臺灣博碩士論文加值系統

我們已經製備還原石墨烯氧化物和鉬酸銀修飾電極及其應用於電化學感測器、生物感測器和光催化反應。例如，在第一部分我們使用石墨烯(graphene)和β-環糊精(β-CD)的奈米複合材料來修飾玻璃碳電極(GCE)以固定血紅蛋白(Hb)的模型。以掃描式電子顯微鏡(SEM)、紫外光-可見光吸收光譜(UV-vis)和傅里葉轉換紅外光譜(FTIR)偵測複合材料的特徵。修飾電極顯示對血紅蛋白具有增強和明確的可逆峰在形式電位為-0.284 V (vs. Ag/AgCl)的位置。和未與石墨烯或β-CD修飾的電極相比， Hb的直接電化學反應在此修飾電極大大的增強了電化學訊號。非均相電子轉移速率常數(Ks)為3.18 ± 0.7 s‾¹，表示電子轉移快速。在-0.33V的工作電位之下，溴酸鹽(bromate)的濃度在0.1到177 μM 範圍內電流反應為線性關係，結果表示生物感測器對溴酸鹽的還原有極好的電催化活性，靈敏度為3.39 µA µM‾¹ cm‾²，偵測極限(LOD)為33 nM。此生物感測器具有快速、良好的選擇性、重複性和再現性，因此可以在水溶液樣品中檢測溴酸鹽。第二部分研究以還原石墨烯氧化物(RGO)和聚多巴胺(PDA)複合修飾玻璃碳電極(GCE)檢測氯丙嗪(CPZ)。RGO@PDA複合材料是由電化學還原的氧化石墨烯(GO)和PDA複合材料製成。所製備的複合材料利用SEM、拉曼和FTIR偵測材料特徵。RGO@PDA複合修飾電極表現出對CPZ優異的電催化氧化行為，與其他修飾電極相比，如GO、RGO和GO@PDA。以安培i-t法測定CPZ，顯示RGO@PDA複合材料能在0.03到967.6 µM的線性範圍內檢測CPZ。此感測器在分析靈敏度為3.74 µA µM–1 cm–2下，具有最低的偵測極限。RGO@PDA複合材料顯示在其他潛在干擾藥物如甲硝唑、苯巴比妥、馬來酸氯苯那敏、吡哆醇和核黃素等存在下，具有高選擇性。所製備的感測器也顯示對藥物片劑中的CPZ適當的回收率。在最後一部分我們研究所合成的鉬酸銀(Ag2MoO4)修飾電極的光催化反應。微觀結構像馬鈴薯般的Ag2MoO4在經由尿素的幫助下利用簡單水熱法合成。由各種不同的分析方法和光譜技術分析Ag2MoO4的特性，例如X射線繞射儀(XRD)、FTIR、拉曼、SEM、X射線能量散佈分析儀(EDX)和X射線光電子光譜(XPS)。此次所製備的Ag2MoO4做為降解環丙沙星(CIP)的光催化劑，且首次用於檢測過氧化氫(H2O2)的電化學感測器。比較特別的是UV-vis光譜的結果顯示Ag2MoO4具有優異的可重複使用光催化活性，在UV光照射下降解CIP，40分鐘後擁有98%以上的大降解率。此外，循環伏安法(CV)和安培法的結果顯示，以Ag2MoO4修飾玻璃碳電極(GCE)檢測H2O2具有良好的線性範圍和偵測極限，分別為0.04到 240 µM和0.03 µM，表示具有良好的電催化性能，並顯示出在兒茶酚、果糖、乳糖、蔗糖、葡萄糖、鄰苯二酚、抗壞血酸、尿酸、多巴胺和腎上腺素等生物干擾物存在下，對H2O2選擇性高。因此，Ag2MoO4用於汙水處理和在真實樣品中電化學檢測H2O2有實際的實用性。

We have fabricated different composite modified electrdoes for application to electrochemical sensors, biosensors and photocatalysis. For instance, in the fisrt part we describe the use of a nanocomposite consisting of graphene and β-cyclodextrin (β-CD) which was used to modify a glassy carbon electrode (GCE) to serve as a matrix for immobilization of hemoglobin (Hb). The composite was characterized by scanning electron microscopy (SEM), Ultraviolet-visible spectroscopy (UV-vis) and Fourier-transform infrared (FTIR) spectroscopy. The modified electrode displays an enhanced and well-defined reversible peaks for the heme protein at a formal potential of -0.284 V (vs. Ag/AgCl). The direct electrochemistry of Hb is strongly enhanced at this modified electrode compared to electrodes not modified with graphene or β-CD. The heterogeneous electron transfer rate constant (Ks) is 3.18 ± 0.7 s‾¹ which indicates fast electron transfer. The biosensor exhibits excellent electrocatalytic activity towards the reduction of bromate, with a linear amperometric response in the 0.1 to 177 μM concentration range at a working voltage of -0.33 V. The sensitivity is 3.39 µA µM‾¹ cm‾², and the detection limit (LOD) is 33 nM. The biosensor is fast, selective, well repeatable and reproducible, and therefore represents a viable platform for sensing bromate in aqueous samples. The part II deals with the fabrication of novel and sensitive amperometric sensor for chlorpromazine (CPZ) based on the reduced graphene oxide (RGO) and polydopamine (PDA) composite modified glassy carbon electrode (GCE). The RGO@PDA composite was prepared by the electrochemical reduction of graphene oxide (GO) and PDA composite. The resulting composite was further characterized by SEM, Raman and FTIR spectroscopy. The RGO@PDA composite modified electrode shows an excellent electro-oxidation behaviour to CPZ when compared with other modified electrodes such as GO, RGO and GO@PDA. An amperometric i-t method was used for the determination of CPZ and shows that the RGO@PDA composite could detect the CPZ in the linear ranging from 0.03 to 967.6 µM. The sensor exhibits a low LOD of 0.0018 µM with the analytical sensitivity of 3.74 µA µM–1 cm–2. The RGO@PDA composite shows its high selectivity in the presence of other potentially interfering drugs such as metronidazole, phenobarbital, chlorpheniramine maleate, pyridoxine and riboflavin. The fabricated sensor has also showed an appropriate recovery towards CPZ in the pharmaceutical tablets. In the final part (Part III) we have investigated the phtocatalytic activity of as-synthesized silver molybdate (Ag2MoO4) modified electrode. The potato-like Ag2MoO4 microstructure was synthesized through simple hydrothermal treatment with the assistance of urea. The successful formation of Ag2MoO4 was confirmed by various analytical and spectroscopic techniques such as X-ray diffraction, FTIR, Raman, SEM, Energy dispersive x-ray and X-ray photoelectron spectroscopies. Furthermore, the as-prepared Ag2MoO4 was used as a photocatalyst for the degradation of ciprofloxacin (CIP) as well as an electrochemical sensor for the detection of H2O2, for the first time. The obtained UV-vis spectroscopy results demonstrate that, Ag2MoO4 had excellent reusable photocatalytic activity for the degradation CIP under Ultraviolet-light illumination possess great degradation rate of above 98% after 40 min. Moreover, the cyclic voltammetry and amperometry results revealed that Ag2MoO4 modified GCE showed good electrocatalytic performance for the detection of H2O2 with good linear range and LOD are 0.04 to 240 µM, and 0.03 µM, respectively. It also exhibit high selectivity of H2O2 in the presence of range of biological interferences such as catechol, fructose, lactose, sucrose, glucose, hydroquinone, ascorbic acid, uric acid, dopamine, and epinephrine. Hence, the potato-like Ag2MoO4 microstructure has great practical applicability for use as wastewater treatment and electrochemical detection of H2O2 in real samples.

摘要 i
Abstract iii
目錄 v
表目錄 x
圖目錄 xi
第一章 緒論 1
1.1 電化學分析方法 1
1.2感測器簡介 2
1.2.1感測器的定義 2
1.2.2生物感測器 4
1.2.3化學感測器 5
1.3 修飾電極簡介 7
1.3.1修飾電極的製備 7
1.3.2修飾電極的應用 8
1.4 藥品簡介 9
1.4.1 石墨烯（Graphene） 9
1.4.2 β-環糊精(β-Cyclodextrin) 10
1.4.3 血紅蛋白(Hemoglobin) 11
1.4.4 溴酸鹽(Bromate) 12
1.4.5還原石墨烯氧化物(Reduced Graphene Oxide, RGO) 12
1.4.6聚多巴胺(Polydopamine, PDA) 13
1.4.7氯丙嗪(Chlorpromazine, CPZ) 14
1.4.8鉬酸銀(silver molybdate) 15
1.4.9環丙沙星(ciprofloxacin, CIP) 15
1.4.10過氧化氫(Hydrogen peroxide) 16
第二章 實驗藥品、器材與分析方法 17
2.1 實驗藥品 17
2.2 實驗器材 18
2.3 分析方法 20
2.3.1 循環伏安法(Cyclic Voltammetry, CV) 20
2.3.1.1原理簡介 20
2.3.1.2實驗方法 22
2.3.1.3實驗裝置 22
2.3.2 安培法(Amperometric i-t cuve) 23
2.3.3 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) 26
2.3.4 傅里葉轉換紅外光譜儀(Fourier Transform Infrared Spectroscopy, FTIR) 27
2.3.5 拉曼光譜(Ramam spectroscopy) 28
2.3.5.1原理簡介 28
2.3.5.2拉曼光譜的應用 30
2.3.5.3實驗裝置 30
2.3.6 紫外光-可見光光譜儀(UV-Visible spectroscopy) 30
2.3.7 X-射線繞射分析儀(XRD) 32
2.3.8 X射線光電子光譜(X-ray photoelectron spectroscopy, XPS) 33
2.3.8.1原理簡介 33
2.3.8.2 XPS的應用 34
2.3.8.3實驗裝置 34
2.3.9能量散佈光譜儀 (Energy Dispersive Spectroscopy, EDS) 34
2.3.10電化學阻抗光譜(Electrochemical Impedance Spectroscopy, EIS) 35
第三章 38
直接電化學固定血紅蛋白在含有石墨烯和β-環糊精的修飾玻璃碳電極對溴酸鹽感測研究 38
3.1 前言 38
3.2 製備graphene/β-CD複合材料和固定Hb 39
3.3 結果與討論 40
3.3.1 材料的選擇 40
3.3.2 材料特徵 40
3.3.3 直接電化學血紅蛋白 44
3.3.4 安培法檢測溴酸鹽 47
3.3.5 graphene/β-CD/Hb修飾電極的選擇性與穩定性 51
3.3.6 graphene/β-CD/Hb修飾電極的實用性、重複性與再現性 54
3.4 結論 55
第四章 56
簡易的電化學製備還原石墨烯氧化物@聚多巴胺複合材料；新型安培法檢測氯丙嗪 56
4.1 前言 56
4.2 合成RGO@PDA複合材料 57
4.3 結果與討論 58
4.3.1材料特徵 58
4.3.2 CPZ的電化學行為 61
4.3.3安培法檢測CPZ 66
4.3.4 感測器的選擇性和實用性 67
4.3.5在藥物片劑中檢測CPZ 69
4.3.6感測器的穩定性、精確度和準確度 69
4.4 結論 70
第五章 71
鉬酸銀光催化降解環丙沙星和電化學安培法檢測過氧化氫 71
5.1 前言 71
5.2 製備鉬酸銀修飾電極 72
5.3 結果與討論 73
5.3.1 Ag2MoO4的材料特徵 73
5.3.2 光催化作用 77
5.3.2.1穩定性和再現性 79
5.3.3 過氧化氫在Ag2MoO4修飾電極的電化學性能 79
5.3.3.1以Ag2MoO4修飾電極安培法測定H2O2 82
5.3.3.2選擇性和穩定性研究 83
5.4 結論 85
參考文獻 86

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