| 复合纳米材料修饰丝网印刷电极检测土壤中铅和镉 |
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| 引用本文： | 刘宁, 赵国, 王旭明, 刘刚. 复合纳米材料修饰丝网印刷电极检测土壤中铅和镉[J]. 农业工程学报, 2021, 37(13): 180-189. DOI: 10.11975/j.issn.1002-6819.2021.13.021 |
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| 作者姓名： | 刘宁 赵国 王旭明 刘刚 |
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| 作者单位： | 1.中国农业大学现代精细农业系统集成研究教育部重点实验室,北京 100083;2.中国农业大学农业农村部农业信息获取技术重点实验室,北京 100083;3.南京农业大学人工智能学院,南京 210031 |
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| 基金项目： | 国家自然科学基金资助项目（32071898,32001411）;中央高校基本科研业务费专项资金资助项目（2021TC111） |
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| 摘 要： | 为了快速、准确、低成本检测土壤中痕量Pb(Ⅱ)和Cd(Ⅱ),该研究应用电化学还原和滴涂方法制备了一种铋膜/Nafion/还原氧化石墨烯/离子液体复合纳米材料修饰的丝网印刷电极(Bi/Nafion/rGO/IL/SPE).通过扫描电子显微镜、循环伏安法和能量色散谱手段表征了修饰电极的电化学分析性能,结果显示修饰材料增大了...
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| 关 键 词： | 重金属 土壤 离子液体 氧化石墨烯 铋膜 Nafion 丝网印刷电极 |
| 收稿时间： | 2021-04-06 |
| 修稿时间： | 2021-05-29 |
Detection of lead and cadmium in soil using composite nanomaterials modified screen-printed electrode |
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| Liu Ning, Zhao Guo, Wang Xuming, Liu Gang. Detection of lead and cadmium in soil using composite nanomaterials modified screen-printed electrode[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2021, 37(13): 180-189. DOI: 10.11975/j.issn.1002-6819.2021.13.021 |
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| Authors: | Liu Ning Zhao Guo Wang Xuming Liu Gang |
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| Affiliation: | 1.Key Laboratory of Modern Precision Agriculture System Integration Research, Ministry of Education, China Agricultural University, Beijing 100083, China;2.Key Laboratory of Agricultural Information Acquisition Technology, Ministry of Agriculture and Rural Affairs, China Agricultural University, Beijing 100083, China;3.College of Artificial Intelligence, Nanjing Agricultural University, Nanjing 210031, China |
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| Abstract: | Lead Pb (Ⅱ) and cadmium Cd (Ⅱ) are toxic heavy metals, particularly difficult to be biodegraded in soil. Furthermore, lead and cadmium at trace levels can cause serious damage to brains, kidneys, blood, nerves, and other organs. A large amount of Pb (Ⅱ) and Cd (Ⅱ) can also be deposited in the soil environment after anthropogenic improper activities, such as sewage irrigation, the abuse of chemical fertilizers and pesticides, as well as the excessive discharge of industrial wastes. Pb (Ⅱ) and Cd (Ⅱ) can be absorbed by crops, and then accumulated in animals, finally enriched thousands of times into the human body under the biomagnification of the food chain, thereby causing economic losses and a great threat to human health. Therefore, it is highly urgent to accurately detect the accumulation of Pb (Ⅱ) and Cd (Ⅱ) in soil. An electrochemical Square Wave Anodic Stripping Voltammetry (SWASV) is widely utilized to combine with chemically modified working electrodes for the detection of heavy metal ions. Screen-Printed Electrodes (SPEs) have also been commonly used in recent years, due to easy preparation, disposable capability, and low cost. Particularly, SPEs with a small size are quite qualified as the sensing device of miniature electrochemical detection equipment, suitable for many detection scenarios, such as flow cells and microfluidics. In this study, electrochemical reduction and coating were applied to fabricate a modified SPE (Bi/Nafion/rGO/IL/SPE) with the bismuth film/Nafion/reduced graphene oxide/ionic liquid composite nanomaterials, to accurately, fast, and reliably detect trace Pb (Ⅱ) and Cd (Ⅱ) in soil with a low-cost. Cyclic Voltammetry (CV) was also selected to characterize the electron transport capability of the modified electrodes. It was found that the composite nanomaterials greatly improved the electron transport capability of SPE and the stripping voltammetry responses for Pb (Ⅱ) and Cd (Ⅱ) on the SPE. Moreover, Scanning Electron Microscopy (SEM) was utilized to characterize the morphology of the modified electrodes. It was found that the rGO greatly enhanced the specific surface area of bare SPEs, thereby obtaining much more active sites for the electro-deposition of heavy metal ions. Energy Dispersive Spectroscopy (EDS) was used to identify the deposition amount of heavy metal ions on the surface of different modified electrodes. The results demonstrated that the modification with the bismuth film, rGO, and Nafion gradually increased the deposition amount of Pb (Ⅱ) and Cd(Ⅱ) on the modified SPE surface. Additionally, the Pb(Ⅱ) and Cd(Ⅱ) standard solutions were selected to optimize the experimental parameters, including the pH value of support electrolyte, bismuth ions concentration, deposition potential, and potential time. There were linear responses of Bi/Nafion/rGO/IL/SPE to Pb(Ⅱ) and Cd(Ⅱ) in the concentration from 1 to 80 μg/L, with the critical values of 0.124 μg/L for Pb(Ⅱ) and 0.232 μg/L for Cd(Ⅱ) (S/N=3), under an optimal experimental condition. The determination coefficients (R2) of linear correction models were 0.993 and 0.985 for Pb(Ⅱ) and Cd(Ⅱ), respectively. In six SWASV measurements, the relative standard deviation (RSD) of Pb(Ⅱ) and Cd(Ⅱ) peak currents were 1.57% and 2.32%, respectively, indicating high stability and repeatability of Bi/Nafion/rGO/IL/SPE. Other heavy metal ions were also added to investigate the anti-interference performance of modified electrodes. It was found that there was no serious interference of other heavy metal ions (except for Cu(Ⅱ)) on the voltammetry responses of Pb(Ⅱ) and Cd(Ⅱ), where the changes of peak currents were all less than 5%. Since Cu(Ⅱ) inhibited the Pb(Ⅱ) and Cd(Ⅱ) peak currents by 40.02% and 62.85%, respectively, the Cu2+ interference could be alleviated by adding ferricyanide. Finally, actual soil samples under the standard addition were used to verify the practicability of modified SPEs. Results demonstrated that the average recovery rates of Pb(Ⅱ) and Cd(Ⅱ) were 98.71% and 98.93%, respectively, indicating that the Bi/Nafion/rGO/IL/SPE can be applied to detect the trace lead and cadmium in soil. |
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| Keywords: | heavy metals soils ionic liquid graphene oxide bismuth film Nafion screen-printed electrode |
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