本研究採用脈衝式電鍍法將奈米結構鉑觸媒沉積於碳基材表面上，將其應用於質子交換膜水電解器之陰極，用以提升氫氣析出的反應活性。電鍍製程採用自終止電化學沉積法，即透過施加高還原電位，使氫原子吸附於已沉積之鉑表面上，防止鉑離子的持續還原；當循環到正電位時，鉑表面的氫原子發生脫附現象而使鉑觸媒得以在後續電位循環中再進一步進行沉積，藉此達成對觸媒承載量的精確控制。
實驗分為兩大部分，第一部分為探討電化學沉積觸媒製程參數最佳化: 調整(1)前驅物溶液之輔助電解質以及(2)脈衝沉積循環次數等參數，再透過在0.5 M硫酸溶液中進行循環伏安法和線性掃描伏安法作為電化學特性分析，並利用SEM、XRD以以及ICP-MS等儀器進行觸媒形貌、結晶性以及承載量之分析，找尋最佳觸媒製備參數。第二部分則為膜電極組製程參數最佳化，利用經過最佳化的奈米結構鉑觸媒作為質子交換膜水電解器的陰極，並調整(1)膜電極組組裝熱壓壓力以及(2)陰極Nafion®承載量，透過水電解器測試極化曲線中之比較獲得最佳製備條件。在水電解器測試中，自製觸媒展現了良好的產氫效能，並且其表現在高電流密度區域優於商用觸媒。

Nanostructured platinum catalysts were developed by pulsed potential electrodeposition technique and used as the cathode for the proton exchange membrane water electrolyzer(PEMWE) to enhance the hydrogen evolution reaction(HER) activity in this study. The electrodeposition process for controlling Pt loading precisely is based on the Self-Terminated Electrodeposition. By the adsorption of hydrogen on the deposited Pt surface at a high reduction potential, the deposition reaction of Pt is quenched. The layer-by-layer growth of Pt is deposited on the surface by periodic pulsed potentials.
The first part of this work is the optimization of the Pt electrodeposition process by adjusting the species of supporting electrolyte and the cycle number of periodic potentials. The electrochemical characteristics of the Pt catalysts were investigated via cyclic voltammetry (CV) and linear sweep voltammetry (LSV) analysis in 0.5 M sulfuric acid solution. The morphologies, crystallinity, and mass loading of catalysts were measured by SEM, XRD, and ICP-MS. The second part is the optimization of the preparation process of membrane electrode assemblies (MEA). The platinum catalyst prepared by the electrodeposition process is used as the cathode of the proton exchange membrane water electrolyzer. By comparing the polarization curves of the electrolyzer test, we can obtain the optimized parameters of hot-pressing pressure and Nafion® loading at the cathode. In the water electrolyzer test, the homemade catalyst was demonstrated remarkable performance in hydrogen production. The performance was superior to that of commercial catalysts in the high current density region.

摘要 i
Abstract ii
總目錄 iv
表目錄 viii
圖目錄 ix
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 水電解技術簡介 4
2.2 質子交換膜水電解結構 5
2.2.1 多孔傳輸層(Porous Transport Layer, PTL) 6
2.2.2 觸媒層(Catalyst Layer, CL) 8
2.2.3 質子交換膜(Proton Exchange Membrane) 11
2.2.4 雙極板(Bipolar Plate) 12
2.3 質子交換膜水電解器工作原理 15
2.4 水電解器極化損失 16
2.4.1 活性極化 17
2.4.2 歐姆極化 18
2.4.3 濃度極化 18
2.5 電化學分析 19
2.5.1 循環伏安法 20
2.5.2 線性掃描伏安法 24
2.6 質子交換膜水電解器半反應 25
2.6.1 陽極氧氣析出反應 25
2.6.2 陰極氫氣析出反應 27
2.7 電化學沉積法製備觸媒 29
2.7.1 定電位沉積法 29
2.7.2 脈衝式電鍍法 31
第三章 研究方法與實驗步驟 35
3.1實驗流程 35
3.2實驗藥品與設備 36
3.2.1實驗藥品與材料 36
3.2.2實驗設備 37
3.2.3 分析儀器 37
3.3 觸媒載體前處理 38
3.4電化學實驗裝置設計 39
3.5 電化學沉積法製備奈米結構鉑觸媒 40
3.6觸媒電化學特性分析 42
3.6.1循環伏安法(CV)測試 42
3.6.2 線性掃描伏安法(LSV)測試 42
3.7觸媒檢測及形貌分析 43
3.7.1 熱場發射掃描式電子顯微鏡(Thermal Field Emission Scanning Electron Microscope, FE-SEM) 43
3.7.2 X光粉末繞射儀(X-Ray Powder Diffractometer，XRPD) 44
3.7.3 感應耦合電漿分析儀 (Inductivity Coupled Plasma-Mass 46
Spectrometer, ICP-MS) 46
3.8 單水電解器測試(Single Cell Test) 47
3.8.1 液態Nafion®佈植 48
3.8.2 商用觸媒漿料配製與塗佈 48
3.8.3 膜電極組製備與組裝 49
第四章 結果與討論 52
4.1 實驗A: 輔助電解質對電化學沉積鉑觸媒之影響 52
4.1.1 場發射掃描式電子顯微鏡之觸媒形貌分析(SEM) 53
4.1.2 X 光粉末繞射分析（XRD） 54
4.1.3 半電池電化學分析 55
4.2 實驗B: 電位循環次數對電化學沉積鉑觸媒之影響 57
4.2.1 場發射掃描式電子顯微鏡之觸媒形貌分析(SEM) 58
4.2.2 半電池電化學分析 60
4.2.3 水電解器測試分析 63
4.3 實驗C: 膜電極組製備參數對水電解器性能之影響 64
4.3.1熱壓壓力對自製觸媒之膜電極組的影響 66
4.3.2 陰極Nafion®承載量對自製觸媒之膜電極組的影響 68
4.4 實驗D:電解器模組中氣密墊片厚度對電解效能之影響 69
4.5 自製觸媒與商用觸媒應用於水電解器之效能比較 71
第五章 結論 74
參考文獻 76

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