表面疏水化修飾 γ-環糊精金屬有機骨架及其耐濕性研究

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研究生：	呂則慶 Tse-Ching Lu
論文名稱：	表面疏水化修飾 γ-環糊精金屬有機骨架及其耐濕性研究 Surface hydrophobically modified γ-cyclodextrin based metal organic framework and its moisture-resistance study
指導教授：	李振綱 Cheng-Kang Lee
口試委員:	李振綱 Cheng-Kang Lee 蔡伸隆 Shen-Long Tsai 林昇佃 Shawn D. Lin
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2021
畢業學年度：	109
語文別：	中文
論文頁數：	118
中文關鍵詞：	γ-環糊精、金屬有機骨架、表面疏水化修飾
外文關鍵詞：	γ-cyclodextrin, metal organic framework, Surface hydrophobically modified
相關次數：	點閱：286 下載：0
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γ-環糊精為八個葡萄糖連結之寡糖所形成的環狀結構，可做為有機配體與金屬鉀離子結合形成多孔性的金屬有機骨架（γ-CD-MOF），金屬有機骨架（Metal Organic Frameworks, MOFs）具有高結晶度、高比表面積，且其孔徑、大小及形狀因有機配體與金屬離子之不同而異，有利於氣體之吸附、儲存及分離。而γ-CD-MOF 則可視為綠色可再生的多孔骨架，可封存大量的 CO2 及用以分離苯系混合物（BTEX），但其主要缺點在於耐水性差。因此本論文旨在研究如何可使γ-CD-MOF具有抗濕性。經由甲醇蒸氣擴散法從水溶液中所製備出之 γ-CD-MOF，經 SEM 分析其大小約在 3～10 μm，具有立方體的形狀，由 XRD 分析得知其結晶度為 69.87% ，比表面積為 1171 m2 g-1，在 77 K 下的 N2 吸附量可達到 300 cm3 g-1。為使 γ-CD-MOF 具耐濕性，因此本論文分別探討以 PDMS-AB、ε-PL-AOT、PDA、Span 80和 HDTMS 等幾種方式在 γ-CD-MOF 表面進行疏水化修飾。其中唯有經 1% HDTMS 表面修飾後仍可保有 γ-CD-MOF 之原有特性及大小，經 XRD 分析其結晶度增加為 76.95%，比表面積則降為 632.78 m2 g-1，在 77 K 下的 N2 最高吸附量亦降為 150 cm3 g-1。而分別接觸濕氣 12 和24 小時後其形態維持不變，但結晶度則分別降為 23.51% 和 38.05%，推測可能是因為 HDTMS 無法完全修飾到 γ-CD-MOF 表面。透過甲基紅呈色定性分析可得知 γ-CD-MOF 具有吸附 CO2 的功能，而經修飾後的 γ-CD-MOF 亦能保有吸附 CO2 的功能。在 298 K 下未修飾之γ-CD-MOF 最多可吸附將近 28 cm3 g-1，經 HDTMS 修飾後的 γ-CD-MOF 的吸附量可達到 30 cm3 g-1。最後在經過薑黃素包封定性驗證，經 HDTMS 修飾後的 γ-CD-MOF在水中不會被溶解釋放出薑黃素，反之未修飾的γ-CD-MOF 則立即溶解釋放出薑黃素，證明經 HDTMS 修飾後表面疏水化的 γ-CD-MOF 具有足夠的抗濕能力。

γ-cyclodextrin (γ-CD) is a 8 glucose connected cyclic oligosaccharide. When used as an organic ligand, it can complex with potassium ion to form porous γ-cyclodextrin metal organic framework (γ-CD-MOF). Metal organic frameworks (MOFs) show some outstanding characteristics, including high crystallinity, and surface area, with specific pore size and shape, those are beneficial to gas adsorption, sequestration, and separation. γ-CD-MOF prepared based on oligosaccharide is considered as a green and renewable porous framework. It has been demonstrated that γ-CD-MOF can be used to sequestrate a large mount of CO2 and separating aromatic mixtures (BTEX). However, the main drawback of γ-CD-MOF is its poor moisture-resistance. Therefore, the aim of this thesis is to improve moisture resistant properties of γ-CD-MOF. γ-CD-MOF prepared by methanol vapor diffusion method is cubic crystals with the size is around 3~10 μm. The crystallinity is 69.87% as analyzed by XRD, the surface area is 1171 m2 g-1, the amount of N2 adsorption at 77K reaches 300 cm3 g-1. In order to make γ-CD-MOF resist the moisture, we explored different hydrophobic modifications on the surface of γ-CD-MOF, such as PDMS-AB, ε-PL-AOT, PDA, Span 80 and HDTMS methods, respectively. Among these methods, only HDTMS surface modification made γ-CD-MOF still maintain its characteristics and size, and crystallinity increased to 76.95%, surface area decreased to 632.78 m2 g-1. The amount of N2 adsorption at 77K also decreased to 150 cm3 g-1. After in contact with moisture for 12 and 24 hours, respectively, the cubic crystal shape was maintained, but the crystallinity decreased to 23.51% and 38.05%, respectively. Probably, the reduced crystallinity after moisture treatment is due to the insufficient modification of HDTMS on the surface of γ-CD-MOF. By employing methyl red dye as indicator, γ-CD-MOF demonstrated its CO2 adsorbing capability, and HDTMS modified γ-CD-MOF also retained about the same capability. The unmodified γ-CD-MOF can adsorb around 28 cm3 g-1 of CO2 at 298K, and HDTMS modified one is around 30 cm3 g-1. Finally, after encapsulation of curcumin, HDTMS modified one didn’t release curcumin while suspended in water. On the contrary, pristine γ-CD-MOF released the encapsulated curcumin immediately when in contact with water. This shows that the surface hydrophobically modified by HDTMS can effectively prevent γ-CD-MOF structure from damaging by moisture.

摘要    i
Abstract    ii
致謝    iv
縮寫表    v
目錄    vi
圖索引    ix
表索引    xiv
第一章    緒論    1
1    前言    1
2    研究目的及內容    4
第二章    文獻回顧    6
1    金屬有機骨架 （MOFs）    6
2    以多醣類配體為基礎合成之 MOFs（Polysaccharide based MOFs）    …………………………………………………………………………7
3    環糊精 （CDs）    11
4    以環糊精和鉀離子製備之 MOFs（γ-CD-MOFs）    13
5    γ-CD-MOF 於 CO2 之應用    15
6    表面疏水化改質    18
6.1    疏水化改質    18
6.2    MOFs 疏水化改質    23
6.3    γ-CD-MOF 疏水化改質    27
6.3.1    交聯法    27
6.3.2    修飾法    28
第三章    實驗方法，流程與材料    32
1    實驗流程    32
2    實驗材料與設備    33
2.1    實驗藥品    33
2.2    實驗儀器與設備    34
3    實驗方法    35
3.1    γ-CD-MOF 合成    35
3.2    γ-CD-MOF 疏水化改質    36
3.2.1    PDMS-AB 修飾法    36
3.2.2    ε-PL-AOT 修飾法    36
3.2.3    PDA 修飾法    37
3.2.4    Span 80 修飾法    38
3.2.5    HDTMS 修飾法    38
3.3    γ-CD-MOF 耐濕性測試    39
3.4    以甲基紅測試 γ-CD-MOF 之 CO2 吸附    39
3.5    以薑黃素包封探討修飾後 γ-CD-MOF 之疏水性    40
4    材料性質測定    41
4.1    掃描式電子顯微鏡 （SEM）    41
4.2    傅立葉轉換紅外線光譜分析儀 （FTIR）    41
4.3    進階式熱重分析儀（TGA）    41
4.4    表面積及孔徑分析儀（BET）    41
4.5    X 光繞射儀（XRD）    43
第四章    結果與討論    45
1    γ-CD-MOF 之製備及性質探討    45
2    γ-CD-MOF 之表面疏水化改質    52
2.1    ε–PL–AOT 修飾法    52
2.2    PDA 修飾法    58
2.1    PDMS-AB 修飾法    61
2.2    Span 80 修飾法    66
2.3    HDTMS 修飾法    71
3    γ-CD-MOF 之疏水化改質前後耐濕性探討    79
3.1    疏水化改質前    79
3.2    HDTMS 修飾法    83
4    γ-CD-MOF 之 CO2 吸附探討    90
5    以薑黃素包封探討修飾後 γ-CD-MOF 之疏水性    92
第五章    結論    94
第六章    參考資料    96


                                

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全文公開日期 2024/09/13 (校內網路)
全文公開日期 2026/09/13 (校外網路)
全文公開日期 2026/09/13 (國家圖書館：臺灣博碩士論文系統)

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