Abstract

Mesoporous alumina (Al2O3) in the gamma (γ) phase is widely used as a support in catalytic applications because of its high surface area, large pore volume, acid-base characteristics, and thermal stability. To improve the thermal stability of gamma alumina, dopants such as lanthanum, magnesium, zirconia, and silica are often introduced. Current laboratory-based methods for synthesizing gamma alumina generally involve 10-15 steps and/or use toxic, expensive surfactants and solvents. Industrial methods, while simpler, lack control of pore properties and surface chemistry. In contrast, we have developed an innovative solvent deficient, one-step method that is able to synthesize a wide range of pure and silica-doped aluminas with high surface areas, pore volumes from 0.3 to 1.8 cm3/g, and pore diameters from 5 to 40 nm. More significantly, our silica-doped aluminas are stable up to temperatures as high as 1300<°>C, which is 200<°>C higher than other pure and doped gamma alumina materials.The usefulness of gamma-alumina as a catalyst support is dependent on its favorable combination of textural, thermal, structural, and chemical properties, yet the relationship between structure and these other properties is still not clearly understood due to the poorly crystallized nature of the material. In particular, the mechanism by which the gamma structure is stabilized thermally by so many dopants is still not well understood. Based on our previous PDF experiments on pure and La-doped alumina, we have developed a hypothesis regarding the mechanism by which dopants increase thermal stability. To validate or refute this hypothesis, we collected PDF data on a wider range of laboratory and industrial alumina samples. Herein, we have utilized PDF analysis to study the local to intermediate-range structure of a series of our pure and silica-doped aluminas calcined at 50<°>C intervals between 50 and 1300<°>C as well as pure and silica-doped aluminas from commercial sources and other synthetic methods. This thorough study of alumina local structure will allow us to separate general trends in the local structure from idiosyncrasies based on synthetic method/conditions, and it will help us identify the structural features responsible for improved thermal stability. Having access to these PDF experiments, we have validated our current hypothesis on the nature of stabilization afforded by dopants and, more generally, developed a better understanding of the role structure plays in the properties of aluminas.

Degree

PhD

College and Department

Physical and Mathematical Sciences; Chemistry and Biochemistry

Rights

http://lib.byu.edu/about/copyright/

Date Submitted

2018-08-01

Document Type

Dissertation

Handle

http://hdl.lib.byu.edu/1877/etd10279

Keywords

mesoporous ordered and disordered alumina and doped alumina material, synthesis, solvent deficient method, crystal structure characterization, pair distribution function analysis

Language

english

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