金修饰磁性石墨烯基分子印迹复合材料的制备及对水中邻苯二甲酸二正丁酯的电化学传感检测

doi:10.7503/cjcu20180521

摘要/Abstract

摘要：

以金修饰磁性石墨烯(Au@Fe₃O₄@RGO)为载体, 通过表面分子印迹技术, 选择水环境中邻苯二甲酸二正丁酯(DBP)为模板分子, 制备了金修饰磁性石墨烯基分子印迹复合膜(Au@Fe₃O₄@RGO-MIP); 通过扫描电子显微镜(TEM)、 X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)等测试手段对其进行了分析表征. 以Au@Fe₃O₄@RGO-MIP作为传感器识别元件的敏感材料, 利用循环伏安(CV)、电化学阻抗谱(EIS)和差分脉冲(DPV)等电化学分析方法, 对构建的分子印迹电化学传感器进行了性能分析, 结果表明, 该传感器对水环境中DBP的响应平衡时间为6 min, 在0.01~0.1 μmol/L范围内, DBP浓度与响应电流之间呈现良好的线性关系, 检出限为0.3049 nmol/L(S/N=3).

关键词: 分子印迹技术, 石墨烯, 金纳米粒子, 传感器, 邻苯二甲酸酯

Abstract:

Gold-modified magnetic graphene(Au@Fe₃O₄@RGO) was used as a carrier to select gold-modified magnetic properties and using surface molecular imprinting technique to select dinbutyl phthalate(DBP) as a template molecule in water environment. Graphene-based molecularly imprinted composite membrane(Au@Fe₃O₄@RGO-MIP) was prepared and characterized by means of transmission electron microscopy(TEM), X-ray diffraction(XRD) and Fourier transform infrared spectroscopy(FTIR). Au@Fe₃O₄@RGO-MIP was used as the sensitive material for sensor identification components. The performance of molecularly imprinted electrochemical sensors was analyzed by cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS) and differential pulse(DPV). The results show that the equilibrium time of the molecularly imprinted electrochemical sensor for dinbutyl phthalate in water environment is 6 min. In the concentration range of 0.01—0.1 μmol/L, there is a good linear relationship between DBP concentration and response current. The minimum detection limit is 0.3049 nmol/L(S/N=3).

Key words: Molecular imprinting technique, Graphene, Gold nanoparticle, Sensor, Phthalate

中图分类号:

O657.15

TrendMD:

李颖, 康君君, 赵雪茹, 徐文凯, 齐琦. 金修饰磁性石墨烯基分子印迹复合材料的制备及对水中邻苯二甲酸二正丁酯的电化学传感检测. 高等学校化学学报, 2019, 40(3): 448.

LI Ying, KANG Junjun, ZHAO Xueru, XU Wenkai, QI Qi. Preparation of Gold-modified Magnetic Graphene-based Molecularly Imprinted Composites and Electrochemical Sensing Detection of Dinbutyl Phthalate in Water^†. Chem. J. Chinese Universities, 2019, 40(3): 448.

图/表 12

Scheme 1 Construction and detection of electrochemical sensor modified by gold modified magnetic graphene-based molecularly imprinted composites

Fig.1 TEM images of Au@RGO(A), Fe3O4@RGO(B), Au@Fe3O4@RGO(C) and Au@Fe3O4@RGO-MIP(D)

Fig.2 XRD patterns of Au@RGO(a), Fe3O4@RGO(b) and Au@Fe3O4@RGO(c)

Fig.3 FTIR spectra(A) of GO(a), Au@RGO(b), Fe3O4@RGO(c), Au@Fe3O4@RGO(d) and Au@Fe3O4@RGO-MIP(e) and ultraviolet(UV) spectra(B) of Au@RGO(a), Au@Fe3O4@RGO(b) and Au@Fe3O4@RGO-MIP(c)

Fig.4 CV curves of Au@RGO(a), Au@Fe3O4@RGO(b), Au@Fe3O4@RGO-MIP(c), Au@Fe3O4@RGO-MIP(d) after binding templateCV curves were recorded between -0.5 V to 0.5 V in 5 mmol/L K3[Fe(CN)6] solution containing 0.1 mol/L KCl at a scan rate of 50 mV/s.

Fig.5 Electrochemical impedance spectra of Au@RGO(a), Au@Fe3O4@RGO(b)(A), Au@Fe3O4@RGO-MIP(a) and Au@Fe3O4@RGO-MIP(b)(B) after binding templateEIS of various electrodes were recorded between -0.5 V to 0.5 V in 5 mmol/L K3[Fe(CN)6] solution containing 0.1 mol/L KCl at a scan rate of 50 mV/s.

Fig.6 CV curves of DBP detectionCV curves of various electrodes were recorded between -0.5 V to 0.5 V in 0.1 mol/L PBS solution at a scan rate of 50 mV/s.

Fig.7 Adsorption kinetic curve on the response to DBP for Au@Fe3O4@RGO-MIPs electrode in PBS solution containing 10 μmol/L DBPThe insert is the DBP for Au@Fe3O4@RGO-MIP at different times. DPV of various electrodes were recorded between -0.5 V to 0.5 V in 0.1 mol/L PBS solution at a scan rate of 50 mV/s, the amplitude of 50 mV, the pulse width of 50 ms, pulse cycle of 200 ms.

Fig.8 Different concentration curves of DBP on Au@Fe3O4@RGO-MIP and Au@Fe3O4@RGO-NIP(A) and linear relationship curve of Au@Fe3O4@RGO-MIP detects DBP(B)Inset is the DPV curves of Au@Fe3O4@RGO-MIP for different concentrations of DBP. DPV of various electrodes were recorded between -0.5 V to 0.5 V in 0.1 mol/L PBS solution at a scan rate of 50 mV/s, the amplitude of 50 mV, the pulse width of 50 ms, pulse cycle of 200 ms.

Table 1 Comparison with the other electrochemical sensors for determination of DBP

Sensor	LOD/(nmol·L^-1)	Linear range/(μmol·L^-1)	Ref.
MWCNTs@GONRs/GCE	25.15	1.44—229.93	[12]
DBP-MMIP-CL	2.09	20.8—38400	[37]
MGO@Au NPs-MIPs	0.80	2.5—5	[38]
Nano-Ni(OH)₂ QCM	17.96	0.018—0.072	[39]
Au@Fe₃O₄@RGO-MIP	0.305	0.01—0.1	This work

Fig.9 Response currents of Au@Fe3O4@RGO-MIP and Au@Fe3O4@RGO-NIP for DBP, DNHP, DNOP, DINP and DIDP analogs

Fig.10 Response curve of Au@Fe3O4@RGO-MIP modified electrode to DBP concentration in lake water(A) and reproducibility of Au@Fe3O4@RGO-MIP for the detection of DBP(B)Inset of (A) is the calibration curve.

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