近年來，隨著非再生能源不斷地減少，能源需求也隨人口數成長，需求量增加，而大部分的能源經由燃燒石化燃料所得，但伴隨的副產物二氧化碳，是造成全球暖化的主因，因此發展出乾淨、零碳的再生能源是當今重要的議題，氫能源剛好符合上述需求，經由裂解水產生的氫氣可視為一種新的能源型式，燃燒伴隨的副產物為無汙染的水，符合無汙染能源的概念，因此設計出便宜且效率高的催化劑，使裂解水的還原電位將低是目前科學家所追求的。
本研究以2,5,8,11,14,17-hexamethyl-2,5,8,11,14,17-hexaazaoctadecane （HMHAOD）為配位基合成出金屬參核錯合物[(HMHAOD)(Fe(NO)2)3]（1）與雙核[(HMHAOD)(Fe(NO)2)2][BF4]2（2），並探討其反應性及應用性。
將[(HMHAOD)(Fe(NO)2)2][BF4]2（2）在水相下進行OER實驗，可有效的幫助降低裂解水所需的氧化電位，在中性的Na2SO4水溶液下，藉由氣相層析儀偵測氧氣的產生，並進一步進行長時間電解，電解時間可長達24小時，在同相催化下是非常優異的。

In recent years, many scientists are dedicated to develope renewable energy with the limited reserves of fossil fuels and the increasing concentration of by product - CO2, which is believed to be the main cause of global warming. Therefore, the development of clean, zero carbon renewable energy is an important issue today. Hydrogen energy is just in line with tha above requirements due to it’s combustion product - water. Water is the promising source for the production of hydrogen as its abundance. So, the designed catalyst that assists in lowering oxidation potential of water oxidation is a significant challenge for scientists.
In this study, 2,5,8,11,14,17-hexamethyl-2,5,8,11,14,17-hexaazaoctadecane (HMHAOD) was synthesized as ligand to yield an amine-bound Dinitrosyl Iron Complexes (DNIC), [(HMHAOD)(Fe(NO)2)3] (1) and [(HMHAOD)(Fe(NO)2)2][BF4]2 (2) . Reactivity and applicability of DNICs were investigated.
Among DNICs synthesized, [(HMHAOD)(Fe(NO)2)2][BF4]2 (2) shows the potential to serve as a catalyst promotiong water splitting.

第一章 緒論.....................................................1
1-1. 一氧化氮 (Nitric oxide) ……………………………………………………... 1
1-2. 一氧化氮 (Nitric oxide) 的生成…………………………………………...... 4
1-3. 一氧化氮在體內的運送與儲存........................................................................ 6
1-4. 雙亞硝基鐵錯合物 (DNIC)…………………………………………………. 9
1-5. 二氧化碳的還原 ……………………………………………………………..16
1-6. 氫能源………………………………………………………………………..23
1-7. 研究方向..........................................................................................................32
第二章 實驗部分..............................................33
2-1. 一般實驗……………………………………………………………………..33
2-2. 儀器…………………………………………………………………………..33
2-3. 溶劑與藥品 …………………………………………………………………..35
2-3-1. 溶劑……………………………………………………………………...35
2-3-2. 藥品……………………………………………………………………...36
2-4. 化合物的合成與鑑定 ………………………………………………………..36
2-4-1. 合成2,5,8,11,14,17-hexamethyl-2,5,8,11,14,17-hexaazaoctadecane
(HMHAOD).............................................................................................36
2-4-2. Complex [(HMHAOD)(Fe(NO)2)3] (1) 的合成.......................................38
2-4-3. Complex [(HMHAOD)(Fe(NO)2)2] [BF4]2 (2) 的合成........................... 39
2-5. 高壓實驗……………………………………………………………………..39
2-6. 電化學方法 …………………………………………………………………..41
2-7 氣相層析儀 (GC) 之氣體檢量線………………………………………...... 41
第三章 結果與討論...........................................44
3-1. Complex [(HMHAOD)(Fe(NO)2)3] (1) 之結構與性質……………………...44
3-2. Complex [(HMHAOD)(Fe(NO)2)3] (1) 對小分子氣體的反應性……….......46
3-2-1. Complex 1 對O2(g) 的反應……………………………………………..46
3-2-2. Complex 1 對CO2(g) 的反應…………………………………………...47
3-2-3. Complex 1 對CO(g) 的反應…………………………………………….49
3-2-4. Complex 1 對 H2(g) 的反應……………………………………………50
3-3. [(HMHAOD)(Fe(NO)2)3] (1) 與CO2(g) 和各種不同還原劑之反應………..52
3-3-1. Complex 1與CO2(g) 和 Na(s) 的反應.....................................................52
3-3-2. Complex 1與CO2(g) 和 Zn(s) 的反應.....................................................53
3-3-3. Complex 1與CO2(g) 和 Al(s) 的反應.....................................................53
3-3-4. Complex 1與CO2(g) 和 K(s) 的反應......................................................54
3-3-5. Complex 1與CO2(g) 和 H2(g) 的反應…………………………………. 54
3-3-6. 還原劑與CO2(g) 反應之實驗…………………………………………. 54
3-4. [(HMHAOD)(Fe(NO)2)3] (1) 與CO2(g) 和Zn 在HMHAOD下之反應…. 55
3-5. [(HMHAOD)(Fe(NO)2)3] (1) 與還原劑在高壓CO2(g) 下之反應…………. 58
3-5-1. Complex 1與Zn(s) 和高壓CO2(g) 的反應..............................................58
3-5-2. Complex 1與高壓CO2(g)、H2(g) 的反應.................................................59
3-6. [(HMHAOD)(Fe(NO)2)3] (1) 與CO2(g) 的反應機構探討…………………. 60
3-7. [(HMHAOD)(Fe(NO)2)2] [BF4]2 (2) 之結構與性質.......................................62
3-8. [(HMHAOD)(Fe(NO)2)2] [BF4]2 (2) 於OER的研究.....................................65
3-9. [(HMHAOD)(Fe(NO)2)2] [BF4]2 (2) 進行OER的反應機構探討.................77
第四章 結論...................................................79
References......................................................81

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