近年來CO2透過觸媒催化轉換成燃料與化學品一直受到高度的關注，因為其產物除了能作為化石原料之替代品外，還有利於大規模的CO2轉化與封閉的碳循環利用。而本實驗設計在較低的反應溫度(573K以下)進行CO2氫化反應，為了適用於工廠排放廢熱之溫度，此外利用過度金屬作為活性金屬材料以降低觸媒成本，在探討添加金屬團簇對於材料表面修飾後局部協同作用對二氧化碳甲烷化增進之影響。
本研究利用濕式化學法合成二元金屬(鈷、鈀)尺度結構觸媒，並利用不同當量鈷團簇修飾於觸媒表面，再探究其在近室壓環境中，將CO2熱催化還原成低碳數產物(如CO, CH4)。利用X光繞射光譜(XRD),X光吸收光譜(XAS),高解析電子顯微境(TEM)等儀器分析觸媒物性結構，並由電化學循環伏安法與一氧化碳剝除法確認表面組成，與協同作用之間的關係。當有0.8wt%的鈷團簇點綴下(CoOx@PdCo0025)，在573K的反應環境中CH4產量為 CoOx@Pd 的 1.95 倍，Co團簇和Pd之間形成了新的界面，形成更強協同作用，對CO2甲烷化產生影響。

In recent years, the conversion of CO2 into fuels and chemicals through catalyst catalysis has been receiving high attention, because its products can not only be used as substitutes for fossil raw materials, but also conducive to large-scale CO2 conversion and closed carbon recycling. This experiment is designed to carry out the CO2 hydrogenation reaction at a lower reaction temperature (below 573K). In order to be suitable for the temperature of the waste heat of the factory, in addition to using the transition metal as the active metal material to reduce the cost of the catalyst, we are discussing the effect of adding metal clusters to the material. The effect of local synergy after surface modification on the enhancement of carbon dioxide methanation.
This study uses wet chemical methods to synthesize binary metal (cobalt, palladium) scale structure catalysts, and uses different equivalent cobalt clusters to modify the surface of the catalyst, and then explores its thermal catalytic reduction of CO2 in a near-room pressure environment. Low carbon number products (such as CO, CH4). Use X-ray diffraction spectroscopy (XRD), X-ray absorption spectroscopy (XAS), high-resolution electron microscopy (TEM) and other instruments to analyze the physical structure of the catalyst, and confirm the surface composition by electrochemical cyclic voltammetry and carbon monoxide stripping , and the relationship between synergy. When 0.8wt% of cobalt clusters are dotted (CoOx@PdCo0025), the output of CH4 is 1.95 times that of CoOx@Pd in a reaction environment of 573K. A new interface is formed between Co clusters and Pd, forming a stronger synergistic effect on CO2 methanation has an impact.

摘要 i
Abstract ii
誌謝 iv
目錄 vi
表目錄 x
圖目錄 xi
第一章 緒論 15
1.1 研究背景 15
1.2 環境中二氧化碳之減量 16
1.3 二氧化碳的轉換方法種類 18
1.3.1 光催化 20
1.3.2 電催化 21
1.3.3 熱催化 22
1.4 研究動機 24
第二章 文獻回顧 25
2.1 二氧化碳甲烷化轉換機制 25
2.2 影響二氧化碳觸媒效能之因素 26
2.2.1 觸媒載體 26
2.2.2 活性金屬 28
2.2.3 促進劑 29
2.3 觸媒材料元素選擇 29
2.3.1 貴金屬 29
2.3.2 過度金屬 30
2.4 文獻回顧總結 31
第三章 實驗方法 32
3.1 實驗設計 32
3.2 實驗藥品 34
3.3 實驗步驟 35
3.3.1 合成步驟 35
3.3.2 熱催化實驗步驟 36
3.4 材料結構分析 37
3.4.1穿透式電子顯微鏡 (Transmission Electron Microscopy, TEM) 37
3.4.2 X光繞射分析儀 (X-ray diffraction, XRD) 39
3.4.3 X光光電子圖譜 (X-ray photoelectron spectroscopy, XPS) 42
3.4.4 X光吸收光譜 (X-ray absorption spectroscopy, XAS) 44
3.5 電化學分析 47
3.5.1 循環伏安法 (Cyclic Voltammetry, CV) 48
3.5.2 一氧化碳剝除 ( CO-stripping ) 50
3.6 氣相層析儀產物分析(Gas chromatograph, GC) 51
第四章 結果與討論 54
4.1. 實驗項目說明 54
4.2 對照組樣品二元鈷鈀奈米觸媒(CoOx@Pd)結構分析結果與二氧化碳轉化反應特性........ 55
4.2.1. CoOx@Pd 樣品之X光繞射分析(X-ray Diffraction) 55
4.2.2. CoOx@Pd 樣品之高解析穿透式電子顯微鏡分析 (HRTEM) 58
4.2.3. CoOx@Pd 樣品之X光吸收光譜分析 (X-ray absorption spectroscopy, XAS)....... 60
4.2.4. CoOx@Pd 樣品之循環伏安法分析 (Cyclic Voltammetry, CV) 64
4.2.5. CoOx@Pd 樣品之一氧化碳剝除分析 (CO-stripping) 66
4.2.6. CoOx@Pd 樣品之氣相層析儀產物分析( Gas chromatograph, GC ) 67
4.3 實驗組樣品三元鈷鈀鈷奈米觸媒(CoOx@Pd-Co) 結構分析結果與二氧化碳轉化反應特性 71
4.3.1. CoOx@Pd-Co 樣品之X光繞射分析(X-ray Diffraction) 71
4.3.2. CoOx@Pd-Co 樣品之高解析穿透式電子顯微鏡分析 (HRTEM) 74
4.3.3. CoOx@Pd-Co 樣品之X光吸收光譜分析 (X-ray absorption spectroscopy, XAS) 76
4.3.4. CoOx@Pd-Co 樣品之X光光電子能譜分析 (X-ray photoelectron spectroscopy, XPS) 80
4.3.5. CoOx@Pd-Co 樣品之循環伏安法分析 (Cyclic Voltammetry, CV) 81
4.3.6. CoOx@Pd-Co 樣品之一氧化碳剝除分析 (CO-stripping) 83
4.3.7. CoOx@Pd-Co 樣品之氣相層析儀產物分析( Gas chromatograph, GC ) 85
第五章 結論 88
參考文獻 90

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