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研究生： 榮翌穅
Yi-Kang Rong
論文名稱： 鈷氮鍵結修飾有機金屬架構之觸媒應用於鹼性陰離子交換膜燃料電池
Co-N Bonding Decorated MOF-derived Catalyst for Alkaline Anion Exchange Membrane Fuel Cell
指導教授： 王丞浩
Chen-Hao Wang
口試委員: 陳燦耀
Tsan-Yao Chen
王冠文
Kuan-Wen Wang
邱德威
Te-Wei Chiu
黃信智
Hsin-Chih Huang
王丞浩
Chen-Hao Wang
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： 2023
畢業學年度： 111
語文別： 中文
論文頁數： 94
中文關鍵詞： 氧氣還原反應 、燃料電池 、非貴金屬觸媒 、MOF-808觸媒 、鈷-氮結構
外文關鍵詞： Oxygen Reduction Reaction, Fuel cell, Non-precious metal catalysts, MOF-808 structure, Co-N structure
相關次數： 點閱：249  下載：1 
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    • 氫能是當今非常有發展潛力的能源之一，因其廣泛的應用領域以及在反應後產生較乾淨、低汙染且可再生的產物，成為全球矚目的替代能源之一。鹼性陰離子交換膜燃料電池是其中一種重要的應用，它以高效率的方式將化學能轉化為電能供應使用。然而由於鹼性陰離子交換膜燃料電池使用的白金觸媒價格昂貴，造成無法大規模普及的問題。因此，近年來研究的趨勢是開發成本較低且高效能的非白金觸媒，以減少對貴金屬的使用量，以此來解決觸媒成本高昂的問題。
    本研究選用MOF-808作為觸媒前驅物，通過鈷氮元素的添加，分別做二次熱處理，即可製備出最佳條件之觸媒（MOF-Co-900-NH3）。在電化學測試中此觸媒有優秀的氧氣還原活性，且電子轉移數可達3.99，非常接近理想電子轉移數4.00，在30,000圈穩定性測試後，半波電位僅衰退35 mV。將觸媒於鹼性陰離子交換膜燃料電池下進行全電池測試，可展現出359.2 mW/cm2之高輸出功率，由此可知此觸媒在鹼性環境中具備極佳之穩定性與效能。
    材料的結構分析可由X光繞射分析儀（XRD）中看出觸媒擁有t-ZrO2，而穿透式電子顯微鏡（TEM）影像分析可進一步確認其結構結構。觸媒在X光吸收光譜（XAS）證實Co-N結構之存在，且X射線光電子能譜（XPS）的分析中也可再次確認Co-N鍵結，並含有高比例的Pyridinic-N官能基。因MOF-808之穩定性，以及含有高比例的含氮官能基與Co-N基團，使此觸媒（MOF-Co-900-NH3）在氧氣還原反應中表現出優異的性能。

    Hydrogen energy is one of the most promising alternative energy sources today, as it has wide-ranging applications and produces clean, low-pollution, and renewable byproducts after reactions. Among its important applications is the alkaline anion exchange membrane fuel cell, which efficiently converts chemical energy into electrical energy for use. However, the use of platinum catalysts in alkaline anion exchange membrane fuel cells leads to high costs and hinders large-scale adoption. Therefore, recent research trends focus on developing cost-effective and high-performance non-platinum catalysts to reduce the reliance on precious metals and address the issue of expensive catalysts.
    In this study, MOF-808 was chosen as the catalyst precursor, and by introducing cobalt and nitrogen elements and conducting secondary heat treatment, the optimized catalyst (MOF-Co-900-NH3) was synthesized. The electrochemical tests showed excellent oxygen reduction activity for this catalyst, with an electron transfer number close to the ideal value of 4.00 (measured at 3.99). After 30,000 cycles of stability testing, the half-wave potential only decayed by 35 mV, indicating remarkable stability. Full-cell testing of the catalyst in alkaline anion exchange membrane fuel cells exhibited a high power density of 359.2 mW/cm2, indicating outstanding performance in alkaline environments.
    The structural analysis of the catalyst revealed the presence of t-ZrO2 through X-ray diffraction (XRD), and transmission electron microscopy (TEM) further confirmed its structure. X-ray absorption spectroscopy (XAS) confirmed the existence of Co-N bonds in the catalyst, and X-ray photoelectron spectroscopy (XPS) analysis also confirmed the Co-N bonding and the high proportion of Pyridinic-N functional groups. The stability of MOF-808 and the high content of nitrogen functional groups and Co-N moieties contributed to the excellent performance of the MOF-Co-900-NH3 catalyst in the oxygen reduction reaction.

    中文摘要 I Abstract II 致謝 IV 目錄 VI 圖目錄 IX 表目錄 XII 第一章 緒論 1 1.1 研究背景 1 1.2 綠色能源之燃料電池介紹 4 1.2.1 燃料電池的種類 6 1.2.2 陰離子交換膜燃料電池（AEMFC）介紹 8 1.2.3 陰離子交換膜燃料電池結構介紹 9 1.2.4 燃料電池的極化現象 11 第二章 電化學原理與文獻探討 14 2.1 電化學原理 14 2.1.1 氧化還原反應 14 2.1.2 氧氣還原途徑 14 2.1.3 氧氣還原反應機制 16 2.1.4 氧氣還原反應之電化學催化 18 2.2 文獻探討 20 2.2.1 氮摻雜之非貴金屬觸媒 20 2.2.2 金屬有機架構（MOF）之非貴金屬觸媒 22 2.2.3 鈷氮鍵結有機金屬框架之觸媒 24 2.3 研究動機 27 第三章 實驗步驟與研究方法 28 3.1 實驗規劃 28 3.2 實驗材料及藥品 29 3.3 實驗流程 30 3.4 實驗儀器與設備 31 3.5 實驗步驟 32 3.5.1 陰極觸媒製備 32 3.5.2 半電池觸媒工作電極製備 33 3.6 儀器分析原理 34 3.6.1 X光繞射分析儀（X-ray diffraction Spectrometer，XRD） 34 3.6.2場發射掃描式電子顯微鏡（Field Emission Scanning Electron Microscope，FSEM） 36 3.6.3 X射線光電子能譜（X-ray Photoelectron Spectroscopy，XPS） 37 3.6.4 X光吸收光譜（X-ray Absorption Spectroscopy，XAS） 38 3.6.5穿透式電子顯微鏡（Transmission Electron Microscope，TEM） 41 3.6.6比表面積分析儀（Surface Area Analyzer ） 42 3.6.7拉曼光譜分析儀（Raman Spectrum） 43 3.6.8 電化學分析儀 44 3.6.9 燃料電池測試儀 47 第四章 結果與討論 48 4.1 MOF-Co之合成 48 4.1.1 觸媒之形貌分析 49 4.1.2 MOF-Co與常見MOF的氧氣還原反應活性比較 50 4.2 不同熱處理方式之MOF-Co 52 4.2.1 觸媒氧氣還原反應活性比較 52 4.2.2 不同熱處理方式觸媒之X光繞射圖譜分析 56 4.2.3 觸媒之形貌與結構分析 58 4.2.4 不同熱處理方式觸媒之X光電子能譜分析 63 4.2.5 不同熱處理方式觸媒之X光吸收光譜分析 66 4.2.6 MOF-Co-900-NH3觸媒之穩定性測試 69 4.2.7 MOF-Co-900-NH3觸媒之單電池測試 71 第五章 結論 73 第六章 參考文獻 75

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