臺灣博碩士論文加值系統

本論文主要的研究在於(1)製備二氧化矽中孔洞基本材料及其衍生化三種不同官能基之材料(2)利用衍生化後之材料，進行金屬離子銅及鎘的吸附研究。
製備方法方面，使用有機物的界面活性劑(Cetyltrimethylammonium bromide(C16TABr))當模板，加上矽酸鈉無機物為骨材並且在酸性環境下添加KNO3鹽類，再經由溶劑萃取後，得到中孔洞的二氧化矽材料。並在移除界面活性劑時加入silane即可達到衍生化目的。
衍生化部分，有胺基(-NH2)、硫醇基(-SH)及磺酸基(-SO3H)三種，並利用BET、IR、EA、TGA、SEM、TEM等方法鑑定。鑑定後計算其修飾量分別約為-NH2: 2.9mmol/g、-SH: 2.1mmol/g、SO3H: 1.5mmol/g。
吸附實驗使用金屬離子銅及鎘兩種溶液。吸附實驗結果顯示隨著溶液的pH增加至4.0及4.5，分別對銅離子及鎘離子的吸附效果越好。吸附溫度方面，隨著溫度的提升。對金屬離子的吸附效果越好。吸附時間的方面，在短時間90mins內期吸附效果就有不錯的表現。在恆溫吸附模式推導下，符合Langmuir isotherm model。在再生能力表現上，以SiO2-SO3H最佳，對銅可達到84%，對鎘更可達到90%，符合吸附材的條件。所以就吸附能力及再生能力上，以SiO2-SO3H為最佳的吸附材。

This thesis covers two major areas of research: First, the preparation of SiO2 mesoporous materials and deriving of three functional groups, -SH, -NH2 and –SO3H on the surface of SiO2 mesoporous materials Second, the study of adsorption ability of metal ions (copper and cadmium) for all SiO2 mesoporous materials.
The organic template used surfactant Cetyltrimethylammonium bromide (C16TABr) to form micelle and added inorganic sodium silicate to synthesis silica mesoporous in acidic environment. The removal of surfactant is used by solvent-extraction-reflux method.
There are three functional group derivatives of mesoporous, -SO3H, -SH and –NH2. which are identified by BET, FT-IR, EA, TGA, SEM and TEM instruments. After identification, the amount of functional group were around as follows: -NH2: 2.9mmol/g, -SH: 2.1mmol/g, –SO3H: 1.5mmol/g.
The results of adsorption are: Firstly, the best conditions of pH value are 4 for copper and 4.5 for cadmium ions respectively. Secondly, the ability is good in a short time (within 90 minutes) for all mesoporous. Lastly, the best ability of regeneration is SiO2-SO3H material and the abilities are 84% and 90% for copper and cadmium ions respectively. Hence, SiO2-SO3H material is the best adsorbent.

第一章 緒論………………………………………………………….. 1
1-1 中孔洞材料簡介………………………………………………. 1
1-2 中孔洞材料的合成……………………………………………. 2
1-3 界面活性劑介紹……………………………………………… 5
1-4 矽酸鹽化學概念…………………………………………..….. 6
1-5 中孔洞材料製備方法…………………………………………. 9
1-6 孔洞材料的表面衍生化………………………………………. 10
1-7.表面衍生化有機官能機之應用……………………………….. 13
1-8 吸附理論、等溫模式及HSAB理論介紹……………………. 16
1-8-1 吸附理論………………………………………………….. 16
1-8-2 溫吸附模式……………………………………………….. 17
1-8-3硬軟酸鹼系統(HSAB)理論………………………………. 20
1-9 銅及鎘金屬簡介……………………………………………… 21
1-10 研究目的………………………….…………………………. 22
第二章 實驗部份…………………………………………………….. 23
2-1 實驗流程………………………………………………………. 23
2-2 化學藥品……………………..……………………………….. 24
2-3 產物鑑定儀器………………..……………………………….. 24
2-3-1 掃描式電子顯微鏡……………………………………….. 24
2-3-2 穿透式電子顯微鏡……………………………………….. 25
2-3-3 元素分析儀……………………………………………….. 25
2-3-4 熱重分析儀……………………………………………….. 26
2-3-5 氮氣等溫吸附脫附量測………………………………….. 26
2-3-6霍式紅外線光譜儀………..……………………………… 29
2-3-7石墨式原子吸收光譜儀………………………………….. 29
2-4 材料製備方法..………………………………………………. 30
2-4-1二氧化矽中孔洞材料製備………..……………………… 30
2-4-2二氧化矽中孔洞材料模板移除………..………………… 30
2-4-3二氧化矽中孔洞材料胺基(-NH2)衍生化………………… 31
2-4-4二氧化矽中孔洞材料硫醇基(-SH)衍生化………………. 32
2-4-5二氧化矽中孔洞材料衍生化磺酸基…………..………… 33
第三章 中孔洞材料的鑑定及吸附實驗結果探討………………….. 35
3-1 中孔洞材料製備方法比較……………………………………. 35
3-2 中孔洞材料鑑定結果…..…………………………………….. 37
3-2-1表面積及孔洞size鑑定結果…………………………….. 37
3-2-2 FT-IR鑑定結果…………………………………………… 42
3-2-3 EA元素分析鑑定結果…………………………………… 43
3-2-4 TGA熱重分析鑑定結果………………………………… 44
3-2-5 SEM鑑定結果……………………………………………. 46
3-2-6 TEM鑑定結果……………………………………………. 46
3-3 中孔洞材料的吸附實驗………..…………………………….. 48
3-4 吸附實驗步驟…………………………………………………. 49
3-4-1 金屬溶液的配置………………………………………….. 49
3-4-2 AAS的檢量線…………………………………………….. 50
3-5 重金屬的吸附結果探討………………………………………. 51
3-5-1 pH改變吸附實驗………..……………………………….. 51
3-5-1-1 SiO2-Unmodify吸附特性分析……………..……….. 53
3-5-1-2 SiO2-NH2 及SiO2-SH吸附特性分析……………….. 54
3-5-1-3 SiO2-SO3H吸附特性分析……………..…………….. 54
3-5-2 吸附時間改變吸附實驗………………………………….. 56
3-5-3 溫度改變吸附實驗……………………………………….. 58
3-5-4 恆溫吸附實驗…………………………………………….. 59
3-5-5 恆溫吸附模式探討……………………………………… 61
3-5-6 再生實驗………………………………………………….. 62
第四章 結果與討論………………………………………………….. 64
參考文獻……….…………………………………………………….. 65

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