本研究分為兩階段。第一階段先以反應程序控制成長銅鎳鈀至酸化奈米碳管上，形成銅-鎳鈀堆疊結構的三元金屬奈米顆粒(hierarchical structure Cu-NiPd ternary metallic nanoparticles, namely CNP)。利用濕式化學還原法(wet chemical reduction method)，並以硼氫化鈉(NaBH4)作為還原劑，依序加入銅以及鎳鈀之前驅溶液，同時改變鎳與鈀之莫耳比例，合成銅鎳鈀莫耳比例為10: 5: 10以及10: 10: 5兩種奈米顆粒(命名CNP0510以及CNP1005)。以循環伏安法及電化學阻抗分析儀推定其表面化學組成和電性後，再使用氣相層析儀以電化學二氧化碳還原法進一步確認其表面組成。高解析穿透式電子顯微鏡、X光繞射儀、X光光電子能譜儀、X光吸收光譜儀確認此兩種奈米顆粒的表面形貌及細部結構。
第二階段以次毫秒雷射退火不同脈衝能量退火處理此兩種奈米顆粒，達成擴散控制奈米顆粒表面原子分佈。實驗結果顯示，經由不同脈衝能量之次毫秒雷射退火處理後，奈米顆粒表面原子能夠移動的距離隨之改變。在受到每發1毫焦耳的能量照射，CNP0510奈米顆粒表面的Pd會稍微受到氧化，且有些微的NiPd合金相出現。提高脈衝能量至每發10毫焦耳後，奈米顆粒能夠吸收的單發雷射能量變大，導致有序的NiPd合金出現。CNP1005奈米顆粒在每發1毫焦耳的雷射照射後，原先的氧化鎳與金屬鈀的混和相會因為氧化鎳繼續成長的緣故，使金屬鈀慢慢與氧化鎳產生分離相。但是在受到每發10毫焦耳的雷射照射後，會因為未受到氧化的金屬鎳與金屬鈀原子交互擴散的關係，再次出現NiPd合金。

This study is divided into two parts. In the first part, carbon nanotube supported CuNiPd ternary metallic nanoparticles (namely CNP NPs) were synthesized by a wet chemical reduction method with sequential control and tuned the Ni and Pd molar ratio. To characterize the CuNiPd nanoparticles, cyclic voltammetry and electrochemical impedance spectroscopy were introduced to confirm the chemical compound on the particle’s surface and gas chromatography to analyze the products of carbon dioxide reduction. The morphology and its fine structure are revealed by high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. In the second part, surface atoms were rearranged by diffusion-controlled using a different sub-millisecond pulsed laser.
Electrochemical results revealed that the Pd atoms on CNP0510’s surface were slightly oxidized with 1 mJ/pulse and a less amount of NiPd alloy formed. When the pulse energy increased to 10 mJ/pulse, interdiffusion/alloying of Ni and Pd occurs due to the high absorption energy induced the longer distance of atomic migration. In CNP1005, NiOx and Pd mixing phase will transfer to NiOx and metallic Pd separated phase because of the growth of NiOx when the absorption energy is 1mJ/pulse. But when the pulse energy increased to 10 mJ/pulse, Ni, which did not form a NiOx, will mix with Pd atom to become NiPd alloy again.

致謝 i
摘要 ii
英文摘要 iii
目錄 iv
圖目錄 vii
表目錄 xii
第一章 緒論 1
1-1 研究背景 1
1-2 熱退火對奈米顆粒的影響 2
1-3 快速熱退火對奈米顆粒的影響 3
1-4 雷射退火對奈米顆粒的影響 4
1-5 奈米顆粒對二氧化碳還原的應用(表面特徵) 6
1-6 研究動機 8
第二章 文獻回顧 9
2-1 雷射材料製程與應用 9
2-2 連續波雷射退火 10
2-3 脈衝雷射 10
2-4 奈米顆粒對電化學二氧化碳還原影響 14
2-5 文獻回顧總結 17
第三章 實驗方法 19
3-1 前言 19
3-2 實驗設計 19
3-2-1 實驗研究方向 19
3-2-2 實驗藥品 20
3-2-3 奈米碳管酸處理 20
3-2-4 次毫秒雷射退火處理 21
3-3 實驗流程 21
3-4 材料特性分析 24
3-5 物理特性分析 24
3-5-1 穿透式電子顯微鏡 (Transmission Electron Microscopy, TEM) 24
3-5-2 X光繞射分析儀 (X-ray Diffraction, XRD) 26
3-5-3 X光吸收光譜 (X-ray Absorption Spectroscopy, XAS) 28
3-5-4 X光光電子能譜 (X-ray Photoelectron Spectroscopy, XPS) 32
3-5-5 感應耦合電漿分析 (Inductively Coupled Plasma, ICP) 35
3-6 電化學分析 36
3-6-1 循環伏安法(Cyclic Voltammetry, CV) 38
3-6-2 一氧化碳剝離試驗(CO-Stripping) 40
3-6-3 電化學阻抗圖(Electrochemical Impedance Spectroscopy, EIS) 40
3-6-4 氣相層析儀(Gas Chromatography) 43
第四章 結果與討論 45
4-1 不同鎳鈀比例的奈米顆粒分析 46
4-1-1 X光繞射(X-ray Diffraction) 46
4-1-2 高解析穿透式電子顯微鏡(High Resolution Transmission Electron Microscopy) 48
4-1-3 X光吸收光譜(X-ray Absorption Spectroscopy) 49
4-1-4 X光光電子能譜(X-ray Photoelectron Spectroscopy) 56
4-1-5 電化學分析(Electrochemical testing) 57
4-1-6 氣相層析儀(Gas Chromatography, GC) 60
4-2 次毫秒雷射退火對銅鎳鈀三元奈米顆粒的效應 62
4-2-1 X光繞射 (X-ray Diffraction) 63
4-2-2 高解析穿透式電子顯微鏡 (HRTEM) 66
4-2-3 X光吸收光譜(X-ray Absorption Spectroscopy) 69
4-2-4 X光光電子能譜(X-ray Photoelectron Spectroscopy) 79
4-2-5 電化學分析(Electrochemical Testing) 80
4-2-6 氣相層析儀(Gas Chromatography) 86
第五章 結論 89
第六章 未來工作與建議 90
第七章 參考資料 91

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