二氧化鈦修飾中孔洞分子篩之合成、結構特性與光催化反應

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謝明宏(Ming-Hung Hsieh) 查詢紙本館藏

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論文名稱

二氧化鈦修飾中孔洞分子篩之合成、結構特性與光催化反應
(Synthesis, Characterization and Photocatalytic Reaction of Titanium-modified Mesoporous Materials)

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摘要(中)

本研究利用化學嫁接法將二氧化鈦薄膜嫁接於 SBA-15 表面，修飾後的材料具有高比表面積及高規則的中孔洞結構，在亞甲基藍光降解反應中亦有相當優異的表現。
XRD 與 HRTEM 的結果顯示Ti/SBA R1nc 經由鍛燒處理後，鍛燒溫度的提高不會破壞材料結構的規則，且二氧化鈦的單分子層亦無晶相的特徵峰。若是比較 Ti/SBA R1c500、Ti/SBA R2c500 與 Ti/SBA R3c500，隨著迴流次數的增加，材料結構的規則性略微下降，比表面積由SBA-15的765 m2/g等間距下降至Ti/SBA R3c500的480 m2/g。ICP-OES的分析顯示含Ti量由Ti/SBA R1c500的6.5 wt% 增加至Ti/SBA R3c500的22.7 wt%。然而，經由水熱處理的Ti/SBA R1HT，其結構的規則性明顯下降許多且出現 TiO2 Anatase 晶相的特徵峰；在氮氣等溫吸附-脫附曲線中的遲滯迴圈，呈現 H3 type 的狹縫型孔洞，表示可能產生TiO2奈米顆粒堆積在原有規則孔道中，顯示孔道高度規則性已不復見，與 FESEM 看到的分子篩表面被TiO2 奈米顆粒緊密包覆的影像相符。
亞甲基藍光催化降解實驗顯示水溶液中亞甲基藍的移除可分為吸附量與降解量兩部份。實驗結果顯示隨著鍛燒溫度的增加，對亞甲基藍的吸附量亦隨之增加，推測是高溫熱處理使二氧化鈦的單分子薄膜收縮，連帶裸露出擔體 SBA-15 的表面，造成吸附量的提升；在降解部分Ti/SBA R1c500 的光催化能力最佳，兩小時內可降解 42.8 % 的亞甲基藍，優於 Ti/SBA R1nc 的 36.8 %，一階反應常數k 值則由Ti/SBA R1nc的 0.0856 ( min-1 ) 增加到 0.1213 ( min-1 )。以水熱法處理的Ti/SBA R1H吸附量僅有12.9 %，兩小時內可降解 58.1%，其 k 值為0.1152 ( min-1 )。藉由增加化學嫁接的次數提昇材料的鈦含量，Ti/SBA R2c500與Ti/SBA R3c500的k 值大幅提升至0.2260 ( min-1 ) 與0.2001 ( min-1 )。然而，Ti/SBA R2HT與Ti/SBA R3HT的光催化活性與Ti/SBA R1HT相較並無顯著增加。本研究利用化學嫁接法並調控鍛燒溫度與嫁接次數的最適化，成功地製備出結構規則且二氧化鈦均勻批覆的中孔洞光觸媒材料，適度增加材料的含鈦量可使光催化降解亞甲基藍的活性提昇將近1倍。

摘要(英)

In this study, the prepared SBA-15 was grafted with a TiO2 thin layer via chemical grafting method. The resulting TiO2-modified material with high surface area and well-ordered mesoporous structure can be demonstrated efficiency in MB photoblenching reaction.
XRD and HRTEM images showed that under the process of calcination, Ti/SBA R1nc increase calcined temperature didn’t caused destroy of the structure of Ti/SBA R1nc, whereas TiO2 monolayer was hardly observed. Comparing Ti/SBA R1c500 , Ti/SBA R2c500 and Ti/SBA R3c500, we concluded that the surface areas decreased regularly with the increasing times of reflux from 765 m2/g ( SBA-15 ) to 480 m2/g ( Ti/SBA R3c500 ). ICP-OES revealed the contents of Ti had risen from 6.5% ( Ti/SBA R1nc ) to 22.7% ( Ti/SBA R3c500 ). However, the regularity of structure decreased enormously and TiO2 anatase phase characteristic peak was observed after hydrothermal treatment of Ti/SBA R1HT. The hysteresis loop of N2 adsorption-desorption isotherm presented that the slit from pore of H3 type, indicated the TiO2 nanoparticle had piled up and destroyed the high regularity of the original channels. The conclusion corresponded to the FESEM image which molecular sieves were tightly surrounded by TiO2 nanoparticles.
The result of MB photoblenching reaction was exhibited by two parts: adsorption and degradation. In adsorption part, we assumed the higher calcined temperature could make TiO2 monolayer shrink and exposed the surface of SBA-15 that resulted in increase of MB adsorption. In degradation part, Ti/SBA R1c500 performed the best photocatalytic ability that decomposed 42.8% MB in 2 hours while Ti/SBA R1nc performed only 36.8%. K values of first-order reaction elevated from 0.0856 min-1 ( Ti/SBA R1nc ) to 0.1213 min-1 ( Ti/SBA R1c500 ). Ti/SBA R1HT under hydrothermal treatment adsorbed only 12.9% MB and decomposed 58.1% MB in 2 hours ( K = 0.1152 ). By incresing times of chemical grafting, the k values of 0.2260 min-1 and 0.2001 min-1. However, the photocatalytic activities of Ti/SBA R2HT and Ti/SBA R3HT didn’t perform such a significant improvement as Ti/SBA R1HT.
In this study, we found the optimal condition by adjusting calcined temperature and grafting times and successfully prepared a photocatalytic material that nearly multiplied the degradation of MB photobleaching reaction.

關鍵字(中)

★ 化學嫁接法
★ 二氧化鈦
★ SBA-15
★ 亞基甲藍光降解反應

關鍵字(英)

★ MB photoblenching reaction
★ SBA-15
★ Chemical grafting method
★ Titianium dioxide

論文目次

摘要………………………………………………………………………I
Abstract…………………………………………………………………III
誌謝……………………………………………………………………..V
目錄…………………………………………………………………….VI
圖目錄………………………………………………………………….XI
表目錄………………………………………………………………..XVI
第一章緒論……………………………………………………………1
1-1 中孔洞氧化矽材料發展……………………………………1
1-2 M41S系列……………………………………………………1
1-3 SBA系列…………………………………………………….5
1-4 二氧化鈦簡介………………………………………………9
1-4-1 二氧化鈦的光催化原理…………………………………13
1-4-2 二氧化鈦修飾中孔材料…………………………………14
1-4-2-1 後合成嫁接法 ( Post synthesis grafting method
...........................................14
1-4-2-2 含浸法 ( Impregnation method )……………….15
1-4-2-3 直接水熱法 (Direct Hydrothermal method )….15
1-5 研究動機…………………………………………….…………16
第二章實驗方法…………………………………………………….17
2-1 化學藥品………………………………………………….17
2-2 實驗儀器………………………………………………….18
2-3 分子篩的製備…………………………………………….19
2-3-1 水熱法 (Hydrothermal) 製備 SBA-15中孔洞分子篩..19
2-3-2 後合成嫁接法 (Post synthesis grafting) 製備 TiO2
修飾 SBA-15分子篩………………………………………19
2-3-3 不同鍛燒溫度的 TiO2 修飾 SBA-15 分子篩………..20
2-3-4 不同嫁接次數之 TiO2 修飾SBA-15分子篩……………21
2-3-5 以水熱結晶方式製備 TiO2 修飾 SBA-15分子篩…….22
2-4 觸媒之結構分析與鑑定……………………………………….22
2-4-1 X光粉末繞射 (Powder X-ray Diffraction；XRD)….22
2-4-2 熱重分析法 (Thermal Gravimetric Analysis；TGA)23
2-4-3 氮氣等溫吸附-脫附曲線 (N2 adsorption –
desorption isotherm) ..........................24
2-4-3-1 以 BET 理論求得表面積………………………………27
2-4-3-2 以 BJH 理論求得孔徑分布……………………………28
2-4-3-3 孔洞總體積的計算…………………………………….30
2-4-4 場發射掃描式電子顯微鏡 (Field-emission Scanning
Electron Microscopy；FESEM)…………………………….31
2-4-5 高解析度穿透式電子顯微鏡 (High Resolution
Transmission Electron Microscopy；HRTEM)..........32
2-4-6 紫外光-可見光吸收光譜 (UV-Visible spectroscopy；
UV-Vis)……………………………………………………...32
2-4-7 傅立葉紅外線吸收光譜 (Fluorier Transform Infrared
Spectroscopy；FT-IR)………………………………………33
2-4-8 誘導偶電漿原子發射光譜儀 (Inductivity Coupled
Plasma-Optical Emission Spectroscopy ; ICP – OES)33
2-4-9 X-光吸收精細結構光譜 (X-ray Absorption
FineStructure spectroscopy；XAFS)……………………34
2-4-10 拉曼光譜 (Raman spectroscopy)……………………… 35
2-5 亞甲基藍光脫色反應測試…………………………………….36
第三章結果與討論………………………………………………….39
3-1 中孔洞分子篩 SBA-15………………………………………..39
3-1-1 XRD 鑑定........................................39
3-1-2 氮氣等溫吸附 – 脫附曲線.........................41
3-1-3 熱重分析 (TGA) 鑑定..............................42
3-1-4 傅立葉轉換紅外線光譜 (FT-IR).....................43
3-1-5 場發射掃描式電子顯微鏡 (FESEM)...................44
3-1-6 高解析穿透式電子顯微鏡 (HRTEM)...................45
3-2 後合成法嫁接 TiO2 修飾中孔分子篩 SBA-15……………..46
3-3 鍛燒溫度的影響………….............................46
3-3-1 XRD 鑑定.........................................47
3-3-2 氮氣等溫吸附 – 脫附曲線.........................49
3-3-3 場發射掃描式電子顯微鏡 (FESEM)...................52
3-3-4 高解析穿透式電子顯微鏡 (HRTEM)...................55
3-3-5 Raman 光譜.......................................55
3-3-6 Ti K-edge XANES 光譜.............................57
3-3-7 亞甲基藍光降解活性測試...........................58
3-4 迴流嫁接鈦源次數………………………………...........64
3-4-1 XRD 鑑定.........................................64
3-4-2 氮氣等溫吸附 – 脫附曲線.........................67
3-4-3 場發射掃描式電子顯微鏡 (FESEM)...................69
3-4-4 高解析穿透式電子顯微鏡 (HRTEM)...................69
3-4-5 Raman 光譜.......................................72
3-4-6 Ti K-edge XANES 光譜.............................73
3-4-7 亞甲基藍光降解活性測試...........................74
3-5 鍛燒與水熱結晶方式的比較…………………………….....76
3-5-1 XRD 鑑定.........................................76
3-5-2 氮氣等溫吸附 – 脫附曲線.........................78
3-5-3 場發射掃描式電子顯微鏡 (FESEM)...................80
3-5-4 高解析穿透式電子顯微鏡 (HRTEM)...................80
3-5-5 Raman 光譜.......................................84
3-5-6 亞甲基藍光降解活性測試...........................85
第四章結論………………………………………………………….89
參考文獻……………………………………………………………..92
附錄……………………………………………………………………101

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指導教授

簡淑華、高憲明

審核日期

2009-2-4

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