臺灣博碩士論文加值系統

過氧化氫 (H2O2) 是一種常見且乾淨的氧化劑與燃料，在工業上有多種用途。目前量產過氧化氫的方法是一種高耗能的製程，過程中不但需要提供氫氣還要以貴重金屬作為催化劑，因此，如何更永續地製造H2O2成為近年來的研究方向。在此研究中，我們以太陽光催化一種新興的平面奈米碳材──氧化石墨烯 (GO)，並且討論此反應下生成H2O2 的效率，我們發現在六小時的模擬太陽光催化下，含有GO的溶液中產生了超過1 mM的H2O2，過程中不需要多數光催化反應中必須的有機電子提供者，而且H2O2的產率在類似的系統中是最高的。我們還發現氧氣 (O2) 在此反應中是必要的，雙電子的氧還原是可能的反應路徑，另外，溶液的pH值也扮演著重要的角色，較高的pH值有較高的H2O2產率，但是在高pH值中也加速了GO本身的光還原反應而失去光催化的活性。 H2O2的量子產率 (AQYs) 也有在本研究中被討論。 研究結果指出，以太陽光催化GO產生H2O2 相當具有潛力，不但只需要太陽光能，更不需要有機的電子提供者，對環境相對友善。

Hydrogen peroxide (H2O2) is a clean oxidant and fuel that is desirable in many real-world applications. Current industrial manufacturing of H2O2 involves expensive, noble metal-based catalysts with high energy demand. Searching for more environmentally sustainable process for H2O2 production merits greater attention in research. In this work, the potential of graphene oxide (GO), an emerging, two-dimensional carbon-based nanomaterial, as a new photocatalyst toward H2O2 photoproduction driven by solar energy was explored. The result indicates that 〉 1 mM of H2O2 can be photoproduced within 6 h of solar irradiation even without organic electron donors present. This is particularly attractive considering that photocatalytic H2O2 production processes usually require organic electron donors. To our knowledge, the H2O2 photoproduction reported here is among the highest values in related work. O2 is needed for this process and greater yield is favorable at increased pH. The greater yield at increased pH contrasts the more rapid loss of GO’s long-term photocatalytic stability that can be attributed to greater phototransformation of GO at increased pH. Two-electron O2 reduction is the likely pathway toward H2O2 formation. The apparent quantum yields (AQYs) were also reported. The results indicate that GO is a promising photocatalyst toward H2O2 production that can be driven by renewable sunlight energy under organic electron donor-free condition.

摘要 I
ABSTRACT II
誌謝 III
CONTENTS IV
LIST OF TABLE VI
LIST OF FIGURE VII
CHAPTER 1. INTRODUCTION 1
1.1 Background and Motivation 1
1.2 Objective 3
CHAPTER 2. LITERATURE REVIEWS 4
2.1 Properties and Applications of GO 4
2.1.1 GO as a Photocatalysis 4
2.1.2 Photocatalytic ROS Formation of GO 5
2.2 Photocatalytic H2O2 Production 7
CHAPTER 3. EXPERIMENTAL PROCEDURE 11
3.1 Experimental Materials 11
3.2 Simulated Sunlight Irradiation 11
3.3 Photoreaction Quantum Yield Studies 14
3.4 Analysis 15
3.4.1 Hydrogen Peroxide 15
3.4.2 X-ray Photoelectron Spectroscopy (XPS) 16
3.4.3 Atomic Force Microscope (AFM) 17
CHAPTER 4. RESULT AND DISCUSSION 18
4.1 Graphene Oxide Characterizations 18
4.2 Photocatalytic Formation of H2O2 by GO 19
4.3 Solution Chemistry on Photoproduction of H2O2 21
4.4 Role of Superoxide. 23
4.5 Effect of Organic Electron Donor Addition 26
4.6 Structural Evolution of GO during Photocatalysis 28
4.7 Apparent Quantum Yields 32
4.8 Optimal Photocatalytic Conditions 33
4.9 Reusability and Stability 35
CHAPTER 5. CONCLUSION 37
5.1 Conclusion 37
APPENDIX 39
REFERENCE 43

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