矽鉬酸鹽與黃素腺嘌呤二核苷酸複合薄膜之製備、電催化反應以及聚合錳紫質電化學顯微研究

Preparation and Electrocatalytic Reactions of Silicomolybdate and Flavin Adenine Dinucleotide Hybrid Films and Electrochemical Microscopy Study of the PolyMnTAPP

林國強(Kuo-Chiang Lin)

指導教授 ： 陳生明

國立臺北科技大學/工程學院/工程科技研究所/博士(2005年)

摘要

本論文主要進行對於薄膜修飾電極電化學生成的研究。根據修飾材料的不同，可分成無機-無機、有機-無機、有機-有機以及無機-生化混合薄膜的型態進行探討。文中呈現不同材料型態的製備、薄膜生成、電催化特性以及電化學表面技術等重要的資訊，共分為七項主題進行研究。
亞錫矽鉬酸鹽與氧化亞錫矽鉬酸鹽兩種型態薄膜，可以連續循環伏安法製備獲得，薄膜沉積過程與電催化性質也亦可獲得研究。於強酸條件混合Sn2+與SiMo12O404-的水溶液，再分別控制不同的掃描電位範圍，因而獲得亞錫矽鉬酸鹽與氧化亞錫矽鉬酸鹽兩種不同型態的循環伏安圖。使用電化學石英晶體微天平、循環伏安法與紫外/可見光吸收光譜，可研究薄膜的反應機制。其結果發現有趣的Sn2+與SiMo12O404-的緩慢反應生成一藍色新物種的化合物，其吸收波峰出現在λ = 320、645與744 nm等位置。於pH = 1.5酸性水溶液中，亞錫矽鉬酸鹽薄膜具有兩對氧化還原對；氧化亞錫矽鉬酸鹽薄膜則有三對。兩種薄膜於電化學與電化學石英晶體微天平系統均有良好的固定化狀態。氧化亞錫矽鉬酸鹽薄膜於pH = 1.5酸性水溶液中具有電催化還原活性，被催化的反應基質包括：ClO3-、BrO3-、IO3-、NO2-、SO52-與S2O82-等。其中，IO3-的電催化還原反應，可進一步使用碟電極固定氧化錫矽鉬酸鹽薄膜的旋轉-環碟電極，進行產物分析研究。
由聚合發光胺與奈米大小的聚多氧金屬氧化物(SiMo12O404-)所構成的混合薄膜，已能夠於酸性水溶液中製備獲得。此薄膜具穩定性與電化學活性，能製備於玻璃碳電極、白金電極、黃金電極以及透明半導體銦錫氧化物等電極表面上。使用電化學石英晶體微天平與循環伏安法，進行對於聚合發光胺與SiMo12O404-混合薄膜生成的即時監測。此混合薄膜具有四對氧化還原對，進行其電催化性質的研究並與SiMo12O404-本身作比較。製備好的薄膜於不同酸鹼值的環境具有pH效應。混合薄膜能電催化還原的物質，包括：ClO3-、BrO3-、IO3-、S2O82-與NO2-等，其中對鹵氧化物的電催化還原活性大小，依序為IO3- > BrO3- > ClO3-。混合薄膜亦包括電催化氧化的能力，可電催化氧化的物質包括：多巴胺與腎上腺素等。可進一步使用旋轉環-碟電極研究電催化反應的物質，以了解其電催化反應機制及鑑定產物。
黃素腺嘌呤二核苷酸(flavin adenine dinucleotide, FAD)修飾氧化鋅薄膜可使用循環伏安法獲得研究其製備和電催化特性等過程。本研究成功的利用電化學方法進行存取電化學活性分子於氧化鋅薄膜。直接於含有鋅離子和FAD的水溶液，控制不同的掃描電位範圍以循環伏安法記錄FAD/ZnO薄膜沉積的過程。使用電化學石英晶體微量天平(EQCM)、紫外/可見光吸收分光譜，和靜止流動方法(stopped-flow method)研究薄膜成長機制和FAD/ZnO薄膜的特性。實驗結果顯示，鋅離子和FAD進行電化學反應過程以達成自組裝FAD/ZnO薄膜。FAD/ZnO薄膜呈現包括電子和質子轉移的一對氧化還原對，其形式電位亦證實具有質子效應。利用製備好的FAD/ZnO薄膜進行對於NAD+的電催化還原，同時也使用紫外-可見光吸收分光譜進行研究。可被FAD/ZnO薄膜電催化還原的基質，包括：S4O62–、SO52–、S2O82–、ClO3–、BrO3–、IO3–等。
利用電化學自組的黃素腺嘌呤二核苷酸/鋅氧化物修飾薄膜(FAD/ZnO)，其製備過程已可於適當條件以循環伏安法完成，並進一步探討其電催化特性。可使用FAD/ZnO薄膜進行對於血紅素電化學反應的研究，其中並包括薄膜本身的電催化性質的探討。本論文成功的利用電化學方法，存取具電化學活性的物種於ZnO表面上，這些活性物種包括血紅素與黃素腺嘌呤二核苷酸。使用電化學石英晶體微天平配合循環伏安法以研究薄膜的成長機制及薄膜本身的特性。FAD/ZnO薄膜具有一氧化還原對，使得血紅素-FeIII與血紅素-FeII的電化學轉換反應得以完成，FAD/ZnO薄膜能夠電催化還原O2、H2O2、三氯醋酸與SO32–等物質，並進一步研究這些反應在有血紅素存在下的影響。由FAD/ZnO薄膜電催化還原電流的發展，可獲知電催化過程，涉及血紅素與電極表面上的FAD作用，因而增大電催化還原電流的結果。也使用循環伏安法與旋轉環-碟電極，進一步研究FAD/ZnO薄膜對於氧氣電催化還原反應。
發光胺電聚合誘導黃素腺嘌呤二核苷酸(FAD)吸附薄膜修飾電極，可於酸性水溶液中製備獲得。此類型薄膜可製備於玻璃碳電極、白金電極、黃金電極、過渡半導體氧化錫銦等電極表面上。製備獲得的聚合發光胺/FAD混合薄膜於循環伏安圖，可發現兩對氧化還原對。使用電化學石英晶體微天平配合循環伏安法，以研究聚合發光胺/FAD混合薄膜的成長機制及薄膜本身的特性。當此薄膜移至不同pH環境時，兩對氧化還原對的形式電位均具有pH效應。即使於不同pH條件下，聚合發光胺/FAD混合薄膜，仍具有對NADH電催化氧化活性。聚合發光胺/FAD混合薄膜，可電催化氧化NADH，並研究其對於NADH/NAD+的可逆電催化反應。
可將吖啶黃/黃素腺嘌呤二核苷酸，電聚合固定於電極表面，形成poly(AFFAD)的薄膜修飾電極。此薄膜可使用玻璃碳電極、白金電極、黃金電極以及透明半導體銦錫氧化物電極，於中性條件製備獲得，具有穩定性及電化學活性。在電化學系統中，poly(AFFAD)混合薄膜有兩對氧化還原對。使用電化學石英晶體微天平配合循環伏安法，以研究poly(AFFAD)混合薄膜的成長機制，以及薄膜本身的特性。poly(AFFAD)混合薄膜，具有對NADH電催化氧化與對NADH/NAD+可逆電催化的活性。poly(AFFAD)混合薄膜，對L-cystine、S4O62-、SO52-、S2O82-、NO2-、O2與H2O2 具電催化還原活性。
四鄰胺苯基錳紫質(MnTAPP)可於強酸條件製備，具有電化學活性的聚合四鄰胺苯基錳紫質poly(MnTAPP)的穩定薄膜。使用掃描式電化學顯微鏡(SECM)，研究固定於玻璃碳電極表面的poly(MnTAPP)薄膜。MnTAPP是一個具有四個苯胺單體分支的分子，可以進一步聚合形成樹狀物，此聚合物具有兩對氧化還原對。根據Fe3+/Fe2+氧化還原的反應系統，利用掃描式電化學顯微方法，以探針逼近曲線(Probe Approach Curve)研究電流對距離的關聯性，並進一步測定poly(MnTAPP)薄膜的電化學影像。取得探針對substrate電極合適的逼近位置，控制適當的探針電位進行二維平面掃描，實驗結果所獲得的表面掃描曲線，是對應於固定有poly(MnTAPP)薄膜的絕緣substrate所測得的電流回應。

關鍵字

錫 ； 矽鉬酸鹽 ； 薄膜修飾電極 ； 電催化 ； 電化學石英晶體微天平 ； 發光胺 ； 異質聚陰離子 ； 黃素腺嘌呤二核苷酸 ； 氧化鋅 ； NAD+ ； 血紅素 ； NADH ； 吖啶黃 ； 掃描式電化學顯微

並列摘要

This paper investigated electrochemical formation and properties of film modified electrodes. It can contribute to seven parts according to various modified materials include inorganic-inorganic, organic-inorganic, organic-organic, and inorganic-biomaterial hybrid film types. Inside these articles, we show some important information about preparation, film formation, electrocatalytic properties, and electrochemical surface techniques of various materials types.
Two types film of tin silicomolybdate and tin oxide/silicomolybdate films have been prepared directly from the mixing of Sn2+ and SiMo12O404- ions from the strong acidic solutions over different scanning potential ranges. The cyclic voltammogram of the growing type I film (assigned as a tin silicomolybdate film) is characterized by two redox couples and the type II film(assigned as a tin oxide/ silicomolybdate film) exhibits three redox couples and both films were confined to the immobilized film when transferred to a pH = 1.0 aqueous solution. In addition to cyclic voltammetry, an electrochemical quartz crystal microbalance (EQCM) and UV-visible absorption spectroscopy were used to study the growth mechanism of the tin silicomolybdate and tin oxide/silicomolybdate films. The results show that Sn2+ and SiMo12O404- ions react slowly to form a new blue-coloured species with absorption peaks at λ = 320, 645, and 744 nm. The electrocatalytic reduction of ClO3-, BrO3-, IO3-, SO52-, S2O82-, and NO2- ions by a tin oxide/silicomolybdate film or a tin silicomolybdate film were investigated in acidic aqueous solutions. The electrocatalytic reactions of IO3- ions with a tin oxide/silicomolybdate film were investigated using the rotating ring-disk electrode method.
Hybrid films composed of poly(luminol) and nanometer-sized clusters of polyoxometalate, SiMo12O404-, have been prepared in acidic aqueous solutions. These films are stable and electrochemically active, and produced on glassy carbon, platinum, gold, and transparent semiconductor tin oxide electrodes. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of the hybrid poly(luminol)/SiMo12O404-. Both the poly(luminol)/SiMo12O404- hybrid films showed four redox couples and the electrochemical properties were compared to SiMo12O404-. When transferred to various acidity aqueous solutions, the four redox couples and the formal potentials of hybride film were observed to be pH-dependent. The electrocatalytic reduction of ClO3-, BrO3-, IO3-, S2O82-, and NO2- by a poly(luminol)/ SiMo12O404- hybrid film in an acidic aqueous solution showed an electrocatalytic reduction activity of IO3- > BrO3- and ClO3-.
The flavin adenine dinucleotide (FAD) modified zinc oxide films have been prepared using repeated cyclic voltammetry to investigate both the deposition process and the films' electrocatalytic properties. This paper describes the successful loading of electrochemically-active molecules into ZnO by electrochemical method. The cyclic voltammograms recorded the direct deposition of the FAD/zinc oxide films over different scanning potential ranges from the mixed aqueous Zn2+ ions and FAD. In addition to the cyclic voltammetry, an electrochemical quartz crystal microbalance, UV-visible absorption spectroscopy, and the stopped-flow method were used to study the growth mechanism and their properties of the FAD/zinc oxide films. The results showed that the Zn2+ ions and FAD reacted by an electrochemical process to form a self-assembly FAD modified zinc oxide film. The FAD/zinc oxide films exhibited a single redox couple that included both the electron and proton transfer, with a formal potential that demonstrated a proton effect in acidic and basic solutions. The electrocatalytic reduction of NAD+ employing the FAD/zinc oxide films was investigated by cyclic voltammetry and UV-visible absorption spectroscopy methods. The electrocatalytic reduction of S4O62–, SO52–, S2O82–, ClO3–, BrO3–, and IO3– ions using a FAD/zinc oxide film occurred in neutral aqueous solutions.
Flavin adenine dinucleotide (FAD) modified zinc oxide self-assembly films were prepared using repeated cyclic voltammetry to investigate the films' electrocatalytic properties. The electrochemical reaction of the hemoglobin with the FAD/ZnO self-assembly film-modified electrodes and their electrocatalytic properties were investigated. This paper describes the successful loading of the electrochemically- active molecules of hemoglobin and FAD alongwith ZnO by electrochemical method. In addition to the cyclic voltammetry, an electrochemical quartz crystal microbalance was used to study the growth mechanism and the properties of the films. The FAD/zinc oxide films exhibited a single redox couple and the electrochemical reaction transferred hemoglobin-Fe(III) to hemoglobin-Fe(II). The electrocatalytic properties of the O2, H2O2, trichloroacetic acid and SO32– were studied by the FAD/zinc oxide films in the absence or in the presence of hemoglobin. The electrocatalytic reduction current had been developed from the cathodic peak of the FAD/zinc oxide redox couple. The electrocatalytic process involved an interaction of hemoglobin and FAD/GC film-modified electrode to increase the electrocatalytic reduction current. The electrocatalytic reduction of O2 using the FAD/zinc oxide films was investigated by cyclic voltammetry, and rotating ring-disk electrode methods.
Hybrid films composed of luminol electropolymerization induced FAD(flavin adenine dinucleotide) adsorption film modified electrodes have been prepared in acidic aqueous solutions. The films are stable and electrochemically active, and can be produced on glassy carbon, platinum, gold, and transparent semiconductor tin oxide electrodes. The hybrid poly(luminol)/FAD films showed two redox couples. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of the hybrid poly(luminol)/FAD and poly(luminol) films. When transferred to various acidity aqueous solutions, the two redox couples and the formal potentials of hybride films were observed to be pH-dependent. The electrocatalytic oxidation of NADH by a polyluminol/FAD hybrid film in various pH aqueous solutions showed an electrocatalytic oxidation activity. The electrocatalytic oxidation of NADH and Reversible electrocatalytic reaction for NADH/NAD+ by a poly(luminol)/FAD hybrid film also were investigated.
Hybrid films composed of electropolymerized acriflavine-flavin adenine dinucleotide (AF/FAD) adsorbed film modified electrodes have been prepared in neutral aqueous solutions. These films are stable and electrochemically active, and can be produced on glassy carbon, platinum, gold, and transparent semiconductor tin oxide electrodes. The hybrid poly(acriflavine)/FAD film showed two redox couples. Electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of hybrid poly(acriflavine)/FAD films. The electrocatalytic oxidation and reduction of NADH and NAD+ by a poly(acriflavine)/FAD hybrid film in aqueous solutions was carried out. The electrocatalytic oxidation of NADH and the reversible electrocatalytic reactions of NADH/NAD+ using a poly(luminol)/FAD hybrid film were found active. The electrocatalytic reduction of L-cystine, S4O62-, SO52-, S2O82-, NO2- and H2O2 by a poly(acriflavine)/FAD hybrid film in a neutral aqueous solution showed an electrocatalytic reduction activity.
The electropolymerization of manganese tetra(o-aminophenyl)porphyrin (MnTAPP) produces stable and electrochemically active films from strong acidic aqueous solutions. An scanning Electrochemical Microscopy were used to study the poly(MnTAPP) films on glassy carbon electrode surface. MnTAPP is a molecule that has four branched monomers, and its polymerization forms a dendrimer. The polymerized MnTAPP films showed two redox couples. The scanning electrochemical microscopy current-distance curves of the redox system of Fe3+/Fe2+ system was measurement and investigated the imaging of bare glassy carbon electrode and poly(MnTAPP) modified electrodes. The result is shown by two-dimensional contour of tip current with the substrate electrode was kept at a potential. The curve is recorded of the response on the surface of the poly(MnTAPP) modified electrode, the glassy carbon electrode surface and the conducting substrate.

並列關鍵字

Tin ； Silicomolybdate ； Film Modified Electrode ； Electrocatalysis ； EQCM ； Luminol ； Heteropolyanion ； Flavin Adenine Dinucleotide ； Zinc Oxide ； NAD+ ； Hemoglovin ； NADH ； acriflavin ； SECM

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