全球暖化的問題已經不容忽視，再生能源的發展以及尋找替代性能源減少化
石燃料的使用，是近年來非常重要的議題，氫能，被視為最有可能取代化石燃料
的綠色能源，擁有燃燒後的產物只有水，對環境友善等特性，因此如何簡易且低
成本的製造氫氣會是目前研究的主要方向。在本實驗中選擇鈣鈦礦結構氧化物
（ABO3），其具有有優秀的電子結構、電子遷移率以及特殊的物理、化學特性，
利用過渡金屬擁有3d 軌域利於與氧原子混層，透過對鈣鈦礦B 位元素的設計，
降低催化所需的能障，將此鈣鈦礦結構應用於電解水產氫陽極析氧反應（Oxygen
evolution reaction ， OER ）， 實驗結果成功地合成出鈣鈦礦結構氧化物
（PrCo0.8Fe0.2O3），其表現出低的過電位282 mV 以及塔菲爾斜率（Tafel slope）
140 mV-dec-1，然而析氧反應是一個涉及多個電荷轉移的複雜反應，我們藉由先
進的X 光分析技術，解析樣品結構組成，以及可能的活性關鍵因素。設計鈣鈦礦
氧化物以調整其電子結構，有助於提升催化劑活性，應用於析氧反應有很大的研
究潛力。

The global warming is become an issue cannot be ignored. To reduce the use of
fossil fuels, developing renewable energy and searching for alternative energy sources
have been very important topic in recent years. Hydrogen as the green energy is friendly
to the environment, regarding most likely to replace fossil fuels. Therefore, how to
manufacture hydrogen at low cost will be the main direction of current research.
Perovskite is applied to the oxygen evolution reaction (OER) because it has flexible
electronic structure and unique electron mobility. The perovskite be designed to reduce
the energy barrier for water oxidation. In this study we successfully synthesized a
perovskite structure oxide (PrCo0.8Fe0.2O3) show the low overpotential of 289 mV and
the Tafel slope of 109 mVdec-1. However, the OER is a complex reaction involving
multiple charge transfers. By mean of X-ray analysis techniques to analyze the structure
and composition of the sample, find the possible activity site of the catalyst.
Accordingly, design the perovskite to adjust electronic structure, boosting to improve
the performance of catalyst. The application of perovskite to OER has great research
potential.

摘要 ................................................................................................................................ i
Abstract ........................................................................................................................ ii
誌謝 .............................................................................................................................. iii
目錄 .............................................................................................................................. iv
圖目錄 .......................................................................................................................... vi
表目錄 ........................................................................................................................ viii
第一章、 緒論 ............................................................................................................. 1
1-1 前言 ............................................................................................................................................. 1
1-2 研究背景 ..................................................................................................................................... 2
1-3 研究動機 ..................................................................................................................................... 2
第二章、 理論基礎與文獻回顧 ................................................................................. 4
2-1 電化學 ......................................................................................................................................... 4
2-2 電極級化 ..................................................................................................................................... 5
2-2-1 活性極化 ............................................................................................................................. 5
2-2-2 濃度極化 ............................................................................................................................. 6
2-2-3 歐姆極化 ............................................................................................................................. 6
2-3 電極電位 ..................................................................................................................................... 7
2-4 循環伏安法（Cyclic Voltammetry，CV） ............................................................................... 9
2-5 電化學阻抗頻譜（Electrochemical Impedance Spectroscopy，EIS） .................................. 10
2-6 鈣鈦礦 .......................................................................................................................................... 12
2-6-1 鈣鈦礦結構與特性 ........................................................................................................... 12
2-6-2 鈣鈦礦於催化的應用 ....................................................................................................... 12
第三章、 實驗方法與步驟 ....................................................................................... 14
3-1 樣品製備流程 ........................................................................................................................... 14
3-2 實驗樣品製備材料 ................................................................................................................... 15
3-3 電化學量測條件 ....................................................................................................................... 16
3-4 同步加速器光源分析 ............................................................................................................... 17
3-4-1 同步加速器光源特色 ....................................................................................................... 17
3-4-2 X 光繞射圖譜（X-ray diffraction，XRD） ................................................................... 19
v
3-4-3 X 光吸收光譜（X-ray Absorption Spectroscopy，XAS） ............................................ 19
3-4-4 X 光光電子發射能譜（X-ray photoemission spectroscopy，XPS） ............................ 21
第四章、 結果與討論 ............................................................................................... 23
4-1 過渡金屬鈣鈦礦氧化物（PrCo1-xFexO3） .............................................................................. 23
4-1-1 X 光繞射圖譜分析（XRD） .......................................................................................... 23
4-1-2 X 光吸收光譜分析（XAS） ........................................................................................... 25
4-1-3 X 光光電子能譜分析（XPS） ....................................................................................... 28
4-1-4 電催化析氧反應（OER） ............................................................................................... 30
4-1-5 電化學表面積（Electrochemically active surface area，ECSA） ................................. 33
4-1-6 電化學阻抗頻譜分析 ....................................................................................................... 35
4-2 氮化鈣鈦礦氧化物（N-PrCo0.8Fe0.2O3） ................................................................................ 36
4-2-1 X 光繞射圖譜分析（XRD） .......................................................................................... 36
4-2-2 X 光吸收光譜分析（XAS） ........................................................................................... 37
4-2-3 X 光光電子能譜分析（XPS） ....................................................................................... 40
4-2-4 電催化析氧反應（OER） ............................................................................................... 42
4-2-5 電化學表面積（Electrochemically active surface area，ESCA） ................................. 44
4-2-6 電化學阻抗頻譜分析 ....................................................................................................... 45
第五章、 結論與未來展望 ....................................................................................... 46
參考文獻 ..................................................................................................................... 47

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