Nafion/石墨烯量子点修饰电极对重金属和氯霉素的电化学检测
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摘要
本文采用简单的原位电解石墨棒方法,在一定的电流密度下成功制备出粒径均匀的石墨烯量子点(GQDs),并构建Nafion/GQDs修饰玻碳电极(Nafion/GQDs/GCE)。采用阳极溶出伏安法和示差脉冲伏安法分别应用于重金属Pb(Ⅱ)、Cd(Ⅱ)和氯霉素的电化学检测。研究结果表明,Pb(Ⅱ)和Cd(Ⅱ)的溶出电流随着他们浓度的增加而增加,并呈现良好的线性关系,Pb(Ⅱ)线性范围为4.82×10~(-8)～9.65×10~(-7)mol/L(R2=0.9923),Cd(Ⅱ)线性范围为1.07×10~(-7)～1.96×10~(-6) mol/L(R2=0.9912),所得Pb(Ⅱ)和Cd(Ⅱ)检出限分别为1.61×10~(-8) mol/L和3.57×10~(-8) mol/L。该Nafion/GQDs/GCE对氯霉素具有明显的电催化还原作用,电催化机理是6电子参与的不可逆反应,电子转移速率常数ks为105.4s-1。该修饰电极对氯霉素的催化还原电流与其浓度在5.00×10~(-7)～2.50×10~(-3) mol/L范围内呈良好的线性关系,检出限(S/N=3)为1.67×10~(-7) mol/L。该Nafion/GQDs/GCE还具有良好的抗干扰性、稳定性和重现性,对实际样品的检测取得满意的结果。
In this paper,homogeneous graphene quantum dots(GQDs)were successfully prepared by a simple,environmental-friendly way of in-situ electrolyzing graphite rod at a certain current density.The GQDs were dispersed into Nafion solution,Nafion/GQDs composites modified glassy carbon electrode(Nafion/GQDs/GCE) was prepared. As-prepared Nafion/GQDs/GCE was studied for the electrochemical detection of Pb(Ⅱ),Cd(Ⅱ)and chloramphenicol by anodic stripping voltammetry and different pulse voltammetry,respectively.The results demonstrated that Nafion/GQDs/GCE had excellent electrochemical properties for the detection of Pb(Ⅱ),Cd(Ⅱ)and chloramphenicol.With the increase of Pb(Ⅱ)and Cd(Ⅱ)concentration,the anodic stripping currents of Pb(Ⅱ)and Cd(Ⅱ)were proportional to their concentrations in the linear range of 4.82×10~(-8)-9.65×10~(-7) mol/L(R2=0.9923)for Pb(Ⅱ)and 1.07×10~(-7)-1.96×10~(-6) mol/L for Cd(Ⅱ)(R2=0.9912).The detection limits(S/N=3)were 1.61×10~(-8) mol/L for Pb(Ⅱ)and 3.57×10~(-8) mol/L for Cd(Ⅱ),respectively.The chloramphenicol was also obviously electrochemically reduced at the Nafion/GQDs/GCE.The electrocatalytic mechanism of chloramphenicol was involved 6 electrons for an irreversible reaction,and the electron transfer rate constant was 105.4 s-1. The reduction current of chloramphenicol was also proportion to its concentration ranged from 5.00×10~(-7) to 2.50×10~(-3) mol/L,and the detection limit was 1.67×10~(-7) mol/L.Moreover,the Nafion/GQDs modified electrode exhibited good anti-interference,stability and reproducibility and it was successfully applied to detect targets in real samples with satisfactory results.
In this paper,homogeneous graphene quantum dots(GQDs)were successfully prepared by a simple,environmental-friendly way of in-situ electrolyzing graphite rod at a certain current density.The GQDs were dispersed into Nafion solution,Nafion/GQDs composites modified glassy carbon electrode(Nafion/GQDs/GCE) was prepared. As-prepared Nafion/GQDs/GCE was studied for the electrochemical detection of Pb(Ⅱ),Cd(Ⅱ)and chloramphenicol by anodic stripping voltammetry and different pulse voltammetry,respectively.The results demonstrated that Nafion/GQDs/GCE had excellent electrochemical properties for the detection of Pb(Ⅱ),Cd(Ⅱ)and chloramphenicol.With the increase of Pb(Ⅱ)and Cd(Ⅱ)concentration,the anodic stripping currents of Pb(Ⅱ)and Cd(Ⅱ)were proportional to their concentrations in the linear range of 4.82×10~(-8)-9.65×10~(-7) mol/L(R2=0.9923)for Pb(Ⅱ)and 1.07×10~(-7)-1.96×10~(-6) mol/L for Cd(Ⅱ)(R2=0.9912).The detection limits(S/N=3)were 1.61×10~(-8) mol/L for Pb(Ⅱ)and 3.57×10~(-8) mol/L for Cd(Ⅱ),respectively.The chloramphenicol was also obviously electrochemically reduced at the Nafion/GQDs/GCE.The electrocatalytic mechanism of chloramphenicol was involved 6 electrons for an irreversible reaction,and the electron transfer rate constant was 105.4 s-1. The reduction current of chloramphenicol was also proportion to its concentration ranged from 5.00×10~(-7) to 2.50×10~(-3) mol/L,and the detection limit was 1.67×10~(-7) mol/L.Moreover,the Nafion/GQDs modified electrode exhibited good anti-interference,stability and reproducibility and it was successfully applied to detect targets in real samples with satisfactory results.
引文
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[7]Zhai H Y,Liang Z X,Chen Z G,et al.Electrochimica Acta,2015,171:105.
[8]Luo Y,Li M,Sun L,et al.Journal of Colloid and Interface Science,2018,529:205.
[9]Zhang M,Bai L L,Shang W H,et al.Journal of Materials Chemistry,2012,22:7461.
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[15]Ruengpirasiri P,Punrat E,Chailapakul O,et al.Electroanalysis,2017,29:1022.
[16]Borowiec J,Wang R,Zhu L H,et al.Electrochimica Acta,2013,99:138.
[17]LUO S Z,ZHAO J L,CHEN H Y,et al.Journal of Analytical Science(罗世忠,赵金龙,陈怀银,等.分析科学学报),2016,32(4):561.
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