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Template synthesis and surface modification of metal oxides

Agarose gel was used as a template to prepare zirconium titanium mixed oxide pellets with bimodal porosity. The materials were fully characterized to assess the effect ofZr:Ti ratio on the physical properties. It was found that the metal oxide ratio had an impact on surface acidity, the number of surface hydroxyl groups, the surface area the crystallinity and the mesopore diameter. The oxides were tested for the adsorption of vanadium ions to determine which Zr mole fraction exhibited the highest loading capacity and the fastest kinetics. A comparative study demonstrated that a hierarchical pore structure had enhanced mass transport properties over a monomodal pore structure of similar Zr:Ti composition. / Three porous zirconium titanium oxides (25 mol% Zr) were synthesized using sol-gel chemistry. One of the materials was templated from agarose gel, the second was produced without the use of a template and the third was templated from stearic acid. All three materials varied in pore architecture. Surface modification was performed post-synthetically using propionic acid (a monomer), glutaric acid (a dimer) and three molecular weights of poly(acrylic acid). Higher loading within the inorganic support was obtained for the polymers than for the smaller molecules. It was found that the pore architecture had a strong bearing on the quantity of polymer incorporated into the metal oxide framework and some effect on the rate of polymer adsorption. Thus there is great value in using templates to control pore structure. The materials were subjected to irradiation with 60Co γ-rays to determine the stability of the inorganic support and the organic functionality. / Hybrid materials were prepared by coating five distinct macroporous commercial membranes with zirconium titanium oxide using sol-gel chemistry. Calcination of these templated materials produced oxide membranes which had a suite of macropore and mesopore architectures, pore volumes and surface areas. These differences in physical properties were used to conduct a fundamental study on the relationship between the mesopore size and volume and the capacity for polymer incorporation. It was found that the polymer loading capacity was highly dependent on the pore size and pore volume. As surface area increased, loading capacity decreased, indicating that much of the increased internal surface was inaccessible to the macromolecules. Thus, mesopore diameter and pore volume must be considered when designing a mesoporous solid support. / Hierarchically porous zirconium titanium oxide and carbon zirconium titanium oxide beads with adjustable meso- and macroporosity were prepared in a one-pot, engineering-friendly process. Poly(acrylonitrile) and block copolymer Pluronic F127 were used as structure directing agents. These millimeter sized spheres were fabricated through drop-wise addition of the template-metal alkoxide solution into either water or liquid nitrogen. Carbon zirconium titanium oxide beads were produced by carbonizing the beads at 550 °C in an inert atmosphere. The (carbon) zirconium titanium oxide beads were assessed for surface accessibility and adsorption rate by monitoring the adsorption of uranyl from solution. / Porous metal oxide monoliths, specifically silica, titania, zirconia and mixed oxides containing aluminum and yttrium, were prepared in a one-pot synthesis. Macroporosity was induced using the phase separation of furfuryl alcohol. These materials have a suite of mesopore and macropore structures, the domains of which can be controlled by adjusting the synthesis conditions. These conditions were studied in detail to optimize the pore interconnectivity, the monolith stability, the pore volume and the surface area.

Identiferoai:union.ndltd.org:ADTP/273058
Date January 2010
CreatorsDrisko, Glenna Lynn
Source SetsAustraliasian Digital Theses Program
LanguageEnglish
Detected LanguageEnglish
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