No description available.

Mesoporous aggregates of nanocrystalline zeolites with MFI and BEA frameworks have been synthesized using a one-pot and single structure directing agent method. The effect of different reaction conditions, such as temperature, time, pH and water content, on the particle size, surface area and mesopore volume has been studied. Nanocrystalline and mesoporous ZSM-5, β and Y zeolites were modified with different transition metals and the resulting single- and double metal containing catalyst materials were characterized. Nanocrystalline Silicalite-1 zeolite samples with varying particle size were functionalized with different organosilane groups and the cytotoxic activity of the zeolite nanocrystals was studied as a function of particle size, concentration, organic functional group type, as well as the type of cell line. Framework stability of nanocrystalline NaY zeolite was tested under different pH conditions. The synthesized zeolites used in this work were characterized using a variety of physicochemical methods, including powder X-ray diffraction, Solid State NMR, nitrogen sorption, electron microscopy, Inductively Coupled Plasma - Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy.

Silica is one of the most abundant elements on the planet, has flexible bonding properties and generally excellent stability. Because of these properties, silica has been a vital component in technologies ranging from ancient glassware to modern supercomputers. Silica is able to form a wide range of materials both alone and as a component of larger material frameworks. Porous silica based nanomaterials are rapidly growing in importance because of their many applications in a wide variety of fields. This thesis focuses on the synthesis of silica based porous nanomaterials: nanocrystalline zeolites, mesoporous silica nanoparticles, and iron oxide core/shell nanocomposites. The synthetic conditions of these materials were varied in order to maximize efficiency, minimize environmental impact, and produce high quality material with far reaching potential applications. The materials were characterized by physicochemical techniques including Transmission Electron Microscopy, Dynamic Light Scattering, Powder X-Ray Diffraction, Solid State NMR, and Nitrogen Adsorption Isotherms. The materials were evaluated and conditions were controlled to produce high yields of quality nanomaterials and hypothesize methods for further synthetic control. The products will be used in studies involving nanoparticle toxicity, environmental remediation, and drug delivery.

Zeolites ZSM-5 (SiO2/Al2O3=30~280) and Y(SiO2/Al2O3=5.2~80) are bound with silica gel (Ludox HS-40 and Ludox AS-40) and alumina (γ- Al2O3 and boehmite) by different binding methods, namely, gel-mixing, powder-mixing and powder-wet-mixing methods. The acidities of the bound catalysts and the zeolite powder are determined by NH3-TPD and FTIR. The textures of these catalysts are analyzed on a BET machine with nitrogen as a probe molecule. The micropore surface area and micropore volume are determined by t-plot method. Micropore volume distribution is determined by Horvath-Kawazoe approach with a cylindrical pore model. Mesopore volume distribution is determined by BJH method from the nitrogen desorption isotherm. Silica from the binder may react with extra-framework alumina in zeolites to form a new protonic acid. SiO2-bound catalysts have less strong acidity, Bronsted acidity and Lewis acidity than the zeolite powder. Also, the strength of strong acid sites of the zeolites is reduced when silica is embedded. Micropore surface area and micropore volume are reduced by about 19% and 18%, respectively, indicating some micropores of ZSM-5 are blocked on binding with silica. SiO2-bound ZSM-5 catalysts have less catalytic activity for butane transformation (cracking and disproportionation) and ethylene oligomerization than ZSM-5 powder. When alumina is used as a binder, both the total acid sites and Lewis acid sites are increased. Micropore surface area and micropore volume of ZSM-5 powder are reduced by 26% and 23%, respectively, indicating some micropores of ZSM-5 are blocked by the alumina binder. Alumina-bound catalysts showed a lower activity for butane transformation and ethylene oligomerization than ZSM-5 powder. Alkaline metals content in the binder is a crucial factor that influences the acidity of a bound catalyst. The metal cations neutralize more selectively Bronsted acid sites than Lewis acid sites. Alkaline metal cations in the binder and micropore blockage cause the bound catalysts to have a lower catalytic activity than the zeolite powder.

Water is a continuous source of fascination to scientist because of its many counterintuitive low-temperature properties. Although the stable from of water at low temperature is crystalline, liquid water can also exist below the melting point. Many people study the interesting phenomenon of water at low temperature and it is found that two critical points may even coexist in a single component liquid [1]. The other properties of water, like melting point, viscosity, compressibility, self-diffusion constant have also been studied below low temperature [2-4]. Now, we want to take the advantage of the equipment we have in our laboratory to measure the temperature dependence of Cp of water confined in different scale of nano-pores. This is also the beginning for people to study the thermodynamic properties of water confined in nano-pores. In addition, I have learned a lot, such as to understand LabView graphical programming language, the skill to measure AC specific heat, DSC specific heat, and to set up TGA. It will be helpful for me in the future, I think.

Zeolites ZSM-5 (SiO2/Al2O3=30~280) and Y(SiO2/Al2O3=5.2~80) are bound with silica gel (Ludox HS-40 and Ludox AS-40) and alumina (γ- Al2O3 and boehmite) by different binding methods, namely, gel-mixing, powder-mixing and powder-wet-mixing methods. The acidities of the bound catalysts and the zeolite powder are determined by NH3-TPD and FTIR. The textures of these catalysts are analyzed on a BET machine with nitrogen as a probe molecule. The micropore surface area and micropore volume are determined by t-plot method. Micropore volume distribution is determined by Horvath-Kawazoe approach with a cylindrical pore model. Mesopore volume distribution is determined by BJH method from the nitrogen desorption isotherm. Silica from the binder may react with extra-framework alumina in zeolites to form a new protonic acid. SiO2-bound catalysts have less strong acidity, Bronsted acidity and Lewis acidity than the zeolite powder. Also, the strength of strong acid sites of the zeolites is reduced when silica is embedded. Micropore surface area and micropore volume are reduced by about 19% and 18%, respectively, indicating some micropores of ZSM-5 are blocked on binding with silica. SiO2-bound ZSM-5 catalysts have less catalytic activity for butane transformation (cracking and disproportionation) and ethylene oligomerization than ZSM-5 powder. When alumina is used as a binder, both the total acid sites and Lewis acid sites are increased. Micropore surface area and micropore volume of ZSM-5 powder are reduced by 26% and 23%, respectively, indicating some micropores of ZSM-5 are blocked by the alumina binder. Alumina-bound catalysts showed a lower activity for butane transformation and ethylene oligomerization than ZSM-5 powder. Alkaline metals content in the binder is a crucial factor that influences the acidity of a bound catalyst. The metal cations neutralize more selectively Bronsted acid sites than Lewis acid sites. Alkaline metal cations in the binder and micropore blockage cause the bound catalysts to have a lower catalytic activity than the zeolite powder.

No description available.

The separation characteristics of binary alcohol-water mixtures were studied overa wide range of feed concentration and temperature using polymeric and zeoliticpervaporation membranes. For the hydrophilic PVA membrane, the total flux (at 55 0C)for the ethanol-water system decreased from 0.45 to 0.05 kg/m2/hr as the feed ethanolconcentration was increased from 30 to 95 wt. %. The separation factor (water/ethanol)was found to increase by about 100 times for the same range of concentration. TheUNIQUAC theory was used to predict the activity of binary alcohol-water mixtures in thePVA membrane. The UNIQUAC theory successfully takes into account the nonidealitiespresent in the alcohol/water-PVA membrane system. The transport of waterand alcohol species through the PVA membrane was modeled using the UNIQUACtheory in conjunction with the conventional activity driving force model. Using themodel and the experimental pervaporation data, the diffusivity correlations andconcentration profiles for various species through the membrane were developed. Basedon the developed diffusivity correlations, the water and alcohol fluxes through the PVAmembrane were predicted at 80 ??C.Experiments were also conducted on the water selective zeolite (type NaA)membrane using various alcohol-water mixtures and with dimethylformamide-watermixture over a wide range of temperatures (25 to 70 ??C) and solvent concentrations (0 -100 wt. %). The total flux for the ethanol-water mixture was found to decrease from 2 to0.05 kg/m2/hr at 60 ??C as the feed ethanol concentration was increased from 0 to 100 wt.%. Both, the water to ethanol and water to isopropanol separation factors were observedto lie between 1000 and 5000 over a wide range of solvent concentrations. The Maxwell-Stefan theory was used to model the permeation of water through zeolite NaAmembranes. The precise micropore structure of the zeolite cage helps in a partialmolecular sieving of the large solvent molecules leading to high separation factors. Thezeolite membrane active layer may contain certain non-zeolitic interstitial pores withpreferential water sorption. A high degree of hydrophilicity of the zeolite membrane issuggested from a pure water sorption value of 0.6 gm/gm zeolite. The detailedinterpretation of this result, however, requires consideration of both true zeoliticmicrocavity uptake as well as interstitially held water between crystallites. The use ofpervaporation for volume reduction and solvent recovery applications in thepharmaceutical industry has been demonstrated.

Thesis (M.S.)--Villanova University, 2007. / Chemistry Dept. Includes bibliographical references.

Thesis (Ph.D.)--University of Delaware, 2007. / Principal faculty advisors: Jingguang G. Chen and Raul F. Lobo, Dept. of Chemical Engineering. Includes bibliographical references.