【作者】 李晓娟；

【导师】 赫春香；

【作者基本信息】 辽宁师范大学 ， 有机化学， 2009， 硕士

【摘要】 金属铁氰化物修饰电极具有制备方法简单、化学性质稳定、良好的电催化性能、电色效应、价格低廉等优点,因而成为电分析化学领域的研究热点。本论文的研究目的旨在进一步拓宽这类化合物在电催化领域及生物电化学传感器方面的应用。本论文全新研制了铁氰化钕/银（NdHCF/Ag）复合型修饰电极,利用电化学沉积法制备了铁氰化镍/银（NiHCF/Ag）复合型修饰电极以及铁氰化钴（CoHCF）修饰电极,讨论了三种修饰电极的制备方法和制备原理,对其结构、化学组成、电化学性质进行了表征,并研究了三种修饰电极对几种生命物质、药物和有机物的电化学催化性能。本论文主要开展了以下三方面的工作:1.在含有Ag⁺、Nd³⁺、K₃Fe（CN）₆的胶体混合溶液中,用电化学沉积方法制备了铁氰化钕/银复合无机膜修饰电极（NdHCF/Ag/SG）,并对其电催化性能进行了研究。结果表明,该修饰电极具有良好的化学和电化学稳定性,且对同型半胱氨酸、还原型谷胱甘肽和对硝基苯酚的电极反应均有良好的电催化作用。2.在含有Ag⁺、Ni²⁺、K₃Fe（CN）₆的胶体混合溶液中,用电化学沉积法制备了铁氰化镍/银复合型修饰电极（NiHCF/Ag/SG）,并研究了该电极的电催化性能。结果表明:NiHCF/Ag/SG修饰电极对氟康唑和盐酸麻黄碱的电极反应均有催化作用。当氟康唑的浓度在8.00×10^-7～5.00×10^-5mol/L范围内时,其还原峰的峰电流与浓度呈良好线性关系（r=0.986）,检出限为2.50×10^-8mol/L。当盐酸麻黄碱的浓度在8.00×10^-6～1.30×10^-3mol/L范围内时,其还原峰的峰电流与浓度呈良好线性关系（r=0.982）,检出限为5.00×10^-7mol/L。该电极已成功用于注射液中氟康唑和盐酸麻黄碱含量的测定,回收率分别为96.5～109%、95.4～104%。3.用电化学沉积法制备了铁氰化钴膜修饰电极（CoHCF/SG）,利用循环伏安法研究了该修饰电极的电催化性能。结果表明:该电极对次黄嘌呤、黄嘌呤、鸟嘌呤、腺嘌呤的电化学氧化均具有催化作用。更多还原

【Abstract】 The metal hexacyanoferrate modified electrodes have the characters of easy to prepare and low cost, and have stable chemical properties, good electrocatalytic performance, and good electrochromic properties. So they attract great interest for the electrochemists. The aim of our work was to develop the new metal hexacyanoferrate modified electrodes and improve their applications in the fields of the electrocatalysis and the bioelectrochemical sensors. In this paper, a new kind of modified electrode with mixed silver and neodymium hexacyanoferrate （NdHCF/Ag） was developed. Beside, other two kinds of silver and nickel hexacyanoferrate （NiHCF/Ag） and cobalt hexacyanoferrate （CoHCF） modified electrodes were prepared by electrochemical deposition on the surface of the graphite （SG）. The structures, the chemical compositions and the electrochemical properties of three kinds of modified electrodes have been characterized. The methods and mechanism for the preparation were discussed. Furthermore, their electrocatalytic activities for several living matters, medicaments and organic compounds have been investigated.The main contributions of this paper were summarized as follows:1. The modified electrode of the combined inorganic film of silver and neodymiumhexacyanoferrate （NdHCF/Ag） was prepared by the electrochemical deposition on thesurface of graphite （SG） in a colloidal mixing solution containing Ag⁺, Nd³⁺, andK₃Fe（CH）₆. The experimental testing indicated that this metal hexayaoferrates possesses good chemical and electrochemical stabilities, and has strong electrocatalytic activity for homocysteine （Hcy）, reducible type of glutathione （GSH）, and p-nitrophenol in a buffer solution of HAC-NH4AC.2. The modified electrode of the mixed silver and nickel hexacyanoferrate （NiHCF/Ag） was prepared by the electrochemical deposition on the surface of graphite （SG） in a colloidal mixed solution containing Ag⁺, Ni²⁺, and K₃Fe（CN）₆. Its catalytic performance for the electrode reaction of fluconazole and ephedrine hydrochloride has been studied. The results indicated that in the range of 8.00×10^-7～5.00×10^-5mol/L of fluconazole, there is an excellent linearity （r=0.986） between the reduction current and the concentration of fluconazole with a detection limit of 2.50×10^-8mol/L . For ephedrine hydrochloride in the range of 8.00×10^-6～1.30×10^-3mol/L, there is an excellent linearity （r=0.982） between the reductive current and the concentration with a detection limit of 5.00×10^-7mol/L. The electrode have been successfully applied to determine the content of fluconazole and ephedrine hydrochloride in jections. Its recovery rate is between 96.5% and 109% to fluconazole or between 95.4% and 104% to ephedrine hydrochloride.3. The modified electrode of the cobalt hexacyanoferrate（CoHCF） film on the surface of graphite（SG） was successfully prepared by the electrochemical deposition method, and its electrocatalytic properties have been studied by cyclic voltammetry. The results indicated that CoHCF modified electrode has the electrocatalytic activities toward the electrochemical oxidation of hypoxanthin, xanthin , guanine, and adenine.更多还原