中孔洞二氧化矽的孔洞與形貌調控及其於轉酯化反應的研究

The Structural and Morphological Control of Mesoporous Silica Material and Their Application in Transesterification

魏竹君(Tsu-chun Wei)

指導教授 ： 楊家銘

國立清華大學/理學院/化學系/碩士(2011年)

https://doi.org/10.6843/NTHU.2011.00234

摘要

本論文主要研究PO-EO-PO型三塊狀共聚高分子與鋯離子對SBA-15合成系統的影響，及中孔材料Ca-MCF及Zr-SBA-15催化轉酯化反應的研究，並利用粉末X光繞射、氮氣物理吸脫附、熱重分析、固態核磁共振光譜、電子顯微鏡及穿透式電子顯微鏡鑑定材料以及氣相層析分析催化結果。一般合成SBA-15材料是在加入矽源之後繼續攪拌24小時後熟化過濾乾燥，我們發現在加入矽源後攪拌時間降至30分鐘，混合PO14EO25PO14在氮氣吸脫附鑑定有兩階段脫附，藉由填入金屬鉑發現孔洞由直通狀變成較不規則的波浪狀，並且加入鋯離子會使得微孔越來越大；而混合PO26EO8PO26以及鋯離子發現在維持p6mm結構的有序性以及直通孔洞下，有均勻3-4μm的球狀形貌，球狀顆粒內部有兩種區塊，一種是規則的二維六方堆積，以隨機的走向分布於內部，另一種則是不規則的區塊分布於表面以及二維六方堆積區域的空隙。另外研究轉酯化的催化反應，在催化劑的製備上改良了硫酸處理的方法，利用在熟化時加入硫酸，可選擇性的開通中孔洞，並且可提高結構的有序性。

關鍵字

中孔洞二氧化矽 ； 奈米球 ； 反三塊狀重共聚高分子 ； 界面活性劑的混合 ； 轉酯化反應 ； 孔洞拓譜學

並列摘要

In this thesis, we applied mixture of PO-EO-PO type reverse triblock copolymer and P123 with the aid of zirconium ion (IV) to study their effect on structure and morphology of mesoporous silica materials, and they applied in transesterification by Ca-MCF and Zr-SBA-15. The elemental and structural characterizations were conducted by powder X-ray diffraction, N2 physisorption, TGA, NMR, SEM and TEM and the results of catalysis of transesterification were measure by GC analysis. The synthesis of SBA-15 synthesis generally stirred 24 hours after adding TEOS, but now we found that stirring time decreased to 30 minutes, the pore topography changed from straight to curved when mixing with PO14EO25PO14, it could be observed by N2 physisorption of two step desorption; the morphology became sphere particle about 3-4μm with p6mm symmetry when adding PO26EO8PO26and Zr4+ which observed by SEM and TEM, it contained two kinds of domains inside, one was p6mm domain with random orientation, the other was worm-like domain located on the sphere surface and the rest spaces of p6mm domains. On the other hand, we studied catalysis of transesterification; for preparing catalyst, we improved the H2SO4 treatment by adding H2SO4 before aging. It could selectively remove surfactant in mesopores by ether cleavage and improved silica condensation at the same time.

並列關鍵字

Mesoporous silica material ； microsphere ； reverse triblock copolymer ； mixed surfactant ； transesterification ； pore topology

參考文獻

38. Imperor-Clerc, M.; Davidson, P.; Davidson, A., J. Am. Chem. Soc. 2000, 122 (48), 11925-11933.

20. Wan, Y.; Shi, Y. F.; Zhao, D. Y., Chem. Commun. 2007, (9), 897-926.

1. Ying, J. Y.; Mehnert, C. P.; Wong, M. S., Angew. Chem. Int. Ed. 1999, 38 (1-2), 56-77.

61. Chen, S. Y.; Tang, C. Y.; Chuang, W. T.; Lee, J. J.; Tsai, Y. L.; Chan, J. C. C.; Lin, C. Y.; Liu, Y. C.; Cheng, S. F., Chem. Mater. 2008, 20 (12), 3906-3916.

48. Yang, C. M.; Zibrowius, B.; Schmidt, W.; Schuth, F., Chem. Mater. 2004, 16 (15), 2918-2925.