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    多壁碳纳米管和聚1,3,5-三(2-噻吩基)苯修饰玻碳电极的制备及其在环境水中痕量Cu2+测定中的应用

    Fabrication of Multi-Walled Carbon Nanotubes and Poly1,3,5-tri(2-thienyl)benzene Modified Glassy Carbon Electrode and Its Application in Determination of Trace Cu2+ in Environmental Water

    • 摘要: 为实现环境水中痕量Cu2+的简单、快速、低成本、高灵敏测定,制备了多壁碳纳米管(MWCNTs)和聚1,3,5-三(2-噻吩基)苯(PTTB)修饰的玻碳(MWCNTs/ PTTB/GC)电极,并将其用于湖水中Cu2+的检测。采用循环伏安法(CV)聚合制备修饰电极,并分别采用扫描电子显微镜(SEM)、衰减全反射红外(ATR-TR)光谱法进行形貌和组成表征,以CV、交流阻抗谱(EIS)、塔菲尔(Tafel)曲线进行电化学行为表征。湖水样品经0.45 μm滤膜过滤后,分取5 mL,加入15 mL乙酸-乙酸钠缓冲液,混匀后用乙酸调节pH至5。以MWCNTs/ PTTB/GC电极作为工作电极,铂丝作为辅助电极,Ag/AgCl电极作为参比电极,在恒定电位−0.8 V下采用计时电流法富集Cu2+ 150 s,静止20 s后在−0.4~0.4 V内进行示差脉冲伏安法(DPV)检测。结果显示:MWCNTs/ PTTB/GC电极CV响应、内阻、Tafel斜率和自由腐蚀电位均显著优于GC电极的,说明修饰层能有效提升GC电极的电子转移效率和催化活性,且该修饰电极对Cu2+的响应是一个受吸附控制的双电子转移的不可逆过程;Cu2+的质量浓度在0.5~200 mg·L−1内和DPV溶出峰电流呈线性关系,检出限(3S/N)为0.166 mg·L−1;重复性(n=20)、再现性(n=5)试验测得的相对标准偏差均小于5.0%,放置一周后修饰电极的溶出峰电流还能保持初始值的95%以上。常见阴、阳离子K+、Ag+、Ca2+、Pb2+、Cd2+、Zn2+、SO42−、CO32−、Cl、Mg2+、Fe3+对Cu2+检测无干扰(溶出峰电流相对差值绝对值小于6.0%);方法用于湖水样品分析,结果显示Cu2+检出量为19.15 mg·L−1,4个加标浓度水平下的回收率为85.1%~92.9 %。

       

      Abstract: In order to achieve simple, rapid, low-cost, and highly sensitive detection of trace Cu2+ in environmental water, the glassy carbon electrode modified with multi-walled carbon nanotubes (MWCNTs) and poly1,3,5-tri(2-thienyl)benzene (PTTB) (denoted as MWCNTs/PTTB/GC electrode) was prepared and applied to the detection of Cu2+ in lake water. The modified electrode was prepared by cyclic voltammetry (CV) for polymerization, and its morphology and composition were characterized by scanning electron microscopy (SEM) and attenuated total reflection infrared (ATR-IR) spectrometry, while its electrochemical behavior was characterized by CV, electrochemical impedance spectroscopy (EIS), and Tafel curve. The lake water sample was passed through a 0.45 μm filter membrane, and an aliquot (5 mL) was taken. After mixing with 15 mL of acetic acid-sodium acetate buffer solution, the mixed solution was adjusted to pH 5 using acetic acid. Using the MWCNTs/PTTB/GC electrode as the working electrode, the platinum wire as the counter electrode, and the Ag/AgCl electrode as the reference electrode, Cu2+ was accumulated at constant potential of −0.8 V for 150 s using chronoamperometry, followed by a 20 s-rest period, and then detected by differential pulse voltammetry (DPV) in the range of −0.4−0.4 V. It was shown that the CV response, internal resistance, Tafel slope, and free corrosion potential of the MWCNTs/PTTB/GC electrode were significantly better than those of the GC electrode, indicating that the modification layer effectively enhanced the electron transfer efficiency and catalytic activity of the GC electrode, and the response of this modified electrode to Cu2+ was an adsorption-controlled irreversible process involving two-electron transfer. The mass concentration of Cu2+ showed a linear relationship with the DPV stripping peak current in the range of 0.5−200 mg·L1, with detection limit (3S/N) of 0.166 mg·L1. RSDs for repeatability (n=20) and reproducibility (n=5) tests were both less than 5.0%, and the stripping peak current of the modified electrode remained above 95% of its initial value after one week of storage. Common anions and cations, including K+, Ag+, Ca2+, Pb2+, Cd2+, Zn2+, SO42, CO32, Cl, Mg2+, and Fe3+, did not interfere with the detection of Cu2+ (the absolute values of the relative difference in stripping peak current were less than 6.0%). The method was applied to the analysis of lake water samples, and it was shown that the detected amount of Cu2+ was 19.15 mg·L1, and the recoveries at 4 spiked concentration levels ranged from 85.1% to 92.9%.

       

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