臺灣博碩士論文加值系統

本研究使用水熱法和溶膠凝膠兩種方法製備Pd-Au/TiO2-WO3納米顆粒作為光還原二氧化碳的光觸媒。使用X光繞射儀(XRD)，描式電子顯微鏡(SEM)，穿透式電子顯微鏡(TEM)，X光光電子能譜儀(XPS)，BET，UV-vis，光致發光光譜儀（PL）對製備的鑑定。與市售TiO2(P25)相比，在TiO2-WO3複合材料加入適量的Pd和Au會有較高的光還原活性。CH4產率(39.1 μmol g-1 h-1)是TiO2 (P25)的100倍；除此之外，還產出有大量的CO (271.3 μmol g-1 h-1)是TiO2 (P25)的300倍。光催化活性的大幅提高可能來自比表面積的增加(72.9 m2 g-1)，及在可見光吸收的增加。摻入Pd-Au於TiO2也提高了太陽能的利用率及減少Pd-Au/TiO2-WO3複合材料電子電洞對再結合的機會而提高光還原活性。CH4產量的量子產率計算為(1.05 %)。最後在Pd-Au / TiO2-WO3的光還原反應中提出了CO2的還原反應機構，而本研究可以為TiO2應用於太陽能轉換和儲存等帶來新的發展。

This study presents Pd-Au/TiO2-WO3 nanoparticle prepared by a hydrothermal and sol-gel method as a CO2 conversion photocatalysts. The catalysts were characterized by X-ray diffraction (XRD), Scan electron microscope (SEM), Tunneling electron microscope (TEM), XPS, BET, UV-visible and Photoluminescence (PL) instruments. The appropriate amounts of Pd and Au on TiO2-WO3 composites exhibited enhanced photocatalytic activity for CO2 reduction compared with commercial TiO2 (P25). It showed the photocatalytic CH4 production rate (39.1 μmol g-1 h-1) was 100 fold that of TiO2 (P25); moreover, a large amount of CO was produced (at a rate of 271.3 μmol g-1 h-1) was 300 fold that of TiO2 (P25). The significantly improved photocatalytic activity was not only due to the increased specific surface area (72.9 m2g-1) but also UV-vis showed a remarkable enhancement of light absorption. It owes to the incorporation Pd-Au with TiO2 the visiblelight active the UV light-responsive for increased solar energy utilization. Furthermore, PL spectra revealed that the Pd-Au content can influence the charge transfer efficiency of the Pd-Au/TiO2-WO3 composites. The quantum yield of CH4 production was calculated as 1.05 %. A CO2 reduction reaction mechanism was proposed on Pd-Au/TiO2-WO3. This study can bring new insights into designing TiO2 nanostructures for applications such as solar energy conversion and storage.

謝誌 I
摘要 III
ABSTRACT IV
目錄 V
圖目錄 IX
表目錄 XII
第一章 緒論 1
1-1前言 1
1-2甲烷發展狀況 3
1-2-1開發天然資源(海洋、沼澤) 3
1-2-2 利用微生物產甲烷 3
1-2-3有機物分解 4
1-2-4全球議題 5
1-4 觸媒簡介 5
1-4-1觸媒奈米化 5
1-4-2二氧化鈦(TiO2)介紹 6
1-4-3三氧化鎢(WO3) 介紹 10
1-4-4鈀(Pd)金屬介紹 10
1-4-4金(Au)金屬介紹 12
1-5光催化反應 13
1-5-1光觸媒 13
1-5-2光還原二氧化碳轉化成甲烷原理 15
第二章 文獻回顧 20
2-1文獻回顧 20
2-2研究動機 29
第三章 實驗方法 30
3-1 實驗藥品 30
3-2光觸媒製備 31
3-2-1 TiO2-WO3複合材料製作 31
3-2-2 摻雜金屬到TiO2-WO3複合材料 33
3-2-3 Pd-Au/TiO2-WO3複合材料製作 33
3-3 材料定性之貴重儀器簡介 35
3-3-1簡易水熱釜 35
3-3-2 X光繞射儀(X-ray Diffraction, XRD) 36
3-3-3反射式紫外-可見光光譜儀(UV-Vis Spectrophotometer) 39
3-3-4掃描式電子顯微鏡(Scaning Electron Microscope, SEM) 42
3-3-4穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 及能量分散光譜儀(Energy Dispersive Spectrometer, EDX) 44
3-3-5 X光光電子能譜儀(XPS/ESCA) 47
3-3-6光致發光光譜儀(Photoluminescence) 49
3-3-7高解析比表面積分析儀(High Resolution surface Area and Porosimetry Analyser,ASAP/BET) 50
3-4 實驗儀器 51
3-4-1氣相層析儀(Gas Chromatography) 51
3-4-2甲烷校正氣體 53
3-4-3光催化反應使用之光源(light source) 54
3-4-4光催化反應系統(Photocatalyst reactor) 56
第四章 結果與討論 57
4-1 XRD繞射分析 57
4-2掃描式電子顯微鏡(SEM)分析 60
4-3穿透式電子顯微鏡(TEM)分析 62
4-4反射式紫外-可見光光譜儀(UV-Vis Spectrophotometer)分析 67
4-5光致發光光譜儀(Photoluminescence)分析 71
4-6高解析比表面積分析儀((High Resolution surface Area and Porosimetry Analyser,ASAP/BET) 72
4-7 X光光電子能譜儀(XPS/ESCA)分析 73
4-8光還原反應實驗結果 77
4-9觸媒再利用性測試 86
4-10量子產率 87
4-11反應機構討論 89
第五章 結論 93
參考資料 95

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