- 學位論文
染料聚合物與多層奈米碳管結合之複合薄膜修飾電極的製備及其對生化物質電催化性質之研究
Preparation of Dye Polymers - Multiwalled Carbon Nanotubes Composite Film Modified Electrodes and their Electrocatalytic Properties with Biomolecules
摘要
本研究第一部份實驗的傳導複合型薄膜，是用多層奈米碳管與新豔紅結合所形成的複合薄膜，並以定電位的方法將其修飾在玻璃碳電極(GCE)、黃金電極(Au)、ITO導電玻璃上。由於多層奈米碳管存在於複合薄膜當中的關係，提高了表面覆蓋濃度(Γ)、增加了電荷轉移速率常數(Ks)並且減少了新豔紅在多迴圈長膜中的損失。另外由實驗結果也顯示出此複合薄膜對腺嘌呤(AD)、鳥嘌呤(GU)、胸腺嘧啶(TY)這些生化物質的混合物有增加電催化活性的發展性。而複合薄膜與高分子聚合物的表面型態，是將其製備在透明的ITO導電玻璃上，再利用掃描式電子顯微鏡以及原子力電子顯微鏡來進行觀察。由這兩種儀器觀測可以觀察到新豔紅結合在多層奈米碳管上。對於複合薄膜的電催化訊號的分析，是利用循環伏安法(CV)以及微分脈衝伏安法(DPV)來進行測量。從複合薄膜修飾玻璃碳電極的電催化研究中可以看到腺嘌呤、鳥嘌呤和胸腺嘧啶三個分別獨立不重疊的電催化訊號波峰。從研究中可以觀察出，多層奈米碳管-新豔紅修飾電極比起僅有新豔紅薄膜修飾電極有更高的靈敏度。而從電化學石英晶體微天平的研究中顯示出多層奈米碳管與新豔紅很好的電化學沉積過程。 第二部的傳導複合型薄膜(MWCNTs-NF-CR)是用多層奈米碳管結合Nafion與剛果紅(CR)所形成的複合修飾薄膜，並以定電位的方法將其修飾在玻璃碳電極(GCE)、黃金電極(Au)、ITO導電玻璃上。由於多層奈米碳管與Nafion存在於複合薄膜當中的關係，提高了表面覆蓋濃度(Γ)、增加了電荷轉移速率常數(Ks)並且減少了剛果紅在多次迴圈電沉積中的損失。另外由實驗結果也顯示出此複合修飾薄膜在5’-腺核甘單磷酸鹽(AMP)和5’-鳥嘌呤核甘單磷酸鹽(GMP)兩者混和的狀態下有加增電催化活性良好的發展趨勢。針對剛果紅以及複合薄膜的表面型態，是將其製備在透明的ITO導電玻璃上，再利用掃描式電子顯微鏡以及原子力電子顯微鏡來進行觀察。由這兩種顯微鏡的技術可以觀察到Nafion、剛果紅與多層奈米碳管緊密的結合在一起。並且利用循環伏安法(CV)以及微分脈衝伏安法(DPV)對複合修飾薄膜進行電催化反應的分析與測量。在電催化的研究當中，利用此複合修飾薄膜同步對兩個分析物進行反應，可以獲得AMP和 GMP兩者區隔開來的明顯獨立訊號。此外多層奈米碳管-Nafion-剛果紅複合薄膜修飾電極比起Nafion-剛果紅薄膜修飾電極有更好的靈敏度。 第三部份為，由釕紅 (RR)結合多層奈米碳管所組成的新沈積薄膜，成功利用電化學的方法製備於玻璃碳，黃金及銦錫氧化ITO電極上。因為多層奈米碳存在的關係，增加了生物沉積薄膜的表面覆蓋濃度（Γ），並使電子轉移常數（Ks）提高，除此之外還可以減緩釕紅的降解。而在電催化效果上，對於酪胺酸（L-tyrosine，TYR）、半胱胺酸（L-cysteine，CYS）等生化分子的氧化反應都具有相當大的增強效果。而生物沉積薄膜修飾於透明的ITO電極上則可以在掃描式電子顯微鏡（SEM）和原子力顯微鏡（AFM）觀察到薄膜的表面型態，並展現出釕紅與多層奈米碳管的結合。另外並利用循環伏安法(CV)、旋轉碟電極(RDE)、計時安培法(i-t curve)對複合修飾薄膜進行電催化反應的分析與測量。藉由電催化反應研究的比較，多層奈米碳管- 釕紅複合薄膜修飾電極比起釕紅薄膜修飾電極有更好的靈敏度。
並列摘要
Part Ⅰ：A conductive composite film (MWCNTs-NF) which contains multi-walled carbon nanotubes (MWCNTs) along with the incorporation of poly(new fuchsin) (NF) has been synthesized on glassy carbon electrode (GCE), gold (Au) and indium tin oxide (ITO) by potentiostatic methods. The presence of MWCNTs in the composite film enhances the surface coverage concentration (Γ), increases the electron transfer rate constant (Ks) and decreases the degradation of NF during the cycling. The composite film also exhibits a promising enhanced electrocatalytic activity towards the mixture of biochemical compounds such as adenine (AD), guanine (GU) and thymine (TY). The surface morphology of the polymer and composite film deposited on transparent semiconductor tin oxide electrodes were studied using scanning electron microscopy and atomic force microscopy. These two techniques showed that the NF incorporated on MWCNTs. The electrocatalytic responses of analytes at composite films were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). From electrocatalysis studies, well separated voltammetric peaks were obtained at the composite film modified GC for AD, GU and TY. The sensitivity values of MWCNTs-NF modified GCE are higher than the values which are obtained for NF film modified GCE.Electrochemical quartz crystal microbalance studies revealed the enhancements in the functional properties of MWCNTs and NF. PartⅡ：A conductive composite film (MWCNTs-NF-CR) which contains multi-walled carbon nanotubes (MWCNTs) along with the incorporation of nafion and poly(congo red) (CR) has been synthesized on glassy carbon electrode (GCE), gold (Au) and indium tin oxide (ITO) by potentiostatic methods. The presence of MWCNTs and NF in the composite film enhances the surface coverage concentration (Γ), increases the electron transfer rate constant (Ks) and decreases the degradation of CR during the cycling. The composite film also exhibits a promising enhanced electrocatalytic activity towards the mixture of biochemical compounds such as adenosin-5'-monophosphate (AMP) and guanosine-5'-monophosphate (GMP). The surface morphology of the polymer and composite film deposited on transparent semiconductor tin oxide electrodes were studied using scanning electron microscopy and atomic force microscopy. These two techniques showed that the nafion and CR incorporated on MWCNTs. The electrocatalytic responses of analytes at composite films were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). From electrocatalysis studies, well separated voltammetric peaks were obtained at the composite film modified GC for AMP and GMP. The sensitivity values of MWCNTs-nafion-CR modified GCE are higher than the values which are obtained for nafion -CR film modified GCE. Electrochemical quartz crystal microbalance studies revealed the enhancements in the functional properties of MWCNTs, nafion and CR. Part Ⅲ：A composite film (MWCNTs-RR) which contains multi-walled carbon nanotubes (MWCNTs) along with the immobilization of ruthenium red (RR) has been synthesized on glassy carbon electrode (GCE), gold (Au) and indium tin oxide (ITO) by potentiostatic methods. The presence of MWCNTs in the composite film enhances the surface coverage concentration (Γ), increases the electron transfer rate constant (Ks) and decreases the degradation of RR during the cycling. The composite film also exhibits a promising enhanced electrocatalytic activity towards the mixture of biochemical compounds such as tyrosine (TYR) and cysteine (CYS). The surface morphology of the RR and composite film deposited on transparent semiconductor tin oxide electrodes were studied using scanning electron microscopy and atomic force microscopy. These two techniques showed that the RR incorporated on MWCNTs. The electrocatalytic responses of analytes at composite films were measured using cyclic voltammetry (CV), hydrodynamic experiments (RDE) and amperometric experiments (i-t curve). From electrocatalysis studies, it is obvious that, the sensitivity values of MWCNTs-RR modified GCE are higher than the values which are obtained for RR film modified GCE.