本實驗利用脈衝式沉積法製備銥觸媒於多壁奈米碳管 (Muti-walls carbon nanotubes, MWCNT) 載體上，並應用於質子交換膜水電解器 (Proton exchange membrane water electrolyzer, PEMWE) 的陽極端。但由於 PEMWE 陽極端於高過電位 (>1.48 V) 下進行，因此大多數觸媒載體並不適用，使增加了陽極端貴重金屬的負載量。而奈米碳管擁有高機械強度、抗化學性以及高導電度，因此廣泛被作為觸媒載體，相較於傳統碳黑載體，有較佳的抗腐蝕能力，因此將其應用於 PEMWE 的陽極端。
掃描式電子顯微鏡 (Scanning electron microscopy, SEM)、循環伏安法 (Cyclic voltammetry, CV)、線性掃描伏安法 (Linear sweep voltammetry, LSV) 和感應耦合電漿質譜分析儀 (Inductively coupled plasma-mass spectrometer, ICP-MS) 以及 X-光繞射儀 (X-ray Diffractometer, XRD) 用以測試觸媒表面形貌、活性和負載量以及商用觸媒的晶體結構，最後經由 PEMWE 測試產氫效率以及長效測試。在 PEMWE 測試中，透過脈衝式沉積銥觸媒於奈米碳管上，水電解效率於 1 A/cm2 有 1.625 V，且觸媒負載量只有 0.167 mg/cm2。
另外，本實驗也同時探討了商用氧化銥 (Iridium oxide) 應用於 PEMWE 陽極端的電解效率，並和自製觸媒做比較。經過參數優化後，結果顯示電解效率於 1 A/cm2 僅 1.73 V。最後，耐久性測試中發現利用脈衝式電鍍於奈米碳管載體 (CNT@Ir) 相較於商用觸媒 (IrO2) 擁有穩定的降解效率。

This experiment utilizes the pulse electrodeposition method to prepare iridium catalyst on multi-wall carbon nanotubes (MWCNT) as a support, which is then applied to the anode side of a proton exchange membrane water electrolyzer (PEMWE). However, due to the high operating potential (>1.48 V) at the anode side of PEMWE, most catalyst supports are not suitable, resulting in an increased loading of precious metals at the anode side. On the other hand, carbon nanotubes have high mechanical strength, chemical resistance, and conductivity, making them widely used as catalyst supports. Compared to traditional carbon black supports, they exhibit superior corrosion resistance, thus making them suitable for application at the anode side of PEMWE.
The surface morphology, activity, loading, and the crystal structure of commercial catalysts were characterized by SEM, CV, LSV, ICP-MS, and X-ray diffractometer (XRD). Finally, the catalyst was tested through PEMWE to evaluate its hydrogen production efficiency and durability. In PEMWE testing, the iridium catalyst was pulse-deposited on carbon nanotubes, resulting in electrolysis efficiency of 1.625 V at 1 A/cm2, with a catalyst loading of only 0.167 mg/cm2.
Additionally, the electrolysis efficiency of commercial iridium oxide (IrO2) applied to the anode side of PEMWE was also investigated and compared with a homemade catalyst. After parameter optimization, the results showed that the electrolysis efficiency at 1 A/cm2 was only 1.73 V. In the durability test, it was found that the catalyst prepared using pulse electrodeposition on a carbon nanotube support (CNT@Ir) exhibited a more stable degradation efficiency compared to the commercial catalyst.

摘要 i
Abstract ii
目錄 iii
表目錄 vi
圖目錄 vii
第一章 緒論 1
1.1 前言 1
1.2 研究動機 1
第二章 基本原理與文獻回顧 3
2.1 氫氣生產方式 3
2.2 電解種類 5
2.2.1 鹼性水電解 5
2.2.2 固態氧化物電解 5
2.2.3 微生物電解 6
2.2.4 質子交換膜電解 6
2.3 質子交換膜電解水原理 7
2.4 質子交換膜電解器結構 8
2.4.1 氣體擴散層 9
2.4.2 觸媒層和離子聚合物 10
2.4.3 質子交換膜 10
2.4.4 雙極板 11
2.5 PEM水電解極化損失 13
2.6 觸媒種類和觸媒載體 15
2.6.1 析氧反應 (OER) 16
2.6.2 析氫反應 (HER) 17
2.6.3 觸媒載體 18
2.7 觸媒製備方式 19
2.7.1 定電位沉積法 20
2.7.2 脈衝式沉積法 21
第三章 實驗方法 23
3.1 實驗流程 23
3.2 實驗藥品和設備 24
3.2.1 實驗藥品 24
3.2.2 實驗設備 24
3.2.3 實驗氣體 25
3.2.4 分析儀器 26
3.3 電化學系統 26
3.4 製備觸媒載體 27
3.4.1 奈米碳管 28
3.4.2 枝晶狀白金結構 29
3.5 觸媒製備 29
3.5.1 自製陽極觸媒 30
3.5.2 商用陽極觸媒 31
3.5.3 陰極觸媒 32
3.6 觸媒檢測與分析 33
3.6.1 循環伏安法 (CV) 33
3.6.2 線性掃描伏安法 (LSV) 34
3.6.3 表面形貌分析 (SEM) 35
3.6.4 觸媒負載量分析 (ICP-MS) 36
3.6.5 觸媒結晶型態分析 (XRD) 36
3.7 水電解測試 37
3.7.1 膜電極組製備 37
3.7.2 水電解器極化掃描測試 38
3.7.3 耐久性測試 40
第四章 結果與討論 41
4.1 觸媒載體之探討 41
4.1.1 奈米碳管載體 (CNT) 41
4.1.2 枝晶狀白金載體 (Pt) 42
4.2 脈衝式電鍍陽極觸媒 43
4.2.1 沉積銥於奈米碳管載體 (CNT@Ir) 43
4.2.2 沉積銥於白金枝晶狀載體 (Pt@Ir) 48
4.2.3 不同載體應用於水電解效率和觸媒負載量分析 50
4.3 熱壓參數優化和探討 52
4.4 CNT@Ir 的電鍍參數優化和電解測試 54
4.5 商用陽極觸媒 62
4.5.1 晶體結構 62
4.5.2 商用觸媒的電解效率 63
4.6 耐久性測試 66
第五章 結論 69
參考文獻 72

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