隨著科技快速發展，能源需求日益增加，但目前大量使用的化石燃料對環境造成許多影響，二氧化碳和溫室氣體濃度逐年升高，伴隨著地球暖化的問題。因此尋找乾淨且可再生的替代能源至關重要，氫能源因為具有高能量密度等優點而備受青睞，許多研究致力於開發產氫技術。其中，光催化產氫利用太陽光分解水產生氫氣，是一種有效產生氫氣的方法。
本研究在合成時，透過調整還原劑的含量合成出不同1T/2H比例的二硒化鉬MS4、MS6和MS8。其中，1T含量最高的MS6擁有較低的阻抗及較高的光吸收能力，接著與硫化鋅鎘(CdZnS，CZS)結合成異質結構並量測其催化產氫表現。實驗結果顯示，相較於純CZS，添加二硒化鉬的異質結構能大幅提升產氫效率，MS4/CZS和MS8/CZS的產率分別為5.1 mmol g-1 h-1和4.2 mmol g-1 h-1，而擁有最高產率的異質結構MS6/CZS，產率高達6.4 mmol g-1 h-1，為純CZS的6倍之多。而增強的光催化性能可歸因於二硒化鉬加強異質結構的可見光吸收且降低電子-電洞再結合，進而提高產氫性能。而在三種異質結構中，有最高的光催化性能為MS6/CZS，因為金屬特性的1T二硒化鉬有良好之電子傳遞速率，大幅提升載子分離效果。總結來說，適當調整二硒化鉬的1T/2H比例能增強光催化產氫效率。

With the rapid advancement of technology, the demand for energy is increasing. The use of fossil fuels has significant environmental impacts, leading to rising levels of carbon dioxide and greenhouse gases, and contributing to global warming. Therefore, finding clean and renewable alternative energy sources is important. Hydrogen energy has gained considerable attention due to its high energy density, and numerous research efforts are focused on developing hydrogen production technologies. Among these, photocatalytic hydrogen production, which utilizes solar energy to split water and generate hydrogen gas, is an effective method for producing hydrogen.
In this thesis, we synthesized different ratios of 1T/2H MoSe2 by adjusted the amount of reducing agent, label as MS4, MS6 and MS8. Among these, MS6 with highest 1T phase has lower impedance and higher visible light absorption. Subsequently, the MoSe2 were combined with CdZnS (CZS) to form heterostructure and measured the hydrogen production by GC. The hydrogen production rates for MS4/CZS and MS8/CZS were 5.1 mmol g-1 h-1 and 4.2 mmol g-1 h-1, respectively. MS6/CZS exhibited highest H2 production rate up to 6.4 mmol g-1 h-1, which was six times than that of pure CZS. The enhanced activity of MS6/CZS can be attributed to increasing visible light absorption and inhibiting electron-hole recombination, thereby improving the hydrogen production. Among these composites, MS6/CZS exhibited the highest photocatalytic performance due to the fast electron mobility of 1T-MoSe2, leading to a significant enhancement of carrier separation. In conclusion, this research highlights that adjusting the 1T/2H ratio of MoSe2 can enhance photocatalytic hydrogen production.

摘要 II
Abstract III
致謝 IV
目錄 V
圖目錄 VIII
表目錄 XI
第一章 緒論與文獻探討 1
1.1 氫能源 1
1.2 水分解產氫 3
1.3 光催化水解產氫機制 6
1.4 犧牲試劑對光催化產氫之影響 8
1.5 光催化劑的發展 9
1.6 異質結構 10
1.7 硫化鋅鎘材料 12
1.7.1 硫化鋅鎘基本性質 12
1.7.2 硫化鋅鎘合成方法 12
1.7.3 硫化鋅鎘作為光催化劑 14
1.8 二維材料 17
1.9 二硒化鉬材料 19
1.9.1 二硒化鉬基本性質 19
1.9.2 二硒化鉬合成方法 21
1.9.3 二硒化鉬作為光催化劑 24
1.9.4 二硒化鉬1T/2H相變化調控 26
1.10 研究動機 30
第二章 實驗方法與儀器 31
2.1 實驗架構 31
2.2 光催化劑之製備流程 32
2.2.1 二硒化鉬(MoSe2)之合成 32
2.2.2 硫化鋅鎘(CdZnS)之合成 33
2.2.3 二硒化鉬/硫化鋅鎘異質結構(MoSe2/CdZnS)之合成 34
2.3 電化學分析之系統架設 36
2.4 光催化水解產氫反應 36
2.5 實驗儀器介紹 37
2.5.1 X光繞射分析儀(X-Ray Diffractometer, XRD) 37
2.5.2 掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 38
2.5.3 穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 39
2.5.4 顯微拉曼散射光譜儀(Micro-Raman Spectroscope) 41
2.5.5 X光光電子能譜儀(X-ray Photoelectron Spectroscope, XPS) 42
2.5.6 紫外光-可見光吸收光譜儀(UV-Visible Spectroscopy) 43
2.5.7 光致螢光光譜儀(Photoluminescence Spectroscopy, PL) 44
2.5.8 電化學分析儀(Electrochemical analyzer) 45
2.5.9 氣相層析儀(Gas Chromatography, GC) 46
第三章 結果與討論 47
3.1 二硒化鉬和硫化鋅鎘之材料鑑定 47
3.1.1 XRD分析 47
3.1.2 SEM影像分析 48
3.1.3 TEM分析 49
3.1.4 Raman光譜分析 52
3.1.5 XPS能譜分析 53
3.1.6 UV-vis 光譜分析 56
3.1.7 EIS分析 58
3.2 異質結構之材料鑑定 59
3.2.1 XRD分析 59
3.2.2 SEM影像分析 60
3.2.3 TEM分析 61
3.2.4 XPS能譜分析 63
3.2.5 UV-vis 光譜分析 65
3.2.6 PL分析 66
3.2.7 EIS 分析 67
3.2.8 TPC 分析 68
3.3 光催化產氫反應 69
3.4 能帶位置圖與光催化機制 72
3.5 產氫反應比較 74
第四章 結論 75
第五章 未來展望 76
參考文獻 77

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