Weng Xueyu, Huang Jingqi, Ye Huazhu, Xu He, Cai Dongqing, Wang Dongfang
College of Environmental Science and Engineering, Donghua University, Shanghai 201620, China.
State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China.
Anal Methods. 2022 Aug 11;14(31):3000-3010. doi: 10.1039/d2ay00702a.
Herein, a high-performance electrochemical sensor was constructed based on a metal-organic framework (Zr-UiO-66)/multi-carbon nanotubes/gold nanoparticles (Zr-UiO-66/MWCNTs/AuNPs) composite modified glassy carbon electrode for sensitive determination of tetracycline. The morphology, structure, and performance of Zr-UiO-66/MWCNTs/AuNPs were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), and electrochemical techniques. The Zr-UiO-66/MWCNTs/AuNPs nanohybrids exhibited excellent electrocatalytic activity towards the oxidation of tetracycline, mainly because of the synergistic effect of the MOFs, MWCNTs, and gold nanoparticles. The electrochemical kinetics and catalytical mechanism of tetracycline were demonstrated, proving that tetracycline's electrocatalytic oxidation reaction was an absorption-controlled two-step process involving the transfer of two protons and two electrons, respectively. Furthermore, a simple and facile method was used to achieve the regeneration of the absorbed saturated electrode. A low concentration of tetracycline was detected by amperometry with the linear ranges of 5 × 10 to 2.25 × 10 mol L ( = 0.9941), the sensitivity was 45.4 mA L mol, and the limit of detection was as low as 1.67 × 10 mol L (S/N = 3). In addition, the composite electrode demonstrated high selectivity (interference deviation of ± 5%), satisfactory reproductivity (RSD of 5.31%), and long-term stability (easy regeneration) and was successfully applied in the analysis of tetracycline antibiotics in actual samples. Thus, the proposed electrode provides a promising and prospective MOFs-based sensing platform for the detection of tetracyclines in the environment.
在此，基于金属有机框架（Zr-UiO-66）/多壁碳纳米管/金纳米颗粒（Zr-UiO-66/MWCNTs/AuNPs）复合材料修饰玻碳电极构建了一种高性能电化学传感器，用于灵敏测定四环素。通过扫描电子显微镜（SEM）、X射线光电子能谱（XPS）、能量色散光谱（EDS）、傅里叶变换红外光谱（FT-IR）和电化学技术对Zr-UiO-66/MWCNTs/AuNPs的形貌、结构和性能进行了表征。Zr-UiO-66/MWCNTs/AuNPs纳米杂化物对四环素的氧化表现出优异的电催化活性，这主要归因于金属有机框架、多壁碳纳米管和金纳米颗粒的协同效应。阐述了四环素的电化学动力学和催化机理，证明四环素的电催化氧化反应是一个吸附控制的两步过程，分别涉及两个质子和两个电子的转移。此外，采用一种简单易行的方法实现了吸附饱和电极的再生。通过安培法检测到低浓度的四环素，线性范围为5×10至2.25×10 mol L（ = 0.9941），灵敏度为45.4 mA L mol，检测限低至1.67×10 mol L（S/N = 3）。此外，复合电极表现出高选择性（干扰偏差±5%）、令人满意的重现性（相对标准偏差为5.31%）和长期稳定性（易于再生），并成功应用于实际样品中四环素类抗生素的分析。因此，所提出的电极提供了一个有前景的基于金属有机框架的传感平台，用于环境中四环素的检测。
