- 學位論文
鋁、鋯和鉿之功能性多孔金屬有機骨架：設計，合成，鑑定 及功能應用
Aluminium, Zirconium and Hafnium based Functional Porous Metal-Organic Frameworks: Design, Synthesis, Characterization and Functional Applications
摘要
本論文含有四個部分來研究奈米多孔性金屬有機骨架的合成與功能應用。共製備了三 種新穎的MOF和六種已知的MOF，以應用至混合基質膜和做為催化劑。 第一部分研究一個新的二維層狀微孔Al-MOF, [Al(OH)(MBA)] (CYCU-7, MBA = diphenylmethane-4,4'-dicarboxylate anion)以及其被報導過的類似物[Al(OH)(SDBA)] (CAU-11) 可以使 用水熱和溶劑熱方法被顯著合成出來，並且在它們的結構中，其結晶度和缺陷孔隙率通過N2吸附等 溫線和27Al固態NMR測量被仔細控制和紀錄。有趣的是，基於乙醇的溶劑熱法（即CYCU-7）合成的 MOFs顯示出比由水基熱液法（即CAU-11）合成的MOFs還有著顯著程度的鍵結缺陷。我們進一步將 合成的CYCU-7和CAU-11引入到殼聚醣（CS）生物聚合物中以製備CYCU-7 @ CS和CAU-11 @ CS混 合基質膜（MMMs），其載荷量為2.5, 5.0或10 wt％的MOF。所製備的CYCU-7 @ CS和CAU-11 @ CS MMM用於通過滲透蒸發過程分離水/乙醇混合物，並且研究CYCU-7和CAU-11的結構性質（例如結 晶度和缺陷）對分離性能之影響。發現富含缺陷的CYCU-7 @ CS MMM表現出較高的通量，而具有 較高結晶度的CAU-11 @ CS MMM表現出較高的分離因子。此外，載有5.0wt％CAU-11的CAU-11 @ CS MMM表現出最好的分離性能（分離因子= 2741，通量= 458 g / m2h）。 第二部分通過使用溶劑熱反應這一有效方法，合成由三種微孔鋁基金屬有機骨架 （MOF），[Al（OH）（BPDC）]（DUT-5）製備的乙醇/水滲透蒸發之混合基質膜。有趣 的是，所有Al-MOF都顯示出DUT-5具有12.3 Å的吸引人注目之表面積，並通過氮氣氣體吸附 測量證實MOF。通過熱重分析和粉末X射線衍射測量證實此微孔化合物具有高度穩定之性質。 此外，DUT-5的合成微孔MOF顆粒成功地併入生物殼聚醣（CS）膜中以形成DUT-5＠CS膜。 製備出不同MOF載體，例如0.1，0.15和0.2 wt％的MOF至CS網絡中，並且皆在滲透蒸發過程 中在25 ℃下用於分離水和乙醇的混合物。特別是，當負載0.15 wt％的DUT-5時，DUT-5CS 膜在乙醇/水分離中顯示出優於先前文獻的滲透性和選擇性。 這些基於CS的混合基質膜通過 官能化微孔MOF分離揭示了設計用於生物乙醇純化的新型MOF膜的關鍵控制因素。 第三部分研究一系列鋁基配位聚合物或金屬有機骨架（Al-MOFs），DUT-4，DUT-5， MIL-53，NH2-MIL-53和MIL-100通過微波（MW）輔助反應容易製備，並可用於作為選擇性 磺化氧化反應的催化劑。MW輔助合成將反應時間從幾天縮短到幾小時。與傳統方法相比， 製備的MOF具有更小且均勻的粒徑和更好的收率。此外，在溫和條件下，Al-MOFs已被成 功地用作甲基苯基硫化物與雙氧水作為氧化劑的氧化反應的催化劑。 第四部分為開發新型Zr（IV）和Hf（IV）基四嗪包含金屬有機骨架ZrTz-68和HfTz-68的 合成含有高度中孔（2.1 nm），可以從具有UiO-68拓撲結構的廉價起始材料H2TzDB，其線 性有機連接體以數克的範圍內有效地進行反應。H2TzDB（4,4'-(1,2,4,5-四嗪-3,6-二基)二苯甲 酸）與(ZrCl4或HfCl4)的反應可以很容易地用DMF作為溶劑和CF3COOH調節劑在溶劑熱條件 下合成。通過改變合成方法中的不同調節劑對ZrTz-68和HfTz-68的晶體粉末的生長起重要作 用。這些MOFs作為π-共軛四嗪基團的優良候選物經歷了 “點擊” 化學，在官能化後實現了 定量轉化並保持了骨架的結晶度。特別是，它作為廣泛應用的新通用平台顯示出巨大的前景。 可以可靠地放大ZrTz-68和HfTz-68的製備程序。整個合成過程中不需要色層分析管分離純化 即可完成，完成時間可在2-3天內達成。 總結四個部分研究結果顯示，鋁、鋯和鉿金屬有機骨架奈米孔洞材料，具有優異的孔 洞與應用性質，值得繼續研究開發。
並列摘要
Accordingly many gas and liquid sorption and with growing industrial resources, aluminum is one element of choice for the synthesis of such MOFs since it leads to stable and highly porous materials that can also be formed in water as a green solvent. The potential application of the Albased MOFs is well documented in various patents mainly issued by the pioneers of this field-BASF and the groups of Ferey and Loiseau and press releases have been issued announcing large scale testing and their solvent-free synthesis At a molecular level, simulation can provide microscopic insights from the bottom-up and establish structure-function relationships. In this thesis, the objectives are to investigate heterogeneous catalysis, ethanol/water separation and functionalization in chemically and thermally stable MOFs. The whole thesis primarily consists of four parts: A new 2D microporous Al-MOF, [Al(OH)(MBA)] (CYCU-7, MBA = diphenylmethane- 4,4'-dicarboxylate anion) and its reported analogue, [Al(OH)(SDBA)] (CAU-11) were distinctly synthesized using hydrothermal and solvothermal methods, and their structural crystallinities and defect porosities were carefully controlled and characterized with N2 sorption isotherms and 27Al solid-state NMR measurements. Interestingly, the MOFs synthesized by the ethanol-based solvothermal method (i.e. CYCU-7) showed significant degree of linker-missing defects than that synthesized by the water-based hydrothermal method (i.e. CAU-11). We further incorporate the synthesized CYCU-7 and CAU-11 to chitosan (CS) biopolymer to make CYCU-7@CS and CAU- 11@CS mixed matrix membranes (MMMs) with the loading amount of MOF to be 2.5, 5.0 or 10 wt%. The prepared CYCU-7@CS and CAU-11@CS MMMs were applied for separation of water/ethanol mixtures through pervaporation process, and the effects of the structural properties (e.g. crystallinity and defects) of CYCU-7 and CAU-11 on the separation performance are studied. It is found that defects-rich CYCU-7@CS MMMs exhibit higher flux while CAU-11@CS MMMs with higher crystallinity exhibit higher separation factor. In addition, the CAU-11@CS MMM with 5.0 wt% loading of CAU-11 displayed the best separation performance (separation factor = 2741 and flux = 458 g/m2h). An effective approach to enhance the ethanol/water pervaporation of mixed matrix membranes prepared from three microporous aluminium based metal-organic framework (MOF), [Al(OH)(BPDC)] (DUT-5), have been synthesized by employing solvothermal reactions. Interestingly, all Al-MOFs showed attractive surface area with microporous 12.3 Å for DUT-5, MOF which are confirmed through N2 gas sorption measurements. The microporous compound is highly stable as confirmed by thermogravimetric analysis and powder X-ray diffraction measurements. Furthermore, the synthesized microporous MOF particles of DUT-5 were successfully incorporated into biological chitosan (CS) membranes to form DUT-5@CS membranes. The different MOF loadings such as 0.1, 0.15, and 0.2 wt% in CS networks have been prepared and the same were used to separate mixtures of water and ethanol at 25 ºC in the pervaporation process. In particular, when 0.15 wt% of DUT-5 was loaded, DUT-5@CS membrane displayed excellent permeability and selectivity in ethanol/water separation than that of the previous literatures. These CS based mixed matrix membranes separation through functionalized microporous MOFs reveals the key governing factors that are essential for designing novel MOF membranes for bioethanol purification. A series of aluminum based coordination polymers or metal-organic frameworks (Al-MOFs), DUT-4, DUT-5, MIL-53, NH2-MIL-53, and MIL-100 have been facile prepared by microwave (MW)-assisted reactions and used as catalysts for selective sulfoxidation reactions. The MW-assisted synthesis drastically reduced the reaction time from few days to hours. The prepared MOFs have smaller and uniform particle sizes and better yield compared to conventional method. Furthermore, the Al-MOFs have been successfully demonstrated as catalysts in oxidation reaction of methyl phenyl sulfide with H2O2 as oxidant even under mild conditions. The synthesis of new Zr(IV) and Hf(IV)-based tetrazine containing metal-organic frameworks, ZrTz-68 and HfTz-68 containing a highly mesoporous (2.1 nm) can be conducted efficiently on a multigram scale from inexpensive starting materials H2TzDB linear organic linker having a UiO-68 topology. The reactions of H2TzDB (4,4’-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid) and (ZrCl4 or HfCl4) can easily synthesized using DMF as a solvent and CF3COOH modulator under solvothermal condition. By varying the different modulators in synthesis method play an important role to grow up the crystalline powders of ZrTz-68 and HfTz-68. These MOFs as an excellent candidate for the л-conjugated tetrazine groups were subjected to a “click” chemistry, achieving quantitative conversion and maintaining the crystallinity of the framework after functionalization. In particular, it shows great promise as a new generic platform for a wide range of applications. The procedure for the preparation of ZrTz-68 and HfTz-68 can be scaled up reliably. The entire synthesis is performed without purification by column chromatography and can be completed within 2-3 days.