臺灣博碩士論文加值系統

直接甲酸燃料電池系統中，甲酸氧化過程所產生的副產物一氧化碳，會吸附在貴金屬鈀觸媒表面，使得觸媒毒化，同時甲酸可能浸溶出鈀觸媒，導致觸媒電催化的活性下降。過去研究顯示，金鈀固溶體的貴金屬奈米觸媒，可以改善毒化及浸溶的現象，提升了觸媒使用率以及使用壽命。本研究比較兩種不同方式，分別為還原劑硼氫化鈉和光還原反應，還原金鈀合金披覆於氧化石墨烯以製備金鈀/還原氧化石墨烯電觸媒。這兩種合成方式皆不用進行加熱處理。接著，將合成材料進行物理化學和電催化特性比較。本研究使用FT-IR和XRD進行官能基及結構分析，TGA和ICP進行組成確認，FE-SEM觀察材料表面的微觀形貌。CV循環伏安和I-t曲線用來測試材料的電化學反應及穩定性。
FE-SEM結果顯示光還原的金鈀奈米顆粒塗覆在還原石墨烯氧化物表面顆粒直徑約7-9nm，且均勻地分散。然而，EDS分析的結果，顯示金鈀成分與實驗設計有很大偏差。ICP-OES分析，證實同樣結果。 金鈀電催化劑的電化學分析中，金鈀/RGO-01A樣品具有較好的電氧化電流密度。此外，它的電流穩定性優異很多在掃描20週期的實驗。計時電流分析（CA）結果，顯示金鈀/ RGO-01A比金鈀/RGO-硼氫化鈉有更高的響應和壽命。但這些樣品的穩定性和壽命時間，在實際應用還不足夠，因商業測試需至少兩萬圈的循環伏安後，仍有百分之八十的電流穩定性。

In a direct formic acid fuel cell system, the carbon monoxide produced during the oxidation of formic acid will adsorb on the surface of palladium catalyst and poisoning palladium, also formic acid may leaching and dissolving palladium, leads to decrease the electro-catalytic activity. Previous studies indicated the nano-gold-palladium solid solution can inhibit CO poisoning and prevent the leaching of palladium that may increase electrocatalytic activity and lifetime. This study compared two different methods to reduce gold-palladium alloy on reduced graphene oxide. Two methods are included using reducing agent of sodium borohydride and photoreduction by X-ray irradiation. These two methods can easy to synthesize at room temperature. The gold-palladium nanoparticles are homogeneously deposited on the surface of reduced graphene oxide (RGO). The physical, chemical and electrochemical properties are applied to examine these samples. In this study, FT-IR and XRD are used for functional group and structural analysis, TGA and ICP for compositional measuremnet, the FE-SEM for observing the surface morphology of samples. Cyclic voltammetry (CV) and I-t test are used to evaluate the electrochemical properties of these catalysts.
The results of FE-SEM images indicate the diameters of Au-Pd nanoparticles are about 7-9nm and it uniformly disperse on the graphene oxide. However, the results of EDS analysis indicate its composition is not closed to original design. ICP-OES analysis is confirmed EDS results. In electrochemical analysis of Au-Pd electrocatalysts, AuPd/RGO-01A has the better electro-oxidizing current density. Also, its current stability is excellent up to 20 cycles of experiment. Chronoamperometry analysis (CA) results show AuPd/RGO-01A one has the higher response and life time than that of AuPd/RGO-NaBH4. But the stability and life time of these samples are not good enough for practical applications.

Table of Contents
誌謝 i
Abstract ii
摘要 iv
Table of Contents v
List of Tables vii
List of Figures viii
Chapter 1 Introduction 1
Chapter 2 Literature Review 4
2.1 Introduction of Fuel cells 4
2.1.1 Direct Formic Acid Fuel Cells (DFAFCs) 5
2.2 Introduction of Carbon Materials 8
2.2.1 Carbon Nanotubes 8
2.2.2 Graphene 11
2.2.3 Graphene Oxide 14
2.2.4 Reduced Graphene Oxide 16
2.3 Introduction of Anode Catalysts 18
2.3.1 Characteristics of Pd Catalyst 20
2.3.2 Characteristics of Au Catalyst 22
2.3.3 Au-Pd Bimetallic Catalysts 25
2.4 Synthesis technology 27
2.4.1 Reducing Agent of Sodium Borohydride 27
2.4.2 Synchrotron X-ray Irradiation Method 29
2.5 Electrochemistry 32
2.5.1 Cyclic Voltammetry 32
2.5.2 Chronoamperometry Analysis 32
Chapter 3 Experiment 33
3.1 Materials 33
3.2 Samples Fabrication 34
3.2.1 Acid Treatment of MWCNTs Preparation 34
3.2.2 Graphene Oxide 35
3.2.3 Noble Metal Catalysts Fabrication 36
3.3 Material Characteristics 40
3.3.1 Fourier Transform Infrared Spectroscopy (FT-IR) 40
3.3.2 Raman Scattering Spectroscopy (RS) 40
3.3.3 X-Ray Diffraction Analysis (XRD) 41
3.3.4 Field Emission Scanning Electron Microscopy (FE-SEM) 42
3.4 Contents Analysis 43
3.4.1 Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) 43
3.4.2 Thermogravimetric Analyzer (TGA) 44
3.5 Cyclic Voltammetry Measurement (C-V) 45
Chapter 4 Results and Discussion 46
4.1 Fourier Transform Infrared Spectroscopy 46
4.2 Raman Spectroscopy 48
4.3 Structure Analysis by XRD 53
4.4 Morphological Observations by FE-SEM 55
4.5 Elements Composition by ICP 62
4.6 Thermogravimetric Analysis (TGA) 62
4.7 Cyclic Voltammetry Measurement 64
4.8 I-t Curve 69
Chapter 5 Conclusions 70
Chapter 6 Suggestion of Future Studies 72
References 73

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