【作者】 廖家耀；

【导师】 袁若；

【作者基本信息】 西南大学 ， 分析化学， 2006， 硕士

【摘要】 离子选择电极分析法是以离子选择电极作为指示电极的一种电位分析法,是电化学分析的一个重要分支。离子选择电极是比较成熟的已获得广泛应用的一类电化学传感器。PVC膜离子选择性电极由于具有构造简单、成本低廉、使用起来非常简便快捷等优点,所以其作为一种常规的检测各种阴阳离子的手段而被广泛的运用于临床医学研究、环境科学和工业生产等各个领域。离子选择性电极载体的设计、合成和应用是离子选择性电极研究的一个重要方向,寻找和研究能识别各种特定离子、性能更加优良的活性物质,用于PVC膜离子选择性电极的构建有着重要的理论和实践意义。近年来,研究反Hofmeister行为的阴离子选择性电极成为电分析和电化学传感器研究领域中重要的方向之一。自从人们发现了Schiff碱金属配合物能对特定的阴离子有选择性的识别作用后,以其为载体的、有着广阔应用前景的离子选择电极正成为研究的热点。 本论文综述了离子选择电极的基础理论,介绍了阴离子选择电极的发展及其现状。研究了基于水杨醛缩邻氨基苯酚合钴（Ⅱ）金属配合物[Co（Ⅱ）-SAAP]为中性载体的PVC膜阴离子电极。该电极对水杨酸根（Sal^-）具有优良的电位响应性能和选择性并呈现出反Hofmeister选择性行为,其选择性次序为Sal^->ClO₄^->SCN^->I^->NO₂^->NO₃^->Br^->Cl^->SO₃^2->SO₄^2-。在pH为5.0的磷酸盐缓冲体系中,电极电位呈现近能斯特响应,线性响应范围为9.0×10^-6～1.0×10^-1mol/L,斜率为-54.3mV/dec（20℃）,检出下限为5.0×10^-6mol/L。还首次研究了以2′-（2-呋喃亚甲基）水杨酰腙Schiff碱铜（Ⅱ）配合物[Cu（Ⅱ）-THBH]为中性载体的PVC膜电极,该电极更多还原

【Abstract】 The application of ion-selective electrode is a typical kind of potential analytical method that acts as an indicator electrode, which is also an important branch of the electrochemical analysis. The ion-selective electrode is a kind of mature chemical sensor applied very widely and with long time. The PVC membrane ion-selective electrode has many virtues such as simple construction, low cost, simple pretreat and rapidly online determination and so on. So as a conventional detecting approach to a variety of cations and anions, this kind of electrode is applied widely in the field of clinical medicine, environmental science, industrial production and such like. Design, synthesis and application of neutral carriers of high selectivity and sensitivity are main research interests in the ion-selective electrode study fields, so it has important theory and practice meaning that search and research electrical activity material that can recognize the special target ion with more performance and apply this material to construct the PVC membrane ion-selective electrode. Recently, studies on ion-selective electrodes with anti-Hofmeister selectivity patern are an important and interesting project in the fields of electroanalytical chemistry and electrochemistry sensor. Shortly after the peoples discovered that the Shiff base metallic complexes have the special selective to the specific anion, the study of this sort of electrode that there are widely application prospect has been a hotspots in this field.The thesis has given an overview of elementary theory of the ion-selectiveelectrode, introduction to the ion-selective electrode’s development and existing actuality. A new Highly salicylate-selective PVC membrane electrode based on o-salicyladehyde- aminophenol cobalt(II) complex [Co(II)-SAAP] as a neutral carrier is described, which displays a preferential potentiometric response to salicylate and an anti-Hofineister selectivity sequence in following order: Sal’> C1C?4"> SCN> I"> NO2"> NO3"> Br"> Cr> SO32"> SO42". The electrode exhibits near Nernstian potential linear range of 9.0* 10"*—1.0*10"’ mol/mL with a detection limit of 5.0X10"6 mol/mL and a slope of-54.3 mV/decade in pH 5.0 of phosphorate buffer solution at 20°C. At the same time, a new highly selective thiocyanate electrode based on Copper(II) Complex with 2’-(2-Thienylidence)-Hydroxybenzoylhydrazide [Cu(II)-HTBH] as neutral carrier is developed, which displays an anti-Hofmeister selectivity sequence: SCN> Sal" > CIO4’> I" > Br" > NO3" > Cl" > NO2" > SO32" > SO42" > H2PO4". The electrode exhibits Nernstian potential linear range to thiocyanate from 1.0x10"’ to 5.0><10"6 mol/L with a detection limit 1.2*10"6 mol/L and a slope of 53.4 mV/dec in pH 5.0 of phosphorate buffer solution at 25 "C. To the two sorts of electrodes, the response mechanism is discussed in view of the a.c. impedance technique and the UV spectroscopy technique. These deviations result from the direct interaction between the central metal and the analyte ion and steric effect associated with the structure of the carrier. The electrode s have the advantages of simplicity, fast response, fair stability and reproducibility and low detection limit. The electrode s can be applied to analysis of medicine and waste water and the result obtained is fair agreement with the result given by HPLC methods or precipitation method.This paper explored two kinds of new the Shiff base metallic complexes as the ionophores of the ion-selective electrode, which have provided a sort of rapidly determination method and have high selective to salicylate and thiocyanate in the intricate and actual sample system for determining medicine, waste water and so on.更多还原