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研究生： 巴尼締
Frizka Vietanti
論文名稱： 應用於AEMFC 的氮參雜還原氧化石墨烯之負載的三元鈀基陰極催化劑
Ternary Palladium based Cathode Catalyst Supported on Nitrogen doped Reduced Graphene Oxide for AEMFC
指導教授： 王丞浩
Chen-Hao Wang
口試委員: 王丞浩
Chen-Hao Wang
郭俞麟
Yu-Lin Kuo
施劭儒
Shao-Ju Shih
蘇威年
Wei-Nien Su
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： 2018
畢業學年度： 106
語文別： 英文
論文頁數： 108
中文關鍵詞： 三元Pd-M（M = Fe，Ni，Co） 、N-rGO 、氧還原反應 、穩定性 、甲醇氧化
外文關鍵詞： ternary Pd-M (M = Fe, Ni, and Co), N-rGO, oxygen reduction reaction, stability, methanol oxidation
相關次數： 點閱：266  下載：3 
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    • 氧還原反應是燃料電池中產生電力的基本反應，對於該反應，三元Pd基碳基催化劑起重要作
    用。在此，我們報導了三步合成三元Pd-M（M = Fe，Co，Ni）摻入氮摻雜石墨烯（N-rGO）複
    合材料，其產生高氧還原反應活性，良好的穩定性和對甲醇氧化的耐受性在鹼性介質中。該方
    法包括微波水熱合成氮摻雜石墨烯，合成三元Pd-M的乳液，以及旋轉蒸發器技術製備複合材
    料。對於氧還原反應，發現PdFeCo / N-rGO> PdCoNi / N-rGO> PdFeNi / N-rGO的活性降低。 PdFeCo / N-rGO催化劑已經證明具有最高的電子轉移數，其接近主導的四電子途徑，並且還產
    生最少的羥基產率。這證實了PdFeCo / N-rGO的X射線衍射圖也顯示出最小的微晶尺寸和最高的
    ID / IG，其導致碳上的額外缺陷，因此導致氧還原反應活性增加。沒有明顯的團聚，並且通過 場發射掃描電子顯微鏡可以清楚地觀察到PdFeCo / N-rGO納米顆粒在層狀石墨烯片上的均勻分
    佈。此外，研究了X射線光電子能譜的元素組成和存在最高的石墨百分比。氮可以增加活性部
    位，從而提高氧還原反應活性。

    The oxygen reduction reaction (ORR) is a fundamental reaction in fuel cells to generate power, for which ternary Pd-based with carbon based catalyst plays an important role. Herein, we report the three-steps synthesis of ternary Pd-M (M= Fe, Co, Ni) incorporated nitrogen doped graphene (N-rGO) composite, which generated high ORR activity, good stability, and tolerance for methanol oxidation in alkaline media. This method involved a microwave hydrothermal to synthesize nitrogen doped graphene, an emulsion to synthesize ternary Pd-M, and a rota-evaporator technique to make a composite. For ORR, decreased activity were found PdFeCo/N-rGO > PdCoNi/N-rGO > PdFeNi/N-rGO. The PdFeCo/N-rGO catalyst has demonstrated the highest electron transfer number, which is close to dominant four electron pathway, and also generated least yield of % HO2-. This confirmed to X-ray diffraction (XRD) pattern of PdFeCo/N-rGO also showed the smallest crystallite size and the highest ID/IG which caused extra defects on carbon, thus led to increase ORR activity. There is no obvious agglomeration and the homogeneous distribution of PdFeCo/N-rGO nanoparticles over the layered graphene sheets were clearly observed from field emission scanning electron microscopy (FE-SEM) and representative field emission transmission electron microscope (FE-TEM) images. In addition, the X-ray photoelectron spectroscopy (XPS) was studied for elemental composition and presence highest precentage of graphitic-N which can increase active site leading to enhance the ORR activity.

    ABSTRACT i 摘要 iii ACKNOWLEDGEMENTS v TABLE OF CONTENT vii LIST OF FIGURE xi LIST OF TABLE xv CHAPTER I INTRODUCTION 1 1.1 Research Background 1 1.2 Scope Problems 1 1.3 Research Objectives 2 1.3 Research Advantages 2 CHAPTER II LITERATURE REVIEW 5 2.1 Fuel Cell 5 2.2 Electrochemical Reactions in Fuel Cell 6 2.3 Anion Exchange Membrane Fuel Cell 6 2.4 Palladium-based Catalayst for ORR 8 2.5 Palladium-based with Transition Metals for ORR 13 2.6 Graphene 15 2.6.1 Structure and Morphology of Graphene 16 2.6.2 Electrochemical Activity of Graphene 19 2.7 Nitrogen doped Graphene 22 2.7.1 Structure and Morphology of N-doped Graphene 22 2.7.2 Electrochemical Activity of N-doped Graphene 26 2.8 Influence of Methanol Oxidation 27 2.9 Emulsion Method 29 2.10 Hydrothermal Method 29 CHAPTER III EXPERIMENTAL DETAIL 33 3.1 Materials 33 3.2 Experimental Procedurs 34 3.2.1 Synthesize Nitrogen doped Reduced Graphene Oxide 34 3.2.2 Synthesize Ternary Pd-M Nanoparticles 34 3.2.3 Synthesize Ternary Pd-M Nanoparticles Supported N-rGO 35 3.3 Flowchart of Experimental 37 3.4 Experimental Matix 40 3.5 Materials Characterization 40 3.4.1 X-Ray Diffraction 40 3.4.2 Field Emission Scanning Electron Microscopy 41 3.4.3 Raman Spectroscopy 42 3.4.4 Field Emission Transmission Electron Microscopy 43 3.4.5 X-Ray Spectrometry 43 3.6 Electrochemical Measurement 44 3.6.1 Cyclic Voltammetry 45 3.6.2 Rotating Ring-Disk Electrode 45 3.6.2 Methanol Oxidation 45 3.6.3 Stability Test 45 CHAPTER IV RESULTS AND DISCUSSION 47 4.1 The Effect of Carbon Support 47 4.4.1 X-Ray Diffraction 47 4.4.2 Raman Spectra 48 4.4.3 Field Emission Scanning Elctron Microscopy with Energy Dispersive X-Ray Spectroscopy 50 4.4.4 Cyclic Voltammogram 52 4.4.5 Oxygen Reduction Reaction 53 4.2 The Effect of Transition Metals on Ternary Palladium-based Catalyst 56 4.2.1 X-Ray Diffraction 56 4.2.2 Raman Spectra 57 4.2.3 Field Emission Scanning Elctron Microscopy with Energy Dispersive X-Ray Spectroscopy 58 4.2.4 Cyclic Voltammogram 63 4.2.5 Oxygen Reduction Reaction 65 4.2.6 Field Emission Trasnmission Electron Microscopy 66 4.2.7 X-ray Photoelectron Microscopy 69 4.2.8 Methanol Oxidation 71 4.2.9 Stability Test 72 CHAPTER V CONCLUSIONS 75 REFERENCES xvii

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