臺灣博碩士論文加值系統

介孔(mesoporous)材料由於具有高比表面積及孔洞分佈均勻之特性，其應用相當廣泛，是近年來在奈米材料科學領域中引人注目的研究領域。本研究是利用三嵌段兩性共聚物(block copolymer)作為天然模板，TiCl4為反應前驅物，以模板輔助溶膠-凝膠法製備高比表面積的奈米介孔TiO2。實驗是以熱重分析、X-ray繞射分析、穿透式電子顯微鏡及N2吸脫附曲線分析該材料之微結構及比表面積，探討各種合成因素例如三嵌段兩性共聚物的添加量、煆燒溫度與加水反應對介孔TiO2結構之影響。
實驗結果顯示，本實驗所合成之介孔TiO2，經300 ~ 400 ℃煆燒後，可獲得anatase之結構。使用三嵌段兩性共聚物的添加量為 1.5 g，煆燒溫度 300 ℃，可合成出最大比表面積約為284.75 m2/g、孔洞直徑約為4.8 nm；三嵌段兩性共聚物添加量對試樣介孔結構影響甚大，當添加量從0.1改變至1.5 g時，經煆燒溫度350℃，其比表面積會從63.14增加至229.17 m2/g，孔徑從11.04縮小至5.0 nm。
此外，在反應系統中水濃度的含量亦會影響TiO2之結晶相，在純酒精的情況下可合成單一anatase晶相的介孔TiO2，在有純水取代酒精時，可合成anatase晶相和rutile晶相兩種結構之混合相。三嵌段兩性共聚物的添加量為1.0 g，而以純水取代酒精含量為25%時，煆燒溫度在300 ℃時，可合成出最大比表面積約為565.4 m2/g、孔洞直徑約為5.2 nm。

Recently, mesostructured materials with high surface areas and large pore sizes have attracted much attention because of their potential applications in the areas of adsorption and catalysis. In this study, mesoporous TiO2 was prepared by sol-gel process and the synthesis was accomplished by using block copolymer as the template, and TiCl4 as the inorganic precursor. TGA, XRD, TEM and N2 adsorption-desorption isotherms were used to characterize the microstructure of the samples.
Using F108 block copolymer as the template, mesoporous TiO2 with the anatase structure was obtained at 300~400°C. Mesoporous TiO2 exhibits a high BET surface area of 284.75 m2/g, and an average pore size of 4.8 nm for 300℃ calcination and using 1.5 g block copolymer. The addition of block copolymer can affect the structure of mesoporous. The addition of block copolymer increased from 0.1 to 1.5 g, and the specific surface area increased from 63.14 to 229.17 m2/g, but the average pore size decreased from 11.04 to 5.0 nm after calcined at 350°C for 5hrs.
The water content in the reaction system is believed to determine the crystal structure formation. Mesoporous TiO2 with pure anatase have been successfully synthesized with pure alcohol, but bicrystalline (anatase and rutile structures) were obtained when replaced with H2O. The results showed that mesoporous TiO2 prepared with 25 % replacement of H2O and calcined at 300°C for 5 hrs exhibits a high surface area of 565.4 m2/g and an average pore size of 5.2 nm.

目錄
摘要 I
Abstract II
誌謝 III
表目錄 V
圖目錄 VI
第1章 緒論 1
1.1 前言 1
1.2 孔洞材料簡介 1
1.3 研究動機及目的 2
第2章 理論基礎與文獻回顧 4
2.1 界面活性劑性質簡介 4
2.1.1 界面活性劑分類 4
2.2 微胞理論 6
2.3 界面活性劑分子聚集體之結構 9
2.4 介孔材料之合成與分析 12
2.4.1 介孔材料的合成 12
2.4.2 介孔材料之孔洞及比表面積分析 16
2.5 二氧化鈦基本特性 18
2.5.1 二氧化鈦結構特性 18
2.5.2 二氧化鈦之製備方法 18
第3章 實驗方法與步驟 23
3.1 化學藥品 23
3.2 二氧化鈦合成步驟 23
3.3 合成奈米介孔二氧化鈦之製程參數 23
3.3.1三嵌段兩性共聚物濃度對奈米介孔二氧化鈦比表面積之影響 23
3.3.2不同濃度乙醇對奈米介孔二氧化鈦比表面積之影響 25
3.4材料分析與性質量測 25
第4章 結果與討論 29
4.1 三嵌段兩性共聚物添加量對合成奈米介孔二氧化鈦粉末之晶粒成長及介孔結構之影響 29
4.1.1熱重分析 29
4.1.2 FTIR 分析 31
4.1.3 XRD 分析 31
4.1.4 TEM 分析 37
4.1.5 小角度X-ray 散射分析 41
4.1.6 氮氣吸脫附曲線分析 41
4.2 煆燒溫度對奈米介孔二氧化鈦粉末之影響 48
4.2.1 XRD 分析 48
4.2.2 TEM 分析 48
4.2.3 介孔對晶粒成長機制探討 49
4.2.4氮氣吸脫附曲線分析 49
4.3 加水反應對奈米介孔二氧化鈦粉末之影響 51
4.3.1 FTIR 分析 51
4.3.2 XRD 分析 51
4.3.3 TEM 分析 53
4.3.4氮氣吸脫附曲線分析 59
第5章 結論 64
參考文獻 65
作者簡介 69

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