臺灣博碩士論文加值系統

本研究以奈米碳黑(Nano carbon black)結合碳量子點(Carbon quantum dot，CQD)並混參金屬有機骨架配位化合物(Metal-organic frameworks，MOFs)修飾玻璃碳電極(Glassy carbon electrode，GCE)，偵測咖啡酸，並探討此修飾電極的電化學特性。以X-射線繞射分析儀與傅立葉紅外線光譜儀鑑定金屬有機骨架配位化合物的合成，並以螢光光譜儀與穿透式電子顯微鏡鑑定碳量子點的合成，以掃描式電子顯微鏡(Scanning electron microscope，SEM)與能量散射光譜儀(Energy dispersive spectrometer，EDS)對修飾電極進行表面特徵與元素組成進行分析，證實修飾材料可成功的製備奈米碳黑/碳量子點/金屬有機骨架配位化合物修飾電極。在實驗最佳化的條件下，由差式脈波伏安法(Differential pulse voltammetry，DPV)與電化學交流阻抗分析(Electrochemical impedance spectroscopy，EIS)，證實奈米碳黑/碳量子點/金屬有機骨架材料MIL-101(Cr) 有減少電傳阻抗與良好的電子傳遞特性。
奈米碳黑/碳量子點/金屬有機骨架配位化合物修飾電極於咖啡酸之檢量線(Calibration curve)範圍為0.1-20 μM，偵測極限 (Detection limit，S/N = 3)為20 nM。另外，修飾電極的重複性(Repeatability)以同日間 (Intra-day)與異日間(Inter-day)進行測量，其相對標準偏差(Relative standard deviation，RSD)分別小於6.93 %與1.15 %，證實此修飾電極具有良好的再現性。連續測量20次後電流保持率有94.52 %，在電極放置一週後的電流保持率仍有84.78 %，證實此修飾電極具有良好重複性與穩定性。
最後奈米碳黑/碳量子點/金屬有機骨架配位化合物修飾電極應用於偵測市售飲品中的咖啡酸，其回收率介於95.01 %至113.14 %之間。

In this study, using nano carbon black/carbon quantum dot (CQD)/metal-organic frameworks (MOFs) modified electrode detecting caffeic acid, and investigating the electrochemical properties of the modified electrode. The metal organic frameworks have been successfully scrutinized by using Fourier transform infrared spectroscopy (FT-IR) and powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and fluorescence spectrometer successful identify the CQD, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) confirmed that carbon black/carbon quantum dots/metal-organic frameworks modified electrode can be successfully prepared.
In these optimal conditions, differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) were used to confirm nano carbon black/carbon quantum dots/metal-organic frameworks modified electrode has excellent electron transfer characteristics, low electron transfer resistance and increase oxidation current signal characteristics.
After the optimization process, the electrochemical detection of CA in a wide concentration range, from 0.1 μM to 20 μM concentration range, with the limit of detection (S/N = 3) of 20 nM.
In addition, the repeatability of the CB/CQD/MOFs/GCE was measured in the intra-day and inter-day and the relative standard deviation (RSD) was less than 6.93 % and 1.15 %, respectively. Stability remained above 94.52 % after 20 scan by DPV, long-term stability remained above 84.78 %, which confirmed that the modified electrode has good repeatability and stability.
Finally, CB/CQD/MOFs/GCE applied in determination of caffeic acid in commercial beverages. The recovery was between 95.01 to 113.14 %, which shows the feasible detection of CA in real sample.

摘要 I
Abstract III
目錄 IV
圖目錄 VIII
表目錄 XI
一、緒論 1
1-1修飾電極介紹 1
1-1-1修飾電極的方式 2
1-2修飾電極的特性與應用 5
1-2-1電催化 5
1-2-2預濃縮 6
1-2-3薄膜阻隔 7
1-3 碳材簡介 9
1-3-1石墨烯 9
1-3-2奈米碳管 10
1-3-3 奈米碳黑 11
1-4金屬有機骨架配位化合物 (Metal-organic frameworks，MOFs) 14
1-5 碳量子點 (Carbon quantum dot，CQD) 17
1-6 分析物簡介 20
1-6-1咖啡酸 20
第二章、研究方法 21
2-1實驗基本架構 21
2-2實驗藥品 22
2-3實驗儀器與設備 23
2-4 實驗步驟 24
2-4-1 金屬有機骨架配位化合物之製備 24
2-4-2碳量子點之製備 24
2-4-3修飾劑之製備 25
2-4-3玻璃碳修飾電極之製備 25
2-5 儀器參數 26
2-5-1 循環伏安法 (Cyclic voltammetry) 26
2-5-3 差式脈波伏安法 (Differential pulse voltammetry，DPV) 26
2-6 材料鑑定 27
2-6-1 傅立葉紅外光譜儀 (Fourier transform infrared spectrometry, FT-IR) 27
2-6-2 粉末X-射線繞射分析儀 (Powder X-ray diffraction, PXRD) 28
2-6-3 螢光光譜儀 (Fluorescence spectrometer) 29
2-6-4 接觸角 (Contact angle) 29
2-6-5 穿透式電子顯微鏡 (Transmission electron microscope, TEM) 30
2-6-6 掃描式電子顯微鏡 (Scanning electron microscope, SEM) 31
2-6-7 能量散射光譜儀 (Energy dispersive spectrometer, EDS) 32
三、結果與討論 33
3-1 修飾電極及咖啡酸之電化學特性 33
3-2 修飾電極的最佳化探討 35
3-2-1 探討奈米碳黑比例之最佳化 35
3-2-2 探討碳量子點比例之最佳化 37
3-2-3 探討金屬有機骨架配位化合物的比例最佳化 39
3-2-4三維平面曲線圖探討修飾材料比例最佳化 41
3-2-5 探討修飾劑之最佳化劑量 43
3-2-6 探討緩衝溶液之最佳化pH值 44
3-3 材料鑑定 47
3-3-1 MIL-101(Cr)官能基之鑑定 47
3-3-2 MIL-101(Cr)晶格結構之鑑定 48
3-3-3 碳量子點螢光之鑑定 49
3-3-4 碳量子點尺寸之鑑定 51
3-3-5 MIL-101(Cr)與修飾電極表面型態之觀測 52
3-3-6 修飾電極表面元素之鑑定 54
3-3-7 接觸角 56
3-4 修飾電極之電化學特性探討 57
3-4-1 擴散與吸附之特性 57
3-4-2 電化學交流阻抗分析 62
3-4-3 探討修飾電極之活性面積 64
3-4-4 修飾電極之傳導係數及電子轉移速率 67
3-5 方法建立與確效 69
3-5-1 檢量線建立 69
3-5-2 干擾物 71
3-5-3 修飾電極的重複性與穩定性探討 77
3-5-4 真實樣品測試 80
第四章、結論 83
第六章、參考文獻 85

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