二維及三維孔道結構中孔洞碳材之合成與鑑定及吸附應用

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研究生：	蔡宜霖 Yi-Lin Tsai
論文名稱：	二維及三維孔道結構中孔洞碳材之合成與鑑定及吸附應用 Synthesis and Characterizations of Mesoporous Carbons with Two Dimensional and Three Dimensional Pore Structure and Their Application in Adsorption
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
論文出版年：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	158
中文關鍵詞：	中孔洞碳材、奈米模鑄法、簡單一步合成法、染料吸附、等溫吸附圖、吸附動力學
外文關鍵詞：	Mesoporous carbon, Nanocasting, Simple one-pot, Adsorption of dye, Adsorption isotherm, Adsorption kinetics
相關次數：	點閱：8 下載：0
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本研究主要是利用奈米模鑄法及簡單一步合成法來合成具有相同結構 (二維六角柱狀 (p6mm) 及三維立方體/四面體 (Ia3 ̅d/ I41/a) ) 的中孔洞碳材，希望比較這兩種方法所合出碳材的孔洞結構性質差異，藉此探討對不同染料分子吸附能力的影響，特別是二維及三維孔道結構對不同大小染料分子 (一維鏈狀結構的小分子亞甲基藍、三維結構的大分子維多利亞藍) 吸附能力的影響，並藉由另一種不帶電荷染料蘇丹紅 G，來探討碳材孔洞表面的電荷性質對其吸附能力的影響。
對於吸附一維小分子結構的亞甲基藍，發現碳材不管是二維或三維孔道結構，大致上隨著其孔洞表面積愈大，吸附量就愈大，且由 Langmuir 及 Freundlich 等溫吸附模型的分析，發現其比較符合 Langmuir 所假設的單層吸附模式，所以證明孔洞表面積為影響其吸附此小分子染料的主要因素。
而對於吸附三維大分子結構的維多利亞藍，實驗發現反而是孔洞體積及孔道結構才是影響碳材吸附能力的主要因素，且由 XRD 及 N2 等溫吸脫附結果，發現三維四面體 (I41/a) 的碳材都發生程度不等的結構相轉變，使其孔道結構比二維六角柱狀 (p6mm) 碳材還複雜許多，造成其吸附量甚至是吸附速率都大幅下降。另外，由於結構相轉變會產生孔徑更大的孔洞造成雙孔徑的分佈，所以亦發現雙孔徑分佈的程度愈高，其孔道結構愈複雜，愈不利於吸附大分子維多利亞藍。
至於對於吸附不帶電荷的染料蘇丹紅 G，發現碳材孔洞表面與染料分子之間的靜電吸引力為影響其對前述兩種帶正電荷染料吸附能力較優越的原因之一，顯示碳材孔洞表面的電荷性質也會大大影響其對染料的吸附能力。
另外，藉由 pseudo-first-order 及 pseudo-second-order 動力學模型的分析，發現所有碳材對這三種染料的吸附都比較適合用 pseudo-second-order 動力學模型來描述。

Mesoporous carbons with the same structure (2D hexagonal p6mm and 3D cubic/tetragonal (Ia3 ̅d/ I41/a) ) were synthesized by the strategies of nanocasting and simple one-pot, and used for the adsorption of dyes. The goal was to compare the pore structure difference between the carbon materials synthesized by these two strategies, and investigate how these structure difference effect the adsorption of different dyes. Especially how the pore structure in two dimensions and three dimensions effected the adsorption of different molecule size dyes (such as small size methylene blue with 1D chain structure and large size victoria blue with 3D structure). In addition, we used another dye molecule with zero net charge, such as sudan red G, to investigate how the charge on the pore surface of mesoporous carbons effected the adsorption properties.
For the adsorption of methylene blue with 1D small molecule size, we found that no matter the pore structure of mesoporous carbons was in two dimensions or three dimensions, generally the bigger the pore surface area, the larger the adsorption capacity for the dye. After analyzing the adsorption isotherm data by the Langmuir and Freundlich models, we also found that they could be better described by the Langmuir model. The pore surface area of carbon materials was therefore the main factor for adsorption of small-size methylene blue.
In contrast, for the adsorption of victoria blue with 3D large molecule size, the adsorption capability was mainly dependent on the pore volume and the pore structure of the materials. The structure of 3D tetragonal (I41/a) mesoporous carbons all had different degree of phase transformation as revealed from XRD and N2 adsorption results, indicating that their pore structure were more complicated than the mesoporous carbons with 2D hexagonal (p6mm) symmetry. As a result, their adsoption capacities and adsorption velocities all dramatically decreased. On the other hand, due to phase transformation might produce more pores with much bigger size and result in bimodal porosity, our results also indicated that the higher the degree of bimodal porosity, the more complicated the pore structure, and therefore the less the adsorption capability for large-size victoria blue.
As for the adsorption of sudan red G with zero net charge on mesoporous carbons, it was found that the electrostatic attraction between the pore surface and dye molecules was the determinative factor for the better adsorption of last two dyes with positive charge, suggesting that the charge on the pore surface of carbon materials might greatly contribute to its adsorption capability for dyes.
In addition, after analyzing experimental data by the pseudo-first-order and pseudo-second-order kinetic models, we found that the adsorption of last three dyes on carbon materials all could be well depicted by the pseudo-second-order kinetic model.

中文摘要..................................................I
Abstract...............................................III
謝誌.....................................................V
目錄.....................................................VI
圖目錄...................................................IX
表目錄...................................................XII
第一章 緒論.................................................1
1-1 中孔洞碳材合成發展文獻回顧.................................1
1-1-1 奈米模鑄法 (Nanocasting) 合成概念及機制.................4
1-1-2 奈米模鑄法合成規則有序中孔洞碳材發展簡介...................9
1-1-3 界面活性劑模造法 (Surfactant templating) 合成規則有序中孔洞碳材發展簡介...............................................22
1-1-4 簡單一步合成法 (Simple one-pot) 合成規則有序中孔洞碳材簡介.......................................................25
1-2 研究動機與目的.........................................28
第二章 實驗部分............................................30
2-1 藥品.................................................30
2-2 二維及三維孔道結構中孔洞碳材之合成方法總覽..................32
2-3 奈米模鑄法合成二維孔道結構 (p6mm) 的中孔洞碳材.............33
2-3-1 二維六角柱狀 (p6mm) 中孔洞矽材模板 SBA-15 的合成........33
2-3-2 二維六角柱狀 (p6mm) 中孔洞碳材 NC-CS的合成.............33
2-4 奈米模鑄法合成三維孔道結構 (Ia3 ̅d/ I41/a) 的中孔洞碳材....34
2-4-1 三維立方體 (Ia3 ̅d) 中孔洞矽材模板 KIT-6 的合成.........34
2-4-2 三維立方體 (Ia3 ̅d) 中孔洞碳材 CSU-100 的合成..........35
2-4-3 三維四面體 (Tetragonal I41/a) 中孔洞碳材 (CSU-35, CFA-35) 的合成....................................................36
2-5 簡單一步合成法合成二維六角柱狀 (p6mm) 中孔洞碳材 CS.........37
2-6 簡單一步合成法合成三維四面體 (Tetragonal I41/a) 中孔洞碳材 CCT-1.......................................................38
2-7 染料吸附實驗..........................................39
2-7-1 校正檢量線的製作......................................39
2-7-2 在不同濃度下的吸附 (等溫吸附圖 (Adsorption isotherm) 的製作)......................................................39
2-7-3 在不同反應時間下的吸附.................................40
2-8 實驗鑑定儀器...........................................41
2-9 鑑定儀器之原理.........................................42
2-9-1 同步輻射光束線.......................................42
2-9-2 X 射線粉末繞射 (Powder X-Ray Diffractometer, XRD)....43
2-9-3 氮氣等溫吸脫附曲線、表面積與孔洞特性鑑定..................44
2-9-4 熱重分析儀 (Thermogravimetric Analyzer, TGA)........48
2-9-5 穿透式電子顯微鏡 (Transmission Electron Microscope, TEM)....................................................48
2-9-6 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM)....................................................49
2-9-7 紫外光/可見光光譜儀 (UV-Vis Spectrometer)............50
第三章 結果與討論..........................................51
第壹部分 二維 (p6mm) 及三維 (Ia3 ̅d/ I41/a) 孔道結構中孔洞碳材之合成與鑑定..................................................51
3-1 奈米模鑄法合成二維六角柱狀 (p6mm) 及三維立方體/四面體 (Ia3 ̅d/ I41/a) 中孔洞碳材.........................................51
3-1-1 XRD 結果分析........................................51
3-1-2 氮氣等溫吸附/脫附結果分析..............................55
3-1-3 熱重分析............................................62
3-1-4 HR-TEM 結果分析.....................................64
3-1-5 SEM 結果分析........................................69
3-2 簡單一步合成法合成二維六角柱狀 (p6mm) 及三維四面體 (I41/a) 中孔洞
碳材.....................................................72
3-2-1 XRD 結果分析........................................72
3-2-2 氮氣等溫吸附/脫附結果分析..............................75
3-2-3 熱重分析............................................80
3-2-4 HR-TEM 結果分析.....................................81
3-2-5 SEM 結果分析........................................84
第貳部分 染料吸附實驗.......................................86
3-3 亞甲基藍 (Methylene blue, MB) 吸附實驗.................86
3-3-1 校正檢量線製作結果...................................86
3-3-2 在不同濃度下的吸附結果 (等溫吸附圖 (Adsorption isotherm) 製作結果)..................................................88
3-3-3 等溫吸附模型 (Adsorption isotherm model) 的分析......92
3-3-4 在不同反應時間下的吸附結果.............................99
3-3-5 吸附動力學 (Adsorption kinetics) 分析...............101
3-4 維多利亞藍 (Victoria blue B, VB-B) 吸附實驗............105
3-4-1 校正檢量線製作結果...................................105
3-4-2 在不同濃度下的吸附結果 (等溫吸附圖 (Adsorption isotherm) 製作結果)..................................................107
3-4-3 等溫吸附模型 (Adsorption isotherm model) 的分析......111
3-4-4 在不同反應時間下的吸附結果............................115
3-4-5 吸附動力學 (Adsorption kinetics) 分析...............117
3-5 蘇丹紅 G (Sudan red G, SR-G) 吸附實驗.................121
3-5-1 校正檢量線製作結果...................................121
3-5-2 在不同濃度下的吸附結果 (等溫吸附圖 (Adsorption isotherm) 製作結果)..................................................123
3-5-3 等溫吸附模型 (Adsorption isotherm model) 的分析......126
3-5-4 在不同反應時間下的吸附結果.............................130
3-5-5 吸附動力學 (Adsorption kinetics) 分析................132
第四章 結論...............................................136
參考文獻.................................................138
                                

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