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研究生： 張嘉珊
Chang, Chia-Shan
論文名稱：
指導教授： 鄭沐政
Cheng, Mu-Jeng
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2020
畢業學年度： 108
語文別： 中文
論文頁數： 61
中文關鍵詞： 密度泛函數理論 、金屬卟啉 、四氮錯合金屬之石墨烯 、碳氫鍵活化
外文關鍵詞： Metal-porphyrins, Metal-N4-functionalized graphenes, Metal oxo, C-H activation, Density functional theory
相關次數： 點閱：101  下載：0 
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    • 現今社會經濟發展快速，對於能源的需求也越來越大，因此工業上致力於利用催化劑來轉換能源，將低經濟價值的化合物轉為高經濟價值的化合物，其中常見的催化劑為金屬卟啉和四氮錯合金屬之石墨烯，然而這兩種相似結構的催化劑在進行催化反應時的環境卻有所不同：金屬卟啉為勻相催化劑，而四氮錯合金屬之石墨烯為異相催化劑，因此必須要比較這兩種催化劑的反應性來選擇出適當的催化劑。本篇論文主要探討這兩種催化劑中心金屬形成metal oxo後對於催化反應的反應性，並且以烷類氧化為醇類的反應為依據，比較出哪一種催化劑的反應性較好，並解釋其原因。
    本篇論文中採用的軟體Jaguar 8.4為一種計算小分子的軟體，因此需要對四氮錯合金屬之石墨烯找出適當描述此材料的模型大小，經由計算結果得知以金屬接四氮的核為中心往外擴散兩圈時會達到尺寸收斂(size converge)，因此本論文採用金屬接四氮的核為中心往外擴散兩圈為四氮錯合金屬之石墨烯的模型大小。
    以鐵這種過渡金屬為中心金屬再加上不同取代基的金屬卟啉和四氮錯合金屬之石墨烯進行C-H activation和苯的氧化反應，結果發現不同取代基的金屬卟啉在進行催化反應時反應性都比四氮錯合金屬之石墨烯強，而鐵金屬卟啉受取代基效應的影響比四氮錯合鐵之石墨烯大。接著透過比較鐵金屬卟啉和四氮錯合鐵之石墨烯形成metal oxo後的π*軌域能量，發現鐵金屬卟啉形成metal oxo後的π*軌域能量比四氮錯合鐵之石墨烯來得穩定，成功解釋鐵金屬卟啉比四氮錯合鐵之石墨烯容易進行催化反應，又以氧化能力、hydrogen bonding energy和hydrogen affinity應證鐵金屬卟啉較容易進行催化反應。
    本篇論文得出鐵金屬卟啉比四氮錯合鐵之石墨烯較適合作為熱催化反應的催化劑，並成功解釋及驗證鐵金屬卟啉的反應性比四氮錯合鐵之石墨烯強。

    With the development of economic and technology, energy needs have been important issues for society. Therefore, using catalysts to do chemical transformation is necessary for industrial process. Two of them are metal-porphyrins and metal-N4-functionalized graphenes. However, these two catalysts require different environment when conducting catalytic reaction. One is homogeneous catalyst, the other is heterogeneous catalyst. This study will compare the reactivity between metal-porphyrins and metal-N4-functionalized graphenes by conducting oxidation reaction and explain which is the best catalyst. In this study, we use Jaguar 8.4 to compute electronic energies of each reaction geometry with density functional theory. As for the model of metal-N4-functionalized graphenes, the size will converge with two circles surrounding the metal center.

    We choose iron as metal combined with several axial ligand in metal-porphyrins and metal-N4-functionalized graphenes, catalyzing C-H activation and benzene oxidation. For both reactions, the reactivity of iron-porphyrins is better than iron-N4-functionalized graphenes. In addition, the ligand effect of iron-porphyrins is stronger than iron-N4-functionalized graphenes. In order to explain this result, we compare the energy of π* orbital between iron oxo-porphyrins and iron oxo-N4-functionalized graphenes. We find that the π* orbitals of iron oxo-porphyrins are more stable than iron oxo-N4-functionalized graphenes. We also analyze oxidation ability, hydrogen bonding energy and hydrogen affinity. From the analysis, we can conclude that iron-porphyrins are the better catalysts for thermocatalytic reactions.

    第一章 研究動機 1 第二章 緒論 2 2.1 金屬卟啉 2 2.1.1 細胞色素P450進行羥基化反應之反應機制 3 2.1.2 運用金屬卟啉進行催化反應 4 2.2 四氮錯合金屬之石墨烯表面 7 2.2.1 運用四氮錯合金屬之石墨烯進行催化反應 11 2.3 本篇研究所採用的中心金屬與取代基 13 第三章 計算軟體與方法 14 3.1計算軟體與計算方法 14 3.2四氮錯合金屬之石墨烯模型大小 14 第四章 結果與討論 19 4.1金屬卟啉與四氮錯合金屬之石墨烯進行C-H activation之反應性探討 19 4.1.1抽氫過程位相探討 20 4.1.2 進行C-H activation結構與活化能比較 25 4.1.2(a) 不同取代基的鐵金屬卟啉與四氮錯合鐵之石墨烯抽氫過渡態之結構 26 4.1.2(b) 不同取代基的鐵金屬卟啉與四氮錯合鐵之石墨烯進行C-H activation之反應性比較 31 4.1.3 取代基效應對鐵金屬卟啉與四氮錯合鐵之石墨烯反應性的影響 34 4.2 鐵金屬卟啉與四氮錯合鐵之石墨烯進行苯氧化反應之反應性比較 36 4.3 鐵金屬卟啉與四氮錯合鐵之石墨烯π*軌域能量比較 42 4.4 鐵金屬卟啉與四氮錯合鐵之石墨烯氧化能力之比較 46 4.4.1 鐵金屬卟啉與四氮錯合鐵之石墨烯游離能之比較 49 4.5 鐵金屬卟啉與四氮錯合鐵之石墨烯抽氫能力與活化能的關係 51 第五章 結論 55 參考文獻 56 表一 三種石墨烯模型之能量 17 表二 Top-attack和side-attack能量與結構比較 21 表三 Fe、Fe-OH、Fe-SH、Fe-F、Fe-Cl 和Fe-CF3SO3金屬卟啉抽氫之過渡態 26 表四 Fe、Fe-OH、Fe-SH、Fe-F、Fe-Cl 和Fe-CF3SO3四氮錯合金屬石墨烯抽氫之過渡態 28 表五 不同取代基的鐵金屬卟啉進行C-H activation之能量曲面 32 表六 不同取代基的四氮錯合鐵之石墨烯進行C-H activation之能量曲面 33 表七 不同取代基與對應之σp值 35 表八 不同取代基的鐵金屬卟啉進行苯氧化反應之能量曲面 40 表九 不同取代基的四氮錯合鐵之石墨烯進行苯氧化反應之能量曲面 41 表十 鐵金屬卟啉與四氮錯合鐵之石墨烯π*軌域的能量數值 43 表十一 鐵金屬卟啉與四氮錯合鐵之石墨烯氧化能力數值 48 表十二 金屬卟啉與四氮錯合金屬之石墨烯游離能數值 50 表十三 hydrogen affinity與其他生成能之數值 54 表十四 hydrogen bonding energy之數值 54 圖一 金屬卟啉與四氮錯合金屬之石墨烯催化反應示意圖 1 圖二 細胞色素P450和中心活化位 2 圖三 細胞色素P450進行羥基化反應之反應機制圖 3 圖四 中心金屬為鐵接取代基(-Cl)的金屬卟啉 4 圖五 金屬卟啉進行羥基化反應之反應機制 5 圖六 以亞碘醯苯為氧化劑形成manganese oxo 6 圖七 鈷金屬卟啉來進行羥基化反應 6 圖八 2D材料與單一原子催化劑之電子結構示意圖 7 圖九 四氮錯合金屬之石墨烯結構 8 圖十 熱裂解含模板法 9 圖十一 熱裂解不含模板法 9 圖十二 後處理法 10 圖十三 球磨法 10 圖十四 四氮錯合鐵之石墨烯進行苯的氧化反應 11 圖十五 中空管壁內嵌入四氮錯合鐵之石墨烯材料 12 圖十六 四氮錯合鐵之石墨烯進行甲烷的氧化反應 12 圖十七 本篇採用之中心金屬與取代基 13 圖十八 四氮錯合金屬石墨烯模型 16 圖十九 三種石墨烯模型之能量圖 18 圖二十 C-H activation 反應機構 19 圖二十一 Top-attack 之過渡態 20 圖二十二 Side-attack 之過渡態 21 圖二十三 Top-attack和Side-attack過渡態之EAO和EDO示意圖 22 圖二十四 metal oxo之π*軌域示意圖(以金屬卟啉為例) 23 圖二十五 metal oxo之σ*軌域示意圖(以金屬卟啉為例) 24 圖二十六 受質為環己烷之碳氫化合物進行C-H activation 25 圖二十七 不同取代基在鐵金屬卟啉抽氫過渡態的分子模型圖 29 圖二十八 不同取代基在四氮錯合鐵之石墨烯抽氫過渡態的分子模型圖 30 圖二十九 鐵金屬卟啉與四氮錯合鐵之石墨烯反應性比較 31 圖三十 取代基效應對鐵卟啉與四氮錯合鐵之石墨烯反應性的影響 35 圖三十一 苯進行氧化反應形成苯酚 36 圖三十二 鐵金屬卟啉與四氮錯合鐵之石墨烯進行第一步過渡態(4,5-TS)之反應性比較 37 圖三十三 進行第一步過渡態(4,5-TS)時取代基效應對鐵卟啉與四氮錯合鐵之石墨烯反應性的影響 38 圖三十四 鐵金屬卟啉與四氮錯合鐵之石墨烯進行第二步過渡態(5,6-TS)之反應性比較 39 圖三十五 鐵金屬卟啉與四氮錯合鐵之石墨烯π*軌域的能量比較 42 圖三十六 鐵金屬與各個取代基的π*軌域圖(Por：金屬卟啉，G：四氮錯合金屬之石墨烯) 44 圖三十七 鐵金屬與各取代基的π*軌域圖(Por：金屬卟啉，G：四氮錯合金屬之石烯) 45 圖三十八 金屬卟啉與四氮錯合金屬之石墨烯進行氧化反應 46 圖三十九 鐵金屬卟啉與四氮錯合鐵之石墨烯氧化能力比較 47 圖四十 鐵金屬卟啉與四氮錯合鐵之石墨烯的氧化能力與抽氫活化能之線性關係圖 47 圖四十一 以MO角度來分析鐵與氧的鍵結 48 圖四十二 氧化還原反應示意圖54 49 圖四十三 游離能示意圖 49 圖四十四 鐵金屬卟啉與四氮錯合鐵之石墨烯游離能比較 50 圖四十五 hydrogen bonding energy示意圖 51 圖四十六 hydrogen bonding energy和活化能之線性關係圖 52 圖四十七 hydrogen affinity與活化能之線性關係 53

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