https://scholars.lib.ntu.edu.tw/handle/123456789/177254
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor | 牟中原 | en |
dc.contributor | 臺灣大學:化學研究所 | zh_TW |
dc.contributor.author | 吳振麟 | zh |
dc.contributor.author | Wu, Chen-Lin | en |
dc.contributor.author | 牟中原指導 | - |
dc.creator | 吳振麟; 牟中原 | - |
dc.date | 2004 | en |
dc.date.accessioned | 2007-11-26T02:20:46Z | - |
dc.date.accessioned | 2018-07-10T05:02:54Z | - |
dc.date.available | 2007-11-26T02:20:46Z | - |
dc.date.available | 2018-07-10T05:02:54Z | - |
dc.date.issued | 2004 | - |
dc.identifier | zh-TW | en |
dc.identifier.uri | http://ntur.lib.ntu.edu.tw//handle/246246/51663 | - |
dc.description.abstract | 摘要 本論文的第一個主要研究方向,是希望能夠開發出ㄧ高效能之非均相催化劑,除了具有能被再回收利用的特性之外,還包含了極佳的催化活性,並且能夠盡量降低催化劑流失到溶液中的量。我們先合成出具 bipyridine 配位基之鈀金屬錯合物,再以後修飾法 (post-synthesis) 將其修飾到擔體上,這部份將由本實驗室所開發出之特殊中孔洞材料 (NS-MCM) 來扮演擔體角色。由於本中孔洞材料的顆粒大小在奈米尺度 (約100 nm ),在反應系統中具有極佳的分散性,並且具有高表面積 (約900 cm2/g ) 的特性,和相當狹窄的孔徑分布,使其成為極佳的非均相催化劑擔體。我們將探討 NS-MCM-Pd 在催化 Heck reaction 方面的能力。 另ㄧ個重要的研究方向,則是採用了本實驗室所研發出來的纖維狀中孔洞材料 (fibrous-MCM) 來擔附同樣的鈀金屬錯合物,並設計了一系列的共軛高分子單體 (monomer) ,可經由鈀金屬錯合物的催化,直接在孔道內合成規則排列的共軛高分子,形成有機無機複合材料,經由一系列的吸收及螢光光譜,與一般狀態下的共軛高分子比較中孔洞之限制空間效應對於共軛高分子物理化學特性的影響。 | zh_TW |
dc.description.abstract | Abstract This thesis is composed of two parts. In the first part, we developed the procedure to modify the bipyridyl palladium complexes onto the NS-MCM (nano-sized MCM) mesoporous materials and used these catalysts for an important carbon-carbon bond coupling reaction (Heck reaction).The NS-MCM mesoporous silica (size 70-100 nm) is of uniform pore diameter (2.9 nm) and high surface area (888 m2/g), which makes this material to be useful supports for a new generation of heterogeneous catalysis. This heterogeneous catalyst proves to be extremely active and recyclable for the Heck reaction with the turn-over-number up to 106 for each cycle. In the second part, we modified the bipyridyl palladium complexes onto fibrous MCM materials and used these materials for the Palladium-catalyzed polymerization of conjugated polymers. The conjugated polymers were formed and encapsulated in the channels of fibrous MCM. We also synthesized bulk conjugated polymers in homogeneous solution for comparison. By measuring photoluminescence spectra, we discussed the confinement effect of fibrous MCM on the physicochemical properties of conjugated polymers. | en |
dc.description.tableofcontents | 目錄 第一章 序論 1 1.1 中孔洞材料 (mesoporous materials)............................... 1 1.2 中孔洞材料在催化方面的應用....................................... 3 1.2.1 催化反應........................................................................... 3 1.2.2 非均相催化劑 (heterogeneous catalysts)........................ 3 1.2.3 以中孔洞材料為擔體之非均相催化劑性質探討....................................................................................... 5 1.3 中孔洞材料在合成有機無機複合材料方面的研究....................................................................................... 13 1.3.1 共軛高分子 (conjugated polymer).................................. 13 1.3.2 有機無機複合材料........................................................... 18 1.3.3 中孔洞材料/共軛高分子複合材料合成.......................... 23 1.4 研究目的................................................................................ 30 第二章 修飾於孔洞材料中 Pd 錯合物催化 Heck reaction之研究 32 2.1 實驗架構簡述.................................................................... 32 2.2 非均相化劑NS-MCM-Pd的合成.................................... 34 2.3 NS-MCM-Pd的鑑定......................................................... 37 2.4 NS-MCM-Pd在催化進行Heck reaction方面的探討..... 39 2.4.1 NS-MCM-Pd 催化 aryl iodides 與 olefins 進行 Heck reaction的結果.................................................................. 39 2.4.2 NS-MCM-Pd 催化 aryl bromides 與 olefins 進行 Heck reaction的結果......................................................... 40 2.4.3 NS-MCM-Pd 催化 aryl chlorides與olefins進行Heck reaction的結果................................................................. 43 2.5 NS-MCM-Pd的再使用活性測試.................................... 43 2.6 鈀金屬流失探討............................................................... 44 2.7 反應前後NS-MCM-Pd之結構性質探討........................ 45 2.8 不同催化系統之催化活性比較........................................ 48 第三章 限制空間內共軛高分子聚合反應的進行及物理化學性質探討 50 3.1 實驗架構簡述.................................................................... 50 3.1.1 合成策略............................................................................ 50 3.1.2 3.2 實驗部份........................................................................... 共軛高分子poly(phenylene vinylene)-PPV的合成及性質探討............................................................................... 50 51 3.2.1 實驗部份............................................................................ 51 3.2.2 複合材料PPV/MCM-41之物理性質鑑定....................... 53 3.2.3 螢光光譜及螢光激子生命期之探討…………………… 59 3.3 共軛高分子poly(p-phenylene)-PPP的合成及性質探討 66 3.3.1 實驗部份............................................................................ 66 3.3.2 複合材料PPP/MCM-41之物理性質鑑定....................... 67 3.3.3 螢光光譜之探討及螢光激子生命期之探討.................... 71 3.4 共軛高分子poly(phenylene thienylene)-PPT的合成及性質探討............................................................................ 75 3.4.1 實驗部份............................................................................ 76 3.4.2 複合材料PPT/MCM-41之物理性質鑑定....................... 76 3.4.3 螢光光譜之探討及螢光激子生命期之探討.................... 79 3.5 共軛高分子poly(phenylene dithienylene)-PPDT的合成及物理化學性質探討....................................................... 84 3.5.1 實驗部份............................................................................ 84 3.5.2 複合材料PPT/MCM-41之物理性質鑑定....................... 85 3.5.3 螢光光譜之探討及螢光激子生命期之探討................... 88 第四章 結論 93 第五章 實驗部份 95 5.1 測試儀器............................................................................ 95 5.2 試劑純化............................................................................ 99 5.3 實驗過程............................................................................ 99 參考文獻 113 附圖一 Bipyridine ligand (by-6) 核磁共振氫光譜 附圖二 Bipyridine ligand (by-6) 核磁共振碳光譜 | zh_TW |
dc.language | zh-TW | en |
dc.language.iso | en_US | - |
dc.subject | 共軛高分子 | zh_TW |
dc.subject | 鈀催化 | en |
dc.subject | 中孔洞材料 | en |
dc.subject | Palladium | en |
dc.subject | Heck Reaction | en |
dc.subject | Polymerization | en |
dc.subject | Mesoporous Silica | en |
dc.title | 修飾於孔洞材料中鈀錯合物之催化與聚合反應的研究 | zh |
dc.title | Heck Reaction and Polymerization Catalyzed by Anchored Palladium Complexes in Mesoporous Silica | en |
dc.type | thesis | en |
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item.languageiso639-1 | en_US | - |
item.cerifentitytype | Publications | - |
item.grantfulltext | none | - |
item.fulltext | no fulltext | - |
item.openairecristype | http://purl.org/coar/resource_type/c_46ec | - |
item.openairetype | thesis | - |
crisitem.author.dept | Chemistry | - |
crisitem.author.dept | Center for Condensed Matter Sciences | - |
crisitem.author.orcid | 0000-0001-7060-9899 | - |
crisitem.author.parentorg | College of Science | - |
crisitem.author.parentorg | Others: University-Level Research Centers | - |
顯示於: | 化學系 |
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