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研究生(外文):Yi﹣Lin Chen
論文名稱(外文):Photocatalytic Hydrogen Production of the CdS/TiO2-WO3 Ternary Hybrid under Visible Light Irradiation
指導教授(外文):Shang-Lien Lo
口試委員(外文):Pei-Te ChiuehYa﹣Hsuan Liou
外文關鍵詞:HydrogenTitanate nanotubesCadium sulfideTungsten trioxidePlatinumTernary hybridFormic acid
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本研究採用CdS,TiO2,WO3三種半導體,通過熱合成與物理結合方式構成三觸媒系統,藉助兩步反應,有效降低電子電洞對複合的機率,提高光催化效率。並進一步對系統進行優化,如: 探究三種半導體的較佳比例,使其發揮較好的整體效能;用微波法合成氧化鈦奈米管,擴大觸媒接觸面積;用金屬批覆法修飾WO3,延長電子電洞對分開的週期。另外,甲酸作為光催化系統的犧牲劑,能夠有效的儲存氫氣並擔任電洞捕捉劑,延緩電子、電洞對再結合。
常溫下以150 W可見光燈源 (350&;#8804;λ&;#8804;800)催化20 vol%甲酸溶液。TNTs作為載體,相較於TiO2,能批覆較高比例之CdS,28 wt%為較佳之批覆比例。0.2 g 28 wt% CdS/TNTs在可見光下的產氫效率為179.35 μmol.h-1,而單純CdS與TNTs的產氫效率僅分別為69.79 μmol.h-1與0.35 μmol.h-1。引入WO3後的三觸媒系統,得益於二步反應,產氫效率提升到212.68 μmol.h-1。其中,CdS/TNTs與WO3各0.2 g為較佳之觸媒比例。本研究之最佳產氫結果為428.43 μmol.h-1,使用之觸媒為0.2 g 28 wt% CdS/TNTs與0.2 g 0.1 wt% Pt/WO3。在批覆鉑金屬後,產氫效率提高了一倍。

Hydrogen gas is one of the most promising renewable energy nowadays as it has high energy yield and zero carbon emission. An attractive and effective method for converting solar energy to hydrogen energy is photocatalytic water splitting over semiconductors. This study investigated the photocatalytic conversion of formic acid solution to hydrogen using visible light (150 W, 350 < λ < 800 nm). The resultant materials were well characterized by high-resolution transmission electron microscope (HR-TEM), X-ray diffraction (XRD), scanning electron microscopy/energy dispersive X-ray (SEM/EDX), and UV-Vis spectra.
The study aimed at utilizing organic sacrificial agents in water, modeled by formic acid, in combination with visible light driven photocatalysts to produce hydrogen with high efficiencies. CdS/TiO2-WO3 ternary hybrid was used as photoactive composite.
Microwave induced titanate nanotubes (TNTs) were used as the main carrier to incorporate with CdS for the reason that it holds higher surface area than TiO2. The optimized CdS content is 28 wt% and the production rate of 28 wt%CdS/TNTs achieved 179.35 μmol.h-1.
Furthermore, WO3 was physically mixed with the optimized CdS/TNTs binary hybrid. The enhanced photocatalytic activity could be attributed to the electron transfer from CdS to TiO2 to WO3 through the interfacial potential gradient in the ternary hybrid conduction bands, which effectively reduces the chance of charge recombination compared with the binary hybrids. The hydrogen production rate reached 212.68 μmol.h-1.
Coating of platinum metal onto the WO3 could further promote the reaction. Results showed that 0.2 g 0.1 wt%Pt/WO3 + 0.2 g 28 wt%CdS/TNTs had the best hydrogen production rate of 428.43 μmol.h-1 , which was more than double compared with CdS/TNTs+ WO3.

口試委員會審定書 i
誌謝 iii
中文摘要 v
英文摘要 vii
目錄 ix
圖目錄 xii
表目錄 xiv
第一章 緒論 1
1.1前言 1
1.2研究目的 2
1.3研究內容 2
第二章 文獻回顧 3
2.1光催化水分解原理 3
2.2光催化材料 5
2.2.1 二氧化鈦 5
2.2.2氧化鈦奈米管 7
2.2.3二氧化鈦的改質 9
2.3犧牲劑 15
2.3.1甲酸的物化性質 15
2.3.2甲酸溶液產氫理論 16
2.4三觸媒催化水分解系統 18
第三章 材料與方法 21
3.1所用試劑 21
3.2所用設備 21
3.3材料製備 24
3.3.1微波法製備氧化鈦奈米管 24
3.3.2水熱法製備CdS/TiO2, CdS/ TNTs 24
3.3.3無電電鍍法製備Pt/WO3 25
3.4光催化材料物化分析 26
3.5光催化材料製氫活性評價 29
3.5.1氫氣發生裝置 29
3.5.2產物檢測裝置 30
3.6實驗設計 31
第四章 結果與討論 33
4.1光觸媒材料特性鑑定 33
4.1.1掃描式電子顯微鏡觀察 (SEM) 33
4.1.2穿透式電子顯微鏡觀察 (TEM) 37
4.1.3 X射線能量分散光譜儀 (EDS) 39
4.1.4紫外光-可見光光譜儀 (UV-Vis) 42
4.1.5廣角X光粉末繞射儀 (XRD) 45
4.2光觸媒材料產氫性能分析 47
4.2.1空白實驗 47
4.2.2單觸媒系統 49
4.2.3雙觸媒系統 50
4.2.4鉑金屬批覆效應 55
4.3 甲酸的降解反應 57
4.4 光催化反應機制 63
4.5 光催化反應結果分析 67
第五章 結論與建議 71
5.1 結論 71
5.2 建議 72
第六章 參考文獻 73
附錄 81

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