Seong Huh

Tuning of particle morphology and pore properties in mesoporous silicas with multiple organic functional groups

A synthetic method has been developed that can control both multifunctionalization and morphology of the mesoporous organic-inorganic hybrid materials by introducing different molar ratios of organoalkoxysilane precursors to a base-catalyzed co-condensation of silicate.

Hyperpolarized 129Xe NMR investigation of multifunctional organic/inorganic hybrid mesoporous silica materials

An extensive study has been made on a series of multifunctional mesoporous silica materials, prepared by introducing two different organoalkoxysilanes, namely 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEPTMS) and 3-cyanopropyltriethoxysilane (CPTES) during the base-catalyzed condensation of tetraethoxysilane (TEOS), using the variable-temperature (VT) hyperpolarized (HP) 129Xe NMR technique. VT HP-129Xe NMR chemical shift measurements of adsorbed xenon revealed that surface properties as well as functionality of these AEP/CP-functionalized microparticles (MP) could be controlled by varying the AEPTMS/CPTES ratio in the starting solution during synthesis. Additional chemical shift contribution due to Xe-moiety interactions was observed for monofunctional AEP-MP and CP-MP as well as for bifunctional AEP/CP-MP samples. In particular, unlike CP-MP that has a shorter organic backbone on the silica surface, the amino groups in the AEP chain tends to interact with the silanol groups on the silica surface causing backbone bending and hence formation of secondary pores in AEP-MP, as indicated by additional shoulder peak at lower field in the room-temperature 129Xe NMR spectrum. The exchange processes of xenon in different adsorption regions were also verified by 2D EXSY HP-129Xe NMR spectroscopy. It is also found that subsequent removal of functional moieties by calcination treatment tends to result in a more severe surface roughness on the pore walls in bifunctional samples compared to monofunctional ones. The effect of hydrophobicity/hydrophilicity of the organoalkoxysilanes on the formation, pore structure and surface property of these functionalized mesoporous silica materials are also discussed.

Aqua­[η1-di­hydro­bis(1,2,4-triazolyl)­borato](5,10,15,20-meso-tetraphenyl­porphyrinato-κ4N)­manganese(III) monohydrate

The crystal structure of the title compound, [Mn(TPP)(η1-H2Btz2)(H2O)]·H2O [where H2Btz = dihydrobis(1,2,4-triazolyl)xadborate, C4H6BN6, and TPP = tetraxadphenylxadporphyrin, C44H20N4], contains a singly coordinated H2Btz2. The TPP ligand is highly distorted even though the coordination environment around MnIII has regular octahedral geometry. Both coordinated and uncoordinated water molxadecules are involved in intermolecular hydrogen bond through O—H⋯O, O—H⋯N and O—H⋯(π-arene) interactions to form a three-dimensional network.

Morphological Control of Multifunctional Mesoporous Silica Nanomaterials for Catalysis Applications

I found an efficient method to control the morphology of the organically monofunctionalized mesoporous silica materials by introducing different types of organoalkoxysilanes in a base-catalyzed co-condensation reaction. The monofunctionalized materials exhibit different particle morphologies relative to the pure MCM-41 material. The concentration dependence of the morphology is a critical factor to determine the final particle shape. A proposed mechanism of the shape evolution is also offered. After understanding the role of organoalkoxysilanes in producing various well-shaped nanomaterials, I also obtained a series of bifunctional mesoporous silica materials with certain particle morphology. A series of bifunctional mesoporous silica nanospheres (MSNs) whose physicochemical properties was investigated via solid state NMR techniques and Cu{sup 2+} adsorption capacity tests, The ratio of two different organic groups inside of mesopores of these MSNs could be fine-tuned. These MSNs serve as a useful model system to study substrate selectivity in catalytic reactions and sorption phenomena. For example, the Cu{sup 2+} adsorption capacity of these materials was dictated by the chemical nature of the mesopores generated by the different organic functional groups. An investigation of the substrate selectivity of the bifunctionalized MSNs in a competitive nitroaldol reaction using an equimolar amount of two competing 4-nitrobenzaldehyde derivatives wasmorexa0» performed. Shape-controlled bifunctional MSNs were employed as the catalysts. The properties of the MSNs were investigated using various spectroscopic methods and electron microscopy. The more hydrophobic the surface organic groups are, the higher the ratio of hydrophobic final product. This is the first example to demonstrate the selection of substrate using physicochemical nature of the mesopore surface other than the conventional shape selection in zeolite systems. I also created a cooperative dual catalyst system that is capable of activating two different substrates in aldol reaction, Henry reaction and cyanosilylation. One catalytic group activates the nucleophile, another organic group simultaneously activates the electrophile to enhance the total reaction rate. I systematically vaned the amount of two organic groups and performed the three model reactions to compare rate enhancements.«xa0less