臺灣博碩士論文加值系統

自工業革命以來，為應付日新月異的各項科技進步對於能源的需求是與日俱增，為了供應如此鉅額的能量而長期使用化石燃料的後果便是溫室效應等全球化的氣候變異。近幾年來環保意識開始抬頭，人們開始意識到尋求替代的綠色能源之重要性，其中的二氧化碳電催化還原反應便是一個可行的解決方案，低成本、高可行性且對反應條件要求極低，在室溫室壓下便能進行反應為其賣點。然而二氧化碳還原反應之產物相對於水分解反應而言較為多元，可能產生: 一氧化碳、甲酸、甲烷、乙烯或乙醇等產物。為了能將產物實際拿來作為能源使用還需透過純化的步驟將各成分分離出來，這必然會使得其中成本上升而減低經濟效益，因此催化劑對於產物之選擇性就會顯得極為重要。
本實驗使用鋅材料作為催化劑來探討在電催化過程中，對產物之選擇性與催化金屬化學價態之間的關聯性，相較於其他大部分文獻都在探討催化劑晶面對於產物選擇性之影響，發現經過電催化的過程後晶面往往無法維持，故推論可能有其他更穩定的變因也會影響產物的選擇性，故選定金屬催化材料之化學價態來做討論。藉由合成一系列的鋅材料之氧化程度來破壞表層之緻密氧化層，進而使鋅材料本身在電化學催化反應下更容易改變其化學價態，再輔以臨場的同步輻射鑑定技術之K邊緣X光吸收光譜及X光繞射來觀測在催化過程中材料之化學價態與結構之變化。推論出鋅之化學價態可能是影響二電子產物甲酸和一氧化碳之選擇性的關鍵因素。

Early from the Industrial Revolution in 19th century, constant science and technology breakthrough have been achieved and also accompanied by elevating energy consumption. For supporting energy needs, fossil fuels have been massively used and caused serious environmental issues. Hence, the development of new strategies for processing excess CO2 emissions is really urgent and electrochemical CO2 reduction reaction could be one of the best candidates for its features of low cost and high accessibility. Unraveling the reaction mechanism of electrocatalysts toward CO2 reduction reaction (CO2RR) is a crucial step for further promoting efficient and selective reduction of CO2 to valuable chemicals. To understand the mechanism of zinc electrocatalyst toward CO2RR, a series of thermal oxidized zinc foils were prepared for achieving the correlation between chemical state of electrocatalyst and selectivity. The destruction of dense oxide layer on the surface of zinc foil through thermal oxidation process resulted in a 4-fold improvement of faradaic efficiency (FE) of formate. Furthermore, the evidence provided by in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction significantly demonstrated that the Zn(II) and Zn(0) species was responsible for the production of carbon monoxide (CO) and formate, respectively. The results from in situ measurements revealed that the chemical state of zinc electrocatalysts dominates the product profile for CO2RR, which provides a promising approach for tuning the product selectivity of zinc electrocatalyst.

誌謝 I
摘要 II
ABSTRACT III
目錄 IV
圖目錄 VII
表目錄 XII
第一章 緒論 1
1.1 全球暖化與能源危機 1
1.2 二氧化碳的捕捉與再利用 3
1.3 電催化二氧化碳還原反應 7
1.3.1 電催化二氧化碳還原之催化劑 7
1.3.2 電催化二氧化碳還原反應之反應條件 9
1.3.3二氧化碳還原反應之困境 10
1.3.4 二氧化碳還原-中間產物 11
1.3.5 產物選擇性之調控 12
1.4 鋅金屬催化劑 26
1.5 研究動機 28
第二章 實驗步驟與儀器分析原理 29
2.1 本研究之實驗流程 29
2.2 本研究所使用之藥品 30
2.3 實驗材料之製備 32
2.3.1 O-Zn-200、O-Zn-300、O-Zn-400、O-Zn-500之製備 32
2.4 樣品之鑑定與分析 33
2.4.1掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 34
2.4.2 能量色散X光光譜儀 (Energy Dispersive X-Ray Spectroscopy, EDS) 36
2.4.3 X光繞射分析 (X-ray Diffraction, XRD) 37
2.4.4 X光光電子能譜儀 (X-Ray Photoelectron Spectroscopy, XPS) 與縱深分析 (Depth Analysis) 41
2.4.5拉曼光譜 (Raman Spectroscopy) 42
2.5電催化二氧化碳還原反應之分析與量測 44
2.5.1 實驗架設 44
2.5.2 線性掃描伏安法 (Linear Sweeping Voltammetry, LSV) 48
2.5.3電化學阻抗 (Electrochemical Impedance Spectroscopy, EIS) 及電阻電降補償 (iR-drop compensation) 48
2.5.4 計時電流法 (Chronoamperometry, CA) 50
2.6二氧化碳還原產物之鑑定與分析 51
2.6.1 氣相層析質譜儀 (Gas Chromatography – Mass Spectrometry, GC-MS) 51
2.6.2 核磁共振光譜儀 (Nuclear Magnetic Resonance, NMR) 54
2.7同步輻射光源與臨場分析 56
2.7.1 同步輻射光源 56
2.7.2 臨場同步X光繞射分析與架設 61
2.7.3 X光吸收光譜 (X-ray Absorption Spectroscopy, XAS) 62
2.7.4 X光吸收近邊緣結構光譜 (X-ray Absorption Near Edge Structure, XANES) 66
2.7.5 X光吸收延伸精細結構光譜 (Extend X-ray Absorption Fine Structure, EXAFS) 68
第三章 實驗結果與討論 71
3.1 鋅材料之鑑定 71
3.1.1 鋅箔之縱深X光光電子光譜分析 71
3.2 氧化鋅衍生物之材料鑑定與分析 74
3.2.1 氧化鋅衍生物之X光光電子能譜分析 74
3.2.2 掃描式電子顯微鏡分析 81
3.2.3 X光繞射分析 84
3.3 氧化鋅衍生物之電催化二氧化碳還原活性分析 87
3.3.1 線性掃描伏安法分析 88
3.3.2 二氧化碳還原產物法拉第效率分析 91
3.3.3 二氧化碳還原產物部分電流分析 93
3.4 氧化鋅衍生物之電化學臨場實驗分析 96
3.4.1 臨場X光繞射分析 97
3.4.2 臨場X光吸收光譜分析 99
3.5 鋅催化材料之二氧化碳還原機構探討 101
第四章 結論 105
參考資料 107

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