电化学微传感器检测水中痕量铜离子

蔡良圣; 林君; 辛青; 臧月

PDF(603 KB)

中国环境科学 ›› 2020, Vol. 40 ›› Issue (8) : 3394-3400.

水污染与控制

电化学微传感器检测水中痕量铜离子

蔡良圣^1,2, 林君^1,2, 辛青^1,2, 臧月^1,2

作者信息 +

The detection of copper ion in water with electrochemical microsensors

CAI Liang-sheng^1,2, LIN Jun^1,2, XIN Qing^1,2, ZANG Yue^1,2

Author information +

文章历史 +

摘要

为改善微电极在阳极溶出伏安法检测重金属离子过程中低电流响应和低电催化能力的缺点，提出了一种在碳纤维微电极表面合成还原氧化石墨烯/纳米金材料制得还原氧化石墨烯纳米金修饰碳纤维微电极（rGO/AuNPs CFMEs）的方法.通过SEM表征，所制备的rGO/AuNPs CFMEs具有比表面积高、吸附能力强和催化活性好的特点，因此改性微电极适合作为方波阳极溶出伏安法（SWASV）测定水中铜离子（Cu²⁺）的工作电极.在构建微传感器测试水中痕量铜离子系统后，对pH值、电导率、富集时间和富集电位等检测条件进行了优化.在pH值为4，电导率为36.1S/m，富集时间为360s，富集电位为-1.2V的最佳条件下，铜的线性范围和检出限分别0~1.0μmol/L和2.4nmol/L.此外，微传感器的可重复性、长期稳定性以及选择性也得到了验证.

Abstract

In order to improve the shortcomings of low current response and low electrocatalytic ability of microelectrodes in the detection of heavy metal ions by anode stripping voltammetry method, a simple and environmental friendly methods was introduced to modify the carbon fibers with reduced graphene oxide and Goldnanoparticles (rGO/AuNPs CFMEs). The modified carbon fibers were observed with SEM. The rGO/AuNPs CFMEs had significantly high specific surface area, strong adsorption capacity and high catalytic activity. Thus, they were utilized as a novel electrochemical microsensors for Cu²⁺ detection using square wave anodic stripping voltammetry (SWASV) method. The operational conditions, such as pH value, conductivity deposition time and potential, were optimized. Under the optimized conditions (pH=4, conductivity = 36.1S/m, deposition time=360s and deposition potential=-1.2V), the linear rage of Cu²⁺ was from 0 to 1.0μmol/L (R²=0.996), with the detection limit concentration of 2.4nmol/L (S/N=3). Besides, the microsensors’ excellent repeatability, long term stability and selectivity were verified by our experiments.

导出引用

蔡良圣, 林君, 辛青, 臧月. 电化学微传感器检测水中痕量铜离子[J]. 中国环境科学. 2020, 40(8): 3394-3400

CAI Liang-sheng, LIN Jun, XIN Qing, ZANG Yue. The detection of copper ion in water with electrochemical microsensors[J]. China Environmental Science. 2020, 40(8): 3394-3400

中图分类号： X13

参考文献

[1] 李杜娟,徐枫,樊凯,等.原位合成纳米金/石墨烯修饰玻碳电极检测水和土壤中痕量铅[J].农业工程学报, 2018,34(11):203-208. Li D J, Xu F, Fan K, et al. In-suit synthesis of graphene/gold nanoparticles modified glassy carbon electrode for detection of lead in water and soil[J]. Transactions of the Chinese Society of Agricultural Engineering, 2018,34(11):203-208.
[2] Wang S, Wang Y, Zhou L, et al. Fabrication of an effective electrochemical platform based on graphene and AuNPs for high sensitive detection of trace Cu²⁺[J]. Electrochimica Acta, 2014,132:7-14.
[3] De Barros A, Ferreira M, Constantino C J L, et al. Nanocomposites based on LbL films of polyaniline and sodium montmorillonite clay[J]. Synthetic Metals, 2014,197:119-125.
[4] Huang C C, He J C. Electrosorptive removal of copper ions from wastewater by using ordered mesoporous carbon electrodes[J]. Chemical Engineering Journal, 2013,221:469-475.
[5] Xiong W, Zhou L, Liu S. Development of Gold-doped carbon foams as a sensitive electrochemical sensor for simultaneous determination of Pb (II) and Cu (II)[J]. Chemical Engineering Journal, 2016,284:650-656.
[6] 傅国伟.中国水土重金属污染的防治对策[J].中国环境科学, 2012, 32(2):373-376. Fu G W. Countermeasures for water and soil heavy metal pollution in China[J]. China Environmental Science, 2012,32(2):373-376.
[7] 王萌,李杉杉,李晓越,等.我国土壤中铜的污染现状与修复研究进展[J].地学前缘, 2018,25(5):311-319. Wang M, LiS S, Li X Y, et al. An overview of current status of copper pullution in soil and remediation efforts in China[J]. Earth Science Frontiers, 2018,25(5):305-313.
[8] Lu Z, Dai W, Liu B, et al. One pot synthesis of dandelion-like polyaniline coated Gold nanoparticles composites for electrochemical sensing applications[J]. Journal of Colloid and Interface Science, 2018,525:86-96.
[9] 辛思洁,林金石.土壤重金属检测方法应用现状及发展趋势[J].福建分析测试, 2018,27(3):32-37. Xin S J, Lin J S. Status application and trend of detection method for soil heavy metal[J]. Fujian Analysis & Testing, 2018,27(3):32-37.
[10] Zhang B, Chen J D, Zhu H, et al. Facile and green fabrication of size-controlled AuNPs/CNFs hybrids for the highly sensitive simultaneous detection of heavy metal ions[J]. Electrochimica Acta, 2016,196:422-430.
[11] Ameen S, Shaheer Akhtar M, Husain M. A review on synthesis processing, chemical and conduction properties of polyaniline and its nanocomposites[J]. Science of Advanced Materials, 2010,2(4):441-462(22).
[12] Bai J, Wu L P, Wang X J, et al. Hemoglobin-graphene modified carbon fiber microelectrode for direct electrochemistry and electrochemical H₂O₂ sensing[J]. Electrochimica Acta, 2015,185:142-147.
[13] 陈立伟,韩庆,张慧敏,等.石墨烯基微电极的制备及其在电化学传感中的应用[J].应用化学, 2018,35(3):286-298. Chen L W, Han Q, Zhang H M, et al. Preparation of graphene-based microelectrode and its application in electrochemical sensing[J]. Chinese Journal of Applied Chemistry, 2018,35(3):286-298.
[14] Mohanaraj S, Wonnenberg P, Cohen B, et al. Gold nanoparticle modified carbon fiber microelectrodes for enhanced neurochemical detection[J]. Journal of Visualized Experiments, 2019,147:3791-3780.
[15] Lv H, Teng Z, Wang S, et al. Voltammetric simultaneous ion flux measurements platform for Cu²⁺, Pb²⁺, and Hg²⁺, near rice root surface:Utilizing carbon nitride heterojunction film modified carbon fiber microelectrode[J]. Jouranl of Sensors Actuatoes, 2018,256:98-106.
[16] Bai J, Qi P F, Ding X T, et al. Graphene composite coated carbon fiber:electrochemical synthesis and application in electrochemical sensing[J]. Royal Society of Chemistry Advances, 2016,6(14):11250-11255.
[17] Sang S, Li D, Zhang H, et al. Facile synthesis of AgNPs on reduced graphene oxide for highly sensitive simultaneous detection of heavy metal ions[J]. Royal Society of Chemistry Advances, 2017,7(35):21618-21624.
[18] Gao C, Yu X Y, Xu R X, et al. AlOOH-reduced graphene oxide nanocomposites:One-pot hydrothermal synthesis and their enhanced electrochemical activity for heavy metal ions[J]. Acs Appl Mater Interfaces, 2012,4(4):4672-4682.
[19] Waheed A, Mansha M, Ullah N. Nanomaterials-based electrochemical detection of heavy metals in water:Current status, challenges and future direction[J]. TrAC Trends in Analytical Chemistry, 2018,105:37-51.
[20] Gnanaprakasam P, Jeena S E, Premnath D, et al. Simple and robust green synthesis of AuNPs on reduced graphene oxide for the simultaneous detection of toxic heavy metal ions and bioremediation using bacterium as the scavenger[J]. Electroanalysis, 2016,28(28):1-10.
[21] 刘诗彧,王荣昌,马翠香,等.氧化石墨烯与聚苯胺修饰阴极的微生物燃料电池电化学性能[J].中国环境科学, 2019,39(9):3866-3871. Liu S Y, Wang R C, Ma C X, et al. Electrochemical performance of microbial fuel cell with graphene oxide and polyaniline modified cathode[J]. China Environmental Science, 2019,39(9):3866-3871.
[22] 罗启枚,刘登友,王辉宪,等.纳米金/碳纳米管修饰石墨电极测定邻苯二酚[J].中国环境科学, 2010,30(10):1349-1352. Luo Q M, Liu D Y, Wang H X. Electrochermical determinnation of catechol with nano-gold/carbon nanotubes modified graphite electrode.China Environmental Science[J]. 2010,30(10):1349-1352.
[23] Yu S, Jiang Y, Wang C. A polymer composite consists of electrochemical reduced graphene oxide/polyimide/chemical reduced graphene oxide for effective preparation of SnSe by electrochemical atomic layer deposition method with enhanced electrochemical performance and surface area[J]. Electrochimica Acta, 2013,114:430-438.
[24] Shao Y, Wang J, Engelhard M H, et al. Facile and controllable electrochemical reduction of graphene oxide and its applications[J]. Journal of Materials Chemistry, 2010,20(4):743-748.
[25] Dharuman V, Hahn J H, Jayakumar K, et al. Electrochemically reduced graphene-gold nano particle composite on indium tin oxide for label free immuno sensing of estradiol[J]. Electrochimica Acta, 2013,114:590-597.
[26] 陈利萍,杨蓉,燕映霖,等.氧化石墨烯还原程度的控制[J].化学进展, 2018,30(12):1930-1941. Chen L P, Yang R, Yan Y L, et al. The control of reduction degree of grahpene oxide[J]. Progress In Chemistry, 2018,114:590-597.
[27] Zbigniew L, Haluk B. Fundamentals of biofilm research second edition[M]. Boca Raton:CRC Press, 2014:291-298.
[28] Chen K, Chen L, Chen Y, et al. Three-dimensional porous graphene-based composite materials:electrochemical synthesis and application[J]. Journal of Materials Chemistry, 2012,22(39):20968-20976.
[29] 高成耀,佟建华,边超,等.锌、镉、铅离子在原位铋修饰掺硼金刚石薄膜电极上的传感分析[J].分析化学, 2018,46(2):217-224. Gao C Y, Tong J H, Bian C, et al. Sensing analysis of zinc, cadmium and lead ions on in-situ bismuth modified boron-doped diamond film electrode[J]. Chinese Journal of Analytical Chemistry, 2018,46(2):217-224.
[30] Burns M, Valdivia H. Modelling the limit of detection in real-time quantitative PCR[J]. European Food Research and Technology, 2008,226(6):1513-1524.