本研究以雙牙基[3-(2-aminoethylamino)propyl] trimethoxysilane (AATPS)和單牙基(3-aminopropyl)triethoxysilane (APTES)為功能性單體製備Cu(II)離子有機-無機複合拓印材料(ionic imprinting polymer, IIP)，研究中藉由分析複合物在不同Cu/氨基比例時的材料特性與對Cu(II)離子吸附能力的影響，探討雙牙基與單牙基在拓印過程中與金屬配位的能力與對材料拓印程度的影響，並藉由對不同離子吸附能力的比較，釐清離子拓印材料選擇性的關鍵。結果顯示當TEOS:MEMO:H2O:ethanol莫耳比例固定在15:10:102:200時，Cu: AAPTS = 1:1及 Cu: APTES= 0.5:1能使IIP-AAPTS與IIP-APTES分別有3.0和1.20 mg/g的最佳吸附量，且根據等溫吸附實驗，IIP-AAPTS與IIP-APTES在pH=5時的最高吸附量分別為27.55 與17.48 mg/g，兩系統中雖然Cu(II)離子對氨基的比例同為2，但AAPTS與Cu(II)離子的錯合行為能夠產生較完整的孔洞提供強吸附位置，因此吸附量較高。對Zn(II)、Ni(II)、Pb(II)、與Hg(II)的吸附選擇性分析中發現，IIP-AAPTS與IIP-APTES拓印材料對Cu(II)離子的吸附選擇性係數(k)分別為89.3與17.5以上，兩者分別在Cu/AAPTS為0.5-1.0與Cu/APTES為0.5時有最高選擇性，吸附能力依序為Cu(II)> Hg(II) > Zn(II) > Ni(II)> Pb (II)，選擇性的依據主要為離子半徑與配體及離子間的錯合能力。以上結果可知，相較於單牙基的APTES，雙牙基的AAPTS能與Cu(II)的產生穩定錯合物，因此以此為功能性單體的離子拓印材料在吸附能力和選擇性上有較優異的表現。

3-(2-aminoethylamino)propyl]trimethoxysilane (AATPS) and 3-aminopropyltriethoxysilane (APTES) were used as functional monomers to prepare Cu-imprinted-organic-inorganic polymers (IIP) while MEMO and TEOS were used as the organic and inorganic cross-linkers, respectively. Adsorption behaviors of the IIPs at different Cu(II)/amino-groups ratios were examined to investigate the complexation between the bidentate/monodentate ligands and the Cu(II) ions and the resulting imprinting extents in the IIPS. In addition, the keys controlling the selectivity of the IIPs were clarified by comparing the adsorption capacities with those for different ions. The results showed that the IIPs exhibited the highest adsorption capability at the Cu: AAPTS = 1:1 and Cu: APTES = 0.5:1 when TEOS: MEMO :H2O:ethanol were controlled at 15:10:102:200. Although the Cu/amino-groups ratios in the two systems were equal, stronger complexation between the AAPTS and the Cu(II) ions resulted in stronger adsorption sites and thus leaded the IIP-AAPTS to perform higher adsorption ability (3.0 mg/g) than APTES-based system (1.2 mg/g). Both the IIP-AAPTS and IIP-APTES had the optimal adsorption performance at pH=5 and the highest adsorption amounts were 27.55 and 17.48 mg/g, respectively. Relative to the adsorptions for Zn(II), Ni(II), Pb(II), and Hg(II) ions, the IIP-AAPTS and IIP-APTES compounds at the Cu/AAPTS=0.5-1.0 and the Cu/APTES= 0.5, respectively, showed the highest selectivity factors (k) of 89.3 and 17.5, respectively, for Cu(II) ions. The selectivity order was Cu(II)> Hg(II) > Zn(II). > Ni(II)> Pb (II), and it is controlled by ionic radii and the complex ability between the ligands and the ions. These results reveal that the bidentate AAPTS can interact with Cu(II) ions to form a more stable complex than monodentate APTES, thus is more suitable to be used as the functional monomer to prepare IIPs exhibiting high adsorption capacity and selectivity.

目錄
摘要 I
Abstract II
目錄 III
表目錄 VI
圖目錄 VII
第一章、前言 1
1.1研究背景與動機 1
1.2研究目的 3
第二章、文獻回顧 4
2.1銅的概述 4
2.1.1銅離子污染 4
2.1.2銅的物化特性 6
2.2拓印技術概念 8
2.2.1 拓印方式 9
2.2.2拓印材料的製備 10
2.3離子拓印材料 11
2.3.1離子拓印材料的基礎 13
2.3.2離子拓印材料的特性 16
2.3.3影響吸附能力的因子 20
2.3.4 選擇性因子 22
2.4離子拓印材料應用 24
第三章、材料研究與方法 25
3.1 實驗架構 25
3.2 離子拓印材料組成成分 26
3.3 拓印高分子合成方法 28
3.4 離子拓印材料表面特性分析 30
3.4.1等溫氮氣吸脫附分析(Nitrogen adsorption-desorption isotherm Measurement) 30
3.4.2熱重分析儀(Thermal gravimetric analysis, TGA) 30
3.4.3場發射掃描式電子顯微鏡及能量散佈光譜儀(SEM-EDS) 32
3.4.4傅立葉轉換紅外線光譜儀(Fourier transform infrared spectrometer, FTIR) 33
3.5吸附實驗 34
3.5.1 Cu(II)離子溶液配置 34
3.5.2 pH實驗 34
3.5.3吸附動力實驗 35
3.5.4等溫吸附實驗 36
3.5.5 Scatchard分析 37
3.5.6感應耦合電漿原子發射質譜儀(Inductively Coupled Plasma,ICP-MS) 37
3.6 選擇性測試 38
第四章、結果與討論 39
4.1 離子拓印複合材的製備 39
4.2 離子拓印複合材的鑑定 40
4.2.1離子拓印複合材型態 40
4.2.2離子拓印複合材特性 41
4.2.3離子拓印複合材料的組成 42
4.3吸附實驗 50
4.3.1 pH調整吸附實驗 50
4.3.2 Cu(II)吸附實驗 51
4.3.3動力吸附實驗 53
4.3.4等溫吸附實驗 56
4.3.5 Scatchard分析 59
4.4選擇性試驗 61
第五章 結論 69
參考文獻 70
附錄 76

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