具羧酸與苯環官能基中孔洞材料之合成、鑑定及應用

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研究生：	陳憶雯 Yi-wen Chen
論文名稱：	具羧酸與苯環官能基中孔洞材料之合成、鑑定及應用 Direct Synthesis, Characterization, and Application of Benzene-Bridged Periodic Mesoporous Organosilicas Functionalized with Carboxylic acid Groups
指導教授：	高憲明 Hsien-Ming Kao
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
畢業學年度：	100
語文別：	中文
論文頁數：	133
中文關鍵詞：	苯環、羧酸、中孔洞
外文關鍵詞：	Benzene-silicas, Carboxylic acid groups, mesoporous silica
相關次數：	點閱：11 下載：0
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本篇論文主要是合成具有雙官能基的中孔洞材料及其應用，共分為兩個部分，第一部分利用 Brij 76 (C18H37(OCH2CH2)10OH) 作為模板試劑，1,4-bis(triethoxysilyl)benzene (BTEB) 與Carboxyethylsilanetriol sodium salt (CES) 為共同矽源，在酸性條件下合成具有苯環與羧酸官能基之中孔洞材料，之後利用 48 % H2SO4 於高溫下裂解模板 Brij 76，即可得孔壁具有苯環排列且表面修飾上羧酸官能基之中孔洞材料，而羧酸官能基含量可高達80 %，且仍具有良好之結構規則度。以上實驗利用 X-ray 粉末繞射、固態核磁共振光譜、熱重分析儀、等溫氮氣吸脫附、穿透式電子顯微鏡及掃描式電子顯微鏡等儀器鑑定材料的特性，藉此瞭解在不同 CES 含量比例之孔洞性質變化趨勢，且對植入的羧酸官能基定量。
而第二部份則是利用上述所合成的中孔洞材料 (簡稱為BC-X，X指 [CES/(CES+BTEB)]之莫耳比例) 應用於吸附染料亞甲基藍(Methylene blue)。研究吸附過程中影響吸附的因素，包括孔洞材料中羧酸官能基的負載量、亞甲基藍吸附系統的溫度及pH值等。由實驗結果可得知，由於孔洞材料的高表面積，羧酸官能基的良好親和力及苯環間 pi-pi 作用力， BC-X系列之中孔洞材料對於亞甲基藍具極佳吸附效果，且具良好的重複使用性，故BC-X系列之中孔洞材料對移除廢水中的亞甲基藍具應用潛力。由吸附實驗結果顯示 Langmuir 等溫吸附模式比 Freundlich 等溫吸附模式更適合描述 BC-X 吸附亞甲基藍的系統，顯示本實驗的吸附形式為單層吸附模式。

The thesis is divided into two parts. In the first part, carboxylic acid functionalized mesoporous benzene-silica (BC-X materials, X refers to the [CES /(CES + BTEB)] molar ratio) have been synthesized with Brij 76 as the structure-directing agent under acidic conditions via co-condensation of 1,4-bis(triethoxysilyl)benzene (BTEB) and carboxyethylsilanetriol sodium salt (CES). The BC-X materials are ordered and uniformed mesoporous with a high loading of carboxylic acid groups (up to 80 mol% based on silica). In this study, a varief of techniques was adopted to characterized the BC-X materials, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), 13C CP-MAS NMR, 29Si MAS NMR , nitrogen sorption measurements, thermogravimetric analyzer (TGA), Fourier transform infrared spectrometer (FTIR) and powder X-ray diffraction (XRD).
In the second part, the BC-X samples with high loadings of carboxylic group is therefore acted as adsorbents for the removal of methylene blue. The adsorption process is carefully studied with various systematic factors, including the loading amount of CES, the quanity of methylene blue, temperature and pH of adsorption system. Due to the high surface area, good affinity of arboxylic groups and pi-pi interaction of benzene rings, the BC-X materials exhibits excellent performance on methylene blue adsorption. The experimental data for the adsorption were analyzed using Freundlich and Langmuir isotherm models. It is found that the Langmuir equation provides an accurate description of these adsorption data, suggesting that monolayer adsorption occurred in all cases of the performed sorption processes.

中文摘要.......................................	I
Abstract.......................................	III
謝誌...........................................	IV
目錄...........................................	V
圖目錄.........................................	VIII
表目錄.........................................	X
第一章	緒論..................................	1
1-1 中孔洞分子篩材料的研究與發展...............	1
1-1-1 中孔洞分子篩材料簡介.....................	1
1-1-2 中孔洞分子篩 M41S 系列...................	3
1-1-3 中孔洞分子篩 SBA 系列....................	5
1-2 界面活性劑性質簡介.........................	8
1-2-1 界面活性劑分子結構.......................	8
1-2-2 界面活性劑種類...........................	9
1-2-3 微胞的形成與結構.........................	11
1-3 矽酸鹽的化學概念...........................	13
1-4 中孔洞分子篩材料的合成機制.................	15
1-5 表面修飾之中孔洞分子篩.....................	20
1-6 相關文獻回顧...............................	22
1-6-1 具羧酸官能基之中孔洞材料.................	22
1-6-2 含苯環官能基之 PMOs......................	24
1-6-3 等溫吸附模式.............................	27
1-7 研究動機與目的.............................	29
第二章 實驗部分................................	30
2-1 藥品.......................................	30
2-2 實驗步驟...................................	31
2-2-1 合成具苯環與羧酸官能基之PMOs.............	31
2-2-2以硫酸溶液裂解孔洞中之模板................	31
2-2-3以酸鹼滴定鑑定BC-X孔洞材料的酸當量........	32
2-2-4 亞甲基藍檢量線之製作.....................	32
2-2-5 利用中孔洞材料吸附溶液中亞甲基藍染料實驗..32
2-2-6 BC-X中孔洞材料不同反應時間對吸附的影響...	33
2-2-7 BC-X中孔洞材料不同反應溫度對吸附的影響...	33
2-2-8 BC-X中孔洞材料在不同pH值下對吸附的影響...	34
2-2-9 BC-X中孔洞材料在不同濃度下的吸附.........	34
2-2-10 BC-60中孔洞材料之重複使用性.............	34
2-3 實驗鑑定儀器...............................	36
2-4 鑑定方法...................................	37
2-4-1 同步輻射光束線 (NSRRC Beam Line).........	37
2-4-2 X射線粉末繞射 (Powder X-Ray Diffractometer, XRD)...	39
2-4-3 氮氣吸脫附等溫曲線、表面積與孔洞特性鑑定...........	40
2-4-4 傅立葉紅外線吸收光譜儀 (Fourier Transform Infrared Spectrometer；FTIR)......................................	45
2-4-5 熱重分析儀 (Thermo Gravimetric Analyzer, TGA)......	47
2-4-6 穿透式電子顯微鏡 (Transmission Electron Microscope, TEM).....................................................	49
2-4-7 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM)50
2-4-8 固態核磁共振儀 (Solid State Nuclear Magnetic Resonance, Solid State NMR)..............................	52
2-4-9 紫外光/可見光光譜儀 (UV-Vis Spectrometer)..........	60
第三章 結果與討論........................................	63
3-1 合成不同矽源比例之 BC-X..............................	63
3-1-1 BC-X 系列 XRD 鑑定.................................	63
3-1-2 氮氣等溫吸脫附鑑定.................................	68
3-1-3 FT-IR 紅外線光譜...................................	71
3-1-4 13C CP/MAS NMR.....................................	73
3-1-5 13C DEPTH NMR......................................	75
3-1-6 29Si MAS NMR.......................................77
3-1-7 1H MAS NMR.........................................	80
3-1-8 13C{1H} HETCOR NMR.................................	81
3-1-9 熱重分析...........................................	83
3-1-8 TEM................................................	86
3-1-9 SEM................................................	88
3-1-10 酸鹼滴定..........................................	90
3-2 亞甲基藍吸附實驗.....................................	92
3-2-1 亞甲基藍 (Methylene blue, MB)......................	92
3-2-2 製作檢量線.........................................	93
3-2-3 BC-X 中孔洞材料在不同反應時間的吸附結果............	94
3-2-4 BC-X中孔洞材料在不同反應溫度的吸附結果.............	96
3-2-5 BC-X 中孔洞材料在不同 pH 的吸附結果................	97
3-2-6 BC-X中孔洞材料在不同濃度的吸附結果.................	98
3-2-7 測試BC-60之重複使用性....................	101
3-2-8 等溫吸附模式.............................	102
第四章 結論....................................	105
參考文獻.......................................	106
附錄一.........................................	112
附錄二.........................................	119

                                

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