以超音波快速合成含苯環官能基之中孔洞材料暨硫醇、苯環及雙硫官能基之中孔洞材料合成與鑑定

宋采倫(Tsai-Lung Sung)

指導教授 ： 高憲明

國立中央大學/理學院/化學系/碩士(2011年)

摘要

本篇論文分為三個部分，第一部分則是利用超音波快速合成含苯環官能基之PMOs (Periodic mesoporous organosilicas)，此部分是以P123 (Pluronic 123) 作為模板試劑，1,4-bis(triethoxysilyl)benzene (BTEB) 為矽源，在酸性條件下利用超音波震盪來合成含苯環的 PMOs，此部分可以將傳統合成所需的時間由數天降為數小時，大幅縮短合成時間且保持良好結構及高表面積。
第二部分是合成雙官能基的中孔洞材料，利用 Brij-76 (C18H37(OCH2CH2)10OH) 為模板試劑，1,4-bis(triethoxysilyl)benzene (BTEB) 與3-Mercaptopropyltrimethoxysilane (MPTMS) 為共同矽源，在酸性條件下合成具有苯環與硫醇官能基之中孔洞材料，之後再利用 THF 酸溶液裂解模板 Brij-76，得到雙官能基化的中孔洞材料 Brij-BTEB-SH，而 SH 含量可達40 %，仍具有良好的結構規則度。
第三部分是比較利用硫醇官能基矽源氧化成雙硫官能基及原本就是雙硫官能基的矽源所合成的材料差異。SS-SBA-15是用MPTMS 和 Tetraethyl orthosilicate (TEOS) 為共同矽源先合成 SH-SBA-15 ，再利用48% H2SO4 裂解模板並且氧化SH 成 SS，而 DS-SBA-15 是用TEOS 與 Bis[3-(triethoxysilyl)propyl] disulfide (BTSPDS) 為共同矽源，合成出具有雙硫官能基的中孔洞材料，藉由 X-ray 繞射儀 (XRD)、固態核磁共振儀 (Solid-state NMR)、熱重分析儀 (TGA) 及氮氣等溫吸脫附儀等儀器鑑定材料的特性。再將 SS-SBA-15 和 DS-SBA-15將所合成之具雙硫官能基中孔洞材料 SBA-15應用於金屬離子吸附，測試此材料對Hg2+ 吸附的能力。

關鍵字

中孔洞材料 ； 苯環官能基 ； 超音波合成 ； 雙硫官能基

並列摘要

This thesis is divided into three parts. Part one, rapid synthesis route to synthesize ordered mesoporous benzene-silicas in a short time developed by using ultrasonic irradiation. This synthesis route effectively reduces the total synthesis time from days to a few hours, which is much shorter than the conventional synthesis methods. The phenylene-bridged mesoporous materials exhibited a hexagonally ordered mesostructure with high surface area over 700 m2/g, pore volume over 0.6 cm3/g and large pore diameter in the range of 4.3–5.2 nm.
In part two, well-ordered hexagonal mesoporous silica SBA-15 functionalized with phenylene and thiol bifunctional groups have been synthesized via co-condensation of 1,4-bis(triethoxysilyl)benzene (BTEB) and 3-Mercaptopropyltrimethoxysilane (MPTMS) under acidic condition. The materials were characterized by a variety of techniques including power X-ray diffraction (XRD), nitrogen sorption measurements, 13C solid-state NMR spectroscopy, and thermogravimetric analysis (TGA).
In part three, well-ordered hexagonal mesoporous silica SBA-15 functionalized with disulfide functional groups have been synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and bis[3-(triethoxysilyl)propyl] disulfide (BTSPDS) templated by P123 under acid condition. Moreover, we synthesized a series of SBA-15 samples with thio functional group via co-condensation of TEOS and MPTMS, and used 48% H2SO4 to remove the template and also oxidized thio groups to disulfide groups. We compared these two series of samples and used those samples to adsorb Hg2+ metal ion.

並列關鍵字

Ultrasonic synthesis ； BTEB ； PMOs ； mesoporous

參考文獻

3. S. Bhatia, CRC press 1990, p.7

6. F. Hoffmann, M. Cornelius, J. Morell, M. Froba, Angew. Chem. Int. Ed. 2006, 45, 3216.

17. Han, Y.; Wu, S.; Sun, Y. Y.; Li, D. S.; Xiao, F. S.; Liu, J.; Zhang, X. Z. Chem. Mater. 2002, 14, 1144.

18. Corma, A.; Navarro, M. T.; Pariente, J. P. J. Chem. Comm. 1994, 147.

19. Park, D. H.; Cheng, C. F.; Klinowski, J. J. Mater. Chem. 1997, 7, 159.