臺灣博碩士論文加值系統

氮化鈦（Titanium nitride，TiN），為一過渡金屬氮化物的陶瓷材料，其具低電阻、良導熱性、化學穩定等特性。本論文研究結合中興大學材料系呂福興教授研究團隊所提供之導電TiN薄膜，並將此導電氮化鈦薄膜作為直接甲醇燃料電池陽極電極，且沉積鉑（Platinum，Pt）、鈀（Palladium，Pd）觸媒探討此陽極觸媒材料對甲醇氧化的活性。
本實驗分成兩部分，第一部分使用電化學沉積法將Pt奈米觸媒沉積於TiN載體上，製備鉑/氮化鈦（Pt/TiN）陽極觸媒材料，利用場發射式掃描式電子顯微鏡（Field emission-scanning electron microscope，FE-SEM）與原子力顯微鏡 （Atomic force microscope，AFM）觀察表面形貌，使用X光繞射分析儀（X-ray diffraction，XRD）作結晶分析與X光能量散譜儀（X-ray energy dispersive spectrometer，EDS）作元素分析，其結果證實Pt觸媒沉積於 TiN載體上。Pt/TiN薄膜陽極觸媒材料在0.5 M硫酸溶液中探討其電化學活性面積 （Electrochemically active surface area，ECSA）及在2 M甲醇和1 M硫酸混合溶液中探討其甲醇的氧化活性，並和商用碳黑（Carbon black，Vulcan XC-72）載體比較，實驗結果得知其擁有較大的ECSA及較良好的甲醇電氧化活性，最後更進一步探討Pt/TiN陽極觸媒材料對甲醇氧化電活性的長時間穩定性。
第二部分使用Pd觸媒來取代Pt觸媒，並在鹼性下探討直接甲醇燃料電池。將製備完成後鈀/氮化鈦（Pd/TiN）陽極觸媒材料同樣FE-SEM和AFM觀察表面形貌，使用XRD作結晶分析與EDS作元素分析。Pd/TiN陽極觸媒材料在0.5 M氫氧化鉀探討其ECSA及1 M甲醇和1 M氫氧化鉀混合溶液中探討甲醇的氧化活性，並和Vulcan XC-72載體比較，實驗結果得知其擁有較大的ECSA及較良好的甲醇電氧化活性，最後更進一步探討Pd/TiN陽極觸媒材料對甲醇氧化電活性的長時間穩定性。

TiN is a transition metal compound which has inert nature, high electrical conductivity and corrosion resistance. In this study, platinum and palladium nanoparticles were successfully deposited on titanium nitride（TiN）and their electrocatalytic activities for methanol oxidation were investigated. The morphology of TiN was inspected by scanning electron microscope. The study include two parts, in part Ι, Pt nanoparticles supported on TiN were investigated as anode electrocatalytic materials for direct methanol fuel cells. The morphology and composition of the Pt/TiN were characterized by scanning electron microscopy, atomic force microscope, X-ray diffraction, and energy dispersive X-ray spectroscopy. The Pt/TiN showed a sharp hydrogen desorption peak at about -0.2 V vs. Ag/AgCl in a solution of 0.5 M H2SO4. In comparison with Vulcan XC-72-Pt modified glassy carbon electrode（Vulcan XC-72-Pt/GCE）, the Pt/TiN exhibited a high value of electrochemically active surface area（ECSA）and an excellent electrocatalytic activity for methanol electrooxidation reaction. The electrocatalytic properties of Pt/TiN for methanol electrooxidation were investigated by cyclic voltammetry in 2 M CH3OH + 1 M H2SO4 solution. The Pt/TiN showed a higher If/Ib value and a better stability than Vulcan XC-72-Pt/GCE.
In partⅡ, Pd nanoparticles supported on TiN were investigated as anode electrocatalytic materials for direct methanol fuel cells in alkaline media. The morphology and composition of the Pd/TiN were characterized by scanning electron microscopy, atomic force microscope, X-ray diffraction, and energy dispersive X-ray spectroscopy.Cyclic voltammetry and chronoamperometry tests demonstrated that the Pd/TiN showed higher activity and stability for the methanol oxidation reaction in alkaline media than the Vulcan XC-72-Pd /GCE did.

摘要 i
Abstract ii
總目錄 iii
圖目錄 v
表目錄 ix
第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
1.3 燃料電池簡介 2
1.3.1 燃料電池的發展 2
1.3.2 燃料電池的特點 3
1.3.3 燃料電池的種類 4
1.4 直接甲醇燃料電池 7
1.4.1 直接甲醇燃料電池基本原理 7
1.4.2 直接甲醇燃料電池基本構造 8
1.4.3 甲醇在陽極的反應途徑及毒化問題 10
1.4.4 鹼性直接甲醇燃料電池 13
1.5 直接甲醇燃料電池之陽極觸媒發展 14
1.5.1 奈米粒徑觸媒的合成方法 14
1.5.2 觸媒載體開發 20
1.6 氮化鈦（Titanium nitide，TiN） 31
1.6.1 導電氮化鈦薄膜之基本性質 31
1.6.2 導電TiN薄膜之製備及其表面微結構控制 32
1.7 電化學原理與方法 32
1.7.1 循環伏安法原理（Cyclic voltammetry，CV） 32
1.7.2 安培法原理（Amperometry） 34
1.8 儀器原理 36
1.8.1 場發射掃描式電子顯微鏡（Field emission-scanning electron microscope，FE-SEM） 36
1.8.2 原子力顯微鏡（Atomic force microscope，AFM） 37
1.8.3 X光線繞射分析儀（X-ray diffraction，XRD） 37
第二章 實驗方法與步驟 39
2.1 實驗藥品 39
2.2 實驗儀器 39
2.3 實驗步驟 40
2.3.1 實驗流程圖 40
2.3.2 TiN的製備 41
2.3.3 Pt/TiN電催化觸媒層電極製備及實驗步驟 42
2.3.4 Pd/TiN電催化觸媒層電極製備及實驗步驟 43
第三章 結果與討論 45
3.1 TiN薄膜之探討 45
3.1.1 TiN薄膜之結晶分析 45
3.1.2 TiN薄膜微觀表面形貌之探討 46
3.1.3 TiN薄膜之電性分析 48
3.1.4 TiN薄膜之電化學探討 48
3.1.5 傅立葉轉換紅外光光譜儀（FT-IR） 49
3.2 Pt/TiN陽極觸媒材料於甲醇燃料電池的探討 51
3.2.1 Pt/TiN陽極觸媒材料之製備 51
3.2.2 電化學沉積Pt於TiN薄膜上的微結構探討 51
3.2.3 Pt/TiN陽極觸媒材料之電化學特性探討 57
3.2.4 Pt/TiN陽極觸媒材料對於甲醇氧化的電活性探討 60
3.2.5 不同Pt製備方式之Pt/TiN對於甲醇氧化探討 64
3.2.6 Pt/TiN陽極觸媒材料穩定性探討 68
3.3 Pd/TiN陽極觸媒材料於甲醇燃料電池的探討 70
3.3.1 Pd/TiN 陽極觸媒材料之製備 70
3.3.2 電化學沉積Pd於TiN薄膜的微結構探討 71
3.3.3 Pd/TiN陽極觸媒材料之電化學特性探討 77
3.3.4 Pd/TiN陽極觸媒材料對於甲醇氧化的電活性探討 79
3.3.5 Pd/TiN陽極觸媒材料穩定性探討 84
第四章 結論及未來展望 87
4.1 結論 87
4.2 未來展望 87
第五章 參考文獻 88

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