共价有机骨架（Covalent organic frameworks, COFs）是一种新型的晶体多孔有机材料。该材料构筑单元间采用刚性的共价键连接，因而骨架结构稳定，被广泛应用于条件复杂的环境领域。目前，对COFs材料的研究着重于新型结构COFs材料的化学合成，在应用方面则主要着力于单一化合物的吸附去除，或在材料中引入金属半导体材料实现催化反应。而在环境的应用中对同类多种化学物质的吸附性能比较研究较为缺失，同时某些被用作吸附材料的COFs也存在着其他诸如催化的功能潜力尚待开发。以双酚A（Bisphenol A, BPA）为代表的双酚类污染物（Bisphenol analogues, BPs）具有类雌激素效应，是石化行业中广泛使用且会对人体和环境造成较大危害的典型污染物之一。这类污染物具有难以生物降解的特点，因而物理和化学类的处理方法常被应用于BPs污染物的去除。但当前研究主要聚集于对BPA的去除，而其他多种因用于代替BPA而逐渐出现于环境中的BPs污染物仍未受到广泛关注，对不同BPs间进行靶向脱除的机理也仍待进一步明确。为此，本研究以TpBD(NO₂)₂材料为基础，探索将该非金属特性的硝基COFs材料应用于光催化领域的可行性，分析其对BPs的光催化降解效率、影响因素、相关机理。在此基础上，进一步通过官能团调控还原硝基制备TpBD(NH₂)₂强化材料吸附性能，探讨硝基向氨基的转化对COFs吸附BPs容量和选择性的影响，并阐释吸附机理差异性。最后，以COFs吸附-光催化协同去除BPs的功能耦合为核心思路，设计三种COFs协同去除模式，并探索评估在三种模式下COFs吸附-光催化协同去除BPs的可行性与经济性。结果发现：

（1）制备非金属特性的TpBD(NO₂)₂材料，开展各因素影响下的BPs光催化降解，识别材料光电作用发生机理，明确污染物降解路径，探索在两种反应器中的使用可行性。结果表明，TpBD(NO₂)₂具有优良的光催化降解潜力，可以有效实现BPs的降解去除。材料在多次循环后保持稳定可重复利用，最佳投料比为0.3 g/L，150 min光照后，20 ppm BPA降解率可达到99.5%。在实际石化废水中，共存复杂有机污染物的竞争效应会对BPA降解产生负向影响。TpBD(NO₂)₂的能带结构表征、自由基猝灭和五种BPs降解结果表明，TpBD(NO₂)₂材料带隙窄，导带位置高，主要依靠超氧阴离子自由基（O₂?^-）的产生实现污染物氧化与矿化，其光催化降解能力对大部分BPs有效。综合BPA的降解路径分析发现，O₂?^-主要通过攻击BPA上异丙基和苯环之间的C-C键实现污染物降解，该路径内的中间产物浓度先上升，但在后续过程中可能因被降解而下降，此类产物有助于体系后续矿化过程的发生。TpBD(NO₂)₂对苯环连接处具有砜基的BPS降解效果相对较差。基于TpBD(NO₂)₂催化性能与机理研究，设计并运行了两种不同结构的循环式流化床光催化反应器，发现圆形结构反应单元中，在上升流速15 mL/min，投料比0.3 g/L条件下，催化剂扰动情况好，传质能力较优，颗粒堵塞出口可能性较小，催化剂受光效率高，可以达到体系内最优的运行状态。该运行条件下，180 min光照下BPA降解效率可达到97.4%。

（2）对TpBD(NO₂)₂中硝基进行还原从而制备TpBD(NH₂)₂，对5种代表性BPs污染物（BPA、BPS、BPC、BPF和4-CP）开展吸附研究，明确官能团调控对吸附行为的贡献，结合材料和污染物理化性质阐明吸附作用机理。结果表明，硝基向氨基转化后，材料形貌并未发生明显差异。动力学拟合结果显示COFs对BPs吸附以化学吸附为主，官能团调控在吸附过程中贡献作用显著。与TpBD(NO₂)₂相比，TpBD(NH₂)₂对BPs污染物具有更好的吸附容量和差异化的吸附选择性。TpBD(NO₂)₂吸附性能主要受疏水性能影响，对疏水性较强的BPC吸附性能最好。TpBD(NH₂)₂的吸附性能与静电力密切相关，对BPF吸附选择性最佳。此外，COFs对BPS和4-CP的吸附以氢键作用为主。与文献中其他吸附材料和含氨基的商业吸附材料进行对比发现，本研究制备的TpBD(NH₂)₂材料展现了具有竞争力的吸附性能，且具有好的重复利用性。

（3）以COFs吸附-光催化协同去除BPs的功能耦合为核心思路，设计三种功能协同模式去除BPs，评估各功能协同模式的性能、经济性与工况场景适应性。结果表明，充分利用TpBD(NH₂)₂吸附功能和TpBD(NO₂)₂光催化性能的分体串联体系中，光催化降解阶段光照时间较短，此模式适用于对以BPS为代表的难降解污染物的去除，可通过预吸附减轻后续光催化降解的压力。以成本降低为思路得出的复合材料g-C₃N₄@TpBD(NO₂)₂研究体系中，5:2和1:12的配比下，分别可得到性价比最优和对材料光催化性能提升明显的复合材料。对杂氮环引入路径优化后获得的吸附-光催化功能复合材料TpBD(NH₂)₂@TpMA研究体系中，1:1的复合配比下可实现催化速率常数的显著提升，20:5配比下可实现保持吸附容量的同时使材料获得良好的光催化效果。该类功能耦合材料在未来环境功能材料研究中具有广阔的发展空间。

Covalent organic frameworks (COFs) are a new type of crystalline porous organic materials. The building blocks of this material are connected by rigid covalent bonds, so the skeleton structure is stable, and it is widely used in the environmental field with complex conditions. At present, the research about COFs focuses on the chemical synthesis of COFs with new structure, and when it comes to the application, it mainly focuses on the adsorption and removal of single compounds, or the introduction of metal semiconductor materials into the materials to achieve catalytic function. However, studies on the comparative adsorption behaviors of various similar chemical substances over COFs are lacking, and some COFs also have other functional potentials such as catalysis yet to be developed. Bisphenol analogues (BPs), represented by bisphenol A (BPA), have estrogen-like effects and are the typical pollutants that are widely used in the petrochemical industry, which can cause great harm to human body and the environment. The BPs pollutants are difficult to biodegrade, so physical and chemical treatment methods are often used to remove these pollutants. However, the current research mainly focuses on the removal of BPA, while other BPs pollutants that gradually appear in the environment because they are used to replace BPA have not received extensive attention, and the mechanism of targeted removal of different BPs still needs to be further clarified. Therefore, based on the TpBD(NO₂)₂ material, this study explores the feasibility of applying this metal-free nitro-COFs material to the field of photocatalysis toward BPs, and analyzes its photodegradation efficiency, influencing factors, related mechanisms and the possibility of application in the reactor system. Furthermore, to enhance the adsorption performance, the TpBD(NH₂)₂ materials was prepared by the reduction of nitro groups through functional-group-tuning. The effect of the conversion from nitro groups to amino groups on the adsorption capacity and selectivity of COFs for BPs was discussed, and the differences in adsorption mechanisms were explained. Three modes were comprehensively designed, namely adsorption-photocatalysis separate series mode, COFs cost-reduction and catalysis-enhancement mode, and COFs functional composite mode, to explore the feasibility and economy of COFs adsorption-photocatalysis synergistic removal of BPs in three different modes. The results show that:

(1) Preparing nitro-COFs material with non-metallic properties, namely TpBD(NO₂)₂, to carry out photocatalytic degradation of BPs in the presence of various influencing factors, identify the characteristic of photoelectricity of materials, clarify the degradation pathway of pollutants, and explore reactor system operational feasibility. The results show that the TpBD(NO₂)₂ has excellent photocatalytic degradation potential and can effectively remove and degrade the BPs. The material remained stable and reusable after multiple cycles, the optimal dosing ratio was 0.3 g/l, and the degradation rate could reach 99.5% after 150 min of illumination with 20 ppm of BPA. In the real wastewater background of petrochemical wastewater effluent, the degradation of BPA will be negatively affected by the competitive effect of complex organic pollutants in the background. The energy band structure characterization, radical quenching and five BPs degradation results of TpBD(NO₂)₂ show that TpBD(NO₂)₂ material has narrow band gap and high conduction band position, by which the oxidation and mineralization of pollutants mainly rely on the generation of superoxide anion radicals (O₂?^-), while its photocatalytic degradation ability is effective for most BPs. Comprehensive analysis of the degradation pathway of BPA shows that O₂?^- achieves the degradation of the pollutants by attacking the C-C bond between the isopropyl group and the benzene ring on BPA, so the degradation effect of BPS with a sulfone group at the junction of the benzene ring is relatively poor. During the degradation process, the concentration of intermediate products first increased, but in the subsequent process may be decreased due to downstream degradation, such kind of products contribute to the subsequent mineralization process. Based on the results abovementioned, two circulating fluidized bed photocatalytic reactors with different structures were designed and operated to expand the application scene of the TpBD(NO₂)₂ photocatalyst. It was found that in the circular structure reaction unit, under the condition of the upward flow rate = 15 mL/min and the dosing ratio = 0.3 g/L, the catalyst has good disturbance, better mass transfer ability, less possibility of particles blocking the outlet, and high light-receiving efficiency of the catalyst, which can achieve the optimal operating state in the system. Under the conditions, the degradation efficiency of BPA can reach 97.4% after 180 min of illumination.

(2) The nitro group in TpBD(NO₂)₂ was reduced to prepare TpBD(NH₂)₂, and the adsorption of five representative BPs pollutants (BPA, BPS, BPC, BPF and 4-CP) was carried out to analyze the contribution of functional-group-tuning to the adsorption behavior. Combined with the physicochemical properties of both the COFs materials and pollution, the mechanism of adsorption was elucidated. The results showed that there was no significant difference in the morphology of two COFs materials after the conversion of nitro groups to amino groups. The kinetic fitting results showed that the adsorption of BPs by COFs was dominated by chemical adsorption, and the functional-group-tuning played a significant role in the adsorption process. Compared with TpBD(NO₂)₂, TpBD(NH₂)₂ has better adsorption capacity and selectivity for BPs pollutants. The adsorption performance of TpBD(NO₂)₂ is mainly affected by the hydrophobicity, so it adsorbed BPC with strong hydrophobicity best. The adsorption performance of TpBD(NH₂)₂ is closely related to the electrostatic force, and it selectively adsorbed BPF best. Meanwhile, the adsorption of BPS and 4-CP by COFs is dominated by hydrogen bonding. Compared with other reported adsorbents and commercial adsorbents containing amino groups, it was found that the TpBD(NH₂)₂ prepared in this study exhibited competitive adsorption performance and good reusability.

(3) Taking the functional coupling of COFs adsorption-photocatalytic synergistic removal toward BPs as the core idea, three functional synergistic modes were designed to remove BPs, and the performance, economy and adaptability of each functional synergy mode were evaluated. The results show that in the separate series system of TpBD(NH₂)₂ with adsorption function and TpBD(NO₂)₂ with photocatalytic performance, the light energy consumption is low. This mode is suitable for the removal of refractory pollutants represented by BPS, and it is obvious that the stress of subsequent photocatalytic degradation is relieved by pre-adsorption. In the system of the composite material g-C₃N₄@TpBD(NO₂)₂ based on the idea of cost reduction, the composite material with the best cost-performance and obvious improvement of photocatalytic performance can be obtained at the composite ratio of 5:2 and 1:12, respectively. In the system of the adsorption-photocatalytic functional composite TpBD(NH₂)₂@TpMA, which was obtained by optimizing the introduction path of the hetero nitrogen ring, the catalytic rate constant can be significantly improved under the composite ratio of 1:1, while the composite materials with ratio of 20:5 can achieve good photocatalytic effect while maintaining the adsorption capacity. Such functional coupling materials have broad development space in the future research of environmental functional materials.