痕量镉离子在原位铋修饰掺硼金刚石电极上的传感分析

doi:10.7503/cjcu20170339

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (3): 447.doi: 10.7503/cjcu20170339

痕量镉离子在原位铋修饰掺硼金刚石电极上的传感分析

高成耀^1,^2,³, 佟建华¹, 边超¹, 孙楫舟¹, 李洋¹, 王晋芬⁴, 龚顺¹, 惠允¹, 夏善红¹()

1.中国科学院电子学研究所传感技术国家重点实验室, 北京 100190
2. 中国科学院大学, 北京 100190
3. 中国人民武装警察部队学院指挥系, 廊坊 065000
4.国家纳米科学中心, 北京 100190

收稿日期:2017-05-31 出版日期:2018-03-10 发布日期:2018-01-23
作者简介:联系人简介: 夏善红, 女, 博士, 研究员, 主要从事传感技术方面的研究. E-mail:shxia@mail.ie.ac.cn
基金资助:
国家重点基础研究发展计划项目(批准号: 2015CB352100)、国家自然科学基金(批准号: 61306010)和河北省自然科学基金(批准号: E2014507012)资助

Electroanalytical Sensing of Trace Cd(Ⅱ) Using in-situ Bismuth Modified Boron Doped Diamond Electrode^†

GAO Chengyao^1,^2,³, TONG Jianhua¹, BIAN Chao¹, SUN Jizhou¹, LI Yang¹, WANG Jinfen⁴, GONG Shun¹, HUI Yun¹, XIA Shanhong^1,^*()

1. State Key Laboratory of Transducer Technology, Institute of Electronics, Chinese Academy of Sciences, Beijing 100190, China
2. University of Chinese Academy of Sciences, Beijing 100190, China
3. Chinese People’s Armed Police Force Academy, Langfang 065000, China
4. Chinese National Center for Nanoscience and Technology, Beijing 100190, China

Received:2017-05-31 Online:2018-03-10 Published:2018-01-23
Contact: XIA Shanhong E-mail:shxia@mail.ie.ac.cn
Supported by:
† Supported by the National Basic Reasearch Program of China(No.2015CB352100), the National Natural Science Foundation of China(No.61306010) and the Natural Science Foundation of Hebei Province, China(No.E2014507012)

摘要/Abstract

摘要：

以原位铋修饰掺硼金刚石电极为工作电极, 利用方波脉冲阳极溶出伏安法对重金属镉离子进行检测. 考察了扫描方式、铋离子浓度、电极硼掺杂浓度、支持电解液pH值、富集电位、脉冲参数和富集时间等因素对镉溶出峰电流的影响并进行了优化. 结果表明, 原位铋修饰能有效提高检测的灵敏度, 镉离子浓度与溶出峰电流值在1~10 μg/L范围内呈线性关系, 相关系数为0.9979, 检出限为0.15 μg/L. 干扰实验结果表明, 相邻溶出电位干扰离子铅和锌对镉的检测影响相对较小, 而铜有较大干扰. 实际水样测试结果表明, 回收率在96%~107%之间.

关键词: 掺硼金刚石薄膜电极, 阳极溶出伏安, 镉离子分析, 电化学分析, 原位铋修饰电极

Abstract:

Electroanalytical determination of Cd(Ⅱ) by square wave anodic stripping voltammetry(SWASV) using abismuth in-situ modified boron doped diamond(BDD) electrode was studied. In presence of Bi(Ⅲ), the sensitivity for the determination of Cd(Ⅱ) was remarkably enhanced. Various experimental parameters such as the concentrations of Bi(Ⅲ), boron doped concentrations of BDD electrode, pH value, deposition potential, pulse frequency, pulse size and deposition time were optimized. Under the optimal conditions, the stripping peak currents of Cd(Ⅱ) increased linearly with increasing concentrations of Cd(Ⅱ) in the ranges of 1—10 μg/L(R²=0.9979) . The limit of detection was estimated to be 0.15 μg/L. The sensor was successfully applied to the determination of trace Cd(Ⅱ) in the real water samples with recoveries in the range from 96% to 107%. This developed electrochemical sensor exhibited high sensitivity, good stability and reproducibility.

Key words: Boron doped diamond thin film electrode, Anodic stripping voltammetry, Cd(Ⅱ) detection, Electrochemistry, in-situ Bismuth modified electrode

中图分类号:

O657
O646

TrendMD:

高成耀, 佟建华, 边超, 孙楫舟, 李洋, 王晋芬, 龚顺, 惠允, 夏善红. 痕量镉离子在原位铋修饰掺硼金刚石电极上的传感分析. 高等学校化学学报, 2018, 39(3): 447.

GAO Chengyao, TONG Jianhua, BIAN Chao, SUN Jizhou, LI Yang, WANG Jinfen, GONG Shun, HUI Yun, XIA Shanhong. Electroanalytical Sensing of Trace Cd(Ⅱ) Using in-situ Bismuth Modified Boron Doped Diamond Electrode^†. Chem. J. Chinese Universities, 2018, 39(3): 447.

图/表 14

Fig.1 SEM image(A) and Raman spectrum of boron doped diamond film electrode(B)

Fig.2 Anodic stripping voltammograms of 100 μg/L Cd(Ⅱ) at scanning modes of LSV(a), DPV(b) and SWV(c)

Fig.3 Square wave anodic stripping voltammograms of 100 μg/L Cd(Ⅱ) at bare BDD(a) and in-situ bismuth modified BDD electrode(b)

Fig.4 Stripping peak current of 100 μg/L Cd on in-situ bismuth modified BDD electrode using different concentrations of Bi(Ⅲ)

Fig.5 Effect of boron doped concentrations of BDD electrode on square wave anodic stripping voltammograms of 100 μg/L Cd(Ⅱ)

Fig.6 Effect of pH values of the electrolyte on the peak heights of 100 μg/L Cd in 0.1 mol/L acetate buffer

Fig.7 Effect of the deposition potential on the peak heights of 100 μg/L Cd in 0.1 mol/L acetate buffer

Fig.8 Effect of the pulse frequency of SWAVS on the peak heights of 100 μg/L Cd in 0.1 mol/L acetate buffer

Fig.9 Effect of the pulse size of SWAVS on the peak heights of 100 μg/L Cd in 0.1 mol/L acetate buffer

Fig.10 Effect of the deposition time on the peak heights of 100 μg/L Cd in 0.1 mol/L acetate buffer

Fig.11 Stripping voltammograms for various concentrations of Cd(Ⅱ) in 0.1 mol/L acetic acid(A) and calibration curves for analysis of 1—10 μg/L of Cd(Ⅱ)(B)

Table 1 Interference study of Cd determination

Forgein ion	Ratio of forgein ions/analyte	Peak current decrease ratio(%)	Forgein ion	Ratio of forgein ions/analyte	Peak current decrease ratio(%)
K⁺	100∶1	-0.3	Hg²⁺	5∶1	4.2
Na⁺	100∶1	-0.1	Cr⁶⁺	5∶1	3.5
Ca²⁺	100∶1	2.1	Zn²⁺	2∶1	2.3
Mg²⁺	100∶1	-0.8	Zn²⁺	3∶1	4.1
HC	100∶1	0.5	Pb²⁺	2∶1	4.3
N	100∶1	-0.2	Pb²⁺	3∶1	11.0
Cl^-	100∶1	0.9	Cu²⁺	1∶1	21.6
S $O 4 2 -$	100∶1	-0.5	Cu²⁺	2∶1	72.4
As³⁺	5∶1	3.6	Cu²⁺	3∶1	88.5

Table 1 Interference study of Cd determination

Forgein ion	Ratio of forgein ions/analyte	Peak current decrease ratio(%)	Forgein ion	Ratio of forgein ions/analyte	Peak current decrease ratio(%)
K⁺	100∶1	-0.3	Hg²⁺	5∶1	4.2
Na⁺	100∶1	-0.1	Cr⁶⁺	5∶1	3.5
Ca²⁺	100∶1	2.1	Zn²⁺	2∶1	2.3
Mg²⁺	100∶1	-0.8	Zn²⁺	3∶1	4.1
HC	100∶1	0.5	Pb²⁺	2∶1	4.3
N	100∶1	-0.2	Pb²⁺	3∶1	11.0
Cl^-	100∶1	0.9	Cu²⁺	1∶1	21.6
S $O 4 2 -$	100∶1	-0.5	Cu²⁺	2∶1	72.4
As³⁺	5∶1	3.6	Cu²⁺	3∶1	88.5

Fig.12 Stripping voltammograms of different concentrations of Cu(Ⅱ) added to a solution of 50 μg/L Cd(Ⅱ)a. 50 μg/L Cd2+; b. 50 μg/L Cd2++50 μg/L Cu2+; c. 50 μg/L Cd2++100 μg/L Cu2+; d. 50 μg/L Cd2++150 μg/L Cu2+; e. 50 μg/L Cd2++150 μg/L Cu2++100 μmol/L Fe(CN.

Table 2 Analysis results of Cd ion in real water samples

Sample	Added/(μg·L^-1)	Found/(μg·L^-1)	Recovery(%)
Tap water		Not found
	10.0	10.2	102
	20.0	20.3	101
	30.0	29.5	98
Pond water 1		Not found
	10.0	10.7	107
	20.0	19.3	97
	30.0	29.5	98
Pond water 2		Not found
	10.0	9.6	96
	20.0	20.5	103
	30.0	31.2	104

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痕量镉离子在原位铋修饰掺硼金刚石电极上的传感分析

Electroanalytical Sensing of Trace Cd(Ⅱ) Using in-situ Bismuth Modified Boron Doped Diamond Electrode^†

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痕量镉离子在原位铋修饰掺硼金刚石电极上的传感分析

Electroanalytical Sensing of Trace Cd(Ⅱ) Using in-situ Bismuth Modified Boron Doped Diamond Electrode†

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Electroanalytical Sensing of Trace Cd(Ⅱ) Using in-situ Bismuth Modified Boron Doped Diamond Electrode^†