本篇論文分成兩部分： 近年來奈米金屬粒子儼然成為材料領域最熱門的研究之一，主要是因為其表面積大的優勢在相催化，氣體儲存與表面增強拉曼散射的應用上相當好的表現。已有報導指出使用金屬有機骨架材料(Metal-organic Frameworks, MOFs) 包覆奈米金屬粒子，不僅可以減少昂貴催化劑損失防止金屬粒子聚集降低催化活性，同時也可以利用外在的孔洞性質去做選擇性催化。然而，目前主要合成Metal@MOF 材料方法大多需要有機溶劑，高溫，高壓或是長時間的反應過程，此類的反應條件相當耗能且不環保，所以開發一個更有效、對環境更友善的合成方法是亟需克服的問題，同時此法課已為後續工業應用方面帶來可觀的經濟效益。因此，本研究課題希望能在Metal@MOF材料的合成中，提供一個快速反應且使用溫和溶劑的合成環境。因此，本論文 第一部份 利用新穎 特別 且有效 的 機械 力化學 法(Mechanochemistry)球磨合成Metal@MOF，其中 Pd@ZIF-90 應用在表面增強拉曼散射光譜的散射效果最好，相較於 Au@ZIF-90 的21.2ppm，其可以偵測到甲苯蒸氣濃度為10.6 ppm。 本篇論文第二部分研究主題為透過機械力化學法，利用微量水輔助方式快速研磨合成類沸石-咪唑骨架材料-90 (Zeolitic Imidazolate Framework 90; ZIF-90) 包覆蛋白質。酵素與骨架材料的結合的複合材料在生物催化上相當具有潛力。本實驗室 2019 年成功透過機械力化學法的有機溶液輔助研磨反應快速合成金屬有機骨架材料包覆蛋白質。由於反應需要有機溶液輔助研磨，所以會讓蛋白質減少催化活性。因此，希望能在 Enzyme@MOF材料的合成中，提供一個快速反應且使用水輔助研磨反應，可以讓蛋白質減少損失催化活性。 ;There are two parts in my dissertation as shown below Part I: Green and Rapid Encapsulation of SERS-active Metal Nanoparticles in MOF matrices via Liquid-assisted Grinding Noble metal nanoparticles have attracted wide attentions due to its great potential applications in heterogeneous atalysis, hydrogen storage, and Surface Enhanced Raman Spectroscopy (SERS) techniques. It is reported that the encapsulation of metal nanoparticles into Metal-organic Frameworks (MOFs) not only prevents the oxidation and agglomeration of nanoparticles but also enhances the selectivity of chemicals transferring through material apertures in catalyzing process. Most of the strategies reported on metal nanoparticles encapsulation was solvothermal methods that required bulk organic solvents, high temperature or pressure and considerable reaction time. Due to this fact, it is necessary to find an alternative method for embedding metal nanoparticles into MOFs that more effective, environmentally-friendly and energy reduction. Therefore, we successfully applied mechanochemical method in embedding metal nanoparticles such as gold and palladium into MOFs of Zeolitic Imidazolate Framework 90(ZIF-90) via mechanochemistry, ZIFs- a sub group of MOFs, and it is so called (Metal@ZIF-90). We further used Metal@MOFs composites as the SERS substrate for the detection of hazardous chemicals, i.e., toluene. The sample of Pd@ZIF-90 shows more sensitive to toluene vapor at 10.6 ppm comparing to Au@ZIF-90 at 21.2 ppm in the value of LOD (limit of detection). Part II: Protein-Assisted Assembly of Zeolitic Imidazolate Framework 90 (ZIF-90) via Mechanochemitry In order to enhance the durability and stability of biomacromolecules, normally the immobilization methods will be performed as well as the biological functions also maintained under a wide range of catalyzing conditions. Recently, our lab had successfully encapsulating enzymes in MOFs via mechanochemical strategy using trace amounts of organic solvents. However, the biological activity of enzymes significantly decreased with the presence of organic solvent. For this reason, the second part of my dissertation is about rapid encapsulation of enzymes into ZIF-90 by Mechanochemistry with water-assisted while maintaining the enzyme biological function. we aim to study a mechanochemical synthesis of encapsulated enzymes in MOFs assisting a trace amounts of water as solvent that can minimize the influence of solvent on the enzyme biological activity and also understand the mechanism by encapsulation of enzymes with different isoelectric points.
