由於氨基與銅離子具有很高的錯合常數kf值(1.1×〖10〗^13)，本研究以氨基修飾的二氧化矽(SiO2-N)為基材製備銅離子負載的複合物，以作為高效能銨離子(NH4+)吸附劑，研究顯示，基材上隨著銅離子負載濃度提升，表面與整體的N/Cu元素比例降低。吸附實驗顯示銅離子負載二氧化矽(SiO2-NCu)吸附量為未負載銅離子之氨基修飾二氧化矽膠體(SiO2-N)的3.8倍，最大NH4+離子吸附量可達21.07 mg/g，等溫吸附表現符合Langmuir模式，且吸附反應在1分鐘內即達平衡，顯示銅離子在SiO2-NCu材料中為一有效的NH4+吸附位址，且由於NH4+離子吸附前後，表面與整體的Cu/Si元素比例均無明顯改變，顯示銅離子能高度穩定地固著在基材表面，XPS的Cu 2p圖譜說明，高濃度的CuCl2，會使材料表面的銅離子大多以Cu+方式存在，吸附時伴隨氧化還原的進行。銅負載複合羧酸基(-COOH)與氨基的二氧化矽(SiO2-HybridCu)顆粒大小為 SiO2-NCu的5.5倍，吸附量僅為SiO2-NCu的0.67倍，儘管-COOH 額外提供SiO2-HybridCu靜電吸附NH4+離子的位址，但相較於SiO2-NCu(表面Cu/Si= 0.10)，較低的銅附載量(表面Cu/Si= 0.04)仍限制其吸附表現。

In this study, copper-loaded composite was prepared using amino-functionalized silicon dioxide (SiO2-N) as the adsorbent for ammonium ions (NH4+) adsorption based on the high formation constant (1.1×〖10〗^13) between amino functional group and copper ions. The SEM-EDX and XPS were used to determine the N/Cu atomic ratio. From the analysis, it was found that the atomic ratio of N/Cu decreased as the copper ions concentration increases. The adsorption results showed that the adsorption capacity of NH4+ ions for copper-loaded silicon dioxide (SiO2-NCu) is 3.8 times higher than the non-loaded SiO2-N. The maximum adsorption capacity of NH4+ obtained from Langmuir isotherm model was 21.07 mg/g, suggesting that the copper ion is an effective adsorption site for NH4+. In addition to that, the SiO2-NCu has a fast kinetic and reach equilibrium adsorption within 1 min. From the result of SEM-EDX and XPS, the atomic ratio of Cu/Si was remained similar after NH4+ adsorption, indicating that the well complexation between copper ions and amino groups on the surface of adsorbent. The Cu 2p spectrum of XPS suggested that the high loading of Cu ions resulted in the surface of adsorbent was mostly complexed with copper(I). The particle size of amino-functionalized and carboxylic acid-functionalized(-COOH) silicon dioxide(SiO2-Hybrid) was 5.5 times bigger than SiO2-NCu. From the XPS analysis, the SiO2-Hybrid has a lower Cu/Si ratio (0.04) compared to the SiO2-NCu (Cu/Si = 0.10). Although -COOH functional group provides additional electrostatic interaction site for NH4+ adsorption, the adsorption capacity of SiO2-HybridCu is only 0.67 times of SiO2-NCu, suggesting that the amount of copper loading control the adsorption capacity of composites.

摘要 I
Abstract II
致謝 III
主目錄 IV
圖目錄 VII
表目錄 IX
第一章 前言 1
1.1 研究動機 1
1.2 研究目的 2
第二章 文獻回顧 4
2.1 現有NH4+吸附劑及吸附機制 5
2.2 重金屬吸附NH3/NH4+ 10
2.3 環境影響因子 12
2.3.1 初始濃度 12
2.3.2 pH值 12
2.3.3 反應時間 13
2.4吸附熱力學 13
2.5 吸附動力學 15
2.5.1 擬一階方程式(pseudo-first-order kinetic model) 15
2.5.2 擬二階方程式(pseudo-second-order kinetic model) 16
第三章 材料與方法 17
3.1 實驗架構 17
3.2 實驗材料 18
3.3 銅負載氨基二氧化矽(SiO2-NCu)合成方法 19
3.4 銅負載複合官能基二氧化矽(SiO2-HybridCu)製備方法 20
3.5材料特性分析 22
3.5.1等溫氮氣吸脫附分析 22
3.5.2奈米粒徑及電位分析儀 23
3.5.3高解析場發射掃描式電子顯微鏡及能量散佈光譜儀(SEM-EDX) 23
3.5.4 X光光電子能譜儀(XPS) 23
3.5.5傅立葉轉換紅外光譜分析(FTIR) 24
3.5.6熱重分析儀 24
3.5.7感應耦合電漿原子發射質譜儀(ICP-MS) 24
3.6 NH4+吸附溶液實驗 25
3.6.1 NH4+溶液配置 25
3.6.2 離子層析儀分析條件 25
3.6.3 pH實驗 25
3.6.4 吸附動力實驗 26
3.6.5 等溫吸附實驗 26
第四章 結果與討論 27
4.1 吸附實驗 27
4.1.1 不同銅離子濃度製備SiO2-NCu之吸附量 27
4.1.2 pH值對吸附量的影響 29
4.1.3 吸附動力與等溫吸附 32
4.2 銅離子負載氨基二氧化矽材料特性鑑定 36
4.3銅離子負載複合官能基二氧化矽材料 42
4.3.1銅離子負載複合官能基二氧化矽材料特性鑑定 42
4.3.2 銅離子負載複合官能基二氧化矽材料之吸附實驗 49
第五章 結論與建議 51
5.1 結論 51
5.2 建議 51
參考文獻 52
附錄A QA/QC 57

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