Copper complex immobilized in functionalized mesoporous silica nanoparticles for aromatic hydrocarbons oxidation
Date Issued
2015
Date
2015
Author(s)
Fu, Cheng-An
Abstract
In this thesis, two kinds of biomimetic catalysts were developed by immobilizing active copper model complexes into the nanochannels of functionalized mesoporous silica nanoparticles (MSNs). These nanocomposites can efficiently catalyze oxidative reaction on C-H bond of aliphatic and aromatic compounds with high turnover number (TON) and selectivity at room temperature. The first kind of catalyst is based on a tricopper complex [(CuICuICuI)L]3+ (L = 3,3''-(1,4-diazepane-1,4-diyl)bis(1-(4-ethylhomopiperazin-1-yl) propan-2-ol) (7-Ethppz) and 3,3''-(1,4-diazepane-1,4-diyl)bis[1-(4-ethylpiperazine-1-yl) propan-2-ol] (7-Etppz)) which can perform oxidation of benzene to phenol and 1,4-benzoquinone in the presence of hydrogen peroxide. By immobilizing the complex in the functionalized MSNs, we observed both improved activity and stability of the complex due to structural stabilization in confinement spaces. Product distribution can, moreover, be altered via changing the property of MSNs. By introducing aluminum into the silica framework, adsorption amount of the complex can be increased because charge density on the surface of MSNs were significantly augmented. Another kind of copper complex is a tripodal tridentate copper complex, CuImph (Imph = bis(4-imidazolyl methyl)benzylamine), which can mediate the oxidation of aliphatic C-H bonds, e.g. toluene to benzyl alcohol and benzaldehyde. Stability and reactivity of the complex can also be promoted by immobilization in the nanospaces of MSNs. We have a go at using various hydrocarbons as starting materials, and we found that different functional groups and steric effect would influence the reactivity and selectivity of the catalyst.
Subjects
mesoporous silica nanoparticles
bio-mimic catalysis
copper complex
benzene oxidation
phenol
benzoquinone
Type
thesis
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