本論文主要在研究利用末端氧化成羧酸基的三塊狀共聚高分子P123和F127當作模板加上二氧化矽前趨物TEOS預水解的方式,以直接共聚合成法製備出不同結構的胺基功能化中孔洞二氧化矽材料。我們發現高分子末端的羧酸可促進二氧化矽前趨物的水解與縮合反應,有效克服胺基有機矽烷和TEOS水解縮合速率不同的問題,並加速模板分子與二氧化矽自組裝成三維有序結構,且增加二氧化矽縮合的程度。我們成功製備出含胺基功能化的SBA-15、KIT-5、SBA-16二氧化矽材料,並利用粉末X光繞射儀、氮氣吸脫附分析儀、熱重分析儀、固態核磁共振光譜儀、電子顯微鏡等對這些材料做結構與成分分析。其中,我們特別以具有穴狀孔洞的胺基功能化中孔洞KIT-5二氧化矽為載體來製備金奈米顆粒。從穿透式電子顯微鏡照片顯示KIT-5中的金奈米顆粒分布很均勻且大小一致,此亦反映出胺基官能基在KIT-5的孔洞表面上的分布狀況。
We report facile syntheses of amino-functionalized large-pore mesoporous silica materials by co-condensation, using the carboxylate -terminated triblock Pluronic copolymers as structural directing agents and pre-hydrolyzed silica source of TEOS. The carboxylate end-groups were found to facilitate the hydrolysis and condensation of silica precursors and overcome the problem of the disturbed kinetics by the presence of the amino-functional silanes. The usage of the carboxylate -terminated triblock copolymers was also found to accelerate the formation of three-dimensional ordered structures of copolymer/silica hybrids in solution and enhance the degree of silica condensation of the materials. By using the carboxylate -terminated triblock copolymers, we have successfully prepared the amino-functionalized mesoporous SBA-15, KIT-5 and SBA-16 silica materials. Their elemental and structural characterizations by powder X-ray diffraction, nitrogen physisorption analysis, thermal analysis, solid-state nuclear magnetic resonance spectroscopy and electron microscopies have been performed. We also applied the amino-functionalized KIT-5 silicas to prepare the supported gold nanoparticles. The images of transmission electron microscopy revealed that the gold nanoparticles were uniform in size and were well dispersed in KIT-5 silicas. The distribution of gold nanoparticles reflected the distribution of the amino functional groups in the host KIT-5 silica materials.