本論文中透過可見光作為驅動力使高分子分解水產生氫氣，我們提出了一系列環鉑化聚合物高分子奈米顆粒（Polymer dots），並且深入探討選擇受體共聚單體影響光催化活性的重要性。此系列環鉑共軛高分子的能隙為2.04~2.81eV，此區間中可以有效地吸收並利用可見光。此外，我們發現電子供應氮（sp3氮）和電子接受氮（sp2氮）引入受體共聚單體可以提高Pdots用於析氫的效率和穩定性是有效的策略。最活躍的PFTBTA-PtPy Polymer dots提供高達7.34±0.82 mmol h-1 g-1的析氫速率（HERs），在無甲醇溶液和可見光下具有31.54±1.39 mmol g-1的最佳氫氣產量驅動系統。 再經由MTT測定實驗證實，相對於將Pt直接添加到溶液系統中的常規方法，使用環鉑化Pdots作為光催化劑可以使毒性最小化。此外，可以通過再循環過程重新回收並製備環化的高分子奈米顆粒以產生氫氣。結果證明，使用環鉑化高分子奈米顆粒不僅可以提高產氫效率及其穩定性，還可以降低毒性，其對環境友善的特性且可以將豐富的太陽能轉換為有極高燃燒密度之氫能，無疑是綠色能源的一大進步。基於這項工作，可以理解選擇高分子奈米顆粒之受體共聚單體以實現光催化反應的高效率和長穩定性的明確設計策略。

By mimicking nature photosynthesis, a series of cycloplatinated polymer dots (Pdots) are presented and investigated the importance of selecting acceptor comonomers to affect the photocatalytic activity. It is found that the introduction of both electron-donating nitrogen (sp3 nitrogen) and electron-withdrawing nitrogen (sp2 nitrogen) into the acceptor comonomers is an effective strategy to enhance the efficiency and stability of Pdots for hydrogen evolution. The most active PFTBTA-PtPy Pdots provide the hydrogen evolution rates (HERs) up to 7.34 ± 0.82 mmol h–1 g–1 with excellent eventual hydrogen productions of 31.54 ± 1.39 mmol g-1 under a methanol-free solution and visible-light-driven system. MTT assay experiments confirm the use of the cycloplatinated Pdots as photocatalysts can minimize the toxicity, relative to the conventional approach that directly adding Pt into a solution system. Furthermore, the cylcoplatinated Pdot can be reactivated for hydrogen generation by the recycling process. The result proves that the use of cycloplatinated Pdots can not only enhance the HER efficiency and stability but also reduce the toxicity. Based on this work, a clear design strategy for the selection of acceptor comonomers of Pdots to achieve the high efficiency and long stability of photocatalytic reaction can be understood.

圖目錄-----7
第一章 緒論-----13
1-1氫能-----14
1-2、光催化分解水系統-----22
1-3、光催化分解水機制-----26
1-4、光催化水分解之影響變因-----29
第二章設計與合成高分子奈米顆粒及其於可見光催化產氫之應用-----33
2-1 研究前言與動機-----34
2-2 環鉑共軛高分子之合成與其鑑定-----49
2-3 新型環鉑共軛高分子之合成與其物理性質探討-----55
光物理性質探討-----55
瞬時放光衰退測量曲線-----66
熱物理性質探討-----68
最高填滿軌域(HOMO)-最低未填滿軌域(LUMO)之測量-----69
高分子奈米顆粒之粒徑與組成元素分析-----75
高分子材料之接觸角測量-----83
2-4 新型環鉑共軛高分子奈米顆粒之產氫系統應用-----87
結論-----95
未來展望-----97
實驗部分-----99
儀器與藥品-----109
參考文獻-----110
附錄-核磁共振光譜及凝膠滲透層析儀圖譜-----115

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