全球能源危機促使科學家們尋求乾淨且可再生的能源，如太陽能、生質能和氫能，其中氫能源高能量轉換效率和環境無害的優點引起廣泛的注意。為了能發展出強大、具經濟效益且效率高的bifunctional HER-OER electrocatalyst，以利電催化水裂解產氫，將{Fe(NO)2}9 DNIC [(MeImN2H)Fe(NO)2][BF4]/CoSO4/NiSO4在1 M phosphate buffer (pH = 7)電解液，透過陰極沉積於石墨碳板和銅片，形成一效率佳且穩定的固態材料。而所製備的GFeCoNi和CuFeCoNi固態電極在鹼性條件下，具有良好的HER和OER的催化活性，此外，進一步應用於水電裂解的全反應，發現相較Pt-IrO2電極，有較低的過電位()和Tafel slope，展現極佳的電催化活性。透過量測電容、SEM-EDX和XPS，可進一步了解電沉積film的電化學活性表面積和元素組成。

The global energy crisis has promoted scientists to search for clean and renewable energy resources such as solar, biomass and hydrogen energy. Due to its high energy conversion efficiency and environmentally friendly merit, the hydrogen energy has attracted widespread attention. In order to develop robust, economic and efficient bifunctional electrocatalyst responsible for overall water splitting with low overpotential and high stability, the solid-state electrodes, GFeCoNi and CuFeCoNi, were prepared from irreversible cathodic deposition of {Fe(NO)2}9 DNIC [(MeImN2H)Fe(NO)2][BF4], CoSO4 and NiSO4 on the surface of graphite plate and copper plate in 1 M phosphate buffer (pH = 7). The as-prepared GFeCoNi and CuFeCoNi electrodes exhibit significant electrocatalytic activity for HER and OER in aqueous alkaline condition. In addition, these electrode-pair settings display excellent electrocatalytic activity for overall water splitting with lower overpotential and Tafel slope, which are comparable to that of Pt-IrO2 electrode-pair setting. CV, SEM-EDX and XPS measurements were conducted to probe the electrochemically active surface area (ECSA), morphology and chemical composition of electrodeposited film.

摘要 I
Abstract II
目錄 III
圖目錄 V
表目錄 VII
第一章 緒論 1
1-1. 一氧化氮(Nitric Oxide, NO) 1
1-2. 雙亞硝基鐵錯合物(Dinitrosyl Iron Complexes, DNICs) 4
1-3. 氫能 8
1-3-1. 電催化產氫 12
1-3-2. 電催化產氧 14
1-3-3. 水裂解 17
1-4. 研究方向 19
第二章 實驗部分 21
2-1. 一般實驗 21
2-2. 儀器 21
2-2-1. 紅外線光譜儀(Infrared Spectrometer, IR) 21
2-2-2. X-ray單晶繞射解析 21
2-2-3. 電子順磁共振光譜儀(Electron Paramagnetic Resonance, EPR) 22
2-2-4. 循環伏安儀(Cyclic Voltammetry, CV) 22
2-2-5. 掃描式電子顯微鏡(Scanning Electron Microscopic, SEM) 22
2-2-6. 高解析電子能譜儀(High-Resolution X-ray Photoelectron Spectrometer, XPS) 22
2-3. 溶劑與藥品 23
2-3-1. 溶劑 23
2-3-2. 藥品 23
2-4. 化合物的合成與鑑定 24
2-4-1. Ligand N,N-Dimethyl-N’-(1-methyl-1H-imidazol-2-ylmethyl)ethane -1,2-diamine (MeImN2H)的合成 24
2-4-2. Complex [(MeImN2H)Fe(NO)2][BF4] (1)的合成 25
2-4-3. Complex [(MeImN2H)Fe(NO)2] (2)的合成 26
2-4-4. Complex [K-18-crown-6-ether][(MeImN2)(Fe(NO)2)2] (3)的合成 27
2-5. 電化學 28
2-6. 晶體結構解析 30
第三章 結果與討論 34
3-1. 錯合物的合成、結構與光譜分析 34
3-1-1. MeImN2H ligand合成與鑑定 34
3-1-2. [(MeImN2H)Fe(NO)2][BF4] (1)合成與鑑定 35
3-1-3. [(MeImN2H)Fe(NO)2] (2)合成與鑑定 38
3-1-4. [K-18-crown-6-ether][(MeImN2)(Fe(NO)2)2] (3)合成與鑑定 40
3-2. 異相電催化(heterogeneous electrocatalysis)水裂解 43
3-2-1. 電沉積過程最佳化 43
3-2-2. 水裂解 50
3-2-3. 電容(Capacitance) 51
3-2-4. 電沉積材料的鑑定(SEM-EDX, XPS) 53
第四章 結論 66
Reference 68

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