鋨普魯士藍矽鉬酸鹽、nano-TiO2/酸性黃色9號與氧化鋅/血清素複合薄膜的製備及其電催化性質的研究

Preparation, Characterization and Their Electrocatalytic Properties of osmiumhexacyanoferrate/silicomolybdate, Nano-TiO2/Poly 4-amino-1-1'- azobenzene-3, 4'-disulfonic acid(acid yellow 9), and zinc oxide/polymer core-shell microparticles hybrid film modified electrodes

董春芳(Chun-Fang Tang)

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(2006年)

摘要

以循環伏安法在含有Os3+, Fe(CN)63-and SiMo12O404- 離子的酸性溶液中製備鋨普魯士藍矽鉬酸鹽多核混價複合薄膜，在鋨普魯士藍矽鉬酸鹽多核混價複合薄膜中具有4對氧化還原對。並利用掃描式電子顯微鏡來研究薄膜表面影像。鋨普魯士藍矽鉬酸鹽多核混價複合薄膜對於多巴胺、抗壞血酸、腎上腺素、正腎上腺素和IO3- 都具有明顯電催化效果。
4-氨基-1-1’-偶氮-3-4’-二磺酸（酸性黃色9號染料（AY））電聚合在奈米二氧化鈦修飾玻璃碳電極上，在含有AY單體的酸性溶液中所製備，奈米二氧化鈦/聚合（AY）修飾玻璃碳電極（nano-TiO2/PAY/GC）利用循環伏安法製備。nano-TiO2/PAY/ GC電極的氧化還原顯示出pH與氧化還原波峰電位為-54 mV/pH是接近於Nernst行為。nano-TiO2/PAY/GC電極顯示出對多巴胺和乙醯氨酚電催化氧化作用在0.1 M PBS（pH 7.0）有極佳的效果。與空白GC電極比較陽極波峰電流多巴胺增大3倍乙醯氨酚增大6倍且縮小了大量的過電壓。比較nano-TiO2/PAY/GC和聚合（AY）直接沉積在GC電極的電催化活性、電極穩定性和染料性質。觀察含有奈米二氧化鈦的存在其穩定性、染料性質和修飾電極自身對於聚合（AY）/GC修飾電極有何改進。然而在對照另一個聚合物修飾電極，由於聚合（AY）具有強大的陰離子結構，進而忽略了重大的干擾，例如抗壞血酸（AA）、尿酸（UA）和NADH在0.1 M PBS（pH 7.0），這些氧化作用的干擾沒有顯示出反應。在高濃度的AA、UA和NADH中存在DA和AP可藉由PAY/ GC此能力同時偵查。利用旋轉環碟電極來研究電極動力學。使用微分脈衝伏安法可以獲得DA和AP在1~120 μM的測量曲線並得知有好的選擇性跟靈敏性，這個方法提供了一個簡單對多巴胺和乙醯氨酚選擇性研究。
在含有血清素單體的溶液中，用電化學聚合作用將血清素（SN）在ZnO玻璃碳電極和銦錫氧化物電極上。成功的在電極表面上製備了氧化鋅/聚血清素核殼奈米微粒電極。氧化鋅/聚血清素奈米微粒電極的表面特性可藉由AFM和SEM所偵測。利用循環伏安法檢測製備在電極上的氧化鋅/聚血清素奈米微粒之電化學性質。此外，在電極上的氧化鋅/聚血清素奈米微粒電極成功的適用於同時對多巴胺、抗壞血酸和尿酸做偵測。

關鍵字

鋨 ； 普魯士藍 ； 聚多氧金屬氧化物 ； 薄膜修飾電極 ； 電催化 ； 聚合（酸黃9） ； 乙醯氨酚 ； 電致聚合物 ； 多巴胺氧化 ； 抗壞血酸 ； 尿酸 ； NADH ； 氧化鋅 ； 核殼聚合物 ； 循環伏安法 ； FIA

並列摘要

Polynuclear mixed-valent osmium hexacyanoferrate/silicomolybdate have been prepared using repetitive cyclic voltammetry. The osmium/hexacyanoferrate/silicomolybdate films have been prepared using repetitive cyclic voltammetry. The cyclic voltammograms recorded for the deposition of the mixed-valent osmium/hexacyanoferrate/silicomolybdate hybrid films directly from the mixing of os3+, Fe(CN)63-and SiMo12O4-40 ions from the acidic aqueous solutions. The polynuclear mixed-valent osmium hexacyanoferrate/silicomolybdate films exhibited four redox couples. The scanning electron microscopy has been used to study the surface morphology of above films. Electrocatalytic reactions of dopamine, ascorbic acid, epinephrine, norepinephrine, and IO3- were carried out using the mixed-valent osmium/hexacyanoferrate/silicomolybdate films.
Electrochemical polymerization of 4-amino-1-1'-azobenzene-3,4'-disulfonic acid (acid yellow 9 dye (AY)) was carried out onto the surface of nano-TiO2 modified glassy carbon (GC) electrode from acidic solution containing AY monomers. A nano-TiO2/poly(AY) modified GC electrode (nano-TiO2/PAY/GC) was characterized by cyclic voltammetry (CV). The redox response of the nano-TiO2/PAY/GC electrode showed a pH dependent redox peak potential was -54 mV/pH which was close to the Nernst behavior. The nano-TiO2/PAY/GC electrode exhibited excellent electrocatalytic activity towards the oxidations of dopamine (DA) and acetaminophen (AP) in 0.1M phosphate buffer solution (pH 7.0). Increased the anodic peak current three times higher for DA and six times higher for AP than bare GC electrode and reduced the considerable over potential. Electrocataltyic activity, electrode stability and antifouling properties of nano-TiO2/PAY/GC was compared with poly(AY) coated GC electrode. It was observed that in the presence of nano-TiO2 the stability, antifouling properties and self-life of modified electrode were improved than poly(AY)/GC modified electrode. However, in contrast to other polymer modified electrode, due to the strong negatively charged back bone of poly(AY) highly neglected the important interference such as ascorbic acid (AA), uric acid (UA) and reduced form of nicotinamide adenine dinucleotide (NADH) in 0.1M phosphate buffer solution (pH 7.0) and did not showed any response for oxidation of these interferences. This behavior makes the PAY/GC for simultaneous detection of DA and AP in the presence of higher concentrations AA, UA and NADH. Rotatable ring disk electrode (RRDE) was used for study electrode kinetics. Using differential pulse volatmmetry the calibration curves for DA and AP were obtained over the range of 1 – 120 μM with good selectivity and sensitivity. The proposed method provides a simple method for selective detection of DA and AP.
Electrochemically initiated polymerization of serotonin (SN) onto zinc oxide (ZnO) coated glassy carbon and indium tin oxide coated electrodes were carried out from its monomer solution. This method results ZnO/polymer(serotonin) core-shell microparticels on electrodes surface. Surface characterizations of ZnO/polymer(serotonin) microparticles were performed by using atomic force microscope and scanning electron microscope. Finally the electrochemical properties of ZnO/polymer(serotonin) microparticles coated electrode were tested by using cyclic voltammetry. In addition, ZnO/polymer(serotonin) microparticles coated electrode is successfully applied to use for simultaneous detection of dopamine, ascorbic acid and uric acid in physiologically relevant condition.

並列關鍵字

Osmium ； Hexacyanoferrate ； Polyoxomolybdate ； Film modified electrodes ； Electrocatalysis ； Poly (acid yellow 9) ； determination of dopamine ； acetaminophen ； electroactive polymer ； ascorbic acid ； uric acid ； NADH ； Zinc oxide ； polymer core-shell ； cyclic voltammetry ； FIA

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