Ouyang Ruizhuo, Zhang Wangyao, Zhou Shilin, Xue Zi-Ling, Xu Lina, Gu Yingying, Miao Yuqing
Department of Chemistry, University of Shanghai for Science and Technology, Shanghai, 200093,China.
Zhejiang Normal University, Jinhua 321004, China.
Electrochim Acta. 2013 Dec 15;113:686-693. doi: 10.1016/j.electacta.2013.09.110.
We report here the successful fabrication of an improved Bi film wrapped single walled carbon nanotubes modified glassy carbon electrode (Bi/SWNTs/GCE) as a highly sensitive platform for ultratrace Cr(VI) detection through catalytic adsorptive cathodic stripping voltammetry (AdCSV). The introduction of negatively charged SWNTs extraordinarily decreased the size of Bi particles to nanoscale due to electrostatic interaction which made Bi(III) cations easily attracted onto the surface of SWNTs in good order, leading to higher quality of Bi film deposition. The obtained Bi/SWNTs composite was well characterized with electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), the static water contact angle and the voltammetric measurements. The results demonstrates the improvements in the quality of Bi film deposited on the surface of SWNTs such as faster speed of electron transfer, more uniform and smoother morphology, better hydrophilicity and higher stripping signal. Using diethylene triaminepentaacetic acid (DTPA) as complexing ligand, the fabricated electrode displays a well-defined and highly sensitive peak for the reduction of Cr(III)-DTPA complex at -1.06 V (. Ag/AgCl) with a linear concentration range of 0-25 nM and a fairly low detection limit of 0.036 nM. No interference was found in the presence of coexisting ions, and good recoveries were achieved for the analysis of a river sample. In comparison to previous approaches using Bi film modified GCE, the newly designed electrode exhibits better reproducibility and repeatability towards aqueous detection of trace Cr(VI) and appears to be very promising as the basis of a highly sensitive and selective voltammetric procedure for Cr(VI) detection at trace level in real samples.
我们在此报告成功制备了一种改进的铋膜包裹单壁碳纳米管修饰玻碳电极(Bi/SWNTs/GCE),作为通过催化吸附阴极溶出伏安法(AdCSV)检测超痕量Cr(VI)的高灵敏度平台。由于静电相互作用,带负电荷的单壁碳纳米管的引入极大地将铋颗粒尺寸减小至纳米级,这使得Bi(III)阳离子易于有序地吸附在单壁碳纳米管表面,从而实现更高质量的铋膜沉积。通过电化学阻抗谱(EIS)、扫描电子显微镜(SEM)、静态水接触角和伏安测量对所得的Bi/SWNTs复合材料进行了充分表征。结果表明,沉积在单壁碳纳米管表面的铋膜质量得到了改善,如电子转移速度更快、形态更均匀更光滑、亲水性更好以及溶出信号更高。使用二乙烯三胺五乙酸(DTPA)作为络合配体,制备的电极在-1.06 V(相对于Ag/AgCl)处对Cr(III)-DTPA络合物的还原显示出明确且高度灵敏的峰,线性浓度范围为0 - 25 nM,检测限相当低,为0.036 nM。在共存离子存在的情况下未发现干扰,对河水样品分析获得了良好的回收率。与先前使用铋膜修饰玻碳电极的方法相比,新设计的电极对水中痕量Cr(VI)的检测具有更好的重现性和重复性,并且作为一种用于实际样品中痕量Cr(VI)检测的高灵敏度和选择性伏安法的基础,似乎非常有前景。