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    百草枯在氧化石墨烯修饰玻碳电极上的电化学行为及其差分脉冲伏安测定

    Electrochemical Behavior of Paraquat at Graphene Oxide Modified Glassy Carbon Electrode and Its DPV Determination

    • 摘要: 将氧化石墨烯悬浮液(1 g·L-1)10 μL滴涂于玻碳电极表面,烘干后,在0.10 mol·L-1的KH2PO4溶液中于-0.9 V还原600 s制备了氧化石墨烯修饰玻碳电极,用扫描电子显微镜、透射电子显微镜和电化学方法对修饰电极进行了表征。用差分脉冲伏安法研究了百草枯在氧化石墨烯修饰电极上的电化学行为,发现此修饰电极对百草枯的还原有明显的电催化作用。百草枯在pH 7.5的磷酸盐缓冲溶液中,在氧化石墨烯修饰电极上产生催化还原反应,在差分脉冲伏安曲线上先后在-0.6,-0.1 V处出现2个还原峰。因后者与底液的还原峰重叠,故测定中采用-0.6 V处的还原峰电流为测量值。经试验,百草枯在修饰电极上的富集电位为-0.6 V,富集时间为200 s,选用的扫描速率为50 mV·s-1。在最佳试验条件下百草枯浓度在9.00×10-7~1.00×10-5mol·L-1和1.00×10-5~5.00×10-5mol·L-1内与其在-0.6 V处的还原峰电流呈线性关系,检出限(3s/k)为1.64×10-7mol·L-1。方法应用于农药中百草枯含量的测定,测定值与标示值相符,对土壤样品进行加标回收试验,回收率在89.5%~114%之间。

       

      Abstract: The graphene oxide modified glassy carbon electrode was prepared by dropping 10 μL of graphene oxide suspension (1 g·L-1) onto the surface of glassy carbon electrode, drying, and reduction at -0.9 V for 600 s in 0.1 mol·L-1 KH2PO4 solution. The modified electrode was characterized by scanning electron microscopy, transmission electron microscopy and electrochemical method. The electrochemical behavior of paraquat at graphene oxide modified electrode was studied by differential pulse voltammetry. It was found that, in a base solution of PBS (pH 7.5) the modified electrode showed obvious electrocatalytic effect on the reduction of paraquat. As shown in the differential pulse voltammogram, 2 reduction peaks (at -0.6, -0.1 V) were observed, with the latter overlapped with the reduction peak of the base solution. The reduction peak at -0.6 V and its peak current (ipc) were taken in the following measurement. As shown by the experimental results, the optimum potential found for enrichment of paraquat at the modified electrode was -0.6 V with a time of 200 s and a scanning rate of 50 mV·s-1. Under optimal conditions, linear relationships were found between reduction peak current at -0.6 V and concentration of paraquat in the ranges of 9.00×10-7-1.00×10-5mol·L-1, and 1.00×10-5-5.00×10-5mol·L-1, with detection limit (3s/k) of 1.64×10-7mol·L-1. The method was applied to determination of paraquat content in pesticides, and the determined value was in consistency with the marked value. Test for recovery was made by standard addition method to soil sample, giving results in the range of 89.5%-114%.

       

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