||Study on Hydrogen Peroxide Sensor Based on Prussian Blue Modified Graphene/ Indium-Tin Oxide Substrate
||Department of BioMedical Engineering
Hydrogen peroxide sensor
過氧化氫是一種基礎並常見之電活性物質，時常作為電化學檢測之目標物，其應用範圍包含工業上試劑之使用與汙染源監測、食品中必需檢驗項目與生物性代謝指標。目前有許多材料例如無機金屬粒子、奈米碳材或有機物之酵素與活性中心蛋白質等，均被引入過氧化氫檢測系統中作為特異性辨識元件，以期望降低過氧化氫反應之過電壓並增加催化性能。其中，普魯士藍物質被視為無機物中催化效果極佳的人工酵素，且適合應用於定電位量測系統。本研究使用普魯士藍粒子修飾單層石墨烯ITO電極，並嘗試建立此一透明且有效之過氧化氫量測平台，最終樣本達到線性範圍6.6 μM~2.8 mM，檢測極限為3.7 μM (S/N=3)。
Graphene is one of the most popular materials because of its unique structure and properties. There are many kinds of them and their analogue which was used in electrochemical sensing fields already for the purpose of the improvement of the conductivity and catalytic ability. It is an attempt to establish a sensing platform by using a defect-less, single layer and continues graphene fabricated by chemical vapor deposition with copper foil as a catalyst and is transferred on a transparent and conductive indium-tin-oxide coated glass. Hydrogen peroxide is a basal electroactive matter as a sensing target due to their widely application in industry and metabolism monitor. Numerous kinds of materials enter this field mentioned above independently or coordinately for electrochemical detection in order to lower the over-potential on interface of solid electrode such as organic and inorganic elements. The effective range is commonly thought to be from μM to mM, which is determined by the application. The Prussian blue material is called as an ‘artificial enzymes’ because of its excellent catalytic ability toward hydrogen peroxide. The reaction activity is thought to be merely slightly smaller than organic enzyme base one and is suitable for amperometric measurement.
In this study, we used the Prussian blue modified graphene based electrode to develop a transparent and effective sensing for hydrogen peroxide detection. This study has successfully developed a hydrogen peroxide sensor by simply modifying PB and reached the linear range from 6.6 μM to 2.8 mM and the limit of detection for 3.7 μM (S/N=3).
List of Figures vi
List of Tables ix
List of Abbreviations and Denotations x
Chapter 1 Introduction 1
1.1 Background and Motivation 1
1.2 Biosensors 2
1.2.1 Composition of Biosensor 3
1.2.2 Hydrogen Peroxide Sensor 4
1.3 Electrochemical Methods for Detection 6
1.3.1 Cyclic Voltammetry Method 7
1.3.2 Amperometric Method for Detection 8
1.4 Graphene Material 8
1.4.1 Graphene Related Materials Comparison 9
1.4.2 Graphene Application in Electrochemical Sensor 13
1.5 Prussian Blue Material 16
1.5.1 Prussian Blue Application in Electrochemical Sensor 17
1.5.2 Methods of Prussian Blue Deposition 20
1.5.3 Stabilization of Prussian Blue Modified Electrode 23
1.6 Research Framework 24
Chapter 2 Materials and Methods 25
2.1 Detergents and Instruments 25
2.1.1. Chemical Reagents 25
2.1.2 Instruments 26
2.1.3 Buffer and Solutions 26
2.2 Electrode Modification and Stabilization 27
2.2.1 Prussian Blue Structure Transformation 27
2.2.2 Nickel Ions Substitute 27
2.3 Three Electrode System 28
Chapter 3 Results and Discussion 30
3.1 Electrochemical Property of the Graphene Based Substrate 30
3.1.1 CV Characteristic for Graphene Based Electrode 30
3.1.2 Response toward Common Electroactive Small Molecular 32
3.1.3 Procedure of Prussian Blue Deposition 38
3.2 The Examination of Modified Electrode 40
3.2.1 CV Characteristic for Surface Modification 40
3.2.2 Variation among Electrodes for Deposition 41
3.2.3 Effect of Graphene in Deposition 42
3.2.4 Surface Examination 44
3.3 The Stability of the Modified Electrode 46
3.3.1 Cyclic Voltammetry Test for Stability 46
3.3.2 Cyclic Voltammetry Test 49
3.4 Hydrogen Peroxide Measurement 50
3.4.1 Selection of Operating Potential 50
3.4.2 Continuous Injection and Amperometric Measurement 52
3.5 Other Test of PB/Graphene/ITO Electrode 54
3.5.1 pH Effect on the Modified Electrode 54
3.5.2 Interference Test 55
3.5.3 Long Term Storage 56
Chapter 4 Conclusions and Future Prospective 58
Curriculum Vitae 66
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