A highly selective and sensitive electrochemical Cu(II) detector based on ion-imprinted magnetic carbon nanospheres
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摘要: 本文报道一种基于Cu(II)离子印迹聚合物为识别元件的电化学传感器。通过耦合表面离子印迹和电化学沉积的制备方法，制备了由磁性碳纳米球组成的离子印迹聚合物电极。所组装的传感器表现出对Cu(II)检测的特异识别性和高灵敏特性。通过场发射扫描电子显微镜和透射电子显微镜对印迹聚合物的微观形貌进行表征，采用傅里叶变换红外光谱对其官能团和化学结构进行表征。传感器电化学性能表明，与非印迹电极和裸电极相比，印迹电极对Cu(II)具有更强的选择性和更高的灵敏度。传感器对浓度为10−6至10−10 mol L−1的Cu(II)表现出良好的线性相应电流，其检测限提升至5.138×10−16 mol L−1 (S/N=3)。此外，该传感器具有良好的抗干扰性、重现性和稳定性，为金属离子的检测提供了新的策略。Abstract: An electrochemical sensor for Cu(II) based on ion-imprinted polymers was prepared by combining surface imprinting with electrochemical polymerization deposition. The sensor was modified by ion-imprinted magnetic carbon nanospheres with a specific selectivity and sensitivity for Cu(II). The morphology and structure of the materials were characterized and analyzed. Sensors with the imprinted electrode had a stronger selectivity and higher sensitivity towards Cu(II) compared with their original counterparts. Within relative concentrations of Cu(II) from 10−6 to 10−10 mol L−1, the detection limit of the sensor was as low as 5.138×10−16 mol L−1 (S/N=3). The sensor is resistant to interference, and has good reproducibility, and stability, making it excellent for the electrochemical detection of metal ions.
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Figure 1. Schematic illustrating the preparation of the Cu(II)-IIPs composite for detecting Cu(II)
Figure 2. FESEM images of (a, b) Fe3O4@C and (c, d) Cu(II)-IIPs; TEM images of (e, f) Fe3O4@C and (g, h) Cu(II)-IIPs
Figure 4. (a) Relationship between the peak current of Cu(II)-IIPs/GCE and pH in 10−3 mol L−1 CuSO4 acetate buffer after elution with phosphate buffers of different pH values. (b) Peak current of Cu(II) at different pH values
Figure 5. DPV curves of GCE in 10−3 mol L−1 CuSO4, Na2SO4 and Cu(NO3)2 acetic acid buffer
Figure 6. Comparison for the DPV responses of GCE, NIPs/GCE, and IIPs/GCE in acetate buffer
Figure 7. (a) Typical DPV curves of Cu(II)-IIPs in acetate buffer with different Cu(II) concentrations (1.0×10−6, 1.0×10−7, 1.0×10−8, 1.0×10−9 and 1.0×10−10 mol L−1). (b) Linear relationship between the peak current and Cu(II) concentration logarithm
Figure 8. (a) Current response of Cu(II)-IIPs/GCE in acetate buffer to 10−3 mol L−1 Cu(II) solution and mixture (containing 10−3 mol L−1 Cu(II), 10−3 mol L−1 Ni(II), and 10−3 mol L−1 Pb(II)) and (b) the corresponding histogram of peak current
Figure 9. (a) Regeneration of Cu(II)-IIPs sensor. (b) DPV current response compared for the fresh and 3-day stored electrodes in 10−3 mol L−1 Cu(II) acetic acid buffer
Figure 10. Schematic diagram of (a) the structure of pyrrole and (b) the complex formed by Cu(II) and pyrrole; (c) HOMO and (d) LUMO orbital formed by the interaction of Cu(II) and pyrrole
Table 1. Energy (eV) calculations for Cu(II), pyrrole, and their complex
Complex Pyrrole Cu(II) ΔE −50331.386 −5713.985 −44606.425 −10.976 
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Table 2. Comparison for the linear ranges and detection limits of the Cu(II) sensors
Material Detection mothod Linear range (ng/L) Detection limit (ng/L) Ref. QDs@IIPs Fluorimetric detection 110-58000 35 [35] OMNiIIP Electrochemical detection 8-7807 1.8 [36] Cu(II)-IIPs Optic
detection2540-317500 1710 [37] CPE/FMC Electrochemical detection 31750-107950 5207 [38] Cu(II)-IIHMC ICP-MS 50-50000 8 [39] MIP Fluorimetric detection 6350-6350000 – [40] CQDs@Cu-IIP Fluorimetric detection 250000-2000000
3000000-10000000– [41] Cu(II)-IIPs/GCE Electrochemical detection 6.35-63500 3.26×10−5 This work
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