Organic – ordered mesoporous silica (OMS) hybrid materials have attracted great interest due to their potential applications for gas separations, and heterogeneous catalysis. Amine-functionalized OMS materials are active in a variety of base-catalyzed reactions. The key to successfully achieving the desired reactivity is the ability to rationally tether the targeted organic functionality onto the OMS surface. Understanding the organic-inorganic interface is crucial for rational design of heterogeneous catalysts, because the local structure and molecule dynamics are paramount in determining the reactivity of the organic groups attached to the OMS surface. This dissertation focuses on three goals that will lead to a description of the organic-OMS interface and designing hybrid catalysts: 1) Determining the dynamics of organic groups attached to the OMS surface, 2) Catalytic testing to understand how the local structure and dynamics of the organic moiety influence the catalytic properties of organic-OMS catalysts, 3) Designing more active hybrid catalysts by introducing higher loadings of organic group using dendrimer structures.
Solid-state NMR is uniquely suited for quantifying dynamics in the milli- to nano-second time scale. Deuterium (2H) NMR is a powerful tool to obtain detailed information about the dynamics or organic molecules. In this study, several simple functional groups isotopically labeled with deuterium have been attached to MCM-41 and SBA-15. The spectra display different molecular motions for different organic moieties. The results have indicated that the interactions between the functional groups and silanol groups on the surface influence the mobility of the organic fragments. Also, the porosity of the solid supports effects dynamics via confinement.
The catalytic properties of simple amine groups attached to MCM-41, containing primary, secondary, and tertiary amines have been compared in the Nitroaldol (Henry) reaction. The effects of amine identity, structure, loading, presence of surface silanols, and the substrate topology on the catalytic properties have been investigated. The dramatic decrease of the activity of amine-functionalized MCM-41 by capping the residual silanol groups with hexamethyldisilazane was ascribed to the decrease of the interactions of hydrogen bonding between the amine functional groups and surface silanols. The result was consistent with the changes of the molecular motions shown by 2H NMR measurements.
Fabricating OMS hybrid materials with high densities of organic functional groups leads to challenges in realizing uniform, catalytically active sites. Our group has immobilized melamine-based dendrimers on the surfaces of amine-functionalized SBA-15 materials by iterative synthesis procedures. The current studies in this dissertation mainly describe the catalytic properties of these dendrimers on SBA-15 and MCM-41 in the Nitroaldol (Henry) reaction, the transesterification reaction of triglycerides and methanol to synthesize methyl esters, and the cross aldol reaction between acetone and 5-hydroxymethylfurfural. The results indicate that the OMS-dendron materials have potential as solid base catalysts for a range of reactions.
| Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-2011-05-9197 |
| Date | 2011 May 1900 |
| Creators | Wang, Qingqing |
| Contributors | Shantz, Daniel F. |
| Source Sets | Texas A and M University |
| Language | en_US |
| Detected Language | English |
| Type | thesis, text |
| Format | application/pdf |
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