摘 要
本實驗將具有電化學活性之iron(Ⅱ) tris(1,10-phenanthroline)(簡寫為Fe(phen)32+)及敏光物質9-methylacridinium (簡寫為AcH+)交換至沸石(Zeolite Y，NaY)的孔洞中，並將其鋪設於二氧化錫(ITO)電極上，其外再以Polystyrene(簡寫為PS)包覆，即完成無銀感光薄膜之製備。此修飾電極(簡寫為ITO/NaY/AcH+/Fe(phen)32+/PS)在pH 4的溶液中、電壓為+0.3 V vs. SCE及照光時可催化N,N-diethyl-2-methyl-1,4-phenylenediamine(簡寫為DEPD)之氧化，並與α-naphthol發生偶合反應，而於電極表面上形成藍色的產物-Indophenol blue。
本實驗也製備Ferric N,N'-bis(salicylidene)ethylenediamine chloride(簡寫為Fe(Salen)Cl)，並以循環伏安法分析其電化學性質，實驗顯示此化合物可穩定存在，其生成常數為7.1×1025 M-1；在非水溶液中，Fe(Salen)+可催化氧氣之還原，吾人便依此特性設計一氧氣偵測電極(簡稱ITO/Fe(Salen)+修飾電極)，於pH 7水溶液中偵測氧氣，其靈敏度為70.7 μA/mM O2。此外，ITO/Fe(Salen)+修飾電極亦可催化過氧化氫之還原，其催化反應符合EC' mechanism及薄層電池(Thin-layer cell)模式，由實驗結果顯示：Fe(Salen)+催化過氧化氫還原的反應速率常數約為4400 M-1s-1，若將葡萄糖氧化酵素(Glucose Oxidase，簡稱GOx)固定於ITO/Fe(Salen)+修飾電極表面，此電極可於飽和氧氣溶液中，偵測葡萄糖之濃度，因此可作為葡萄糖偵測電極之用。實驗結果也顯示：ITO/Fe(Salen)+/Gox修飾電極對葡萄糖的偵測線性範圍為10-2~10-4 M，偵測極限約為10-4 M。此外，Fe(Salen)+的電子轉移與溶液的pH值有關，因此可用以分析水溶液中的氫離子濃度，其線性範圍為2＜pH＜10，靈敏度為-41 mV/pH。
本實驗也對Iron(Ⅱ) tris(5-amino-1,10-phenanthroline)(簡寫為Fe(NH2-phen)32+)之電化學性質加以研究，實驗結果顯示：此化合物可以電化學氧化方式聚合於碳電極表面上(簡稱glassy carbon/Fe(NH2-phen)32+修飾電極)。此電極對水溶液中的氫離子濃度極為敏感，其還原電位隨溶液pH值增加而向負電位偏移，靈敏度為-39.8 mV/pH，有效線性範圍為1＜pH＜10。由於Fe(NH2-phen)32+的形式電位(formal potential)可隨溶液的pH值變化而偏移，因此可藉以控制電極與溶液間的電子傳遞行為。此外，實驗也發現Methyl viologen(簡寫為MV2+)可特別吸附於Fe(NH2-phen)32+薄膜上，根據電化學石英震盪天平(Electrochemical quartz crystal microbalance，簡寫為EQCM)之研究，MV2+可能先吸附於膜層表面繼而進入膜層之內，因而造成電極表面質量下降繼而增加。

Abstract
In this thesis, iron-containing particles or species, such as iron-containing clays (denoted clay), iron-containing zeolites (denoted NaY/Fe2+), ferric
N,N'-bis(salicylidene)ethylenediamine chloride (denoted Fe(Salen)Cl), and iron tris(5-NH2-1,10-phenanthroline) (denoted Fe(NH2-phen)2+) have been investigated for their potential in phototoelectrochemical applications.
Experimental results showed that indophenol blue can be formed on the surface of the modified electrodes made with iron-containing clay or zeolite Y particles and
9-methylacridinium (AcH+) in the solution containing
α-naphthol and N,N-diethyl-1,4-phenylenediamine (DEPD) during photo illumination. A non-silver based photographic film was thus developed.
Fe(Salen)+ species has been immobilized on ITO glass for analyzing the contents of oxygen and hydrogen peroxide in aqueous solutions. Fe(Salen)+ showed a remarkable effect in mediating the reduction of oxygen and H2O2 at ambient conditions. For oxygen, the detection limit at pH 7 is nearly 0.4 mM; a linear calibration ranging from 0.4 to 5 mM was obtained. For H2O2, Fe(Salen)+ showed an EC' catalytical mechanism for the reduction of H2O2; the pseudo-first order reaction rate constant at pH 7 was estimated to be 4400 M-1s-1.
Based on this result, a glucose biosensor was derived. After being incoporated with glucose oxidase (GOx), the Fe(Salen)+ modified electrode displayed a remarkable sensitivity to glucose; the detection limit was about 0.1 mM at pH 7; the linear calibration curve covers a range of 0.1 - 15 mM. Besides, we also found that the formal potential of Fe(Salen)+ is very sensitive to the solution pH; a linear calibration curve covering 2 ＜pH＜10 was thus obtained.
Experimental results also showed that Fe(NH2-phen)2+ could be polymerized on the surface of glassy carbon, ITO glass and Au electrodes, and that the formal potential of the polymerized Fe(NH2-phen)2+ is very sensitive to the solution pH. Because of these effects, the Fe(NH2-phen)2+ modified electrode can be used to gate the electron transfer reaction taking place between the solution and the electrode. Although the redox reaction of methyl viologen (MV2+) should be blocked by the energetics of Fe(NH2-phen)2+, EQCM experiments suggested that MV2+ might be specifically adsorbed on the Fe(NH2-phen)2+ film through two stages, i.e., firstly, on the surface, and then into the Fe(NH2-phen)2+ film.

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