臺灣博碩士論文加值系統

二氧化碳的排放引發全球溫室效應是人類面臨的關鍵議題。除了降低二氧化碳的排放量，科學家發現，利用化學還原反應，將二氧化碳藉由光催化轉換還原成一氧化碳或碳氫化合物，透過此一機制將二氧化碳轉換成燃料，是目前關注的主要課題之一。在添加光催化劑的條件下，將能提高二氧化碳的光催化轉換效率；因此，開發高性能光催化劑以提昇二氧化碳轉化活性和進一步了解機制是非常重要的。二維結之構二硫化鉬具有合適的能隙位置，並且其催化效果可與白金的相比擬，有較強的氫吸附能力以及脫氫效果，將是一個值得探討的研究對象。此外，石墨烯具有極佳的電子導電性、良好的透光率、較大的表面積和優異的化學穩定性。由研究顯示，透過石墨烯與光催化劑的複合將可以調變其半導體特性，藉由改變能隙大小和調整價帶與導帶的位置，可以清楚地了解二硫化鉬/石墨烯複合材料的機制，並期望有效地提升光催化二氧化碳還原成太陽能燃料的效率。
我們將二硫化鉬/石墨烯複合材料應用至二氧化碳還原反應後，透過氣相層析儀分析結果與單層二硫化鉬相比較，結果顯示二硫化鉬/石墨烯複合物檢測出擁有較多種的光催化產物，且二硫化鉬/石墨烯複合材料的量子效率較單層二硫化鉬提升了五倍。由研究成果顯示，二硫化鉬/石墨烯複合材料具有優異的光催化效果，對於二氧化碳還原有著突破性的貢獻。

Carbon dioxide (CO2) emission causing global warming has been a crucial issue these years. In addition to reducing the amount of greenhouse gas emission, scientists discover that photocatalytic conversion of carbon dioxide, a process of chemical reduction whereby carbon dioxide is reduced to CO2 or hydrocarbons under solar excitation, turns out to be a feasible method to solve the environmental emergency and energy shortage by reutilizing CO2 to fuels. As a result, it is very important to develop high-performance photocatalysts to enhance photocatalytic activity of CO2 conversion and further to understand the mechanism. Two-dimensional molybdenum disulfide (MoS2) not only has narrow and tunable band gap, bit its photocatalytic activity and hydrolization are also very similar to platinum (Pt), which makes it a suitable research candidate. On the other hand, a photocatalyst based on graphene has these advantages: high excellent electronic conductivity, large specific surface area, good optical transmittance, and superior chemical stability. Several researches have indicated that the characteristics of semiconductors can be changed with graphene hybrid. By analyzing the change of band gap and band position, we can have a better understanding of its mechanism and further enhancing the photocatalytic activity of CO2 reduction to solar fuels.
Several photocatalytic products of MoS2/graphene hybrid are detected by gas chromatograph (GC) system comparing with pure monolayer MoS2. Quantum efficiency (QE) performance of our hybrid material is about 6 times higher than pure monolayer MoS2., which makes it an outstanding contribution to the excellent photocatalytic CO2 reduction.

致謝 I
摘要 III
Abstract V
Contents VII
List of figures IX
List of tables XI
Chapter 1 Introduction 1
1.1 Global warming and CO2 emissions[1] 1
1.2 CO2 conversion 3
1.3 Criteria of semiconductors as photocatalyst 5
1.4 Photocatalytic ability of MoS2 in CO2 reduction 12
1.5 MoS2 fabrication 17
1.5.1 Top-down process 17
1.5.2 Chemical vapor deposition (CVD) process 19
1.5.2.1 Thermal vapor sulfurization (TVS) 19
1.5.2.2 Thermal vapor deposition (TVD) 22
1.5.2.3 CVD microreactor 26
1.6 Graphene 29
1.6.1 Graphene enhancement in photocatalyst 30
1.7 Motivation 34
Chapter 2 Experimental 38
2.1 Schematic of experimental process 38
2.2 Electrochemical polishing 40
2.3 Chemical vapor deposition growth 41
2.4 Graphene Transfer 43
2.5 Microreactor design for MoS2 fabrication 45
2.6 Photocatalytic CO2 reduction reaction 46
2.7 Micro-Raman and Photoluminescence spectroscopy 48
2.8 Atomic force microscopic 50
Chapter 3 Result and discussion 52
3.1 Graphene growth 52
3.1.1 Coverage analysis by optical microscope images 52
3.1.2 Surface diffusion with different pore sizes 54
3.1.3 Shaped graphene grown by different conditions 62
3.2 MoS2/graphene hybrid 64
3.2.1 Region-dependent Morphologies 64
3.2.2 Raman mapping of characteristic peaks 66
3.2.3 PL measurement 68
3.2.4 AFM images 70
3.3 Hypothesis of growth mechanism 71
3.4 Photocatalytical CO2 reduction 72
Chapter 4 Conclusion 74
Reference 76

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