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  • 學位論文

聚合錳紫質黃素腺嘌呤二核苷酸薄膜和釕金屬錯合物普魯士藍矽鉬酸鹽混合薄膜的製備及其電催化性質的研究

Preparation, Characterization of poly(MnTAPP) with FAD, FMN, RF hybrid film, Ruthenium oxide/Hexacyanoferrate/Silicomolybdate Hybrid Films, Ruthenium oxide /Hexacyanoruthenate /Silicomolybdate Hybrid Films and Their Electrocatalytic Properties

指導教授 : 陳生明

摘要


由聚合四鄰胺苯基錳紫質(Manganese tetra(o-aminophenyl)porphyrin, MnTAPP)和黃素腺嘌呤二核苷酸(flavin adenine dinucleotide, FAD),或黃素單核苷酸(flavin mononucleotide, FMN),或核黃素(riboflavin, RF)吸附薄膜修飾電極,已能夠在酸性水溶液下,製備成具有四對氧化還原波峰的混合薄膜。利用電化學石英晶體微天平與循環伏安法可用來研究poly(MnTAPP)/FAD和poly(MnTAPP)薄膜的即時成長情形。在poly(MnTAPP)/FAD薄膜吸附或是具有血紅素的情形下,來研究薄膜對O2的電催化特性。在電催化過程,涉及血紅素與FAD(或FMN或RF)在混合薄膜上作用,因而增大電催化還原電流的結果。進一步再使用循環伏安法和旋轉環-碟電極,研究混合薄膜對於氧氣電催化還原反應。混合薄膜對於NAD+,NO2-和S2O2- 8具有電催化還原活性,而對於Fe2+則有電催化氧化之效果。在三種不同的混合薄膜對NAD+,NO2-的電催化還原活性比較,可發現poly(MnTAPP)/FAD > poly(MnTAPP)/FMN > poly(MnTAPP)/RF。 藉由循環伏安法在含有Ru3+、Fe(CN)63–和SiMo12O404-離子的酸性水溶液製備ruthenium oxide/hexacyanoferrate /silicomolybdate (RuO/Fe(CN)63–/SiMo12O404-)多核混價薄膜,同樣的利用循環伏安法製備ruthenium oxide/hexacyanoferrate (RuO/Fe(CN)63–)和RuO/silicomolybdate(RuO/SiMo12O404-)薄膜。由循環伏安法聚合的RuO/Fe(CN)63–/SiMo12O404-多核混價薄膜,在酸性水溶液具有五對氧化還原波峰。利用電化學石英晶體微天平、循環伏安法與掃描式電子顯微鏡來研究薄膜的成長機制。RuO/Fe(CN)63–/SiMo12O404-薄膜對於多巴胺、腎上腺素、正腎上腺素、維他命C、S2O82–、SO52–、L-cysteine和IO3–具有電催化效果,而此薄膜對HNO2則同時具有電催化氧化及電催化還原的效果。 使用循環伏安法在含有Ru3+、Ru(CN)64–、SiMo12O404-離子的酸性溶液製備ruthenium oxide/hexacyanoruthenate /silicomolybdate (RuO/Ru(CN)64–/SiMo12O404-)多核混價薄膜,同樣的利用循環伏安法製備ruthenium oxide/ hexacyanoruthenate (RuO/Fe(CN)64–)和RuO/silicomolybdate(RuO/SiMo12O404-)薄膜。由循環伏安法聚合的RuO/Ru(CN)64–/SiMo12O404-多核混價薄膜,在酸性水溶液具有五對氧化還原波峰。利用電化學石英晶體微天平、循環伏安法與掃描式電子顯微鏡來研究薄膜的成長機制。RuO/Ru(CN)64–/SiMo12O404-薄膜對於多巴胺、S2O82–、SO52–、L-cysteine、IO3–、BrO3–和ClO3–具有電催化效果。

並列摘要


Hybrid films composed of electro polymerized manganese tetra(o-amino phenyl)porphyrin(MnTAPP) with flavin adenine dinucleotide (FAD) or flavin mononucleotide(FMN) or riboflavin(RF) adsorbed film modified electrodes have been prepared in aqueous acidic solutions. The hybrid films showed four redox couples. Electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of hybrid poly (MnTAPP)/FAD and poly (MnTAPP) films. The electro catalytic properties of the O2 were studied by the hybrid films in the absence or in the presence of hemoglobin. The electro catalytic process involved an interaction of hemoglobin and FAD (or FMN or RF) on hybrid film to increase the electro catalytic reduction current. The electrocatalytic reduction of O2 using the hybrid films was investigated by cyclic voltammetry, and rotating ring-disk electrode methods. The electro catalytic reduction of NAD+, NO2- and S2O82- and the electro catalytic oxidation of Fe2+ using the hybrid films were investigated. The electro catalytic reduction of NAD+, NO2- by three hybrid films in an acidic aqueous solution showed an electro catalytic reduction activity of poly(MnTAPP)/FAD > poly(MnTAPP)/FMN > poly(MnTAPP)/RF. Polynuclear mixed-valent films of ruthenium oxide/hexacyanoferrate /silicomolybdate (RuO/Fe(CN)63–/SiMo12O404-) have been prepared using repetitive cyclic voltammetry. The ruthenium oxide/hexacyanoferrate (RuO/Fe(CN)63–) and RuO/silicomolybdate(RuO/SiMo12O404-) films have also been prepared using repetitive cyclic voltammetry. The cyclic voltammograms recorded the deposition of the mixed-valent ruthenium oxide/hexacyanoferrate /silicomolybdate hybrid films directly from the mixing of Ru3+, Fe(CN)63– and SiMo12O404- ions from the acidic aqueous solutions. The polynuclear mixed-valent films ruthenium oxide/hexacyanoferrate/silicomolybdate films exhibited five obviously redox couples. The electrochemical quartz crystal microbalance, cyclic voltammetry, and scanning electron microscopy were used to study the growth mechanism of the polynuclear mixed-valent films ruthenium oxide/hexacyanoferrate/silicomolybdate films. The electrochemical quartz crystal microbalance and cyclic voltammetry results indicated that the redox process was confined to the immobilized mixed-valent ruthenium oxide/hexacyanoferrate/silicomolybdate hybrid films. Electro catalytic reactions of dopamine, ascorbic acid, epinephrine, norepinephrine, S2O82–, SO52–, L-cysteine and IO3– were carried out by the mixed-valent ruthenium were carried out by the mixed-valent ruthenium oxide/hexacyanoferrate/silicomolybdate films. The electro catalytic oxidation and reduction of HNO2 by the hybrid films too were investigated. Polynuclear mixed-valent hybrid films of ruthenium oxide/hexacyanoruthenate and silicomolybdate (RuO/Ru(CN)64–/SiMo12O404-) have been prepared using repetitive cyclic voltammetry. The ruthenium oxide/hexacyanoruthenate (RuO/Ru(CN)64–) and RuO/silicomolybdate (RuO/SiMo12O404-) films have also been prepared using repetitive cyclic voltammetry. The cyclic voltammograms recorded the deposition of the mixed-valent ruthenium oxide/hexacyanoruthenate and silicomolybdate hybrid films directly from the mixing of Ru3+, Ru(CN)64– and SiMo12O404- ions from the acidic aqueous solutions. The polynuclear mixed-valent films ruthenium oxide/hexacyanoruthenate and silicomolybdate hybrid films exhibited five obviously redox couples. The electrochemical quartz crystal microbalance, cyclic voltammetry, and scanning electron microscopy were used to study the growth mechanism of the polynuclear mixed-valent hybrid films ruthenium oxide/hexacyanoruthenate/silicomolybdate, ruthenium oxide/ hexacyanoruthenate (RuO/Ru(CN)64–) and RuO/silicomolybdate(RuO/SiMo12O404-) films. Electro catalytic reactions of dopamine, S2O82–、SO52–、L-cysteine, IO3–, BrO3– and ClO3– were carried out by the mixed-valent ruthenium oxide/hexacyanoruthenate and silicomolybdate hybrid films.

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