臺灣博碩士論文加值系統

由於全球能源的需求量日益增加且為了達到維護環境與永續利用的概念，科學家們正積極努力地找尋可替代石化燃料之能源，由於氫氣為一乾淨且具高能量密度之燃料，因此電催化水分解產氫被視為具有解決能源危機與環境汙染的最佳方法，而一般具有高催化活性的物質都為貴重金屬居多，基於成本過高與不易取得之問題，限制其大規模的應用，因此找尋可替代貴重金屬之催化劑被視為近年來研究重點。然而在進行電催化水分解時不僅僅只有陰極的產氫反應，同時也包含了陽極的析氧反應，要是能夠發展出可運用在兩極上的材料的話，更是一舉兩得。
在本研究中，我們利用水熱法合成鈷之前驅物與鈷鐵混合之前驅物，然後再搭配化學氣相沈積法將其在充滿磷的氣體下轉變為磷化物，分別應用於水分解之陰極析氫與陽極析氧反應，由於磷化物本身具有金屬的特性，電子較易傳遞，因此在進行陽極產氧反應時，相對於氧化物而言會更加有利。我們再利用添加不同含量的鐵來修飾其形貌與優化其效能，最後再將磷化物附載於碳布上，結合碳布優異的性能，具有可饒性和良好的導電性，使得在進行電催化時，讓電子能夠快速地從碳布傳導至觸媒上，而且又是三維的立體基材，不僅能夠大幅的增加活性表面積，電催化時氣體更容易能夠脫附於電極表面，大幅降低氣泡窒礙活性的問題。經由整體性能的改善後，我們研究出能夠運用於兩極的材料，且性能能夠媲美貴重金屬，對於取代貴重金屬有了更進一步的發展。

Because the global demand for energy rapidly increased in the past decades, scientists are looking for renewable and clean energy with the aim of substituting for fossil fuels. Hydrogen has been considered as a high density energy and clean fuel, so that the electrolysis of water for hydrogen production may be a promising way to solve the energy crisis and environment pollution. However, most of highly active electrocatalysts are commonly precious metal, their major drawbacks are high cost and insufficient reserve that restricts practical application. As a result, developing earth-abundant, active and stable catalysts which can operate in the same electrolyte for water-splitting is important for many renewable energy conversion processes.
In this research, we utilized the gas-solid reaction to synthesize the cobalt phosphide with dopant of iron. Because the transition metal phosphides (TMPs) are characteristic of metallic properties, which can facilitate the water-splitting reaction owing to an effective charge-transfer. The morphology and catalytic capability can be further modified via doping various amount of iron. Finally, combination of the iron doping and carbon cloth as a hybrid material with flexible and conductive properties can facilitate the charge transfer from substrate to catalyst and lead to an enhanced performance. Besides, bubble releasing problem during the reaction can be remarkably suppressed owing to 3D structure of carbon cloth. Consequently, we successfully synthesized the hybrid material that can perform excellent activities toward both the oxygen and hydrogen evolution reaction. These strategies of TMPs are instructive for designing non-noble metal catalysts for future applications.

目錄
中文摘要 i
Abstract ii
誌謝 iii
目錄 iv
圖目錄 viii
表目錄 xii
第一章 緒論 1
1.1氫氣能源 2
1.2 氫氣的製備技術 2
1.2.1化石燃料產氫 2
1.2.2光催化製氫 4
1.2.3電催化產氫 5
1.3 電解水之原理 6
1.3.1 電催化還原產氫反應（Hydrogen evolution reaction） 7
1.3.2 電催化氧化產氧反應(Oxygen evolution reaction) 9
1.4 材料活性比較之參數 10
1.4.1 總電極活性量測 11
1.4.2 本質活性量測 13
1.5水分解之陰極發展 13
1.5.1 過渡金屬雙硫屬化合物（transition metal dichalcogenides, TMD） 15
1.5.2 過渡金屬磷化物（transition metal phosphides, TMPs） 18
1.6 水分解陽極之發展 20
1.6.1 過渡金屬氧化物（Transition-metal oxides） 21
1.6.2 非氧化物之材料 23
1.7 雙功能水分解之材料 23
1.8 過渡金屬磷化物合成方法 25
1.8.1 液相合成法（solution-phase reaction）43 25
1.8.2 氣-固反應（gas-solid reaction） 25
1.9 研究動機與目的 26
第二章、實驗步驟與儀器分析原理 27
2.1 化學藥品 27
2.2 實驗步驟 29
2.2.1 碳布的清潔 29
2.2.2 Co(CO3)0.5OH･H2O/CC & CoFe(CO3)OH･H2O/CC(X)之製備 29
2.2.3 CoP/CC & CoFeP(X)/CC之製備 31
2.3 三電極電化學系統 32
2.3.1 工作電極之製備 32
2.3.2 三電極化學系統之組裝 32
2.4儀器分析 33
2.4.1 X射線繞射分析儀 33
2.4.2 X射線繞射原理 33
2.4.3 電子顯微鏡 35
2.4.3.1 掃描式電子顯微鏡（scanning electron microscope, SEM） 35
2.4.3.2 能量散佈X光光譜儀（Energy dispersive X-ray spectrometer, EDS） 37
儀器規格 39

2.4.3.3 穿透式電子顯微鏡（transmission electron microscopy, TEM） 39
2.4.4 同步輻射 41
2.4.4.1同步輻射歷史 41
2.4.4.2 同步輻射光源 42
2.4.5 同步輻射吸收光譜原理 43
2.4.5.1 X光吸收光譜（X-ray absorption spectroscopy, XAS） 43
2.4.5.2 X光吸收光譜簡介 44
2.4.5.3 X光吸收近邊緣結構光譜（X-ray absorption near edge structure, XANES） 46
2.4.5.4 X光延伸精細結構吸收光譜（extended X-ray absorption fine structure, EXAFS） 48
2.4.6 伏安法（voltammetry） 48
2.4.6.1 線性掃描伏安法（linear sweep voltammetry, LSV） 49
2.4.6.2 循環伏安法（cyclic voltammetry, CV） 50
2.4.6.3 電化學阻抗譜（electrochemical impedance spectroscopy, EIS） 51
第三章、結果與討論 52
3.1 磷化鈷奈米線結合碳布之複合材料 52
3.1.1 X射線繞射光譜分析 52
3.1.2 掃描式電子顯微鏡分析 53
3.2 摻雜鐵之磷化鈷奈米片結構結合碳布之複合材料 54
3.2.1 X射線繞射光譜分析 54
3.2.2 掃描式電子顯微鏡分析 56
3.3 同步輻射分析 58
3.4 電化學量測 60
3.4.1 電化學還原產氫反應 61
3.4.2 電化學還原產氧反應 65
3.4.3 電化學阻抗分析 70
3.2.4 電雙層電容（double layer capacitance）活性面積量測 72
3.5 雙功能活性分析 74
第四章、結論 77
第五章、參考文獻 78

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