土壤地下水污染普遍存在重金屬污染，而重金屬中六價鉻具有高水溶性、高毒性、不易被分解及生物累積性，進入生物體內透過食物鏈及生物累積，可能對環境及人體健康構成嚴重威脅。金屬-有機骨架(Metal–organic frameworks, MOFs)材料是近年受到關注的新型奈米微孔結晶材料，在各類型MOFs中，多孔結晶結構的沸石咪唑酸酯骨架(Zeolitic imidazolate frameworks, ZIFs)因擁有較好的熱、水熱及化學穩定性，在工業應用上逐漸受到重視。本研究係由實驗室自行合成之沸石咪唑骨架材料(Zeolitic imidazolate frameworks-8, ZIF-8)，探討分散條件、酸鹼值、吸附材用量及初始濃度變化等因素、評估ZIF-8對水體中六價鉻的吸附去除效率與影響，研究亦利用結構化學特性及陰離子交換特性，將六價鉻從水體中移除，並進行貴儀特性分析。研究發現，從不同分散方式的批次試驗中，利用超音波震盪方式可以使ZIF-8顆粒較分散，增加ZIF-8與六價鉻活性位點及接觸面積，進而提升去除效率。而在水解穩定性試驗中可發現，ZIF-8顆粒在7天內結構不會被破壞且適合酸鹼值pH 5.0-11.0範圍之間，具有良好的穩定性。由本研究之結果證實，ZIF-8移除六價鉻之機制包含:吸附、沉澱及還原作用(氧-羥基基團與六價鉻進行電子轉移)；由反應動力學模擬發現本研究符合擬二階速率方程式及符合Langmuir模型，ZIF-8對六價鉻吸附機制較符合化學鍵結吸附；透過X射線光電子能譜儀分析吸附機制表明吸附涉及靜電作用、氫鍵和化學還原過程。綜上所述，研究利用ZIF-8及Zn/Co ZIF處理水中之最大單位移除量分別為39.41 mg/g及46.06 mg/g，其反應過程能調節六價鉻廢水(100 mg/L)酸鹼值由pH 5.13上升至7.45-8.09，顯示ZIFs於水體中能提高OH-濃度，未來若結合生物整治技術，藉由鉻還原菌提高六價鉻廢水鉻之移除能力、利用ZIFs協助處理部分六價鉻及維持水體酸鹼值創造適合微生物生長環境，發展ZIFs應用於地下水整治仍具有潛力。

Hexavalent chromium has low water solubility, high toxicity, and high persistence with bioaccumulation effect. Metal–organic frameworks (MOFs) is the novel nanoporous crystalline material. Compared to other MOFs, zeolitic imidazolate frameworks (ZIFs) have better heat, hydrothermal, and chemical stability. In this study, ZIF-8 was synthesized and tested for its applicability on the treatment of hexavalent chromium contained water via the adsorption mechanisms. In the batch experiments, the tested control factors included dispersion conditions, pH value, amount of adsorbent, and initial concentration. ZIF-8 particles were prepared using ultrasonic vibration method to increase the contact sites and contact areas to improve the removal efficiency. In the hydrolytic stability test, the structure of ZIF-8 was not destroyed within 14 days and had good stability under varied pH conditions (pH 5 to 11). The adsorption behaviors could be effectively simulated using the pseudo-second-order model and Langmuir isotherm model. Results indicate that the adsorption process was the major mechanism for hexavalent chromium removal by ZIF-8. The adsorption mechanism was investigated by X-ray photoelectron spectroscopy (XPS) analysis. The results indicate that the adsorption was related to electrostatic interaction, hydrogen bonding, and chemical reducing process. Results from this study show that ZIF-8 is a simple, convenient, and low-cost absorbent material for separating hexavalent chromium from water.

論文審定書 i
論文授權書 ii
謝誌 iii
中文摘要 iv
Abstract v
表目錄 ix
圖目錄 x
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 3
第二章 文獻回顧 4
2.1 台灣土壤地下水污染現況及重金屬污染概況 4
2.2 污染物定義及特性 8
2.2.1 鉻的性質與危害 8
2.2.2 環境中鉻的型態與現行污染管制 11
2.3 去除水中六價鉻污染之相關研究 12
2.4 六價鉻的吸附處理 14
2.4.1 吸附作用的種類 15
2.4.2 吸附理論 16
2.4.3 等溫吸附曲線 17
2.4.4 等溫吸附模式 19
2.4.5 吸附動力學模式 24
2.4.6 影響吸附因素 25
2.4.7 用於去除六價鉻污染之吸附材料 27
2.5 金屬-有機骨架(Metal–organic frameworks, MOFs) 28
2.5.1 MOFs在環境上的吸附應用 29
2.5.2 有機配位體介紹 30
2.5.3 沸石咪唑酸酯骨架(Zeolitic imidazolate frameworks, ZIFs) 31
第三章 研究與方法 33
3.1 研究架構 33
3.2 研究流程 34
3.2.1 ZIF-8合成及特徵分析 34
3.2.2 水解穩定性試驗 36
3.2.3 六價鉻吸附批次試驗 36
3.2.4 ZIF-8再生及再利用試驗 37
3.3 實驗材料與設備 39
3.3.1 實驗藥品 39
3.3.2 實驗儀器 40
3.4 實驗分析儀器 40
3.4.1 環境掃描式電子顯微鏡 40
3.4.2 X光繞射儀 41
3.4.3 比表面積分析儀 42
3.4.4 X射線光電子能譜儀 43
3.4.5 傅立葉紅外線光譜儀 43
3.5 污染物分析 44
3.5.1 水中六價鉻檢測方法─比色法 44
3.5.2 水中金屬及微量元素檢測方法─感應耦合電漿原子發射光譜法 44
第四章 結果與討論 45
4.1 ZIF-8基本特性及特徵分析 45
4.1.1 合成試驗 45
4.1.2 晶體結構及形態特徵 47
4.1.3 比表面積分析(Specific surface area) 53
4.1.4 等溫吸附曲線及模式探討 54
4.1.5 表面元素分析 60
4.1.6 水解穩定性試驗 63
4.2 ZIF-8處理六價鉻污染批次實驗 66
4.2.1 不同分散條件之影響 67
4.2.2 初始酸鹼值之影響 68
4.2.3 吸附材用量的影響 72
4.2.4 不同初始濃度之影響 74
4.2.5 ZIF-8與Zn/Co ZIFs對六價鉻吸附之比較 78
4.3 ZIF-8再生及再利用試驗 80
4.3.1不同脫附劑試驗 81
4.3.2 再利用試驗 82
第五章 結論與建議 83
5.1 結論 83
5.2 建議 84
參考文獻 85

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