铕离子掺杂类普鲁士蓝化学修饰电极对三联吡啶钌(Ⅱ)的电催化氧化研究

利用电化学沉积法制备了稀土铕(Ⅲ)离子掺杂的类普鲁士蓝化学修饰铂电极,采用循环伏安法(CV)和示差脉冲伏安法(DPV)研究了修饰电极上Ru(bipy)32 的电催化氧化行为,探讨了Ru(bipy)32 的电催化氧化过程对其电致化学发光效率的影响.结果表明,该化学修饰电极对Ru(bipy)32 有稳定、良好的电催化氧化活性;在相同实验条件下,Ru(bipy)32 催化氧化过程的脉冲峰电流与裸铂电极上的脉冲氧化峰电流相比提高约一个数量级,其氧化峰电位也向阴极移动约15 mV,且催化峰电流与Ru(bipy)32 的浓度在0.05~0.5 mmol/L范围内呈良好的线性关系,线性回归方程为Ip=3.84 4.41C(r=0.999 5,n=4).同时,该化学修饰电极还可以大大提高Ru(bipy)32 的电致化学发光效率,非常有利于毛细管电泳电致化学发光联用技术的发展.

Electrocatalytic oxidation of Ru(bipy)32+ at Prussian blue analogue film doped with rare-earth ions electrode

A platinum electrode modified with Prussian blue analogue film which doped with Eu~(3 ) is prepared successfully by means of electrodepositing.The electrochemical oxidation of Ru(bipy)~(2 )_3 at the modified electrode is studied by cyclic voltammogram and differential pulse voltammetry,and the resultant effect on the electrochemiluminescence efficiency of Ru(bipy)~(2 )_3 is discussed as well.The results show that the modified electrode exhibites excellent electrocatalytic activity for the oxidation of Ru(bipy)~(2 )_3 and the pulse peak current from the oxidation of Ru(bipy)~(2 )_3 is approximately enhanced by one order of magnitude compared with the bare platinum electrode,accompanied with the electrocatalytic oxidation peak potential shifted 15 mV.The oxidation peak currents are proportional to the concentrations of(Ru(bipy)~(2 )_3) in the range from 0.05 to 0.5 mmol/L and the regression equation is I_p=3.84 4.41C with a correlation coefficient of 0.999 5(n=4).Besides,the use of the prepared electrode will benefit the development of capillary electrophoresis-electrochemiluminescence technique since the electrochemiluminescence efficiency of Ru(bipy)~(2 )_3 is significantly enhanced by the modified electrode.