具苯環、氰基及羧酸官能基之中孔洞材料 SBA-1 的合成與鑑定

Synthesis and Characterization of Cubic Mesoporous Silicas SBA-1 with Benzene, Cyanide and Carboxylic Acid Functionalities

簡辰芳(Chen-fang Chien)

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

本篇論文主要是合成具有雙官能基之 SBA-1 中孔洞材料，共分為兩個部分，第一部分是利用 界面活性劑 Cetyltriethylammonium bromide (CTEABr) 作為模板試劑，1,4-bis (trithoxysilyl)-benzene (BTEB) 與 3-(Triethoxysilyl)-Propionitrile (CNTES) 為共同矽源，在 HCl/CTEABr = 140 下，合成出具有苯環和氰基官能基之中孔洞材料 SBA-1，之後再利用乙醇和少量鹽酸移除界面活性劑 CTEABr，樣品中 CNTES 含量可達 50%，仍具有良好的結構規則度。接著也是利用CTEABr 作為模板試劑，1,4-bis (trithoxysilyl)-benzene (BTEB) 與 3-(Triethoxysilyl)-Propionitrile (CNTES) 為共同矽源，在 HCl/CTEABr = 230 下，合成中孔洞材料 SBA-1，當反應中酸量提高時，有部分氰基官能基會被氧化成羧酸官能基，使得此中孔洞材料為含有苯環、氰基和羧酸官能基，而樣品中 CNTES 含量可達 50%。
第二部分則是將第一部分所合成出的 SBA-1 中孔洞材料利用 48% H2SO4 反應一天後將樣品中所有的氰基官能基氧化成羧酸官能基。
以上兩部分的實驗都會利用 X-ray 粉末繞射、固態核磁共振光譜、熱重分析儀、FT-IR 紅外線光譜及等溫氮氣吸脫附等儀器鑑定材料的特性，以了解在相同矽源下，增加反應中的酸量對 SBA-1 材料所造成的影響。

關鍵字

羧酸官能基 ； 氰基 ； 苯環 ； 中孔洞材料

並列摘要

The thesis is divided into two parts, both studied on bifunctional periodic mesoporous organosilicas (BPMOs). In part one, the BPMOs containing both benzene functional moieties in the frame work and terminal cyanide groups protruding into the channel pores haved been synthesized with CTEABr as the structure-directing agent under acidic conditions (CTEABr/HCl = 140) via co-condensation of 1,4-bis (trithoxysilyl)-benzene (BTEB) and 3-(Triethoxysilyl)-Propionitrile (CNTES). A high degree of structural ordering is still retained up to 50 mol% CNTES loading (based on silicon) in the synthesis mixture.Then, well-ordered cubic mesoporous silica SBA-1 functionalized with cyanide and carboxylic acid functional groups have been synthesized via co-condensation of 1,4-bis(triethoxysilyl)benzene (BTEB) and 3-(Triethoxysilyl)-Propionitrile (CNTES) templated by CTEABr under acidic condition (CTEABr/HCl = 230). A high degree of structural ordering is still retained up to 50 mol% CNTES loading (based on silicon) in the synthesis mixture.
In part two, the BPMOs, which have been synthesized, hydrolyzed all the cyanide groups to carboxylic acid group by refluxing with 48% sulfuric acid at 343 K for 24 h.
In the thesis, the materials thus obtained were characterized by a variety of techniques including X-ray diffraction (XRD), solid state 13C CP/MAS NMR, thermogravimetric analysis (TGA), FT-IR and nitrogen sorption measurements.

並列關鍵字

mesoporous ； benzene ； cyanide ； carboxylic acid functionalities

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