Xu Qi-Tong, Yu Meng, Xie Chang, Cao Yan, Mei Su-Rong
Key Laboratory of Environment & Health of Ministry of Education,School of Public Health,Huazhong University of Science and Technology,Wuhan 430030,China.
Se Pu. 2025 Jul;43(7):713-725. doi: 10.3724/SP.J.1123.2024.12009.
Pesticides are ubiquitous to human life but their residues are indispensable micropollutants that threaten human health. In recent years, the global use of pesticides has increased significantly in recent years, and their environmental profiles have become increasingly complex as different generations of pesticides have appeared on the market. The residues of various legacy and emerging pesticides are omnipresent in both the environment and food medias. Consequently, developing rapid and sensitive detection technologies for analyzing multiple residues is imperative. Sample pretreatment, particularly adsorbent selection and innovation, is indispensable in this regard. So far, a wide range of hybrid nanomaterials have been used for the enrichment or adsorption of pesticide residues. While traditional solid-phase-extraction-based (SPE-based) sorbents are widely used, they lack specific interactions and are poorly selective. Normal carbon materials (e.g., graphene oxide and carbon nanotubes), which have large surface areas and pore volumes, have progressed significantly; however, they still have insufficient active adsorption sites. Notably, porous materials, including metal-organic frameworks (MOFs), porous organic polymers (POPs) (including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs), conjugated microporous polymers (CMPs), microporous organic networks (MONs, sub-familied by CMPs, porous aromatic frameworks (PAFs), and hyper-crosslinked polymers (HCPs)), nano-porous carbons(NPCs), and zeolites display exceptional properties because they have high porosity, tunable pore sizes, large surface areas, and diverse modification sites. In this review, strategies for the enhancement of adsorption performance of porous-material-based adsorbents, including materials hybridization, monomer modification, configuration regulation, and properties adjustment are first introduced. Furthermore, publications from 2018 to 2024 pertaining to the utilization of porous-material-based adsorbents for diverse types of pesticides were briefly elaborated. The properties of pesticides, the designs and performance of porous materials, and their interaction mechanisms were discussed. A total of 14 types of pesticides are included in the discussion, namely organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs), pyrethroids (PYRs), benzoylurea insecticides (BUs), neonicotinoid insecticides (NEOs), phenyl-pyrazole insecticides (PPZs), phenoxy carboxylic acid herbicides (PCAs), triazine herbicides (TRZHs), benzimidazole fungicides (BZDs), azole/triazoles fungicides, strobilurin fungicides (SFs), carbamate insecticides (Carbs), phenyl-urea herbicides (PUHs), and diamide insecticides. Our summary revealed that an adsorbent was predominantly designed based on the textural properties of the target pesticide and the structural characteristics of the hybrid material, such as its functional groups, polarity, and pore size, to enhance adsorption performance and selectivity. MOFs and POPs are the most commonly used pesticide adsorbents, whereas fewer NPCs have been reported in this regard. Additionally, the applications potentials of porous-material-based adsorbents were explored. The findings revealed that conventional pesticides, such as OPPs, have been significantly researched in the extraction technology field. In contrast, concerns surrounding newer pesticides, including NEOs, PPZs, and SFs, as well as some significantly detected residues (BZDs and TRZHs), have not been fully addressed, highlighting the need for future adsorbent research that prioritizes emerging and significantly detected pesticides.
农药在人类生活中无处不在,但其残留却是威胁人类健康的不可忽视的微污染物。近年来,全球农药使用量显著增加,随着不同代次农药投放市场,其环境特征日益复杂。各类传统和新型农药残留广泛存在于环境和食品介质中。因此,开发快速灵敏的多残留分析检测技术势在必行。在这方面,样品预处理,尤其是吸附剂的选择与创新不可或缺。到目前为止,多种杂化纳米材料已被用于农药残留的富集或吸附。虽然基于传统固相萃取(SPE)的吸附剂被广泛使用,但它们缺乏特异性相互作用且选择性较差。具有大表面积和孔体积的普通碳材料(如氧化石墨烯和碳纳米管)已取得显著进展;然而,它们的活性吸附位点仍然不足。值得注意的是,多孔材料,包括金属有机框架(MOF)、多孔有机聚合物(POP,包括共价有机框架(COF)、共价三嗪框架(CTF)、共轭微孔聚合物(CMP)、微孔有机网络(MON,CMP的子家族)、多孔芳香框架(PAF)和超交联聚合物(HCP))、纳米多孔碳(NPC)和沸石,因其具有高孔隙率、可调孔径、大表面积和多样的修饰位点而展现出优异性能。在本综述中,首先介绍了基于多孔材料的吸附剂提高吸附性能的策略,包括材料杂化、单体修饰、构型调控和性能调节。此外,简要阐述了2018年至2024年期间有关基于多孔材料的吸附剂用于多种农药的相关文献。讨论了农药的性质、多孔材料的设计与性能及其相互作用机制。讨论中涵盖了14种农药,即有机氯农药(OCP)、有机磷农药(OPP)、拟除虫菊酯(PYR)、苯甲酰脲类杀虫剂(BU)、新烟碱类杀虫剂(NEO)、苯基吡唑类杀虫剂(PPZ)、苯氧羧酸类除草剂(PCA)、三嗪类除草剂(TRZH)、苯并咪唑类杀菌剂(BZD)、唑类/三唑类杀菌剂、甲氧基丙烯酸酯类杀菌剂(SF)、氨基甲酸酯类杀虫剂(Carb)、苯基脲类除草剂(PUH)和双酰胺类杀虫剂。我们的总结表明,吸附剂主要是根据目标农药的结构性质和杂化材料的结构特征(如官能团、极性和孔径)来设计的,以提高吸附性能和选择性。MOF和POP是最常用的农药吸附剂,而这方面报道的NPC较少。此外,还探讨了基于多孔材料的吸附剂的应用潜力。研究结果表明,传统农药如OPP在萃取技术领域已得到大量研究。相比之下,围绕新型农药(包括NEO、PPZ和SF)以及一些大量检出的残留(BZD和TRZH)的问题尚未得到充分解决,这凸显了未来吸附剂研究需要优先关注新型和大量检出的农药。
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