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研究生： 劉珈琦
Chia-Chi Liu
論文名稱： 有機金屬骨架修飾Fe2P@CNT於鹼性環境之高氧氣還原活性新穎材料
Novel Fe2P@Carbon Nanotube modified with MOF as a superior material for highly activity of oxygen reduction reaction in alkaline media
指導教授： 王丞浩
Chen-Hao Wang
口試委員: 施劭儒
shao-ju shih
王冠文
Kuan-Wen Wang
梁元彰
Yuan-Chang Liang
張孫堂
Sun-Tang Chang
學位類別： 碩士
Master
系所名稱： 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年： 2016
畢業學年度： 104
語文別： 中文
論文頁數： 109
中文關鍵詞： 氧氣還原反應 、燃料電池 、有機金屬骨架 、奈米碳管
外文關鍵詞： Oxygen Reduction Reaction(ORR), Fuel Cells, Metal Organic Framework (MOF), Carbon Nanotube(CNT)
相關次數： 點閱：312  下載：0 
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    • 本研究利用有機金屬骨架在奈米碳管(CNT)上成長以修飾CNT，之後經過熱處理。在特定的溫度下熱處理時有最佳之氧氣還原活性且其電子轉移數可達3.99，已非常接近理想之電子轉移數。而具有高催化活性的觸媒歸因於兩個因素，首先，此觸媒具有獨特的Fe2P@CNT結構，並且有高比例的Unoccupied Graphitic-N π*之氮官能基，可以做為氧氣還原反應的活性點。另一原因為多孔結構的形成與較高導電度的奈米碳管骨架。此外，中孔結構與高比表面積提高觸媒在電解下的活性點與反應性。另外，觸媒以線性掃描法(LSV)方式進行30000圈穩定性測試，觸媒的半波電位僅衰退為26 mV，可得知其觸媒在反應的過程中穩定性極佳。
    此研究之新型材料，利用簡易的方法製備獨特形貌的高效率電催化劑，在未來應用在許多電化學反應和系統中，實為一具有相當競爭力之選擇。

    We have synthesized ORR electrocatalysts based on MOF modified CNT derived from growth of metal–organic frameworks on carbon nanotubes, followed by pyrolysis. After the pyrolysis in the specific temperature, the catalysts demonstrates an excellent ORR ability with the electron-transfer number of 3.99, which is very close to the ideal four electron-transfer number .
    The high catalytic performance of catalyst is probably attributed to two reasons. One is the co-existence of unique Fe2P@CNT structure and high amount of unoccupied Graphitic-N π*, which are the active sites for ORR. The other reason is attributable to the formation of porous structure and high conductivity skeleton from CNT. Furthermore, Mesoporous structure and high surface area boosts the active sites and reactivity during electrolysis. In addition, the catalyst has an excellent stability after 30,000 cycles of stability test. The decay of half-wave potential is only 2.2 mV.
    Our novel material provides a simple approach for fabricating unique and high efficiency electrocatalysts. It is a very competitive choice to apply in many electrochemical reactions and systems.

    中文摘要 I ABSTRACT II 致謝 III 目錄 V 圖目錄 VII 表目錄 XII 第一章 緒論 1 1.1 人類對能源的反思與新思維 1 1.2 新綠色能源-燃料電池簡介 2 1.2.1 燃料電池的種類 4 1.2.2 鹼性陰離子交換膜燃料電池(AAEMFC)介紹 6 1.2.3 燃料電池內部構造 7 1.2.4 燃料電池極化現象 9 第二章 電化學原理與文獻探討 12 2.1 電化學原理 12 2.1.1 氧化還原反應 12 2.1.2 氧氣還原途徑 12 2.1.3 氧氣還原反應機制 14 2.1.4 氧氣還原反應之電化學催化 15 2.2 文獻探討 18 2.2.1 奈米碳管應用在陰極端之觸媒 18 2.2.2 氮摻雜於奈米碳管之非貴金屬觸媒 19 2.2.3 過渡金屬含氮奈米碳管之非貴金屬觸媒 22 2.2.4 沸石咪唑酯骨架結構(ZIF-8)之非貴金屬觸媒 25 2.2.5 ZIF-8附載於奈米碳管之非貴金屬觸媒 26 2.2.6 研究動機 29 第三章 實驗步驟與方法 31 3.1 實驗規劃 31 3.2 實驗材料及藥品 32 3.3 實驗流程 33 3.4 實驗儀器與設備 34 3.5 實驗步驟 35 3.5.1 陰極觸媒製備 35 3.5.2 觸媒工作電極製備 36 3.6 儀器分析原理 37 3.6.1 X光繞射分析儀 37 3.6.2 場發射掃描式電子顯微鏡 39 3.6.3 X光吸收光譜 40 3.6.4 比表面積及孔徑分析儀 47 3.6.5 穿透式電子顯微鏡 49 3.6.6 拉曼光譜分析儀 51 3.6.7 感應耦合電漿原子發射光譜儀 52 3.6.8 電化學分析儀 53 第四章 結果與討論 57 3.6 氮摻雜奈米碳管之材料 57 4.1.1 氮摻雜奈米碳管之氧氣還原反應活性 58 4.1.2 氮摻雜奈米碳管之X光繞射分析 59 4.1.3 CNT之碳原子K-吸收邊緣的近X光吸收細微結構 61 4.2 ZIF-8/Fe2P@CNT之觸媒材料 63 4.2.1 ZIF-8/Fe2P@CNT之氧氣還原反應活性比較 64 4.2.2 ZIF-8/Fe2P@CNT之X光繞射分析 68 4.2.3 ZIF-8/Fe2P@CNT之SEM分析 72 4.2.4 ZIF-8/Fe2P@CNT之X光吸收光譜分析 76 4.2.5 ZIF-8/Fe2P@CNT之氮原子K-吸收邊緣的近X光吸收細微結構分析 79 4.2.6 ZIF8/Fe2P@CNT之拉曼光譜分析 83 4.2.7 ZIF8/Fe2P@CNT之穿透式電子顯微鏡分析 84 4.2.8 ZIF-8/Fe2P@CNT之金屬定量分析 86 4.2.9 CNT、ZIF-8、Pt/C、ZIF-8/Fe2P@CNT之氧氣還原反應活性比較 87 4.2.10 CNT、ZIF-8、ZIF-8/Fe2P@CNT之氮原子K-吸收邊緣的近X光吸收細微結構分析 89 4.2.11 CNT、ZIF-8、ZIF-8/Fe2P@CNT之等溫吸附曲線與比表面積探討 91 4.2.12 ZIF-8/Fe2P@CNT觸媒之穩定性測試 93 4.2.13 ZIF-8/Fe2P@CNT觸媒之全電池測試 96 第五章 結論 99 參考文獻 101

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