臺灣博碩士論文加值系統

本研究以製備魚鱗膠原蛋白/單寧酸合成奈米粒子對重金屬離子進行吸附實驗。讓魚鱗膠原蛋白與單寧酸藉由自組裝方式形成奈米粒子；該奈米粒子具有100~500 nm之平均粒徑。以FTIR觀察原本單寧酸上OH伸縮震動3338 cm-1因OH參與形成氫鍵而產生往3230 cm-1移動，同時以XRD觀察其結構是否有差異改變等，並藉由TEM、DLS、DSC來觀察奈米粒子的形狀、粒徑分佈、熱性質等。
本研究的主要是探討研究吸附重金屬離子能力，藉由Langmuir等溫吸附模式得到對銅離子、鎳離子的最大吸附量分別為123 mg/g和136 mg/g，吸附動力學模式來進行分析、並探討吸附熱力學之△H0、△G0、△S0的變化。

關鍵詞：魚鱗膠原蛋白、單寧酸、奈米粒子、吸附

This fish scale collagen/tannic acid nanoparticles are formed by self-assembly of collagen and polyphenols, which are used to adsorption of heavy metal ions. The average size of synthetic nanoparticles is 100 ~ 500 nm. FTIR shows a free O-H stretching vibration of tannic acid occurs in the range 3338 cm-1, but the O-H group of the nanoparticles is involved in a hydrogen bond, its position is shifted to lower frequency, usually 3230 cm-1. The characterization of nanoparticles is investigated by XRD, TEM, DLS and DSC. The present study aims to explore the adsorption capacities, kinetics and thermodynamics of Cu(II) and Ni(II) ion from aqueous solution onto fabricated fish scale collagen/tannic acid nanoparticles.
The maximum capacity for the adsorption of Cu(II) and Ni(II) ion onto nanoparticles, deduced from the use of the Langmuir isotherm equation, was 123 and 136 mg/g respectively. The experimental data of Cu(II) and Ni(II) ion adsorption fitted the pseudo-second order kinetic model well, indicating that chemical sorption is the rate-limiting step. The negative Gibbs free energy of adsorption indicated a spontaneous adsorption, while the positive enthalpy change indicated an endothermic adsorption process.

Keywords: fish scale collagen; tannic acid; self-assembly; nanoparticles; adsorption

目錄
明志科技大學碩士學位論文指導教授推薦書 i
明志科技大學碩士學位論文口試委員會審定書 ii
明志科技大學學位論文授權書 iii
誌謝 iv
摘要 v
Abstact vi
目錄 vii
表目錄 x
圖目錄 xi

第一章 前言 1
1-1 研究動機 1
1-2 研究項目 2
1-2-1吸附劑製備 2
1-2-2特性分析 2
1-2-3吸附劑吸附行為探討 2

第二章 文獻回顧 3
2-1 膠原蛋白 3
2-1-1簡介 3
2-1-2結構與特性 4
2-1-3魚鱗膠原蛋白 7
2-2 單寧酸 9
2-3 重金屬 13
2-3-1來源 13
2-3-2重金屬常見處理方式 13
2-3-3銅的特性與影響 15
2-3-3鎳的特性與影響 17
2-4 奈米材料 18
2-4-1簡介 18
2-4-2奈米材料特性 19
2-4-3奈米材料製備法 22
2-5吸附理論 23
2-6等溫吸附模式 27
2-7 動力學吸附模式 28
2-8 熱力學吸附模式 33

第三章 實驗方法與設備 31
3-1 實驗藥品 34
3-2 實驗設備與分析儀器 35
3-3 自組裝奈米粒子之製備 37
3-4 吸附劑吸附銅離子溶液之方法 38
3-4-1吸附銅離子溶液之吸附實驗 39
3-4-2等溫吸附實驗 39
3-4-3動力學吸附探討 41
3-4-4不同pH值吸附實驗 41
3-5 吸附劑吸附鎳離子溶液之方法 43
3-5-1吸附鎳離子溶液之吸附實驗 44
3-5-2等溫吸附實驗 44
3-5-3動力學吸附探討 46
3-5-4不同pH值吸附實驗 46
3-6 ICP-OES分析 48
3-7 XRD分析 49
3-8 FTIR分析 50
3-9 TEM分析 50
3-11 DLS分析 50
3-12 DSC分析 51

第四章 實驗結果與討論 52
4-1 FTIR之探討 52
4-2 TEM之探討 53
4-3 DLS之探討 54
4-4 XRD之探討 55
4-5 DSC之探討 56
4-5 pH值對吸附的影響 57
4-6 等溫吸附模式探討 58
4-7 動力學吸附探討 62
4-8 熱力學吸附探討 67

第五章 結論 69

參考文獻 70

表目錄
表2-1目前膠原蛋白常見的用途 6
表2-2單寧吸附重金屬之研究文獻 11
表2-3藍胞質素在血液中的功能 15
表2-4物理及化學方法製備奈米粒子 22
表2-5物理吸附與化學吸附兩者差別 24
表4-1FSC/tannin奈米粒子的粒徑與Zeta電位值 54
表4-2吸附金屬離子之Langmuir等溫吸附參數 61
表4-3吸附金屬離子之Freundlich等溫吸附參數 61
表4-4RL值對Langmuir等溫吸附模式吸附判定 61
表4-5吸附金屬離子之擬一階吸附動力參數 66
表4-6吸附金屬離子之擬二階吸附動力參數 66
表4-7吸附金屬離子之內部擴散吸附動力參數 66
表4-8吸附金屬離子之熱力學吸附動力參數 68

圖目錄
圖2-1a.脯氨酸(Pro)、b.甘氨酸(Gly)、c.羥脯氨酸(Hyp)結構 4
圖2-2膠原的右手超螺旋結構 4
圖2-3膠原蛋白結構 5
圖2-4a.水解型單寧 b.縮合型單寧 9
圖3-1複合吸附劑製備流程圖 37
圖3-2自組裝示意圖 37
圖3-3銅離子溶液製備 38
圖3-4吸附劑吸附銅離子溶液 38
圖3-5不同初始濃度吸附劑吸附銅離子 40
圖3-6不同pH值之吸附劑吸附銅離子 42
圖3-7鎳離子溶液製備 43
圖3-8吸附劑吸附鎳離子溶液 43
圖3-9不同初始濃度吸附劑吸附鎳離子 45
圖3-10不同pH值之吸附劑吸附鎳離子 47
圖3-11ICP-OES（感應耦合電漿放射光譜儀） 48
圖4-1FSC、tannin與FSC/tannin acid之FTIR光譜 52
圖4-2FSC/tannin不同濃度奈米粒子之TEM圖 53
圖4-3FSC與FSC/Tannin之XRD圖 55
圖4-3FSC與FSC/Tannin之DSC圖 56
圖4-5pH值對吸附之影響 57
圖4-6FSC/tannin吸附劑吸附銅離子之Langmuir等溫吸附模式 59
圖4-7FSC/tannin吸附劑吸附銅離子之Freundlich等溫吸附模式 59
圖4-8FSC/tannin吸附劑吸附鎳離子之Langmuir等溫吸附模式 60
圖4-9FSC/tannin吸附劑吸附鎳離子之Freundlich等溫吸附模式 60
圖4-10吸附銅離子之擬一階吸附動力模式 63
圖4-11吸附銅離子之擬二階吸附動力模式 63
圖4-12吸附鎳離子之擬一階吸附動力模式 64
圖4-13吸附鎳離子之擬二階吸附動力模式 64
圖4-14吸附銅離子之內部擴散吸附動力模式 65
圖4-15吸附鎳離子之內部擴散吸附動力模式 65
圖4-16銅離子之熱力學吸附模式 67
圖4-17鎳離子之熱力學吸附模式 68

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