基于纳米孔金与离子印迹聚合物结合的新型电化学传感器用于测定砷离子(III)

doi:10.13208/j.electrochem.191221

电化学（中英文） ›› 2020, Vol. 26 ›› Issue (6): 900-910. doi: 10.13208/j.electrochem.191221

基于纳米孔金与离子印迹聚合物结合的新型电化学传感器用于测定砷离子(III)

马武威¹^,³, 常启刚¹^,^*, 史雄芳³, 童延斌¹, 周立¹, 叶邦策¹^,², 鲁建江¹, 赵金虎¹

^1. 石河子大学化学化工学院/新疆兵团化工绿色过程重点实验室,新疆石河子 832000
^2. 华东理工大学生物反应工程重点实验室,上海,200237
^3. 新疆湘晟新材料科技有限公司,新疆哈密 839000

收稿日期:2019-12-21 修回日期:2020-06-03 出版日期:2020-12-28 发布日期:2020-06-04
通讯作者: 常启刚
基金资助:
国家重点研发计划项目资助No(2016YFC0400704)

Novel Electrochemical Sensor Based on Integration of Nanoporous Gold with Molecularly Imprinted Polymer for Detection of Arsenic Ion(III)

MA Wu-wei¹^,³, CHANG Qi-gang¹^,^*, SHI Xiong-fang³, TONG Yan-bin¹, ZHOU Li¹, YE Bang-ce¹^,², LU Jian-jiang¹, ZHAO Jin-hu¹

^1. Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Production and Construction Corps/School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832000, China
^2. State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai, 200237, China
^3. Xinjiang Xiangsheng New Material Technology Co., Ltd. Hami Xinjiang 839000, China

Received:2019-12-21 Revised:2020-06-03 Published:2020-12-28 Online:2020-06-04
Contact: CHANG Qi-gang

摘要/Abstract

摘要：

砷是一种有毒的化学元素,尤其对环境和人体健康有害. 因此,简单、快速和准确的砷离子（As³⁺）检测方法的开发引起了广泛的关注. 本项工作研究了基于离子印迹聚合物（MIP）和纳米多孔金（NPG）改性氧化铟锡（ITO）电极（MIP/NPG/ITO）用于检测不同水质中砷离子（As³⁺）测定的电化学传感器. 通过步骤简单、易操控、绿色环保的电沉积方法在ITO表面原位制备具有高导电,大比表面积,高生物相容性的NPG. 然后通过电聚合在NPG表面上原位合成一层MIP,其中As³⁺用作模板分子,邻苯二胺用作功能单体. 通过扫描电镜（SEM）和能谱仪（EDS）对MIP/NPG/ITO的制备过程进行了跟踪. 采用铁氰化钾与亚铁氰化钾螯合物作为电化学探针产生信号,采用循环伏安法（CV）和电化学阻抗谱（EIS）研究了MIP/NPG/ITO的电化学行为. 通过优化实验条件,采用循环伏安法对As³⁺进行了定量检测,其测量As³⁺的线性范围为2.0×10^-11至9.0×10^-9 mol·L^-1,检测下限为7.1×10^-12 mol·L^-1（S/N = 3）. 所构建传感器的检出限远低于10 ppb,符合世界卫生组织（WHO）和环境保护局（EPA）设定的饮用水标准. 另外,该传感器具有制备和确定步骤简单,重复性好,重现性和稳定性优异的优点. 值得一提的是,所制备的传感器已成功应用于测量景观河水、地下水、自来水和生活污水等四种水质中As³⁺. 可以预见,这种简单而廉价的传感器在环境监测,食品分析和临床诊断领域具有潜在的实际应用价值.

关键词: 电化学传感器, 砷, 纳米多孔金, 分子印记聚合物.

Abstract:

Arsenic, a toxic chemical element, is detrimental to environment and human health in particular. Therefore, the development of simple, fast, and accurate arsenic ion (As³⁺) detection methods has attracted extensive attention. In this work, an electrochemical sensor based on molecular imprinted polymer (MIP) and nano-porous gold (NPG) modified indium tin oxide (ITO) electrode (MIP/NPG/ITO) was developed for determination of As³⁺ in water with different quality. NPG with high conductivity, large specific surface area and high biocompatibility was prepared in situ on ITO surface by a green electrodeposition method using simple and controllable steps. Then, a layer of MIP was synthesized in situ on NPG surface by electropolymerization, in which As³⁺ was used as a template molecule and mphenylenediamine as a functional monomer. The preparation process of MIP/NPG/ITO was monitored by scanning electron microscope (SEM) and energy-dispersive X-ray spectroscope (EDS). The potassium ferricyanide and potassium ferrocyanide chelates were used as electrochemical probes to generate signals. The electrochemical behavior of MIP/NPG/ITO was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). After optimizing the experimental conditions, As³⁺ was quantitatively detected by cyclic voltammetry. The linear range of As³⁺ was measured from 2.0 ×10^-11 to 9.0×10^-9 mol·L^-1, and the lower detection limit was 7.1×10^-12 mol·L^-1 (S/N = 3). The detection limit of the constructed sensor is far below 10 ppb, which meets the drinking water standards set by the World Health Organization (WHO) and Environmental Protection Agency (EPA). In addition, the sensor has the advantages of simple preparation, simple procedure of determination, good repeatability, excellent reproducibility and stability. It is worth mentioning that the prepared sensor has been successfully applied to the As³⁺ measurements of four water qualities, including landscape river water, groundwater, tap water and domestic sewage. It can be predicted that the reported simple and cheap sensor has potential practical applications in environmental monitoring, food analysis and clinical diagnosis.

Key words: electrochemical sensor, arsenic, nanoporous gold, molecularly imprinted polymer

中图分类号:

O646
TP212.2

马武威, 常启刚, 史雄芳, 童延斌, 周立, 叶邦策, 鲁建江, 赵金虎. 基于纳米孔金与离子印迹聚合物结合的新型电化学传感器用于测定砷离子(III)[J]. 电化学（中英文）, 2020, 26(6): 900-910.

MA Wu-wei, CHANG Qi-gang, SHI Xiong-fang, TONG Yan-bin, ZHOU Li, YE Bang-ce, LU Jian-jiang, ZHAO Jin-hu. Novel Electrochemical Sensor Based on Integration of Nanoporous Gold with Molecularly Imprinted Polymer for Detection of Arsenic Ion(III)[J]. Journal of Electrochemistry, 2020, 26(6): 900-910.

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参考文献 33

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Sample	Addeda/(μg·L^-1)	Total found/(μg·L^-1)^a	Recovery/%
Landscape river water	-	7.92 ± 0.22	-
	10	17.87 ± 0.06	99.36
	20	28.19 ± 0.13	103.41
	30	37.23 ± 0.15	91.29
Groundwater	-	8.67 ± 0.14	-
	10	18.96 ± 0.07	103.34
	20	27.98 ± 0.12	92.04
	30	39.47 ± 0.04	109.23
Tap Water	-	4.87 ± 0.09	-
	10	14.98 ± 0.03	102.26
	20	24.39 ± 0.05	90.14
	30	35.31 ± 0.16	109.03
Domestic sewage	-	6.27 ± 0.18	-
	10	15.62 ± 0.27	89.63
	20	26.78 ± 0.04	108.13
	30	36.24 ± 0.12	99.52

基于纳米孔金与离子印迹聚合物结合的新型电化学传感器用于测定砷离子(III)

Novel Electrochemical Sensor Based on Integration of Nanoporous Gold with Molecularly Imprinted Polymer for Detection of Arsenic Ion(III)

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