四(三羟甲基氨基甲烷)合铜(II)电催化联吡啶钌/二氧化硅复合纳米粒子电化学发光分析特性研究

doi:10.6023/A15010047

化学学报 ›› 2015, Vol. 73 ›› Issue (7): 749-754.DOI: 10.6023/A15010047 上一篇

研究论文

四(三羟甲基氨基甲烷)合铜(II)电催化联吡啶钌/二氧化硅复合纳米粒子电化学发光分析特性研究

李媛, 刘文娜, 郑行望

陕西师范大学化学化工学院陕西省生命分析重点实验室西安 710062

投稿日期:2015-01-16 发布日期:2015-05-22
通讯作者: 郑行望 E-mail:zhengxw@snnu.edu.cn
基金资助:
项目受国家自然科学基金(No. 21375085)资助.

Investigation into Electrogenerated Chemiluminescence Behavior of Tris(bipyridine)ruthenium(II)/silica Nanoparticles Electrocatalyzed by Cu(tris(hydroxymethyl)aminomethane)₄²⁺ Complex

Li Yuan, Liu Wenna, Zheng Xingwang

School of Chemistry & Chemical Engineering, Shaanxi Normal University, Key Laboratory of Analytical Chemistry for Life Science of Shaanxi Province, Xi'an 710062, China

Received:2015-01-16 Published:2015-05-22
Supported by:
Supporting information for this article is available free of charge via the Internet at http://sioc-journal.cn.Project supported by the National Natural Science Foundation of China (No. 21375085).

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1. 四(三羟甲基氨基甲烷)合铜(II)电催化联吡啶钌/二氧化硅复合纳米粒子电化学发光分析特性研究.PDF(177KB)

摘要/Abstract

水分子与联吡啶钌(Ru(bpy)₃²⁺)之间的电化学发光(ECL)反应早已被人们发现, 但其增敏Ru(bpy)₃²⁺电化学发光信号的能力不强, 很难实现分析应用. 我们发现四(三羟甲基氨基甲烷)合铜(II)(Cu(Tris)₄²⁺)可电催化水的氧化反应生成活性中间产物羟基自由基(·OH), ·OH能够快速进入二氧化硅基质, 有效地增敏联吡啶钌/二氧化硅复合纳米粒子(RuS NPs)的电化学发光, 并利用紫外-可见吸收光谱、电化学方法、电化学发光方法等研究了可能的电化学反应机理. 基于以上研究, 发展了一种以水分子作为共反应试剂, 测定铜离子的电化学发光分析新方法. 该方法在铜离子浓度为2.0×10^-7～1.0×10^-4 mol/L的范围内, 电化学发光强度与铜离子浓度呈现良好的线性, 同时该方法具有很好的灵敏度和选择性, 检出限(S/N=3)达到1.0×10^-7 mol/L, 且Ca²⁺、Mg²⁺、Na⁺、Fe³⁺、Pb²⁺、Cd²⁺、Co²⁺、Ni²⁺、Mn²⁺等常见离子不干扰测定. 使用该法对自来水和黑河水样中铜离子含量进行测定, 分别往两个水样中加入2～3倍的铜离子标准溶液, 其加标回收率在97.0%～102.5%之间; 与原子吸收分光光度法对比, 相对误差分别为4.1%和4.7%, 说明该方法测定结果具有一定的可靠性.

关键词: 电化学发光, 联吡啶钌, 联吡啶钌/二氧化硅复合纳米粒子, Cu²⁺

Although many electrogenerated chemiluminescence (ECL) co-reactants, such as tripropylamine (TPA) and oxalic acid, have been applied in Tris(bipyridine)ruthenium(II)/silica nanoparticles (Ru(bpy)₃²⁺/silica nanoparticles, RuS NPs) ECL system, the poor diffusion behavior of these co-reactants in silica matrix as well as its toxic disadvantages limited their further ECL analytical application. Therefore, it was very meaningful to explore a new type of co-reactant in RuS NPs ECL system for obtaining a good analytical result. In this paper, we found that the electrochemical oxidation reaction of H₂O could be catalyzed by Cu(Tris)₄²⁺ (Tris(hydroxymethyl)aminomethane, Tris) complexes and produce the intermediate (·OH). The ECL of Ru(bpy)₃²⁺-doped RuS NPs could be induced by ·OH and produce the strong ECL signals. The possible ECL mechanism was investigated by ultraviolet-visible (UV-vis) absorption spectrum, electrochemical methods and ECL methods. It may be that when Cu²⁺ was added into the Tris-HCl solution, it would combine with the amino of Tris to form Cu(Tris)₄²⁺ complexes; in the subsequent ECL reaction process, Ru(bpy)₃²⁺inside RuS NPs near by the surface of electrode was firstly oxidized to Ru(bpy)₃³⁺. At the same time, the reduction reaction of Ru(bpy)₃³⁺ would catalyze the oxidization of Cu(Tris)₄²⁺to generate the Cu(Tris)₄³⁺; then, the reduction of Cu(Tris)₄³⁺ would catalyze the electrochemical oxidation reaction of H₂O and was accompanied by the generation of O₂ and strong reducing agents (·OH). On the one hand, the silica substrate could protect Ru(bpy)₃²⁺-doped RuS NPs from O₂ interference, and avoid the quenching effect of Ru(bpy)₃²⁺ ECL induced by O₂. On the other hand, ·OH can rapidly go through the silica substrate and react with the oxidation state of Ru(bpy)₃³⁺ inside of RuS NPs because it is a kind of neutral group. Based on these findings, we develop a new ECL method for sensitive detection of Cu²⁺ using H₂O molecular as a co-reacant. Under the optimal conditions, the proposed method achieved a detection limit of 1.0×10^-7 mol/L with RSD of less than 5.0%.

Key words: electrogenerated chemiluminescence, Tris(bipyridine)ruthenium(II), Tris(bipyridine)ruthenium(II)/silica nanoparticles, Cu²⁺

引用此文

李媛, 刘文娜, 郑行望. 四(三羟甲基氨基甲烷)合铜(II)电催化联吡啶钌/二氧化硅复合纳米粒子电化学发光分析特性研究[J]. 化学学报, 2015, 73(7): 749-754.

Li Yuan, Liu Wenna, Zheng Xingwang. Investigation into Electrogenerated Chemiluminescence Behavior of Tris(bipyridine)ruthenium(II)/silica Nanoparticles Electrocatalyzed by Cu(tris(hydroxymethyl)aminomethane)₄²⁺ Complex[J]. Acta Chim. Sinica, 2015, 73(7): 749-754.

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四(三羟甲基氨基甲烷)合铜(II)电催化联吡啶钌/二氧化硅复合纳米粒子电化学发光分析特性研究

Investigation into Electrogenerated Chemiluminescence Behavior of Tris(bipyridine)ruthenium(II)/silica Nanoparticles Electrocatalyzed by Cu(tris(hydroxymethyl)aminomethane)₄²⁺ Complex

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四(三羟甲基氨基甲烷)合铜(II)电催化联吡啶钌/二氧化硅复合纳米粒子电化学发光分析特性研究

Investigation into Electrogenerated Chemiluminescence Behavior of Tris(bipyridine)ruthenium(II)/silica Nanoparticles Electrocatalyzed by Cu(tris(hydroxymethyl)aminomethane)42+ Complex

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Investigation into Electrogenerated Chemiluminescence Behavior of Tris(bipyridine)ruthenium(II)/silica Nanoparticles Electrocatalyzed by Cu(tris(hydroxymethyl)aminomethane)₄²⁺ Complex