- 學位論文
奈米複合材料結合導電高分子修飾薄膜及其電化學性質分析
Nanocomposited Material with Conducting Polymer Modified Electrode and its Electrochemical Analysis
摘要
本研究主要分為二部分來討論，第一部分主要研究在以循環伏安法製備金屬錳赤血鹽（MnHCF）與聚3,4-二氧乙基噻吩（PEDOT）複合在一起成為複合薄膜電極。由前文所敘，我們將此修飾電極稱之為MnHCF- PEDOT複合電極薄膜。對MnHCF- PEDOT薄膜的玻璃碳修飾電極以原子力顯微鏡（AFM），掃描式電子顯微鏡(FE-SEM )，能量色散型X射線熒光分析裝置（EDS)，X射線繞射儀 (XRD )和電化學阻抗頻譜圖(EIS)等進行檢測及特性分析。而我們採用循環伏安法和計時安培法檢測兒茶酚和褪黑激素來用來佐證這些薄膜的優勢。我們探討了在pH值為1.5的0.1 M KCl 溶液中，於不同修飾電極，如裸電極、 MnHCF / GCE、MnHCF - PEDOT / GCE等其電極表面對兒茶酚與褪黑激素的電催化反應。在電化學感測器中兒茶酚和褪黑激素呈線性反應，兒茶酚濃度範圍是0.1~4.4 mM，R2為0.9965，褪黑激素濃度範圍是0.1~4.6 mM，R2為0.9998，最低檢測範圍為0.01 mM和最快反應時間為3 s。此外， MnHCF - PEDOT / GCE表現出明顯的優勢，如製備過程簡單，獨特性高，穩定性和重複性也很穩定。 第二部分 本研究多功能生物感測器是將2 -氨基噻唑（AT）薄膜電聚合修飾在玻璃碳電極（GCE）上之後再滴上Graphene溶液製備而成。同時透過電子顯微鏡和原子力顯微鏡檢視Graphene，聚-AT和Graphene-AT薄膜修飾電極的表面形貌。此修飾薄膜可做為同時利用計時安培法偵測過氧化氫 (還原端) 及利用脈衝伏安法偵測多巴胺及尿酸 (氧化端) 。Graphene-AT/GCE作為多功能生物感測器對於H2O2的偵測具有較大的線性範圍線性範圍(1*10-5到3.1*10-4 M，R2=0.9973)，最低檢測範圍(10-6 M)，高靈敏度(550.4mA mM-1 cm-2)，相對標準偏差(RSD%)小於2%(n=5) 。並且，此多功能的生物感測器能在AA的干擾下同時測定 DA和UA。對於DA和UA線性範圍分別為(5*10-6到2.5*10-5M，R2=0.994以及2.5*10-6到1.25-10-4M，Ｒ2=0.9955)。此外，此Graphene- AT薄膜修飾電極作用於多功能性生物感測器上有著其製備簡單、特殊性、穩定性和選擇性等優點。
並列摘要
Part Ⅰ： The manganese hexacyanoferrate (MnHCF) with poly(3,4-Ethylene dioxythiophene) (PEDOT) hybrid film (MnHCF-PEDOT) was prepared on glassy carbon electrode by multiple scan cyclic voltammetry. These materials are characterized using atomic force microscopy (AFM), field emission scanning electron microscope (FE-SEM), energy dispersive spectroscopy (EDS),X-ray diffraction studies (XRD) and electrochemical impedance spectroscope (EIS) techniques. The advantages of these films are demonstrated for detection of catechin and melatonin using cyclic voltammetry and amperometric. The electrocatalytic oxidation of catechin and melatonin at different electrode surfaces such as the bare GCE, MnHCF/GCE and MnHCF-PEDOT/GCE modified electrodes was explored in 0.1 M KCl solution at pH 1.5.The electrochemical sensor for catechin and melatonin exhibited a wide linear response range (0.1 to 4.4 M, R2 = 0.9965 for catechin and 0.1 to 4.6 mM, R2 = 0.9998 for melatonin), lower detection limit (0.01 mM) and fast response time (3 s).In addition, the MnHCF-PEDOT/GCE exhibited a distinct advantage of simple preparation, specificity, stability and reproducibility. Part Ⅱ： A novel multifunctional biosensor was prepared by graphene dropped on electro-polymerization 2-Amino-thiazol (AT) film on glassy carbon electrode (GCE). The surface morphology of graphene, AT and graphene-AT film modified GCE has been examined by using SEM and AFM. The advantages of proposed film were demonstrated for the determination of H2O2 (reduction side) using amperometric, DA and UA (oxidation side) using differential pulse voltammetry. The graphene-AT/GCE as a multifunctional biosensor exhibited a wide linear response range for H2O2 determine (from 10-5 to 3.1*10-4 M,R2=0.9973)lowest detection limit (10-6 M), high sensitivity (550.4 mA mM-1 cm-2) and the relative standard deviation (RSD %) less than 2% (n=5). Similarly, the multifunctional biosensor can simultaneously determine the DA and UA with the interference of AA. For the linear response range of DA and UA were,5*10-6to 2.5*10-5M, (R2=0.994) and , 2.5*10-6 to 1.25*10-4 M,(R2= 0.9955). In addition, the multifunctional biosensor of graphene-AT film modified GCE was advantageous in terms of its simple preparation, specificity, stability and selectivity.