世界因過量的二氧化碳排放而產生的全球暖化問題已日趨嚴重，所衍生出的環境問題目前正強烈著衝擊人類的生活，為了改善當今嚴峻之現況，想方設法減少二氧化碳之排放量是當務之急，科學家也正投入大量心力開發降低大氣中二氧化碳濃度之方案，而二氧化碳轉換方案中的熱催化法(即二氧化碳氫化反應)，是最具未來性與發展潛力的方式之一。
本研究分為兩部分，旨在開發二氧化碳氫化反應之甲烷化反應觸媒，第一部分中，發展以二氧化鈦作為載體，並於上方成長以鐵為基底、銅原子作為點綴之觸媒；第二部分則是在鐵銅奈米觸媒上方再添加鈀原子作點綴，以此構型達更良好之甲烷化效果。本研究利用X光繞射儀分析奈米觸媒之主要結晶相；X光吸收光譜分析觸媒中各金屬原子之局部配位環境與局部氧化程度；X光光電子能譜則用以分析觸媒表面化學組態分布；並以一氧化碳剝離試驗了解表面各項成分之活性；最後利用氣相層析儀得到觸媒在真實加氫環境中的二氧化碳氫化反應之產物結果。
本研究之鐵銅/鐵銅鈀觸媒之主要結晶相經分析後都以氧化鐵(Fe2O3、Fe3O4)為主體，上方點綴金屬則多為氧化銅及金屬鈀/氧化鈀之型態。且在點綴原子的添加後，都能發現不同金屬原子間之局部協同作用發生，彼此間對於氣體的吸附能力不同而對二氧化碳氫化有更好的增益效果，實驗結果顯示鐵銅奈米觸媒中，FC(5/0075)有最佳的一氧化碳及甲烷產量，分別為800.3 ppm及102.2 ppm。而在加入鈀點綴後，兩者產量都有顯著提升，其中FCP(03)有最佳一氧化碳產量1313.9 ppm，而FCP(0075)則有最佳甲烷產量130.6 ppm，成功達到良好甲烷化反應效果。

The problem of global warming caused by excessive carbon dioxide emissions in the world has become more and more serious. The resulting environmental problems are currently strongly impacting human lives. In order to improve today’s severe conditions, it is imperative to find ways to reduce carbon dioxide emissions. Scientists are also devoted to develope useful plans to reduce the concentration of carbon dioxide in the atmosphere. The carbon dioxide thermal catalytic method (ie, hydrogenation of carbon dioxide) in the carbon dioxide conversion plan is one of the most promising methods.
There are two parts in this study, aiming to develop the methanation reaction catalyst for the hydrogenation of carbon dioxide. In the first part, titanium dioxide is developed as support material, and the iron-based nano-catalyst with copper decorated has been develop; In the second part, The addition of palladium atoms is on the top of the iron-copper nano-catalyst to achieve a better methanation effect with this configuration. In this study, X-ray diffraction spectroscopy was used to analyze the main crystalline phase of the nano-catalyst; X-ray absorption spectroscopy was used to analyze the local coordination environment and local oxidation degree of each metal atom in the catalyst; X-ray photoelectron spectroscopy was used to analyze the surface chemical configuration distribution of catalyst; and the carbon monoxide stripping test is used to understand the activity of the various components on the surface; finally, the gas chromatograph is used to obtain the product result of the carbon dioxide hydrogenation reaction of the catalyst in the real hydrogenation environment.
The main crystalline phases of the iron-copper/iron-copper-palladium catalyst in this study are all iron oxide (Fe2O3, Fe3O4) as the main body after analysis, and the decorated metallic atom on the top are mostly copper oxide and metallic palladium/palladium oxide. And after the addition of the decorated atoms, it can be found that the local synergetic effect between the different metal atoms occurs, and the adsorption capacity of each other is different, which has a better effect on the hydrogenation of carbon dioxide. The experimental results show that the iron-copper nano-catalyst FC (5/0075) has the best carbon monoxide and methane production at 800.3 ppm and 102.2 ppm, respectively. After the addition of palladium, the yields of both product have been significantly improved. Among them, FCP (03) has the best carbon monoxide yield of 1313.9 ppm, and FCP (0075) has the best methane yield of 130.6 ppm, which successfully achieved a significant methanation reaction effect.

摘要 i
Abtract iii
誌謝 v
目錄 vi
圖目錄 ix
表目錄 ix
第一章 緒論 1
1-1研究背景 1
1-2降低二氧化碳排放量之策略 2
1-2-1 再生能源之使用 2
1-2-2 碳捕捉與封存 3
1-2-3 二氧化碳轉換 4
1-3 二氧化碳轉換 4
1-3-1光催化 4
1-3-2電催化 6
1-3-3熱催化 7
1-4研究動機 8
第二章 文獻回顧 9
2-1二氧化碳氫化之反應路徑及種類 9
2-2 二氧化碳氫化反應之路徑 11
2-3 影響觸媒活性之因素 12
2-3-1 活性金屬之選擇 12
2-3-2 觸媒結構與形貌 14
2-3-3 觸媒載體之選擇 15
2-4文獻回顧總結 16
第三章 實驗方法 18
3-1前言 18
3-2 實驗設計 18
3-2-1 實驗研究方向 18
3-2-2 實驗藥品 18
3-3 實驗步驟 19
3-4 材料物理性質分析 20
3-4-1 X光繞射分析儀 (X-ray diffraction) 20
3-4-2 X光吸收光譜 (X-ray absorption spectroscopy) 22
3-4-3 X光光電子圖譜 (X-ray photoelectron spectroscopy, XPS) 25
3-4-4 高解析度穿透式電子顯微鏡 (HRTEM) 27
3-4-5 感應耦合電漿質譜儀 (ICP-MS) 28
3-5電化學分析 29
一氧化碳剝離試驗 (CO-stripping) 29
3-6產物分析 30
氣相層析儀 (Gas chromatograph) 30
第四章 結果與討論 32
4-1銅原子團簇點綴之鐵基奈米催化劑之材料分析 33
4-1-1鐵銅奈米觸媒之感應耦合電漿質譜儀 33
4-1-2 鐵銅奈米觸媒之X光繞射分析 34
4-1-3 鐵銅奈米觸媒之X光吸收光譜 37
4-1-4 鐵銅奈米觸媒之X光光電子能譜 43
4-1-5 鐵銅奈米觸媒之一氧化碳剝離試驗 47
4-1-6 鐵銅奈米觸媒之氣相層析儀 49
4-2 鈀原子修飾之鐵銅奈米催化劑之材料分析 51
4-2-1鐵銅鈀奈米觸媒之感應耦合電漿質譜儀 51
4-2-2 鐵銅鈀奈米觸媒之X光繞射分析 52
4-2-3 鐵銅鈀奈米觸媒之X光吸收光譜 54
4-2-4 鐵銅鈀奈米觸媒之一氧化碳剝離試驗 59
4-2-5鐵銅鈀奈米觸媒之氣相層析儀 61
第五章 結論 66
參考文獻 68

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