奈米銀微粒、無機/有機複合薄膜與氧化鋅/銅薄膜修飾電極的電化學製備、特性及電催化特性的研究

Electrochemical preparation and characterizations of silver nanoparticles,inorganic/organic hybrid film and copper/zinc oxide film modified electrodes:Electrochemical and electrocatalytic properties

鄭惠文(Hui-Wen Cheng)

指導教授 ： 陳生明

國立臺北科技大學/工程學院/化學工程研究所/碩士(2008年)

摘要

本研究主要分為三部分來討論，第一部分是利用3-巰基-1-丙基磺酸鈉(MPS)-奈米銀/Nafion為一種新的修飾薄膜感測器，在玻璃探電極上自組裝上MPS在使用電化學沉積奈米銀上去和覆蓋上一層Nafion(5 μL)。此外MPS-奈米銀/Nafion修飾薄膜可製備在半導體銦錫氧化物電極(ITO)上被使用在掃描式電子顯微鏡和原子力學顯微鏡技術上。從這些分析，可看出沉積在MPS上的奈米銀是很均勻的分佈，範圍為35~70nm。這MPS-奈米銀/Nafion電極還可使用在電化學組抗光譜法來描述之。此外奈米銀/Nafion薄膜沉積在自組裝MPS上表現出很出色的電化學催化範圍廣的濃度偵測氧氣還原電位（-0.4V）與敏感性佳。而且這修飾電極在玻璃碳上使用脈衝伏安法偵測神經傳感物質，像腎上腺素、正腎上腺素和多巴胺能顯示出良好的電催化活性。此外本研究可從含有高濃度的抗壞血酸（從市售維他命C錠）中檢測腎上腺素和多巴胺，其分析結論是良好的。最後這MPS-奈米銀/Nafion薄膜感測器是很容易被拿來應用和有好的穩定性並且能在混合物中迅速地偵測氧氣還原和個別的兒茶酚胺神經傳導物質。
第二部份是使用電化學方法氧化讓發光胺在奈米氧化鋅修飾玻璃碳電極上。比較裸電極、奈米氧化鋅修飾電極的結果發現氧化電流為聚合發光胺薄膜在奈米氧化鋅表面是最高。這著名複合薄膜為奈米氧化鋅/聚合發光胺（Zn-PL）。在掃描式電子顯微鏡和原子力學顯微鏡結論觀察奈米氧化鋅/聚合發光胺覆蓋在電極表面和氧化鋅的微粒大小是70~120 nm。電化學研究證明出Zn-PL複合薄膜電極是在具導電的中性緩衝溶液對低電位的抗壞血酸中顯現出良好的電催化活性。比較裸電極和只有聚合發光胺、氧化鋅/聚合發光胺電極催化電流較高。當用於一光線照在Zn-PL 表面上30分鐘後觀察出有0.5倍高催化電流顯示出照光會影響氧化鋅催化的能力。使用安培法於抗壞血酸可評估其線性範圍和偵測極限。這新薄膜可以應用於市售抗壞血酸樣品上。我們也證明出偵測在工業用抗壞血酸有好的結論。
第三部份是為一新氧化鋅/奈米銅微粒薄膜沈積在修飾電極上。此方法是奈米銅微粒(Cu-NPs)電化學沈積在氧化鋅薄膜修飾電極。使用原子力學顯微鏡、掃描式電子顯微鏡及X射線繞射儀研究觀察奈米氧化鋅和銅薄膜覆蓋在電極表面。這新氧化鋅/奈米銅微粒覆蓋在玻璃碳電極上探討對葡萄糖在0.1 M NaOH溶液下的電催化活性。其使用計時安培法做線性範圍和偵測極限也將被探討。

關鍵字

3-巰基-1-丙基磺酸鈉 ； 奈米銀 ； Nafion ； 氧氣還原 ； 神經傳導物質 ； 複合薄膜 ； 奈米微粒氧化鋅 ； 聚合發光胺 ； 修飾電極 ； 偵測抗壞血酸 ； 葡萄糖感測器 ； 非酵素感測器 ； 奈米銅微粒

並列摘要

Part I：A novel and easy fabrication of MPS-nano Ag/nafion film modified sensor has been constructed based on the self-assembly of 3-Mercapto-1-propane sulfonic acid (MPS) over a pretreated glassy carbon electrode (GCE) followed by the electrochemical depositions of Ag nano particles (nano Ag) with manual nafion coating (5 μL). Further the MPS-nano Ag/nafion film modified semiconductor indium tin oxide electrodes (ITO) were examined by using SEM and AFM techniques. From these analyses, it was found that the nano Ag particles were uniformly deposited on the MPS layer and the sizes were in the range of 35 to 70 nm, respectively. The MPS-nano Ag/nafion film modified GCE were characterized by using electrochemical impedance spectroscopic studies (EIS). Further the nano Ag/nafion film deposited onto the self assembled surface of MPS exhibited excellent electrocatalytic activity for the detection of oxygen at a reduced potential (-0.4 V) with good sensitivity in a wide concentration range. Furthermore the MPS-nano Ag film/nafion on GCE showed good electrocatalytic activity for the detection of neurotransmitters like epinephrine, norepinephrine, and dopamine by using differential pulse voltammetric technique (DPV). In addition the proposed MPS-nano Ag/nafion film showed obvious results for the detection of epinephrine, dopamine from injection solutions in presence of higher concentrations of ascorbic acid (from vitamin C tablets) for real sample analysis and the results were found satisfactory. Finally the proposed MPS-nano Ag/nafion film sensor is easy to fabricate and has the advantages of good stability, reproducibility, and shows rapid response for oxygen reduction and detection of catecholamine neurotransmitters individually and in mixture.
Part II：Electrochemical oxidation of luminol was performed on nanopowder ZnO modified glassy carbon electrode (GCE). Compared to bare GCE, nano-ZnO modified electrode promoted the high oxidation current which consequently results poly(Luminol) film on nano-ZnO surface.This hybrid film noted as nano-ZnO/Poly(Luminol),(Zn-PL).AFM and SEM results revealed that nano-ZnO/poly(luminol) covered the electrode surface and the particle sizes of ZnO were 70 – 120 nm. Electrochemical studies proved that ZnO-PL hybrid film modified electrodes is electroactive in neutral buffers solution and showed excellent electrocatalytic activities towards ascorbic acid at lower potential. Compared to bare and only PL/GCE, ZnO-PL showed higher catalytic current. When apply a light on the ZnO-PL electrode surface for 30 mints, 0.5 times higher catalytic current was observed which shows the photocatalytic effect of ZnO particles. Using amperometry, linear range and detection limit of ascorbic acid was evaluated. This new method can be applied for detection of ascorbic acid in real samples. We also demonstrated the determination of ascorbic acid in commercial tablets with good results.
Part III：A new modified electrode has been developed based on copper nanoparticles/zinc oxide films. In this method, copper nanoparticles (Cu-NPs) electrochemically deposited onto zinc oxide film modified electrode. Atomic force microscope, scanning electron microscope and x-ray diffraction studies revealed that copper and zinc oxide films were attached onto the electrode surface. This new ZnO /Cu-NPs coated glassy carbon electrode showed excellent electrocatalytic activities towards glucose in 0.1 M NaOH solution. Using amperometric method, linear range and detection limit have been explored.

並列關鍵字

3-mercapto-1-propane sulfonic acid ； nano Ag ； Nafion ； O2 reduction ； Neurotransmitters ； Hybrid films ； ZnO nanoparticles ； Poly-Luminol ； modified electrodes ； determination of ascorbic acid ； Glucose sensor ； non-enzymatic sensors ； copper nanoparticles

參考文獻

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