基于新型Schiff碱铜配合物为中性载体高选择性硫氰酸根离子电极的研究  

Study on highly selective thiocyanate electrode based on new schiff base copper(Ⅱ ) complex as neutral carriers

作　　者：叶光荣[1] 张丽娜[1] 廖家耀[1] 李艳[1] 柴雅琴[1] 袁若[1] 

机构地区：[1]西南大学化学化工学院,重庆400715

出　　处：《化学传感器》2006年第4期28-33,共6页Chemical Sensors

基　　金：重庆自然科学基金(CSTC-2004BB4149);西南大学博士基金(SWNUB2004021)

摘　　要：首次研究了基于水杨醛缩亚辛胺合铜(Ⅱ)金属配合物犤Cu(Ⅱ)-SADOA犦为中性载体的PVC膜电极。该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选择性行为,其选择性次序为SCN->ClO4->Sal->I->Br->NO2->NO3->SO32->Cl->SO42->H2PO4-。在pH=5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3.0×10-6～1.0×10-1mol/L,斜率为-55.7mV/dec(20℃),检出下限为1.0×10-6mol/L。采用交流阻抗技术和紫外可见光谱技术研究了电极的响应机理,结果表明配合物与电极的响应行为之间有非常密切的构效关系。该电极具有响应快、重现性好、检出限低、制备简单等优点。将电极用于实际样品分析,其结果令人满意。The utilization of a newly synthesized Cu （ Ⅱ ） complex, （salicaldehydeoctamine - Cu （ Ⅱ ） complex）, as a novel ionophore for the preparation of anion - selective polymeric membrane electrode was tested. The results show that the electrode based on salicaldehydedioctamine - Cu（ Ⅱ ） complex demonstrates excellent potentiometric response towards thiocyanate ion and anti- Hofmeister selectivity sequence in following order： SCN^-〉 ClO4^-〉 Sal^-〉 I^-〉 Br^-〉 NO2^-〉 NO3^- 〉 SO3^2-〉 Cl^-〉 SO4^2-〉 H2PO4^-. The ionophore presented anti - Hofmeister behavior with enhanced potentiometric toward thioeyanate ion compared to other anions. The influence of some experimental parameters such as membrane composition, and concentration of internal solution on the potential response of the SCN - sensor were investigated. The electrode exhibits a near - Nernstian response for SCN - over a wide concentration range （ 1.0 × 10^ -1 to 3.0 × 10 ^-6 mol/L） with a slope - 55.7 mV per decade and a detection limit of 1.0 × 10^-6 mol/L in a pH range of 5. The response mechanism is discussed in view of the AC impedance technique and the UV spectroscopy technique. The electrode exhibits the advantages of high selectivity, low detection limit, reproducibility and simplicity. The electrode was successfully applied to the determination of thioeyanate ion in waste water and human saliva.

关 键 词：SCN^-离子选择性电极 水杨醛缩亚辛胺合铜(Ⅱ)金属 中性载体 

分 类 号：O657.1[理学—分析化学]