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用于电化学溶出分析的锑膜电极。

Antimony film electrode for electrochemical stripping analysis.

作者信息

Hocevar Samo B, Svancara Ivan, Ogorevc Bozidar, Vytras Karel

机构信息

Analytical Chemistry Laboratory, National Institute of Chemistry, P.O. Box 660, SI-1001 Ljubljana, Slovenia.

出版信息

Anal Chem. 2007 Nov 15;79(22):8639-43. doi: 10.1021/ac070478m. Epub 2007 Oct 20.

Abstract

In this work, an antimony film electrode (SbFE) is reported for the first time as a possible alternative for electrochemical stripping analysis of trace heavy metals. The SbFE was prepared in situ on a glassy carbon substrate electrode and employed in combination with either anodic stripping voltammetry or stripping chronopotentiometry in nondeaerated solutions of 0.01 M hydrochloric acid (pH 2). Several key operational parameters influencing the electroanalytical response of SbFE were examined and optimized, such as deposition potential, deposition time, and composition of the measurement solution. The SbFE exhibited well-defined and separated stripping signals for both model metal ions, Cd(II) and Pb(II), surrounded with low background contribution and a relatively large negative potential range. The electrode revealed good linear behavior in the examined concentration range from 20 to 140 microg L-1 for both test metal ions, with a limit of detection (3sigma) of 0.7 microg L-1 for Cd(II) and 0.9 microg L-1 for Pb(II) obtained after a 120 s deposition step, and good reproducibility, with a relative standard deviation (RSD) of +/-3.6% for Cd(II) and +/-6.2% for Pb(II) (60 microg L-1, n = 12). When comparing the SbFE with the commonly used mercury film electrode and recently introduced bismuth film electrode, the newly proposed electrode offers a remarkable performance in more acidic solutions (pH < or = 2), which can be advantageous in electrochemical analysis of trace heavy metals, hence contributing to the wider applicability of electrochemical stripping techniques in connection with "mercury-free" electrodes.

摘要

在本研究中,首次报道了锑膜电极(SbFE)作为痕量重金属电化学溶出分析的一种可能替代物。SbFE是在玻碳基底电极上原位制备的,并与阳极溶出伏安法或溶出计时电位法联用,用于0.01 M盐酸(pH 2)的非除氧溶液中。研究并优化了影响SbFE电分析响应的几个关键操作参数,如沉积电位、沉积时间和测量溶液的组成。对于模型金属离子Cd(II)和Pb(II),SbFE表现出明确且分离的溶出信号,背景贡献低,负电位范围相对较大。该电极在20至140 μg L-1的检测浓度范围内,对两种测试金属离子均表现出良好的线性行为,在120 s沉积步骤后,Cd(II)的检测限(3σ)为0.7 μg L-1,Pb(II)的检测限为0.9 μg L-1,并且具有良好的重现性,Cd(II)的相对标准偏差(RSD)为±3.6%,Pb(II)的相对标准偏差为±6.2%(60 μg L-1,n = 12)。当将SbFE与常用的汞膜电极和最近引入的铋膜电极进行比较时,新提出的电极在酸性更强的溶液(pH≤2)中表现出显著的性能,这在痕量重金属的电化学分析中可能具有优势,从而有助于电化学溶出技术与“无汞”电极相关的更广泛应用。

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