theconcept of dynamical ergodicity in the context of thesuper-cooled liquid behaviour. The simulations were made usingthe old Dzugutov potential. Paper IVr eports a moleculardynamics simulation using the Dzugutov potential undersuper-cooling. A formation of icosahedrally structured domainswith distinctly slow diffusion which grows with cooling in alow-dimensional manner and percolate around Tc, the criticaltemperature of the mode-coupling theory. A sharp slowing downof the structural relaxation relative to diffusion is observed.It is concluded that this effect cannot be accounted for by thespatial variation in atomic mobility. The low-dimensionalclustering is discussed as a possible mechanism of fragility.Paper Vin vestigates the crystallization of a simple monatomicliquid model which utilizes the Zetterling-1 potential. Thesystem forms a thermodynamically stable solid phase exhibitingcubic symmetry. Its diffraction pattern is identified as thatof γ-brass, a tetrahedrally packed crystalline structurewith 52 atoms in the unit cell. <b>Keywords:</b>simple liquids, molecular dynamics, pairpotential, icosahedral cluster.

Solvent selection is an important factor in chemical process efficiency, profitability, and environmental impact. Prediction of solvent phase behavior will allow for the identification of novel solvent systems that could offer some economic or environmental advantage. A modified cohesive energy density model is used to predict the solid-liquid-equilibria for multifunctional solids in pure and mixed solvents for rapid identification of process solvents for design of crystallization processes. Some solubility data at several temperatures are also measured to further test the general applicability of the model. Gas-expanded liquids have potential environmentally advantageous applications as pressure tunable solvents for homogeneous and heterogeneous catalytic reactions and as novel solvent media for anti-solvent crystallizations. The phase behavior of some carbon dioxide/organic binary systems is measured to provide basic process design information. Solvent selection is also an important factor in the anti-solvent precipitation of solid compounds. The influence of organic solvent on the solid-liquid equilibria for two solid pharmaceutical compounds in several carbon dioxide expanded solvents is explored. A novel solvent system is also developed that allows for homogeneous catalytic reaction and subsequent catalyst sequestration by using carbon dioxide as a miscibility switch. The fundamental biphasic solution behavior of some polar organics with water and carbon dioxide are investigated.

<p>Computer simulations play a profound and fundamental role inmodern theoretical physics, chemistry and materials science. Tounderstand the complex physics of metally liquids, metals,quasicrystals and metally glasses a working model imposing thelocal and global order is needed. Experiments and theory havepredicted the local order in liquid metals to beicosahedral.</p><p>The current work has been done using molecular dynamicscomputer simulations of a monatomic system using a simplepair-potential for the interactions. Two new pair-potentialshas been developed, the Zetterling-1(Z1) and Zetterling-2(Z2)potentials. They are specifically modeled to impose icosahedralorder. The basis for the development of the potentials was theold Dzugutov potential which is known to freeze into adodecagonal quasicrystal. The new Zetterling potentials have alonger interaction range and a narrower first minimum. The morenarrow first minimum will enhance the local icosahedralordering and the longer interaction range was introduced toincorporate a second maximum in the potential mimicing theFriedel oscillations found in metallic systems. These Friedeloscillations are due to the singularity which arises at theFermi surface due to the screening of the positive charge bythe electron gas.</p><p>Five papers are included in the study. The first two papersare studies of icosahedral clustering in the liquid andsupercooled liquid. The simulations in Paper I was done usingthe old Dzugutov potential while the new potentials were usedin Paper II using both molecular dynamics and the Basin Hoppingalgorithm presented in Chapter 5. Paper III considers theconcept of dynamical ergodicity in the context of thesuper-cooled liquid behaviour. The simulations were made usingthe old Dzugutov potential. Paper IVr eports a moleculardynamics simulation using the Dzugutov potential undersuper-cooling. A formation of icosahedrally structured domainswith distinctly slow diffusion which grows with cooling in alow-dimensional manner and percolate around Tc, the criticaltemperature of the mode-coupling theory. A sharp slowing downof the structural relaxation relative to diffusion is observed.It is concluded that this effect cannot be accounted for by thespatial variation in atomic mobility. The low-dimensionalclustering is discussed as a possible mechanism of fragility.Paper Vin vestigates the crystallization of a simple monatomicliquid model which utilizes the Zetterling-1 potential. Thesystem forms a thermodynamically stable solid phase exhibitingcubic symmetry. Its diffraction pattern is identified as thatof γ-brass, a tetrahedrally packed crystalline structurewith 52 atoms in the unit cell.</p><p><b>Keywords:</b>simple liquids, molecular dynamics, pairpotential, icosahedral cluster.</p>

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references (leaves 136-143). Also available on the Internet.