Browsing by Subject "Hybrid materials"
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Item Elucidating the organic-OMS interface and its implications for heterogeneous catalysts(2012-07-16) Wang, QingqingOrganic ? 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.Item Synthesis and characterization of electronic materials for photovoltaic applications(2010-05) Mejia, Michelle Leann; Holliday, Bradley J.; Cowley, Alan H.; Crooks, Richard M.; Dodabalapur, Ananth; Jones, Richard A.Electronic materials are of great interest for use in photovoltaics, sensors, light-emitting diodes, and molecular electronics. Hybrid Inorganic/Organic materials have been studied for device application due to their unique electronic properties. These properties result from the formation of bulk heterojunctions between inorganic (n-type) and organic (p-type) materials. However, due to incomplete pathways for charge transport and poor interfaces between materials, charge trapping and exciton recombination is often high. In an effort to alleviate these problems, we have developed an approach to fabricate bulk heterojunction materials via a seeded growth process. Electropolymerizable Schiff base complexes have been designed, synthesized, and utilized as precursors for conducting metallopolymers. The embedded metal centers are used as seed points for direct growth of size-controllable semiconductor nanoparticles within the polymer film leading to direct electronic communication between the two materials. The synthesis of CdS, CdSe, Ga₂S₃, CuInS₂, CuInSe₂, CuGaS₂, CuGaSe₂, CuGa[subscript x]In[subscript x]-₁S₂, and CuGa[subscript x]In[subscript x]-₁Se₂ has been seen through TEM and EDX. Devices have been fabricated and current studies have focused on the photovoltaic characterization of these materials which have a PCE of 0.11%. As a second but closely related area, polymers have also been studied as organic semiconductors for device applications. However they are hard to process from solution and their polymeric structure can vary. Both of these problems can be solved by using well-defined solution processable oligomers. Thiophene oligomers have been synthesized and characterized through Single Crystal X-Ray Crystallography, Four Point Probe Conductivity, and Powder Diffraction. These oligomers have a well-defined structure and are solution processable from a variety of solvents which can then be used as models to predict and study the properties of polythiophene.Item Synthesis of Novel Polypeptide-Silica Hybrid Materials through Surface-Initiated N-carboxyanhydride Polymerization(2011-08-08) Lunn, Jonathan D.There is an increasing demand for materials that are physically robust, easily recovered, and able to perform a wide variety of chemical functions. By combining hard and soft matter synergistically, organic-inorganic hybrid materials are potentially useful for a number of applications (e.g. catalysis, separations, sensing). In this respect, organic/ordered mesoporous silica (OMS) hybrids have attracted considerable attention, with an increasing emphasis on complex organic moieties achieved through multi-step reactions and polymerizations. It is on this front that we have focused our work, specifically in regard to polypeptides. Polypeptides are well suited organic components for hybrids as they provide a wide range of possible side chain chemistries (NH2, -SH, -COOH, -OH, etc.), chirality, and have conformations that are known to be responsive to external stimuli (pH, electrolytes, solvents, etc.). Our work has shown that N-carboxyanhydride chemistry offers a facile single step approach to the incorporation of dense polypeptide brushes in OMS. Modifying the initiator loading, pore size, pore topology, and monomer identity significantly impacted the properties of the obtained composites and peptide brush layers. Extending this work, a synthesis paradigm for preferentially grafting poly-L-lysine to the external and internal surfaces of SBA-15, a widely used OMS material, was developed. We observed that the pores of these hybrids could be opened and closed by the reversible swelling of the polypeptide layer. Similarly, novel bifunctional hybrids were synthesized by grafting polypeptides to the external surface of monodisperse OMS spheres that contain a thiol-functionalized core. The accessibility of the internal thiols to a fluorescent dye shows the potential of these hybrids for applications such as controlled uptake/release.