結合嵌段共聚物自組裝及微乳化法製備三維侷限多層級結構

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姓名

孫成浩(Cheng-Hao Sun) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

結合嵌段共聚物自組裝及微乳化法製備三維侷限多層級結構
(3D-confinement Tailored Hierarchical Structures through a Combination of Self-assembly and Micro-emulsion.)

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摘要(中)

在通過微乳化方法產生的三維侷限空間下，嵌段共聚物（BCP）
傾向於形成具有洋蔥狀奈米層狀結構的微球、具有軸向堆疊的奈米
層板結構的橢球和具有納奈米柱狀結構的盤狀粒子。這種多層級
（結構中具有結構）結構在許多領域具有潛在的應用，包括生物醫
學，能源，催化劑和光學裝置。微乳化方法是使用具有不同表面性
質的兩種不混溶溶劑，比如氯仿和水來製備嵌段共聚物微結構。在
此研究中，我們將PS-b-P4VP 溶解在氯仿中，然後加入大量含有界
面活性劑CTAB 的水。在CTAB 存在下，水溶液可將PS-b-P4VP/氯
仿溶液乳化，並在混合物中形成膠體微粒。除去氯仿和水後，PS-b-
P4VP 能自發地自組裝並在微粒中形成奈米結構。在三維侷限空間
下，PS-b-P4VP 自組裝產生了幾種結構內具有結構之形態，可以通
過控制共聚物分子量、溶劑性質以及嵌段共聚物的表面能來調控。
最終可獲得洋蔥狀、具凸-凹結構和具雙凸結構微粒或具有六邊形奈
米柱狀陣列的盤型微米粒子。而後，我們將多層級結構用作模板進
一步製造複製模板形態的碳和金屬材料並應用於氧還原反應。

摘要(英)

Under 3D confinement generated through a micro-emulsion approach, block copolymer (BCP) tends to form micro spheres with onion-like nanodomains, ellipsoids with axially-stacked nanolamellae, and Oblate particles with nanocylinders. Such hierarchical (structure-within-structure) structures have potential applications in many fields, including biomedicine, energy, catalyst and optical devices. For the micro Emulsion approach, two immiscible solvents, chloroform and water, with different surface properties were used to produce BCP microstructures. PS-b-P4VP was dissolved in chloroform followed by the addition of a large amount of
water with surfactant CTAB. In the presence of CTAB, the solution of PS-b-P4VP/chloroform was emulsified to form colloidal microparicles in the mixture after adding water. Upon removal of chloroform and water, PS-b-P4VP spontaneously self-assembled to form nanodomains within the
microparicles. Under 3D confinement, self-assembly of PS-b-P4VP produced several structure-within-structure morphologies, which could by tailored by controls over molecular weight, solvent quality, as well as the surface energy of BCPs. As a result, onion-like, convex-concavo, and
convex-convex microparticles or oblate mciroparticles with hexagonal arrays of nanopores were obtained. The hierarchical structures were then used as templates to fabricate carbon and metal materials with replicated morphologies for oxygen reduction reactions.

關鍵字(中)

★ 三維侷限空間自組裝
★ 嵌段共聚物
★ 微乳化法

關鍵字(英)

★ 3D-confinement self-assembly
★ Block copolymer
★ Micro-emulsion method

論文目次

摘要 ............................................................................................................. i
Abstract ...................................................................................................... ii
目錄 ........................................................................................................... iii
圖目錄 ....................................................................................................... vi
表目錄 ..................................................................................................... xiii
第1 章文獻回顧 ...................................................................................... 1
1-1 嵌段共聚物自組裝機制 ............................................................. 1
1-2 塊材系統與三維侷限系統之自組裝 ......................................... 3
1-3 嵌段共聚物奈微米粒子合成方法 ............................................. 6
1-4 碳化嵌段共聚物合成奈米碳材 ................................................. 8
1-5 共聚物微球作為模板混摻前驅物之機制 ............................... 10
1-6 氧還原反應 ............................................................................... 12
1-7 研究動機 ................................................................................... 16
第2 章實驗方法 .................................................................................... 17
2-1 實驗材料 ................................................................................... 17
2-1-1 雙嵌段共聚物 ................................................................ 17
2-1-2 實驗用基材 .................................................................... 18
2-1-3 溶劑 ................................................................................ 18
2-1-4 相關藥品 ........................................................................ 18
2-2 樣品製備 ................................................................................... 19
2-2-1 基材清潔 ........................................................................ 19
2-2-2 製備嵌段共聚物微米粒子 ............................................ 19
2-2-3 以微米高分子粒子為碳源製備奈米碳材 ................... 20
2-2-4 以微米高分子粒子為模板製備白金-碳複合材料 ...... 20
2-3 實驗儀器 ................................................................................... 20
2-4 儀器分析 ................................................................................... 21
2-4-1 拉曼光譜儀 .................................................................... 21
2-4-2 掃描式電子顯微鏡 ........................................................ 21
2-4-3 穿透式電子顯微鏡 ........................................................ 22
2-4-4 X 光繞射分析 ................................................................. 22
2-4-5 氧還原活性 .................................................................... 23
第3 章結果與討論 ................................................................................ 25
3-1 嵌段共聚物微米粒子之自組裝型態與結構探討 ................... 25
3-1-1 對稱型共聚物微米粒子之自組裝行為 ....................... 25
3-1-2 非對稱型共聚物微米粒子之自組裝行為 ................... 32
3-2 碳化嵌段共聚物微米粒子形成之奈米碳材及其形態、結構
探討 ................................................................................................... 34
3-2-1 碳化具洋蔥結構之微米粒子所得奈米碳材之型態與
結構........................................................................................... 34
3-2-2 碳化具六角圓柱結構之微米粒子所得奈米碳材之型
態與結構 .................................................................................. 37
3-3 以洋蔥狀嵌段共聚物微米粒子為模板合成之白金觸媒材料
之結構 ............................................................................................... 39
3-3-1 以洋蔥狀微米粒子製備之奈米白金碗狀粒子 ........... 40
3-3-2 奈米白金碗狀粒子之尺寸與模板分子量的關係 ....... 43
3-3-3 燒結溫度對奈米白金碗狀粒子結構之影響 ............... 44
3-4 奈米碳材及白金觸媒的氧還原活性探討 ............................... 46
3-4-1 白金觸媒之氧還原活性 ................................................ 46
3-4-2 奈米碳材之氧還原活性 ................................................ 53
第4 章結論............................................................................................. 59
參考資料 ................................................................................................... 61

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指導教授

孫亞賢(Ya-Sen Sun)

審核日期

2019-8-20

推文