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Title Page 2

Abstract 5

Contents 7

CHAPTER 1. GENERAL INTRODUCTION 10

1.1. Introduction 10

1.1.1. Fuel cells 10

1.1.2. Classification of fuel cells 14

1.1.3. Proton exchange membrane 17

1.1.4. Classification of membrane materials 18

1.1.5. Proton-conduction mechanism 21

1.1.6. The chemical degradation of PEMs 27

1.1.7. Manganese dioxide used as a radical scavenger 34

1.2. Research objective 37

CHAPTER 2. EXPERIMENT WORK 40

2.1. Materials and methods 40

2.1.1. Materials 40

2.1.2. Synthesis of organic-inorganic hybrid MnO₂ nano-powders 40

2.1.3. Membrane preparation 42

2.1.4. Chemical stability test 43

2.1.5. Characterization 43

2.2. Results and discussions 44

2.2.1. Synthesis of MnNP and characterization 44

2.2.2. Effect of MPTMS/FOTS Ratio 47

2.2.3. Effect of Reaction Time 48

2.2.4. Effect of Synthesis Method 50

2.3. Conclusion 56

References 58

List of Tables 9

Table 1. Preparation of MnNPs with different MPTMS/FOTS ratio, reaction time and... 42

Table 2. Characteristics of MnNPs 46

List of Figures 8

Figure 1. Schematic illustration of the most common fuel cells and normal operating... 15

Figure 2. Schematic diagram of typical PEMFC 18

Figure 3. Classification of membrane materials 19

Figure 4. The simple scheme of the hopping mechanism 22

Figure 5. Schematic representation of vehicular proton transfer mechanism 23

Figure 6. Schematic diagram of commercially available PFSA membranes, where m,... 25

Figure 7. Chemical degradation mechanism of PFSA membranes 34

Figure 8. MnNPs structure 45

Figure 9. Radical scavenging performance of MnNPs with different MPTMS/FOTS... 47

Figure 10. Radical scavenging performance of MnNPs with different reaction time 48

Figure 11. Radical scavenging performance of MnNPs with different synthesis... 50

Figure 12. Particle size of MnNPs. (a-c) Particle size with different MPTMS/FOTS... 52

Figure 13. Inorganic content of MnNPs with different MPTMS/FOTS ratio 53

Figure 14. Inorganic content of MnNPs with different reaction time 53

Figure 15. Inorganic content of MnNPs with different synthesis method 54

Figure 16. XPS results of MnNP. (a - c) XPS results of MnNPs with different MPTMS/FOTS... 55

초록보기

 Proton exchange membranes (PEMs) are crucial in electronics and transportation due to their efficiency and clean hydrogen utilization, but they are prone to degradation caused by free radicals. This study addresses this challenge by enhancing PEM stability through the synthesis of manganese oxide nanoparticles (MnNPs) using the sol-gel method. The MnNPs were developed by integrating MnO2 with 3-Mercaptopropyltrimethoxysilane (MPTMS) and 1H, 1H, 2H, 2H-Perfluorooctyltriethoxysilane (FOTS) to exploit their strong radical scavenging properties. Characterization of the MnNPs revealed that key synthesis parameters, such as MPTMS/FOTS ratios and reaction times, significantly influenced nanoparticle size, inorganic content, and manganese oxidation states, all of which are critical for effective radical scavenging. The Fenton test results demonstrated that PEMs containing MnNPs exhibited a remarkable reduction in fluoride ion release up to 90% compared to membranes without MnNPs, indicating a significant extension in PEM lifespan. These findings highlight the potential of MnNPs to substantially enhance the durability and performance of PEMs.

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