臺灣博碩士論文加值系統

在直接甲醇燃料電池中，陽極的甲醇容易透過質子交換膜擴散到達陰極。這些甲醇會在陰極的白金觸媒上氧化產生一氧化碳和混合電流，因而大幅降低燃料電池的性能。基於此，我們希望通過二氧化鈦修飾白金觸媒來形成一結構上的屏障，降低甲醇分子的影響和阻止甲醇分子的反應，從而提升白金觸媒在氧氣還原反應中的抗甲醇性能。在白金觸媒的乙醇溶液中，加入適量鈦酸四丁酯，再通入水蒸氣緩慢水解和微波熱處理分解，可控制二氧化鈦成長於白金表面。各種測試顯示二氧化鈦的尺寸約爲奈米級，並且表面存在大量的氧缺陷，但只會對白金觸媒有些微的電子和幾何結構的影響。電化學測試表明這些奈米二化氧鈦的修飾能夠顯著提升白金觸媒的抗甲醇性能。

In direct methanol fuel cells, the methanol in anode easily through the proton exchange membrane to reach the cathode. This methanol will oxidize on the surface of platinum and produce carbon monoxide and a mixed potential that will reduce the efficiency. Based on above reasons, it is envisaged to deposit TiO2 nanoparticles on Pt catalyst. By creating purposed steric disturbance to the diffusion of large molecules like methanol in the proximity of Pt surface, it is expected to enhance the methanol- tolerance ability of Pt/C on cathode. Deposition and modification of titanium dioxide on Pt/C were achieved by slow hydrolysis of tetrabutyl titanate and microwave-assisted synthesis. Experimental results showed that TiO2 nanoparticles were deposited on the Pt surface successfully. Oxygen vacancies were shown on the titanium dioxide surface and the presence of such kind of defects was found beneficial in adsorbing methanol molecules. Although the interaction between TiO2 and Pt was not found prominent, electrochemical tests demonstrated that depositing Pt surface with TiO2 nanoparticles can effectively enhance the methanol-tolerance ability of platinum.

摘要 I
Abstract II
誌謝 III
目錄 V
表目錄 XV
第一章 緒論 1
1.1 燃料電池的發展簡介 2
1.2 燃料電池的種類 6
1.3質子交換薄膜型燃料電池 7
1.4 直接甲醇燃料電池 9
1.4.1 直接甲醇燃料電池之電化學原理 10
1.4.2直接甲醇燃料電池所面臨之瓶頸與發展方向 13
1.4.3 DMFC 之陰極材料及其反應機制 14
1.5氧氣還原反應 15
1.5.1 氧氣吸附模式 17
1.6研究目的與方法 20
第二章 文獻回顧 21
2.1 二氧化鈦 21
2.1.1 二氧化鈦應用於能源材料 23
2.1.1.1載體(support) 23
2.1.1.2修飾物(modifier) 27
2.2直接甲醇燃料電池 30
2.2.1抑制甲醇氧化反應 32
第三章 實驗設備與方法 35
3.1實驗設備 35
3.2 實驗藥品 36
3.3 實驗步驟 37
3.3.2電化學漿料與電極的製備 42
3.4儀器原理與材料鑑定 43
3.4.1 X-ray繞射儀(XRD) 43
3.4.2 穿透式電子顯微鏡(TEM) 44
3.4.3庫倫水分測定儀 45
3.4.4 X-ray absorption spectroscopy(XAS) 46
3.4.5 電化學分析方法 46
3.4.6 CO電催化氧化分析(CO stripping) 47
3.4.7 甲醇電催化氧化分析 47
3.4.8 電化學活性表面積計算 47
3.4.9 X光光電子能譜儀 48
3.4.10傅立葉轉換紅外線光譜儀 50
第四章 實驗結果和討論 52
4.1 TiO2-Pt/C的合成原理 52
4.1.1負載TiO2之合成變因 57
4.1.1.1鈦酸四丁酯水解速率 57
4.1.1.2合成實驗裝置調整 58
4.1.1.3鉑與二氧化鈦的溫度和比例的影響 61
4.1.1.4直接覆蓋TiO2薄膜之影響 69
4.1.1.5添加尿素的影響 71
4.1.1.6烘乾程度之影響 73
4.1.1.7分散溶劑的影響 75
4.2 TiO2-Pt/C上的形貌 80
4.3 TiO2-Pt/C中TiO2的結構 86
4.4 TiO2-Pt/C中TiO2表面吸附效應 94
4.5 TiO2-Pt/C中TiO2對Pt結構的影響 97
4.6 TiO2-Pt/C中TiO2對Pt的電化學性質影響 99
4.7 TiO2-Pt/C的電化學測試 100
第五章 結論 105

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