MXene材料在重金属电化学检测应用中的研究进展

李上上; 王洪梅; 何开雨; 王柳; 蓝航镇; 徐霞红

MXene材料在重金属电化学检测应用中的研究进展

李上上^{1, 2},
王洪梅²,
何开雨²,
王柳²,
蓝航镇¹,
徐霞红^2, ,

1.
宁波大学食品与药学学院, 省部共建农产品质量安全危害因子与风险防控国家重点实验室, 宁波 315832
2.
浙江省农业科学院农产品质量安全与营养研究所, 省部共建农产品质量安全危害因子与风险防控国家重点实验室, 杭州 310021

基金项目: 国家自然科学基金面上项目(32072303)

详细信息

通讯作者:
徐霞红，博士，研究员，博士生导师，研究方向为农业环境污染物传感识别　E-mail: xuxiahong@zaas.ac.cn

中图分类号: TB333
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- 被引次数: 0
出版历程
- 收稿日期: 2023-09-25
- 修回日期: 2023-11-26
- 录用日期: 2023-12-01
- 网络出版日期: 2023-12-26
- 刊出日期: 2024-06-15

Research progress of MXene materials in the application of heavy metal electrochemical detection

1.
State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products, School of Food and Pharmacy, Ningbo University, Ningbo 315832, China
2.
State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products, Institute of Agro-product Safety and Nutrition,Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, China

Funds: National Natural Science Foundation of China (32072303)

摘要

摘要: 检测重金属污染已成为风险防控、农业绿色发展、食品安全及生态保护等领域重要的技术保障。目前有许多方法来检测重金属离子，其中电化学检测法对重金属离子的检测具有灵敏度高，分析速度快，可同时对多种金属离子进行检测等优点，成为了重金属快速检测领域的研究热点。MXene是具有类石墨烯结构的过渡金属碳/氮化物材料，它具备良好的亲水性、导电性和丰富可调节的终端基团。本文综述了MXenes在电化学检测重金属离子领域的研究进展：对重金属污染物的来源、危害和检测方法进行了简述；其次，概述MXene的合成方法，并重点综述了近年来MXene电化学检测重金属的研究进展，及其传感机理和检测性能分析；最后，讨论了MXene材料在电化学检测重金属领域面临的挑战和展望。
- 重金属 /
- MXene /
- 电化学传感器 /
- 检测 /
- 食品安全
Abstract: Detecting heavy metal pollution has become an essential technical guarantee in risk prevention and control, agricultural green development, food safety, and ecological protection. At present, there are many technologies to detect heavy metal ions, among which electrochemical detection methods have the advantages of high sensitivity, fast analysis, and simultaneous detection of a variety of metal ions, which have become a research area in the field of rapid detection of heavy metals. MXene is a transition metal-carbon/nitride material with a graphene-like structure with good hydrophilicity, electrical conductivity, and rich adjustable surface terminations. The focus of this study is the research progress of MXenes in the electrochemical detection of heavy metal ions. The sources, hazards, and detection methods of heavy metal contaminants are briefly described. Secondly, the synthesis methods of MXene are summarized, and the research progress of MXene in the electrochemical detection of heavy metals in recent years is reviewed, including the sensing mechanism and detection performance analysis. Finally, the challenges and prospects of MXene materials in the electrochemical detection of heavy metals are discussed.
- Heavy metal /
- MXene /
- electrochemical sensors /
- detect /
- food safety

HTML全文

图 1 MXene基电化学传感器用于重金属检测

Figure 1. MXene-based electrochemical sensors are used for heavy metal detection

CC—carbon cloth; MXA—MXene aerogel; DPASV—anodic dissolution voltammetry; MGMA—melamine-doped graphene oxide/MXene composite aerogel; CB—carbon black; rA—ribose adenine

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图 2 电化学检测重金属装置图^[21]

Figure 2. Diagram of electrochemical detection of heavy metal device^[21]

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图 3 (a)元素周期表显示了MXene的元素组成；(b)示意图表明Ti₃AlC₂ MAX相前驱体蚀刻到Ti₃C₂T_x MXene^[28]

Figure 3. (a) The periodic table shows the elemental composition of MXene; (b) the schematic diagram shows that the Ti₃AlC₂ MAX phase precursor is etched to the Ti₃C₂T_x MXene^[28]

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图 4 (a) Ti₃C₂T_xNRs(Ti₃C₂T_x MXene纳米带)的制备原理图(上)和Cd²⁺的电化学传感(下)；(b) N,P-Ti₃C₂T_xR( N and P co-doped Ti₃C₂T_x MXenes 纳米带)的制备及Cu²⁺和Hg²⁺的电化学传感原理图^{[46, 47]}

Figure 4. (a) Preparation schematic diagram of Ti₃C₂T_xNRs(Ti₃C₂T_x MXene nanoribbons) (top) and electrochemical sensing of Cd²⁺ (bottom); (b) Preparation of N,P-Ti₃C₂T_xR( N and P co-doped Ti₃C₂T_x MXenes nanoribbons) and electrochemical sensing schematic diagram of Cu²⁺ and Hg^{2+[46, 47]}

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图 5 NH₂/SH-Ti₃C₂T_x MXene超声辅助分散微固相萃取(d-μ-SPE)法用于重金属检测的示意图^[49]

Figure 5. Schematic diagram of NH₂/SH-Ti₃C₂T_x MXene ultrasound-assisted dispersion microsolid extraction (d-μ-SPE) method for heavy metal detection.^[49]

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图 6 (a) NH₂-Ti₃C₂T_x(氨基官能化多层碳化钛)制备工艺示意图；(b) NH₂-Ti₃C₂T_x/SPE(丝网印刷电极)测定食品样品中Cd²⁺和Pb²⁺的示意图^[50]

Figure 6. (a) Schematic diagram of NH₂-Ti₃C₂T_x(amino-functionalized multilayer titanium carbide) preparation process; (b) Schematic diagram of NH₂-Ti₃C₂T_x/SPE(screen printed electrode) determination of Cd²⁺ and Pb²⁺ in food samples^[50]

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图 7 MXA-CuO/CC( MXene气凝胶-氧化铜/碳布)传感电极的构建过程及同时检测Cd²⁺和Pb²⁺的原理图^[55]

Figure 7. Construction process of MXA-CuO/CC( MXene aerogel-CuO/carbon cloth) sensing electrode and schematic diagram of simultaneous detection of Cd²⁺ and Pb^2+[55]

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图 8 (a)柔性Ti₃C₂T_x/MWNTs(multiwalled carbon Nanotubes)/Au/PET电极的制备及重金属检测示意图；(b)制备Ti₃C₂T_xR/CNT( Ti₃C₂T_x MXenes 纳米带/碳纳米管)及ASV检测汞的示意图^{[58, 59]}

Figure 8. (a) Preparation of flexible Ti₃C₂T_x/MWNTs(multiwalled carbon Nanotubes)/Au/PET electrode and schematic diagram of heavy metal detection; (b) Schematic diagram of preparation of Ti₃C₂T_xR/CNT( Ti₃C₂T_x MXenes nanoribbons/carbon nanotube) and ASV detection of mercury^{[58, 59]}

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图 9 (a)三维MGMA/SPCE (三聚氰胺掺杂氧化石墨烯/MXene复合气凝胶 )示意图及环境样品中Zn²⁺、Cd²⁺和Pb²⁺检测；(b)Ti₃C₂T_x@CB的合成及Cu²⁺的电化学传感示意图^{[26, 60]}

Figure 9. (a)Schematic diagram of three-dimensional MGMA/SPCE (melamine-doped graphene oxide/MXene composite aerogel ) and detection of Zn²⁺, Cd²⁺ and Pb²⁺ in environmental samples;(b) Synthesis of Ti₃C₂T_x@CB and electrochemical sensing of Cu^{2+[26, 60]}

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图 10 (a) Ti₃C₂@N-C/GCE(Ti₃C₂-MXene异质结构/玻碳电极)制造及重金属检测应用示意图；(b) Cd²⁺和Pb²⁺测定的传感机制以及氮与重金属之间的相互作用^[27]

Figure 10. (a) Schematic diagram of Ti₃C₂@N-C/GCE(Ti₃C₂-MXene heterostructure/glassy carbon electrode) manufacturing and HMI detection applications; (b) Sensing mechanisms for Cd²⁺ and Pb²⁺ assays and nitrogen and HMI interactions^[27]

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图 11 GR5 DNAzyme/Ti₃C₂T_x Mxenes-GCE的制备及其在Pb²⁺检测中的应用^[62]

Figure 11. Preparation of GR5 DNAzyme/Ti₃C₂T_x Mxenes-GCE and its application in Pb²⁺ detection^[62]

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表 1 各种重金属污染物的来源和影响^{[18, 19]}

Table 1. Sources and effects of various heavy metal contaminants ^{[18, 19]}

Heavy metal	Source	Adverse effects on the body	National standards
Pb	Mining and smelting of heavy metal ore, battery manufacturing	Kidney and nervous system damage, as well as mental retardation and cancer	Fresh vegetables and fruits do not exceed 0.1 mg/kg cereals, legumes and nuts do not exceed 0.2 mg/kg, and meat products do not exceed 0.3 mg/kg
Cd	Lead-zinc ore, as well as non-ferrous metal smelting and electroplating	Deformation of intramuscular atrophy joints, unbearable bone pain, inability to sleep, pathological fractures, and death	Fresh vegetables, fruits and eggs do not exceed 0.05 mg/kg, cereals, fish and meat do not exceed 0.1 mg/kg
Hg	Fuel combustion, mining, smelting, waste incineration, fertilization, pesticides, domestic waste	Causes damage to the kidneys, brain, reproductive and respiratory systems	Eggs and meat do not exceed 0.05 mg/kg, vegetables and dairy products do not exceed 0.01 mg/kg, and cereals do not exceed 0.02 mg/kg
As	Industrial wastewater from mining, metallurgy, chemical industry, chemical pharmaceutical, pesticide production, textile, glass, tanning and other sectors	It can cause skin cancer, lung cancer, bladder cancer and liver cancer	Raw milk and oil do not exceed 0.1 mg/kg, cereals, vegetables, meat, condiments and chocolate do not exceed 0.5 mg/kg

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表 2 不同材料电化学检测重金属的比较^[22-27]

Table 2. Comparison of electrochemical detection of heavy metals by different materials^[22-27]

Materials	Metal ions	LOD/(nmol·L⁻¹)	Analytical performance
Glutathione-functionalized gold/multi-walled carbon nanotubes	Pb²⁺	10	Rice phloem sap
Multiwalled carbon nanotube-based ion-imprinted polymer	Cd²⁺	30	Water
Polyglycine-modified graphene paste electrode	Hg²⁺, Pb²⁺	6600, 800	Water and biological samples
Reduced graphene oxide/zinc oxide nanoparticles-ethylenediaminetetraaceticacid	Pb²⁺, Cu²⁺, Cd²⁺, Hg²⁺	6810, 2510, 5610, 1010	Water
Ti₃C₂T_x MXene//carbon black	Cu²⁺	4.6	Water
Ti₃C₂-MXene heterostructure	Cd²⁺, Pb²⁺	2.55, 1.10	Water

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