【作者】 戴建远；

【导师】 柴雅琴； 袁若；

【作者基本信息】 西南师范大学 ， 分析化学， 2005， 硕士

【摘要】 离子电极分析法是一种直接的、非破坏性的分析方法,所需设备简单,操作方便,测量的范围宽广,灵敏度高,能进行快速连续监测,因此离子选择性电极几乎在工农业生产和科学技术的所有部门都获得了实际应用。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。近年来,以金属配合物作为中性载体呈现的反Hofmeister行为的阴离子选择性电极是电化学和电分析研究领域中公认的活跃课题。本论文的研究力求探索新型金属配合物的设计合成,及其作为中性载体的PVC溶剂聚合膜阴离子选择性电极的基础研究,并将电极作为化学传感器初步应用于实际样品分析。 本文第一部分详细研究了高灵敏度高选择性硫氰酸根离子选择性电极。 1.合成了二茂铁丁烯酸合铜（Ⅱ）、钴（Ⅱ）、镍（Ⅱ）金属配合物,首次研究了基于该三种金属配合物为中性载体的阴离子选择性电极的电位响应特性。研究发现,以二茂铁丁二烯酸合铜（Ⅱ）为载体的电极对硫氰酸根离子呈现出优良的电位响应性能和选择性,且呈现出反Hofmeister序列行为。其选择性次序为:SCN^->I^->ClO₄^->Sal^->Br^->NO₃^->Cl^-≈NO₂^->SO₃^2->SO₄^2-。运用紫外光谱技术和交流阻抗技术初步探讨了电极的响应机理。并将电极用于实际样品分析,结果令人满意。 2.合成了对二甲氨基苯甲醛邻氨基苯甲酸合铜（Ⅱ）、镍（Ⅱ）、钴（Ⅱ）、锌（Ⅱ）三配位Schiff碱金属配合物,首次研究了基于该四种金属配合物为中性载体的阴离子选择性电极的电位响应特性。研究发现,以对二甲氨基苯甲醛邻氨基苯甲酸合铜（Ⅱ）为载体的电极对硫氰酸根离子具有优良的电位响应性能和选择性并呈现出反Hofmeister选择序列行为。其选择性次序为:SCN^->I^->Sal^-ClO₄^->NO₂^->Br^->Cl^->NO₃^->SO₃^2->SO₄^2->H₂PO₄^-。运用紫外光谱技术和交流阻抗技术初步更多还原

【Abstract】 The analytical method of ion-selective electrode is direct and nondestructive, it has simple structure, simple handled, wide potentiometric response range, highly sensitive, it can rapidly determine sample continuously, so it has been applied in most departments of industry and agriculture and science technology. Design, synthsis and application of highly selective and sensitive neutral carriers are main research subjects in the ion-selective electrode studies. Recently, study on ion-selective electrodes with anti-Hofmeister selectivity pattern is an important and interesting project in the fields of electrochemistry and electroanalytical chemistry. This thesis focuses on seeking design and synthsis of novel metallic complex and basic studies on solvent polymeric membrane（SPM） anion-selective electrodes containing the novel metallic complex. The electrodes can be applied to practice sample analysis.Part I of this thesis deals with design of neutral carrier for solvent polymeric membrane thiocyanate electrode with high selectivity.1. Bis-[（3-ferrocenyl）-（2-crotonic acid）] metallic complex of copper（II）, cobalt（II） and riickel（II） were synthesized. We firstly study the potentiometric response characteristics of the anion-selective PVC membrane electrode based on these ferrocene derivatives as neutral carrier, and found that the electrode based on bis-[（3-ferrocenyl）-（2-crotonic acid）] copper（II） complex [Cu（II）-BFCA] as neutral carrier demonstrates high selectivity towards thiocyanate ion and anti-Hofmeister selectivity sequence in following order: SCN-’> I^-> C1O₄^-> Sal^-> Br^-> NO₃^-> Cl^-NO₂^- > SO₃^- > SO₄²-. The response mechanism is discussed in view of the UVspectroscopy and the A.C. impedance technique. The electrode was successfully applied to the determination of thiocyanate ion in actual sample.2. Dimethylaminobenzaldehyde-（o-aminobenzoic acid） metallic complexes of Cu（II）, Ni（II）, Co（II） and Zn（II） were synthesized. We firstly study the potentiometric response characteristics of the anion-selective PVC membrane electrode based on these metallic complexes as neutral carrier, and found that the electrode based on dimethylaminobenzaldehyde-（o-aminobenzoic acid） copper（II） complex [Cu（II）-DMABABA] as neutral carrier demonstrates high selectivity towards thiocyanate ion and anti-Hofmeister selectivity sequence in following order: SCN > r > Sal" > C1O4" > NO2" > Br > Cl" > NO3 > SO32 > SO42 > H2PO4^. The response mechanism is discussed in view of the UV spectroscopy and the A.C. impedance technique. The electrode was successfully applied to the determination of thiocyanate ion in actual sample.Part II of this thesis deals with design of neutral carrier for solvent polymeric membrane iodide electrode with high selectivity.1. yV,./V-bis-（acetylferrocene）-ethylenediamine metallic complexes of Hg（II）, Cu（II） and Zn（II） were synthesized. We firstly study the potentiometric response characteristics of the anion-selective PVC membrane electrode based on these metallic complexes as neutral carrier, and found that the electrode based on 7V,A^-bis-（acetylferrocene）-ethylenediamine mercury（II） complex [Hg（II）-BAFEDA] as neutral carrier demonstrates high selectivity towards iodide ion and anti-Hofmeister selectivity sequence in following order: I" > Br > SCN > C1O4" > NO2" > Cl" > SO32 > NO3" > SO42". The response mechanism is discussed in view of the UV spectroscopy technique. The electrode was successfully applied to the determination of iodide ion in actual sample.2. #,A^-bis-（dimethylaminobenzaldehyde）-glycine metallic complexes of Co（II）, Ni（II） and Cu（II） were synthesized. We firstly study the potentiometric response characteristics of the anion-selective PVC membrane electrode based on these更多还原