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研究生：	黃家瑜 Huang, Jia-Yu
論文名稱：	中孔洞氧化矽及氧化鋁之合成與應用 Synthesis and Application of Mesoporous Silica and Alumina
指導教授：	林弘萍 Lin, Hong-Ping
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2021
畢業學年度：	109
語文別：	中文
論文頁數：	79
中文關鍵詞：	中孔洞氧化矽、氧化鋁孔洞材料、智慧玻璃窗、CsPbBr3鈣鈦礦螢光粉、水溶液中氟離子之移除
外文關鍵詞：	mesoporous silica, porous alumina, fluoride ion removal, liquid crystal, CsPbBr3 perovskite nanocrystals
相關次數：	點閱：351 下載：1
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本論文研究主旨為，運用快速合成中孔洞氧化矽的方式，合成出各種不同構型之中孔洞氧化矽材料，並應用於智慧玻璃窗以及做為CsPbBr3鈣鈦礦螢光粉載體。本論文也探討氧化鋁孔洞材料之合成，並將其用於吸附水中之氟離子。首先利用C16TAB作為有機模板，矽酸鈉為氧化矽源，並以倒入大量鹼性緩衝溶液的方法，使矽酸鹽與四級銨鹽快速結合，獲得長條型中孔洞氧化矽材料。為了增加有機模板的多樣性，引入了SDS陰離子界面活性劑，形成陰-陽離子雙界面活性劑系統，形成不同型態的有機模板，合成出囊泡狀型態之中孔洞氧化矽材料。接著討論將陰離子界面活性劑改為硬脂酸鈉，氧化矽源則用單體型的四乙基氧矽(TEOS)，調整陰-陽離子界面活性劑之比例以及反應pH值，得到紅血球構型及繡球花構型之中孔洞氧化矽材料，而將紅血球構型之中孔洞氧化矽經過高溫水熱方式使中間較薄的氧化矽層溶解再析出，使得構型轉變為甜甜圈狀的中孔洞氧化矽材料。將所合成之不同構型之中孔洞氧化矽材料，藉由三甲基氯矽烷進行疏水性官能基修飾後，與向列型液晶5CB(4-Cyano-4'-pentylbiphenyl)均勻混合，形成液晶-氧化矽混合相，孔洞氧化矽材料會擾亂液晶分子的排列並形成許多散射區塊，使智慧玻璃窗具有散射光線的功能並呈現霧態，通入電場後液晶分子整齊排列於電場方向，散射區塊消失而呈現透明態，使用不同構型之中孔洞氧化矽可製備出利用電場控制明暗變化的智慧玻璃窗，具有應用於綠色建材之潛力。全無機元素所組成的CsPbBr3鈣鈦礦螢光粉，因其具有可調控的放光波長以及高放光強度，近年來被大量研究。本研究利用中孔洞氧化矽材料中的孔洞尺寸限制奈米粒子的成長大小，達到良好的粒徑控制，使CsPbBr3鈣鈦礦螢光粉有高放光強度以及狹窄的螢光半高寬，藉由改變中孔洞氧化矽和silica gel之莫耳比，以及CsBr和PbBr2之比例，合成出放光波長位於525 nm且半高寬為25 nm的CsPbBr3@SiO2螢光粉材料。接著再嘗試以CsI或CsCl參雜於材料內，合成出CsPb(Br,I)3@SiO2材料，
放光波長紅移至
550 nm，而CsPb(Br,Cl)3@SiO2材料放光波長則藍移至508 nm。以市售之活性氧化鋁作為氧化鋁材料之來源，將反應pH值調控至6.0~7.0，以攪拌水熱的方式水熱處理二十四小時後，即可得到含有單水鋁石(AlOOH)晶相之氧化鋁材料；若將反應pH值調控至8.0~9.0，則會得到以氫氧化鋁為主的晶相。若將氧化鋁材料經過600℃煅燒處理後，則轉為γ-Al2O3為主的晶相。將不同晶相之材料進行吸附實驗，以單水鋁石或是氫氧化鋁為主的材料會利用OH-基團與氟離子進行離子交換反應，來降低溶液中之氟離子濃度，而若是以γ-Al2O3晶相為主的材料，則是利用結構中的空隙來吸附溶液中之氟離子。
將氧化鋁粉末與褐藻酸鈉進行造粒，探討吸附之動力學，由實驗結果可之，造粒後的材料都有相當良好的吸附效率，100 ppm之氟離子溶液可以在一分鐘之內下降至50 ppm，且符合偽一級動力學模型。之後將造粒之溶液改用硝酸鎳以及氯化鈣，形成雙金屬顆粒，可以發現其吸附效率下降，符合實驗推測之吸附機構。

Porous materials have many advantages, including a tunable pore size and a controllable morphology. This study synthesized and characterized three porous materials for different applications, namely liquid crystal smart windows, stabilized fluorescent materials, and fluoride ion removal in drinking water. The study commenced by using a rapid self-assembling method to synthesize mesoporous silica nanoparticles under different reaction conditions. Rod-like, erythrocyte-like, donut-like and hydrangea macrophylla-like mesoporous silica were synthesized using different ratios of cationic surfactant (C16TAB) to anionic surfactant (sodium dodecyl sulfate or sodium stearate), tetraethyl orthosilicate (TEOS) as the silica source, and pH values in the range of 5.0～9.0. The synthesized nanoparticles were hydrophobically modified with chlorotrimethylsilane and then mixed with 5CB liquid crystal and assembled into LC smart windows. All-inorganic CsPbX3 (X=I, Br, Cl) perovskite nanocrystals have excellent optical properties, including a tunable wavelength, a narrow bandwidth, and a high quantum efficiency. However, they have poor stability. Thus, in the present study, the stability of CsPbBr3 perovskite nanocrystals was improved via encapsulation in mesoporous silica and silica gel. It was shown that the addition of small quantities of iodine and chloride to the CsPbBr3 nanocrystals caused a shift of the PL emission peak to 550 nm and 508 nm, respectively. Fluoride ion pollution in drinking water is a serious problem in many regions of the world. Thus, in this study, porous aluminum species with different crystalline phases were prepared to absorb fluoride in solution. When mixing the prepared alumina powders in a fluoride ion solution, the fluoride ions replaced the hydrated ions on the alumina species, thereby reducing the fluoride ion concentration of the solution. The experimental results showed that the fluoride ion concentration was reduced from 100 ppm to 50 ppm in just 1 minute.

目錄
第一章、緒論...................................................................................................1
1 中孔洞材料................................................................................................................. 1
1.1 中孔洞氧化矽....................................................................................................... 1
1.2 中孔洞氧化鋁....................................................................................................... 3
2 界面活性劑................................................................................................................. 5
2.1界面活性劑基本性質及種類............................................................................... 5
2.2 微胞的形成........................................................................................................... 6
3 氧化矽源介紹............................................................................................................. 9
3.1 矽酸鈉(Sodium Silicate, S.S) ............................................................................... 9
3.2 四乙氧基矽烷(Tetraethyl Orthosilicate, TEOS) ............................................ 11
4 水熱法簡介............................................................................................................... 13
5 智慧玻璃窗(Smart Window)介紹............................................................................ 15
6 鈣鈦礦螢光粉之介紹27, 28........................................................................................ 18
7 吸附水溶液中氟離子之方法簡介34........................................................................ 19
7.1 吸附動力學......................................................................................................... 19
第二章、合成與鑑定.....................................................................................22
1 化學藥品................................................................................................................... 22
2 中孔洞氧化矽材料合成之步驟............................................................................... 23
2.1 合成長條形中孔洞氧化矽................................................................................. 23
2.2 合成特殊型態之中孔洞氧化矽......................................................................... 24
3 智慧玻璃窗的製作................................................................................................... 25
3.1 中孔洞氧化矽之材料疏水性官能基修飾......................................................... 25
3.2 智慧玻璃窗的製作............................................................................................. 26
4 合成CsPbBr3@SiO2螢光粉之步驟......................................................................... 27
4.1 合成中孔洞氧化矽載體..................................................................................... 27
4.2 合成CsPbBr3@SiO2螢光粉.............................................................................. 28
5吸附氟離子之中孔洞氧化鋁材料合成步驟............................................................ 29
6 儀器鑑定分析........................................................................................................... 30
6.1 穿透式電子顯微鏡(Transmission Electron Microscopy, TEM)........................ 30
6.2 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) ............................. 30
6.3 熱重分析儀(Thermogravimetry Analysis, TGA).............................................. 31
6.4 氮氣等溫吸附/脫附測量(N2 Adsorption-Desorption Isotherm)....................... 31
6.5 X-射線粉末繞射光譜(Powder X-Ray Diffraction, PXRD).............................. 35
6.6 螢光光譜儀(Fluorescence Spectrophotometer).................................................. 36
6.7 氟離子電極......................................................................................................... 37
第三章、不同型態之中孔洞氧化矽運用於智慧玻璃窗及螢光粉載體....38
1 研究動機................................................................................................................... 38
2 合成長條狀中孔洞氧化矽材料............................................................................... 39
2.1以倒入大量鹼性緩衝溶液方式合成長條型中孔洞氧化矽............................. 39
2.2探討C16TABr/SDS莫耳比對型態之影響........................................................ 42
3 合成多種形態之中孔洞氧化矽材料....................................................................... 43
3.1 探討硬脂酸鈉/C16TAB莫耳比和反應pH值對型態之影響........................... 44
3.2 探討不同反應時間及水熱與否對型態之影響................................................. 49
4 不同構型之中孔洞氧化矽材料應用於智慧玻璃窗............................................... 51
5 中孔洞氧化矽應用於合成CsPbBr3@SiO2 ............................................................. 56
5.1選擇silica gel/MS莫耳比例.............................................................................. 56
5.2 中孔洞氧化矽之孔洞大小對發光強度的影響................................................. 57
5.3 選擇CsBr/PbBr2之比例.................................................................................... 59
5.4 摻雜不同鹵素對螢光粉之放光波長的影響..................................................... 59
第四章、氧化鋁孔洞材料於吸附水中氟離子之應用................................62
III
1 研究動機................................................................................................................... 62
2 不同金屬氧化物孔洞材料對於吸附氟離子之效率............................................... 63
3 藉由調控反應條件來改變活性氧化鋁之晶相....................................................... 63
4 探討不同氧化鋁晶相對氟離子吸附之效率........................................................... 66
5氧化鋁孔洞材料對於吸附氟離子之動力學探討.................................................... 68
6 探討雙金屬造粒對於吸附氟離子之效率............................................................... 71
第五章、總結.....................................................................................74
參考文獻............................................................................................76
                                    

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