本研究利用脈衝式電化學沉積法在乾淨碳紙上製備新型態鉑觸媒作為質子交換膜燃料電池之觸媒。此新型態鉑觸媒之特殊形貌可增加觸媒反應活性，在無其它碳載體的情況下具有較多的觸媒表面積，進而提升觸媒催化效率及降低觸媒承載量。經由循環伏安法於硫酸及甲醇溶液下進行電化學測試，並利用X光粉末繞射儀(XRD)、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)以及電感耦合等離子體質譜(ICP-MS)對試片做進一步的分析。透過掃描式電子顯微鏡照片發現此新型態鉑觸媒的結構為樹枝狀結構，其主幹長度約為0.3至3 μm，而寬度約為400至600 nm。半電池電化學測試結果顯示，甲醇測試電流可達277.5 mA/cm2，其if/ib值為1.4，顯示鉑樹枝狀結構觸媒具有良好的抗一氧化碳毒化能力。使用最佳參數製備出的鉑樹枝狀觸媒在經由氫氣單電池測試，其功率密度可達506.7 mW/cm2，顯示鉑樹枝狀觸媒具有高催化性及耐久性。

Innovative support-free platinum (Pt) nanostructures were developed in this study for enhancing the anode catalyst activities for proton exchange membrane fuel cell (PEMFC) application. The platinum nanostructures were directly grown on carbon paper by a pulsed electrodeposition technique. The morphology of Pt nanostructures were investigated by SEM, and shown as dendritic structures instead of nanoparticles. The sizes of the dendritic structures are ranged from 0.3 to 3 μm in length and 400 to 600 nm in diameter. A cyclic voltammetry analysis was carried out for characterizing the behavior of methanol oxidation on specimen bearing the Pt dendritic nanostructures in mixed 1 M methanol and 0.5 M sulfuric acid solutions. It was found that the peak current density of methanol oxidation obtained from the cyclic voltammogram on the new Pt dendritic nanostructures specimen was 277.5 mA/cm2. Due to its unique morphology, the Pt dendritic nanostructures could exhibit a good carbon monoxide tolerance and high efficiency without the joined Ruthenium (Ru) catalyst. The catalytic efficiency of prepared Pt dendritic nanostructures was much better than that of a commercial Pt-black catalyst. It is noteworthy that the if/ib value of the Pt dendritic nanostructures is higher than 1.4, which is very different from pure Pt nanoparticles. The outcome signified that the novel catalyst morphology of the Pt dendritic nanostructures have remarkable CO tolerance even if Ru or other metal catalyst were not joined.

摘要 i
Abstract ii
致謝 iii
表目錄 iv
圖目錄 v
目錄 vii
第一章　緒論 1
1.1 前言 1
1.2 研究動機 2
第二章　基本原理與文獻回顧 4
2.1 燃料電池簡介 4
2.2 質子交換膜燃料電池結構 6
2.2.1 氣體擴散層 6
2.2.2 觸媒層 7
2.2.3 質子交換膜 8
2.2.4 雙極板 9
2.3 質子交換膜燃料電池工作原理 10
2.4 全電池極化損失 11
2.4.1 活性極化 12
2.4.2 歐姆極化 13
2.4.3 濃度極化 13
2.4.4 燃料穿透 14
2.5 觸媒製備方法 14
2.5.1 電化學沉積法 14
2.5.2 定電位電鍍法 14
2.5.3 脈衝式(往復式)電鍍法 16
2.5.4 奈米線、奈米柱觸媒製備 18
第三章　實驗方法 22
3.1　實驗流程 22
3.2 實驗藥品與設備 23
3.2.1 實驗藥品 23
3.2.2 實驗用氣體 23
3.2.3 實驗設備 23
3.2.4 分析儀器 24
3.3 電化學實驗裝製設計 25
3.4 碳紙親水化處理 25
3.5 電化學沉積法製備鉑觸媒 26
3.6 觸媒催化性分析 27
3.6.1 電化學分析 27
3.6.2 硫酸測試 (Sulfuric acid test) 28
3.6.3 甲醇測試 (Methanol oxidation test) 30
3.7 觸媒型態分析 31
3.7.1 場發射掃瞄式電子顯微鏡 (Field Emission Gun Scanning Electron Microscopy，FEG-SEM) 31
3.7.2 穿透式電子顯微鏡 (Transmission Electron Microscopy，TEM) 32
3.7.3 X光粉末繞射 (X-ray Powder Diffraction，XPRD) 32
3.7 組成比例分析 33
3.7.1感應耦合電漿質譜分析儀 (Inductively Coupled Plasma-Mass Spectrometer，ICP-MS) 33
3.8 單電池測試 (Single Cell Test) 34
3.8.1 膜電極組(Membrane Electrode Assembly，MEA)製備 34
3.8.2 漿料配製與噴塗 34
3.8.3 MEA壓合 35
3.8.4 單電池極化掃描測試 36
3.8.5 單電池耐久度測試 36
第四章　結果與討論 38
4.1 碳紙親水化處理 38
4.2 場發射掃描式電子顯微鏡之觸媒微影圖像分析(SEM) 39
4.3 穿透式電子顯微鏡之觸媒微影圖像分析(TEM) 44
4.4 X光粉末繞射法分析(XPRD) 44
4.5 半電池電化學分析結果 45
4.5.1 硫酸測試 45
4.5.2 甲醇測試 49
4.6 感應耦合電漿質譜分析儀分析(ICP-MS) 54
4.7 單電池測試分析結果 54
4.7.1 單電池極化掃描測試 54
4.7.2 單電池耐久度測試 57
第五章　結論 59
參考文獻 60

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