摘 要 本研究分為兩部分來討論。第一部分為直接合成立方排列矽酸鈦中孔徑分子篩SBA-16的合成之最佳化與水熱穩定性研究,第二部分為後合成法修飾鋯到中孔徑分子篩 SBA-15最佳化研究與水熱穩定性研究。 一系列立方堆積矽酸鈦中孔徑分子篩SBA-16奈米材料在室溫或高溫下成功合成。利用X射線粉末繞射儀、掃描式電子顯微鏡、氮氣等溫吸附脫附儀、紫外光-可見光分光光譜儀、感應耦合電漿原子發射光譜分析儀等儀器鑑定。在不同合成溫度、時間及不同鈦源、不同鈦含量的條件下,所合成矽酸鈦SBA-16有不同孔洞性質及配位環境,然而大部分的鈦是以四配位存在管壁中。矽酸鈦SBA-16擁有優良水熱穩定性,即使在沸水7天仍然保有良好中孔洞結構。三維空間孔洞擴散性比一維空間孔洞更有利,可使大分子做選擇性氧化催化是被期待。 六方堆積矽酸鋯中孔徑SBA-15奈米材料已成功以後修飾法在室溫下合成。在不同鋯含量的條件下,約有85%的鋯存在於中孔分子篩中,鋯幾乎都以四配位存在管壁中,除了 Si/Zr = 5的樣品,有部分鋯以六配位形式存在。其樣品即使經沸水10天,超過90%孔洞結構物理性質仍被保留,其優越水熱性質,是中孔分子篩文獻上所前未見。
Abstract High quality titanosilicate cubic SBA-16 nanoporous materials with Si/Ti ratios of 5, 7, 10 ,20, and 40 have been successfully synthesized rapidly at room temperature using surfactant within one hour. These materials were characterized by powder X-ray diffraction patterns (XRD), nitrogen adsorption/desorption, diffuse reflectance UV-vis, and HRTEM images. Synthesis parameters of hydrothermal treatment temperature, time, and titanium source and amount were systematically varied and affected the structure of Ti-SBA-16. Most titanium was tetrahedrally-coordinated in pore wall. The cubic Ti-SBA-16 structure was well-preserved even if materials were treated in boiling water for 7 days. The superior hydrothermal stability could be illustrated by thicker wall and titanosilicate protection of mesoporous wall. Three dimensional cubic titanosilicate with large cage is expected to be useful as a selective oxidation catalyst for reactions involving large molecules. Zirconium-containing silicate hexagonal SBA-15 nanoporous materials with Si/Zr ratios of 5, 10 ,20 40, 60, 80 and 1200 have been successfully synthesized via a post-grafting method at room temperature. These materials were characterized by XRD, nitrogen adsorption/desorption, Induced couple plasma-atomic emission spectra(ICP-AES) , diffuse reflectance UV-vis, and HRTEM images. Synthesis parameters of zirconia amount were systematically varied and affected the structure of Zi-SBA-15. Most zirconia were four-coordinated in pore wall except for the sample with Si/Zr = 5. The hexagonal SBA-15 structure was well-preserved even if materials were treated in boiling water for 10 days. The unordinarily hydrothermal stability could be illustrated by thicker wall and Zr-O-Si protection of mesoporous wall. Zirconium-containing SBA-15 is expected to be useful as a selective oxidation catalyst for reactions involving large molecules.