全氟和多氟烷基物质（PFAS）是近年来受到全球广泛关注的新污染物，其中最典型的全氟辛烷磺酸（PFOS）和全氟辛烷羧酸（PFOA）已被公约管控，而替代物PFAS被大量生产和使用。吸附技术是去除水中PFAS的重要方法，其关键是研发高效吸附材料。本文针对PFOS和PFOA及其6种典型替代品（六氟环氧丙烷二聚酸（GenX）、六氟环氧丙烷三聚酸（HFPO-TA）、全氟丁烷磺酸（PFBS）、全氟已烷磺酸（PFHxS）、全氟壬烯基苯磺酸钠（OBS）和6:2氯化多氟烷醚磺酸钾（F-53B）），研制吸附快、吸附量高、选择性强和易于分离回收的系列共价有机骨架（COFs）材料，并阐明吸附特性和机理。首先研究了六边形COFs骨架孔径和疏水性对PFAS吸附性能的影响。孔径太小或太大都不利于COFs吸附PFAS，COFs的孔径为PFAS分子尺寸的2.5～3.5倍时达到最高吸附量。疏水COFs上的气泡易于富集水中PFAS，且气泡上C-F链易于富集在一起，这是COFs上疏水区吸附PFAS的重要机理。然后在COFs骨架上引入不同亲和基团，研制出超快速、高吸附量和高选择性吸附去除水中PFAS的功能化COFs。在COFs上引入氨基环糊精，利用多氢键协同作用吸附PFAS分子，使得氨化COFs能超快速从水中吸附PFAS，吸附平衡时间约为2 min。在COFs上引入季铵基团，利用季铵与PFAS分子间的离子交换作用，使得季铵化COFs对GenX和HFPO-TA均具有高吸附容量，分别为2.06 mmol/g和2.16 mmol/g。在季铵COFs上进一步引入C-F链，利用C-F链间的“亲氟”作用和季铵基团的离子交换作用，制备出吸附量高和选择性强的氟化季铵COFs材料，能从实际废水中高选择性吸附PFAS，优于活性炭和离子交换树脂。最后研制出易分离的颗粒COFs和磁性COFs。利用海藻酸钠和聚丙烯酸双交联制备出颗粒氟化季铵COFs，其吸附PFAS的选择性和吸附量变化较小，且该颗粒化制备技术在粉末COFs应用中具有普适性。利用机械球磨将磁性Fe3O4嵌入COFs骨架制备出磁性季铵化三嗪COFs，其晶体结构和吸附量变化较小，且粉末磁性COFs容易在水中分散，提高其吸附速度，吸附HFPO-TA为44.42 mmol/g/h。氨化COFs利用单一甲醇实现了有效再生，季铵化COFs、氟化季铵COFs和2种易分离COFs均利用甲醇/盐的混合溶液才能实现有效再生，且5种COFs均具有较稳定重复吸附性能。

Per- and polyfluoroalkyl substances (PFAS) are emerging contaminants that have attracted worldwide attention in recent years. The most typical PFAS are perfluorooctane sulfonic acid (PFOS) and perfluorooctane carboxylic acid (PFOA). PFOS and PFOA have been added in the control list of the Stockholm Convention, resulting in a series of PFAS being produced and widely used as substitutes. Adsorption technology is an important method to remove PFAS from water, and the key is to develop efficient adsorption materials. In this paper, covalent organic frameworks (COFs) with fast adsorption, high adsorption capacity, strong selectivity and easy separation and recovery were developed to remove PFOS/PFOA and their six typical substitutes including hexafluoropropylene oxide dimer acid (GenX), hexafluoropropylene oxide trimer acid (HFPO-TA), perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHxS), sodium p-perfluorous nonenoxybenzene sulfonate (OBS) and 6:2 chlorinated polyfluorinated ether sulfonate (F-53B). The adsorption behavior and mechanism of PFAS on COFs were clarified.Firstly, the effects of pore size and hydrophilicity of hexagonal COFs on the adsorption performance of PFAS were studied. COFs with too small or too large pore size were not conducive to PFAS adsorption. When the pore size of COFs is 2.5?3.5 times of PFAS molecular, COFs can achieve the best adsorption capacity. The bubbles on hydrophobic COFs were easy to enrich PFAS in water, and the C-F chains on the bubbles were easy to enrich together, which is an important mechanism for PFAS adsorption in the hydrophobic region on COFs.Secondly, different affinity groups were introduced into COFs to develop functional COFs with fast adsorption, high adsorption capacity and high selectivity for the removal of PFAS in water. Amino cyclodextrin was introduced into COFs, and PFAS were adsorbed via multi hydrogen bond, so that amino functionalized COFs could ultra quickly adsorb PFAS from water, and the adsorption equilibrium time was about 2 min. Quaternary ammonium group was introduced into COFs. Due to the ion exchange interaction between quaternary ammonium and PFAS molecules, quaternary ammonium functionalized COFs had high adsorption capacity for GenX (2.06 mmol/g) and HFPO-TA (2.16 mmol/g). C-F chain was further introduced into the quaternary ammonium COFs. Due to the "Fluorophilicity" among C-F chain and the ion exchange of quaternary ammonium group, fluorinated quaternary ammonium COFs showed high adsorption capacity and strong selectivity for PFAS, and could selectively adsorb PFAS from actual wastewater, which was better than activated carbon and ion exchange resin.Finally, the easily separated granular COFs and magnetic COFs were prepared. Granular fluorinated quaternary ammonium COFs were prepared by double crosslinking technology of sodium alginate and polyacrylic acid, which had little effect on the adsorption selectivity and capacity of COFs, and this granular preparation technology can be widely used in the granulation of various powder COFs. Magnetic quaternized triazine COFs were prepared by embedding magnetic Fe3O4 into COFs framework via mechanical ball milling, which had little effect on the crystal structure and adsorption capacity of COFs. Ball milling could enhance the dispersion of powdered COFs in water and improve their adsorption rate, with 44.42 mmol/g/h for HFPO-TA adsorption.Amino functionalized COFs could be effectively regenerated by using a single methanol solution. Quaternary ammonium functionalized COFs, fluorinated quaternary ammonium COFs and two easily separated COFs could be effectively regenerated by using the mixed methanol/salt solution. The five COFs had relatively stable repeated adsorption performance.