臺灣博碩士論文加值系統

近幾年來，由於二氧化碳排放量的迅速增加，其還原反應受到許多科學家的重視，其中又以能產生碳氫化合物產物的銅金屬備受關注。然而，銅金屬的二氧化碳還原反應機制卻只有推測以及理論計算，並未被證明及詳細闡述。在這個研究中，臨場拉曼量測技術將運用於分析銅金屬表面上的二氧化碳還原反應機制。
拉曼光譜為良好鑑定鍵結的技術，與紅外光譜相比之下，並不會受到水的訊號干擾，十分適合進行臨場電化學量測。然而，當二氧化碳還原反應發生時，將會伴隨氣體產物的產生而干擾拉曼的訊號，為了解決這樣的問題，本實驗設計了一個可以配合拉曼直立式鏡頭及精密電極的反應槽。此拉曼裝置的巧思在於，為了避免產物氣泡的吸附而使用了長焦距鏡頭與水鏡交互搭配，另外還選用面積極小的電極來減少氣泡的生成。除了解決氣相產物對拉曼訊號的干擾外，提高拉曼散射訊號也是本研究的目標，因此本研究合成具有表面增強拉曼效應的銀金屬奈米立方為材料基板，在其表面上成功添加欲觀察的銅金屬薄層，藉此提高銅金屬與二氧化碳鍵結訊號的強度。最後藉由比對獲取的拉曼圖譜以及資料庫，可以鑑定出二氧化碳與催化劑表面反應產生的鍵結。除此之外，這些分析數據也吻合氣相層析–質譜法聯用量測的產物結果。
綜合上述實驗的資訊，本研究將能夠建立一個擁有臨場數據佐證的二氧化碳還原機制。

In recent years, CO2 reduction has been a growing priority for scientists due to the high level of emission. In this field, copper metal catalysts attract much attention because of the hydrocarbon products. However, the mechanism of CO2 reduction using copper metal has not been well-verified. In this work, in situ Raman spectroscopy measurement is applied to study the mechanism of CO2 reduction on copper.
Raman spectroscopy is widely used to identify the bonding states and also less influenced by water molecules than infrared spectroscopy. Thus, it is an effective technique to measure the spectrum of the reactions that happen in a solution. However, when CO2 reduction occurs, gases which interfere with the Raman signals are released as products. Therefore, we designed a new Raman cell coordinated with upright lenses and exquisite electrodes in order to solve this problem. In particular, lense with long focal length was chosen to prevent bubbles from attaching. Three in one electrodes with small surface area were also used to reduce bubble yield. In addition, we also aim to enhance the signal of Raman scattering. Therefore, we synthesized and used the SERS material, silver cubes, as the base of our catalysts, and add the sample copper that we want to investigate on it in order to enhance the signals from the intermediate states of CO2 reduction on copper. Finally, by comparing the obtained Raman spectrum with available data base, we can identify the intermediate bonding state of the CO2 reduction. Furthermore, these analyses can be used to predict the results of gas chromatography–mass spectrometry.
In conclusion, a well‐defined mechanism of CO2 reduction can be established by combining all the informations obtained from the experiments.

目錄
目錄 i
圖目錄 vi
表目錄 xiii
第一章 緒論 1
1.1 奈米材料 1
1.1.1 表面效應 2
1.1.2 電子侷限性 3
1.1.3 奈米材料催化 3
1.1.4 奈米材料合成 4
1.2 雙金屬奈米材料 5
1.2.1 核–殼結構之雙金屬奈米材料合成 6
1.2.2 核–殼結構之雙金屬奈米材料應用 7
1.3 二氧化碳還原反應 8
1.3.1 反應機制 10
1.4 光學檢測方法 13
1.4.1 傅立葉轉換紅外光譜 (Fourier Transform Infrared Spectroscopy, FTIR) 14
1.4.2 拉曼光譜 (Raman spectroscopy) 16
1.4.2.1 表面增強拉曼散射 (Surface-Enhanced Raman Scattering，SERS) 18
1.4.2.2 電磁場增益 (electromagnetic enhancement) 20
1.4.2.3 共振拉曼 (Resonance Raman Scattering，RRS) 20
第二章實驗步驟及實驗分析原理 21
2.1 本研究實驗流程 21
2.2 化學藥品 22
2.3 實驗儀器 23
2.4 銅 – 銀殼核雙金屬奈米材料 24
2.4.1 奈米銀立方 24
2.4.1.1 合成方法 24
2.4.1.2 純化方法 24
2.4.2 奈米銅立方 25
2.4.2.1 合成方法 25
2.4.2.2 純化方法 25
2.4.3 銅 – 銀殼核雙金屬奈米材料 25
2.4.3.1 合成方法 25
2.4.3.2 純化方法 26
2.5 樣品鑑定與分析 27
2.5.1 紫外–可見光吸收光譜 27
2.5.2 電子顯微鏡 30
2.5.2.1 穿透式電子顯微鏡 (Transmission Electron Microscope, TEM) 30
2.5.2.2 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 32
2.5.2.3 能量色散X–射線光譜 (Energy–dispersive X–ray spectroscopy, EDS) 33
2.5.3 同步輻射 34
2.5.3.1　X光吸收光譜 35
2.6 電化學分析 37
2.6.1 線性掃描伏安法 (Linear Sweeping Voltammetry, LSV) 39
2.6.2 定電位測定法 (constant potential amperometry, CA) 40
2.7 產物鑑定 40
2.7.1 氣相層析法–質譜聯用(Gas chromatography–mass spectrometry ,GC-Mass) 41
2.7.2 核磁共振光譜 (Nuclear Magnetic Resonance Spectroscopy ,NMR) 43
2.8 臨場量測 (In situ) 45
2.8.1 拉曼光譜 (Raman spectroscopy) 68 46
第三章 結果與討論 49
3.1 銅 – 銀殼核雙金屬奈米材料製備 49
3.1.1 奈米銀/銅立方電子顯微鏡分析 49
3.1.2 銅 – 銀殼核雙金屬奈米材料 53
3.1.2.1 電子顯微鏡分析 53
3.1.2.2 能量色散X 射線光譜分析 56
3.1.2.3　X光吸收光譜分析 58
3.1.3 紫外–可見吸收光譜 59
3.2 電化學分析 61
3.3 二氧化碳電催化產物及拉曼圖譜比對分析 63
3.3.1 二氧化碳電催化產物分析 63
3.3.2 臨場拉曼量測分析 65
3.3.3 單金屬奈米立方 66
3.3.3.1 銀奈米立方二氧化碳電催產物分析 66
3.3.3.2 銀奈米立方拉曼圖譜分析 68
3.3.3.3 銅奈米立方二氧化碳電催產物分析 82
3.3.3.4 銅奈米立方拉曼圖譜分析 90
3.3.4 銅–銀殼核雙金屬奈米立方 96
3.3.4.1 薄銅–銀殼核雙金屬奈米立方電催產物分析 97
3.3.4.2 薄銅–銀殼核雙金屬奈米立方拉曼圖譜分析 100
3.3.4.3 厚銅–銀殼核雙金屬奈米立方電催產物分析 108
3.3.4.4 厚銅–銀殼核雙金屬奈米立方拉曼圖譜分析 112
3.3.5 拉曼圖譜統整 122
3.4 反應機制統整 123
第四章 結論 128
Reference 129

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