鋁金屬有機骨架超疏水修飾研究及乳化液油水分離應用
Abstract
金屬有機骨架(Metal−Organic Frameworks, MOF)作為有機無機多孔材料，一直以來以其極高的表面積、可調節的孔徑和可調節的內表面特性而聞名。除了這些特性，其結構中有機和無機的部分具有很好的可變性，使MOF在環境保護的應用上越來越受到關注，因此本研究中，結合鋁金屬MOF和美耐皿海綿兩種多孔材料，並進行油水分離應用，以因應日趨頻繁的油洩漏事故和工業有機溶劑廢水排放等問題。本論文第一部分研究中，發現「溶劑置換」和「加熱抽真空」對晶格重排的重要性，並藉由溶劑脫附誘導鋁MOF結晶化，觀察其晶格非序化(Amorphous)到結晶化(Crystalline)的過程。此外，在合成鋁MOF的過程中，試著找出最佳合成條件。第二部分研究中，藉由配位基中四嗪環(tetrazine)結構對雙鍵的點擊反應(click reaction)，以共價鍵的形式將疏水分子多面體倍半矽氧烷寡聚物(POSS)修飾到鋁MOF上，使得鋁MOF產生超疏水特性，其水接觸角高達162.2 o。更進一步，將超疏水鋁MOF與美耐皿海綿結合，形成超疏水複合材料，水接觸角為160.3 o，並在乳化液油水分離中有很好的表現，油純度>99.99 %，對於有機溶劑也有很好的吸附表現，能吸附自身重量的129倍。
Metal−Organic Frameworks(MOFs) as a high porous materials containing organic and inorganic components, which are known for their extraordinarily high surface areas, tunable pore size, and adjustable internal surface properties. Otherwise, both the organic and inorganic components of their structures having extraordinary variability which makes MOF getting more and more attention on environmental protection. Therefore, in this study, we combine two different porous materials which are aluminum MOF and melamine sponge. Then, the composite materials are applied in oil/water separation and cope with frequent oil spill accidents and industry leakage of organic solvent.In the first part, we found the crucial parts in lattice rearrangement which were solvent exchange and heating under vacuum. Afterwards, we observed the process of the structure of aluminum MOF from amorphous to crystallization through the induction of solvent desorption. Otherwise, we try to find optimal conditions in the synthesis process of aluminum MOF.In the second part, due to the click reaction which happened in tetrazine structure in the ligand and C-C double bond, hydrophobic molecular polyhedral oligomeric silsesquioxane (POSS) was successfully modified on aluminum MOF. It showed superhydrophobic, and water contact angle (WCA) could reach 162.2 o. Furthermore, we combined superhydrophobic aluminum MOF and melamine sponge to create superhydrophobic composite materials, the WCA could also reach 160.3 o. It showed excellent performance in water-in-oil emulsion separation, and the oil purity could reach above 99.99 %. In the organic solvent adsorption capacity test, it also showed brilliant performance which the oil adsorption capacity was up to 129 times its own weight.
Metal−Organic Frameworks(MOFs) as a high porous materials containing organic and inorganic components, which are known for their extraordinarily high surface areas, tunable pore size, and adjustable internal surface properties. Otherwise, both the organic and inorganic components of their structures having extraordinary variability which makes MOF getting more and more attention on environmental protection. Therefore, in this study, we combine two different porous materials which are aluminum MOF and melamine sponge. Then, the composite materials are applied in oil/water separation and cope with frequent oil spill accidents and industry leakage of organic solvent.In the first part, we found the crucial parts in lattice rearrangement which were solvent exchange and heating under vacuum. Afterwards, we observed the process of the structure of aluminum MOF from amorphous to crystallization through the induction of solvent desorption. Otherwise, we try to find optimal conditions in the synthesis process of aluminum MOF.In the second part, due to the click reaction which happened in tetrazine structure in the ligand and C-C double bond, hydrophobic molecular polyhedral oligomeric silsesquioxane (POSS) was successfully modified on aluminum MOF. It showed superhydrophobic, and water contact angle (WCA) could reach 162.2 o. Furthermore, we combined superhydrophobic aluminum MOF and melamine sponge to create superhydrophobic composite materials, the WCA could also reach 160.3 o. It showed excellent performance in water-in-oil emulsion separation, and the oil purity could reach above 99.99 %. In the organic solvent adsorption capacity test, it also showed brilliant performance which the oil adsorption capacity was up to 129 times its own weight.
Description
Keywords
鋁金屬有機骨架, 溶劑置換, 加熱抽真空, 多面體倍半矽氧烷寡聚物, 美耐皿海綿, 超疏水, 乳化液分離, aluminum Metal−Organic Frameworks, solvent exchange, heating under vacuum, polyhedral oligomeric silsesquioxane, melamine sponge, superhydrophobic, emulsion separation