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標題: | 聚合物催化容器於有機合成反應之應用 Catalytic Polymer Containers for Organic Reaction |
作者: | Jyun-Cheng Su 蘇俊誠 |
指導教授: | 廖尉斯(Wei-Ssu Liao) |
關鍵字: | 鈀,奈米粒子,聚合物,鈴木催化反應,赫克反應,?頭耦合反應,還原反應,異質催化劑, palladium,nanoparticle,polymer,Suzuki-Miyaura cross-coupling reaction,Mizoroki-Heck reaction,Sonogashira-Hagihara reaction,reduction,heterogeneous catalyst, |
出版年 : | 2018 |
學位: | 碩士 |
摘要: | 本研究成功開發出具備可回收與再生性質之催化性奈米粒子鑲嵌聚合物表面。以鈀金屬與銀金屬為例,聚合物表面經氧氣電漿活化後立即浸入金屬前驅物溶液,便可於表面原位還原生成鈀奈米粒子。於氧氣電漿活化過程中,聚合物表面之化學鍵發生斷鍵,並於表面生成帶有自由基之活性物種。這些自由基能促使金屬離子於介面上還原產生金屬核,均勻地分布鑲嵌於聚合物之表面上。而隨著持續性之還原沉積,最終於表面將形成單層覆蓋之金屬奈米粒子層。在此所製備之鈀奈米粒子鑲嵌聚對苯二甲酸乙二酯薄膜於鈴木催化反應中可展現極佳的催化效率。此外,本研究亦成功鑲嵌鈀奈米粒子於聚丙烯離心管,此金屬奈米管具有催化活性,可在有機溶液和水溶液中催化鈴木反應以及硝基苯酚還原反應之進行。除鈀金屬外,銀奈米粒子亦可合成於聚丙烯表面。結合兩種金屬鑲嵌於離心管之兩側形成雙金屬催化管,可以有效地催化不同的有機催化反應於同一催化管中,完成串聯反應。此結果展現出本製備方法可使用於不同材料或不同基材型貌之多樣性;並在經過數次催化反應後仍能保有相當的催化活性,且其表面催化活性可藉由氧氣電漿之再處理而重新活化。藉由此具備簡單與低成本之表面修飾方法及催化多種有機反應,高度可重複使用之催化反應瓶製作將不再是一項困難的課題。 Catalytic nanoparticle-embedded polymer surfaces for organic synthesis with recyclable and regenerative properties are fabricated. Metal nanoparticles, i.e. palladium (Pd) and silver (Ag), are generated in situ on the oxygen plasma activated polymer surface when encountering the precursor solution. An activation process first initiates polymer surface chemical bond breakage and produces radical species on the substrate. These interface radicals induce metal ion reduction when contact with the precursor solution, leading to numerous metal seeds generation embedded with the polymer surface. Continuous metal deposition advances on dispersed surface-embedded seeds and a monolayer of metal nanoparticle covering the whole polymer substrate is grown. Pd nanoparticles decorated polyethylene terephthalate (PET) surfaces are used for demonstration, which can catalyze Suzuki-Miyaura cross coupling reaction at mild conditions in aqueous solution with high efficiency. Decay of the substrate catalytic activity is negligible within a few uses and the surface can be regenerated with a simple O2 plasma treatment. This strategy is extended to directly synthesize metal nanoparticles on substrates with different morphology, where polypropylene (PP) based centrifuge tubes are selected as the supporting substrate to realize fabrication of catalytic polymer containers suitable for Suzuki-Miyaura cross coupling reaction, Mizoroki-Heck reaction, and Sonogashira-Hagihara reaction processed in both aqueous and organic solvents. Intriguingly, these catalytic tubes can support not only single but also cascade catalytic reactions when Pd and Ag dual metals are decorated at different parts of the centrifuge tube. Upon this simple, low-cost, and widely-applicable polymer surface in situ metal nanoparticle growth and embedment strategy, a promising avenue to fabricate highly reusable catalytic polymer reactors for various reactions is widely opened. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/77566 |
DOI: | 10.6342/NTU201802593 |
全文授權: | 未授權 |
顯示於系所單位: | 化學系 |
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