在過去數十年以來，由於醫療診斷的大量需求，許多團隊都致力於開發高性能葡萄糖感測器。在所有可製備葡萄糖感測器的材料中，銅氧化物(氧化銅/氧化亞銅)因具有低成本、容易合成、催化能力佳等優點而受到矚目。本研究透過控制循環電位掃描法的參數調整，成功製備出具有高表面積的花狀氧化銅(Cu/CuxO)奈米線陣列結構，此試片本身即為可導電的電極，無需將氧化銅奈米線移轉至玻璃碳電極。經由電子顯微鏡的觀測顯示花狀氧化銅(Cu/CuxO)奈米線之中心為純銅線、中間層為氧化亞銅(Cu2O)相，最外層則為花狀的氧化銅(CuO)相。這種花狀結構可大幅增加奈米線陣列結構的表面積，有利於葡萄糖在電極表面行電化學氧化反應。本研究使用循環電位掃描法所得到的花狀氧化銅(Cu/CuxO)奈米線陣列結構電極比用恆電壓法製備之Cu/Cu2O奈米線電極具備更佳之葡萄糖感測效能。藉由改變花狀氧化銅(Cu/CuxO)奈米線的長度可改變其葡萄糖偵測敏度，並在線長為0.88 μm時達到最高的敏度。此外，氧化銅(Cu/CuxO)奈米線的外層結構，則會隨著電解液氫氧化鈉濃度的提高而由花狀轉為片狀結構。本研究所製備的花狀氧化銅(Cu/CuxO)奈米線陣列結構電極具有高敏度(~ 1200 μA∙mM^(-1)∙cm^(-2))，大範圍線性區間(10 μM ~ 7 mM)，以及短反應時間(< 1 sec)等優點。

The development of high-performance glucose sensors has attracted particular attention because of increasing needs in biological sensing and medical diagnostics over the past decades. Due to the advantages of low cost and outstanding catalytic ability, copper oxide modified electrodes are extensively investigated for non-enzymatic glucose sensing applications. We have successfully fabricated a self-supporting flower-like Cu/CuxO nanowire array electrode by a potential cycling method. The flower-like Cu/CuxO structure was identified to be a pure Cu core wrapped with a layer of Cu2O and decorated by petal-like CuO in the outermost layer according to transmission electron microscopy (TEM) analysis. The nanoflower-like structure provides a large electrochemically active surface area for glucose sensing reaction. The sensing performance of the flower-like Cu/CuxO nanowires obtained by the potential cycling method is superior to that of the Cu/Cu2O nanowires obtained by the potential static method. The glucose sensing properties of flower-like Cu/CuxO nanowire array electrode can be modulated by changing the nanowire length and reaches a maximum value at 0.88 μm. Moreover, the flower-like oxide will turn into plate-like nanostructure with the increase of NaOH concentration in electrolyte. The modified flower-like Cu/CuxO nanowire array electrode shows a high glucose sensing sensitivity (up to ~ 1200 μA∙mM^(-1)∙cm^(-2)), wide linear range (10 μM ~ 7 mM) and fast response time (< 1 sec).

摘要 I
Abstract II
誌謝 III
Contents V
List of Figures VIII
List of Tables XIII
Chapter 1 Introduction 1
1.1 Introduction 1
1.2 Thesis guide 2
Chapter 2 Literature Review 1
2.1 Anodic aluminum oxide (AAO) template 1
2.1.1 Formation mechanism of AAO template 1
2.1.2 Two-step anodization process of AAO template 3
2.1.3 AAO template assisted nanowires preparation 4
2.2 Glucose Sensor 5
2.2.1 Development of glucose sensor 5
2.2.2 Metal oxide-based electrode for non-enzymatic glucose sensor 8
2.3 Copper oxide-based electrode for non-enzymatic glucose sensor 9
2.3.1 Glucose detection mechanism of copper oxide modified electrode 9
2.3.2 Fabrication and characterization of copper oxide-based glucose sensors 11
Chapter 3 Experimental Procedure 14
3.1 Experimental process flow 14
3.2 Experimental reagents and apparatuses 15
3.2.1 Chemicals and reagents 15
3.2.2 Experimental apparatuses 16
3.3 Fabrication of AAO template 17
3.4 Electrodeposition of Cu nanowires 18
3.5 Preparation of Cu/Cu2O and Cu/CuxO nanowire array electrode 18
3.5.1 Preparation of Cu/Cu2O nanowire array electrode using a potential static method 18
3.5.2 Preparation of flower-like Cu/CuxO nanowire array electrode using a potential cycling method 19
3.6 Microstructure characteristic and glucose sensing performance test of copper/copper oxide nanowire array electrodes 19
3.6.1 X-ray diffractometry (XRD) analysis 19
3.6.2 Cold field-emission scanning electron microscope (CFE-SEM) analysis 21
3.6.3 Transmission electron microscope (TEM) analysis 21
3.6.4 Cyclic voltammetry (CV) 22
3.6.5 Amperometric response 24
Chapter 4 Results and Discussion 26
4.1 Fabrication and characterization of Cu/CuxO nanowire array 26
4.1.1 Microstructure of Cu/CuxO nanowires 26
4.1.2 Growth mechanism of flower-like Cu/CuxO NWs 30
4.2 Effect of electrochemical parameters on microstructure of Cu/CuxO NW array 37
4.2.1 Scan rate of potential cycling treatment 37
4.2.2 NaOH concentration in electrolyte 42
4.2.3 Cu NWs length 46
4.3 Glucose sensing performance of Cu/CuxO NW array electrode 49
4.3.1 Cu/Cu2O and flower-like Cu/CuxO NW array electrodes 49
4.3.2 Cu/CuxO NW array electrodes prepared with different potential scan rates 53
4.3.3 Cu/CuxO NW array electrodes prepared with different NaOH concentrations 54
4.3.4 Cu/CuxO NW array electrodes prepared with different NW lengths 56
Chapter 5 Conclusion 58
Reference 59

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