[Application progress of covalent organic framework materials in extraction of toxic and harmful substances]

Toxic and hazardous substances constitute a category of compounds that are potentially hazardous to humans, other organisms, and the environment. These substances include pesticides (benzoylureas, pyrethroids, neonicotinoids), persistent organic pollutants (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, perfluorinated compounds), plasticizers (phthalate esters, phenolic endocrine disruptors), medicines (sulfonamides, non-steroid anti-inflammatory drugs, tetracyclines, fluoroquinone antibiotics), heterocyclic aromatic amines, algal toxins, and radioactive substances. Discharge of these toxic and harmful substances, as well as their possible persistence and bioaccumulation, pose a major risk to human health, often to the extent of being life-threatening. Therefore, it is important to analyze and detect toxic and hazardous substances in the environment, drinking water, food, and daily commodities. Sample pretreatment is an imperative step in most of the currently used analytical methods, especially in the analysis of trace toxic and harmful substances in complex samples. An efficient and fast sample pretreatment technology not only helps improve the sensitivity, selectivity, reproducibility, and accuracy of analytical methods, but also avoids contamination of the analytical instruments and even damages the performance and working life of instruments. Sample pretreatment techniques widely used in the extraction of toxic and hazardous substances include solid-phase extraction (SPE), solid-phase microextraction (SPME), and dispersed solid-phase extraction (DSPE). The adsorbent material plays a key role in these pretreatment techniques, thereby determining their selectivity and efficiency. In recent years, covalent organic frameworks (COFs) have attracted increasing attention in sample pretreatment. COFs represent an exciting new class of porous crystalline materials constructed via the strong covalent bonding of organic building units through a reversible condensation reaction. COFs present four advantages: (1) precise control over structure type and pore size by consideration of the target molecular structure based on the connectivity and shape of the building units; (2) post-synthetic modification for chemical optimization of the pore interior toward optimized interaction with the target; (3) straightforward scalable synthesis; (4) feasible formation of composites with magnetic nanoparticles, carbon nanotubes, graphene, silica, etc., which is beneficial to enhance the performance of COFs and meet the requirement of diverse pretreatment technologies. Because of the well-defined crystalline porous structures and tailored functionalities, COFs have excellent potential for use in target extraction. However, some issues need to be addressed for the application of COFs in the extraction of toxic and hazardous substances. (1) For the sample matrix, most of the reported COFs are highly hydrophobic, which limits their dispersibility in water-based samples, leading to poor extraction performance. COFs with good dispersibility in water-based samples are urgently required. (2) Besides, COFs rely on hydrophobic interaction, size repulsion, π-π stacking, and Van der Waals forces to extract target substances, but they are not effective for some polar targets. Thus, it is necessary to develop COFs with high affinity for polar toxic and hazardous substances. (3) Methods for the synthesis of COFs have evolved from solvothermal methods to room-temperature methods, mechanical grinding, microwave-assisted synthesis, ion thermal methods, etc. Most of the existing methods are time-consuming, laborious, and environmentally unfriendly. The starting materials are too expensive to prepare COFs in large quantities. More effort is required to improve the synthesis efficiency and overcome the obstacles in the application of COFs for extraction. This article summarizes and reviews the research progress in COFs toward the extraction of toxic and hazardous substances in recent years. Finally, the application prospects of COFs in this field are summarized, which serves as a reference for further research into pretreatment technologies based on COFs.