Huang Rongfu, Zheng Xingwang, Qu Yingjuan
School of Chemistry and Material Science, Shaanxi Normal University, Xi'an 710062, PR China.
Anal Chim Acta. 2007 Jan 23;582(2):267-74. doi: 10.1016/j.aca.2006.09.035. Epub 2006 Sep 26.
In the present work, a novel method for immobilization of carbon nanotubes (CNTs) on the surface of graphite electrode was proposed. We further found that superoxide ion was electrogenerated on this CNTs-modified electrode, which can react with sulfide ion combing with a weak but fast electrogenerated chemiluminescence (ECL) emission, and this weak ECL signal could be enhanced by the oxidative products of rhodamine B. In addition, the rate constant of this electrochemical reaction k(0) was investigated and confirmed that the speed of electrogenerating superoxide ion was in accordance with the subsequent fast CL reaction. Thus, the fast CL reaction of superoxide ion with target brought in the possibility of high selectivity based on time-resolved, relative to other interferences. Based on these findings, an excellently selective and highly sensitive ECL method for sulfide ion was developed. Under the optimum conditions, the enhancing ECL signals were linear with the sulfide ion concentration in the range from 6.0 x 10(-10) to 1.0 x 10(-8) mol L(-1), and a 2.0 x 10(-10) mol L(-1) detection limits (3sigma) was achieved. In addition, the proposed method was successfully used to detect sulfide ion in environmental water samples.
在本工作中,提出了一种将碳纳米管(CNTs)固定在石墨电极表面的新方法。我们进一步发现,在这种碳纳米管修饰电极上能电生成超氧离子,其可与硫离子反应并伴随微弱但快速的电化学发光(ECL)发射,且罗丹明B的氧化产物可增强这种微弱的ECL信号。此外,研究了该电化学反应的速率常数k(0),证实超氧离子的电生成速度与随后快速的化学发光反应相匹配。因此,相对于其他干扰物,超氧离子与目标物的快速化学发光反应带来了基于时间分辨的高选择性可能性。基于这些发现,开发了一种对硫离子具有优异选择性和高灵敏度的ECL方法。在最佳条件下,增强的ECL信号与硫离子浓度在6.0×10(-10)至1.0×10(-8) mol L(-1)范围内呈线性关系,实现了2.0×10(-10) mol L(-1)的检测限(3σ)。此外,所提出的方法成功用于检测环境水样中的硫离子。