利用廢棄PET衍生配體調控合成hcp UiO-66應用於化學戰劑模擬劑降解

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姓名

謝興樺(Hsing-Hua Hsieh) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

利用廢棄PET衍生配體調控合成hcp UiO-66應用於化學戰劑模擬劑降解
(Modulated Synthesis of hcp UiO-66 Employing Waste PET-Derived Ligands Applied to Chemical Warfare Agent Simulant Degradation)

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至系統瀏覽論文 (2029-6-30以後開放)

摘要(中)

化學戰劑（CWAs）在發生戰爭期間時對人類造成嚴重地威脅及傷害。傳統過濾技術蘊含著幾項缺點，包含飽和後的次級排放、長期活化的低容量以及最終的處置困難。因此，對於利用金屬有機框架材料（MOFs）、金屬氧化物、聚氧化金屬(POMs)來催化和降解化學戰劑的相關領域研究受到高度重視。其中，金屬有機框架材料是一類擁有著超高表面積和孔隙率特點的新型材料。已有文獻顯示，基於鋯金屬的有機框架材料能夠有效地使用在催化化學戰劑及其模擬物上。
本研究使用UiO-66來降解沙林模擬物二氯乙基磷酸酯（DCP），這已被證實是一種合適的模擬劑。此外，使用廢棄的寶特瓶碎片來製備出具有不同於原始晶體結構的UiO-66，即六方最密堆積(hcp) UiO-66。在這裡進一步探索利用ZrOCl2·8H2O作為新的金屬鹽來源合成hcp UiO-66的可能性，並調節丙酮/甲酸的比例來控制缺陷程度。從XRD結果可以看出，hcp UiO-66能夠在全酸的合成環境之下成功地被合成出。此外，從SEM圖中能夠觀察到hcp UiO-66的晶體形狀與原始的八面體極為不同，呈現六角柱型態。最後，利用原位 31P-NMR 測定MOF材料在含有DCP的氘溶劑中降解性能，由於其良好的材料特性，原始的UiO-66和 hcp 系列的UiO-66半衰期分別約為 18 分鐘和 22 分鐘。

摘要(英)

Chemical warfare agents (CWAs) pose a harmful threat in the event of war. Traditional filtration has several disadvantages, including secondary emission after saturation, low capacity for long-term activation, and ultimate disposal. Therefore, research on the degradation and catalysis of CWAs materials using metal oxides, polyoxometalates (POMs), and metal-organic frameworks (MOFs) have been highly motivated. In particular, MOFs are a novel class of materials with high porosity and ultra-high specific surface areas. Some studies have already demonstrated that Zr-based MOF can effectively catalyze CWAs and their simulants.
In this work, UiO-66 was used to degrade the sarin mimic diethyl chlorophosphate (DCP), shown to be a suitable simulant. Additionally, waste PET were used to synthesize a different crystal structure UiO-66, the hexagonal closed-packed (hcp). We explored another possibility utilizing ZrOCl2·8H2O as the new metal salt to synthesize hcp UiO-66 and tuned the acetone/formic acid ratio to control the defects. XRD results indicated that UiO-66 with hcp characteristics was successfully formed in a total acid synthesis environment. It can be observed that the morphology of hcp UiO-66 represent hexagonal shapes from SEM. The half-lives of the original and hcp series were approximately 18 min and 22 min, respectively, as determined by in situ 31P-NMR, owing to their favorable material properties.

關鍵字(中)

★ 化學戰劑降解
★ 沙林
★ 綠色合成
★ hcp UiO-66

關鍵字(英)

★ Degradation of chemical warfare agent
★ sarin
★ green synthesis
★ hcp UiO-66

論文目次

摘要 i
Abstract ii
Acknowledgement iii
Table of Contents iv
List of Figures vi
List of Tables viii
Chapter 1 Introduction 1
1.1. Background 1
1.2. Review of Relevant literature 5
1.2.1. Application of MOFs in the degradation of chemical warfare agents 5
1.2.2. Synthesis and Properties of UiO-66 and its Derivatives 8
1.2.3. Reuse of polyethylene terephthalate (PET) as MOF precursor 11
1.3. Motivation 15
Chapter 2 Experimental 19
2.1. Materials and Reagents 19
2.2. Instruments 19
2.3. Analysis instrument and Characterization 20
2.3.1. Fourier-transform infrared spectroscopy (FTIR) 20
2.3.2. X-ray diffraction (XRD) 21
2.3.3. Scanning electron microscopy (SEM) 22
2.3.4. Dynamic light scattering (DLS) 23
2.3.5. Thermogravimetric analysis (TGA) 24
2.3.6. Surface area and Porosity analysis 25
2.3.7. In Situ Nuclear magnetic resonance spectroscopy (NMR) 27
2.4. Synthesis of metal organic framework 29
2.4.1. Synthesis of the UiO-66 29
2.4.2. Synthesis of the hcp-UiO-66 from ZrCl4 and ZrOCl2·8H2O 30
Chapter 3 Results and Discussion 32
3.1. Characterization of pristine- and hcp series of UiO-66 32
3.1.1. X-ray diffraction pattern 32
3.1.2. Fourier-transform infrared spectrum 36
3.1.3. Morphology and Particle Size 38
3.2. Defects quantification and Surface area 43
3.2.1. Thermogravimetric analysis 43
3.2.2. N2 sorption and Specific surface area 46
3.2.3. Pore size distribution 49
3.3. Degradation performance and Kinetic study 53
Chapter 4 Conclusions 63
Chapter 5 Future works 64
References 65

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指導教授

張博凱

審核日期

2024-7-18

推文