Method for degrading benzene (alpha) pyrene in water by means of gamma rays

Abstract

This invention discloses a method for degrading benzo(α)pyrene in water using gamma rays, belonging to the field of wastewater treatment technology. It addresses the technical problem that the degradation efficiency and extent of benzo(α)pyrene degradation in water using gamma rays in existing technologies need further improvement. This invention constructs an iron cycling-persulfate composite system synergistically composed of quaternized porous aromatic materials, sulfonated silicon-based hybrid channel materials, and cross-linked β-cyclodextrin materials. The quaternized porous aromatic materials achieve stable enrichment of pollutants and persulfate through a positively charged interface; the sulfonated silicon-based hybrid channel materials provide a continuous coordination and electron transfer environment for iron species; and the cross-linked β-cyclodextrin materials confine and secondary encapsulate hydrophobic pollutants and intermediates. These three components form interconnected reaction pathways in structure and function, realizing the construction, maintenance, and continuous organization of reaction microdomains, thereby significantly improving the degradation efficiency and cycling stability of pollutants.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, specifically to a method for degrading benzo(α)pyrene in water using gamma rays. Background Technology

[0002] Benzo(α)pyrene, a typical high-ring polycyclic aromatic hydrocarbon pollutant, is characterized by its stable structure, strong hydrophobicity, and long environmental persistence. For this type of recalcitrant organic pollutant, gamma-ray irradiation technology has attracted attention due to its strong penetrating power and the fact that the process does not rely on chemical additives. Under the action of gamma rays, water molecules undergo radiodecomposition, generating various highly reactive intermediates such as hydroxyl radicals, hydrated electrons, and hydrogen atoms. These reactive species can undergo addition, bond breaking, or oxidation reactions with organic molecules in water, thereby destroying and transforming the molecular structure of benzo(α)pyrene. Currently, research on the degradation of benzo(α)pyrene in water by gamma rays mainly focuses on irradiation dose, reaction kinetics, and the characteristics of radiation products. Related technologies are considered one of the important application directions of radiation chemistry in the field of environmental pollution control.

[0003] In existing oxidation or synergistic treatment processes for hydrophobic organic pollutants such as benzo(α)pyrene in water bodies, the reaction process is mostly dominated by bulk reactions. The spatial distribution of pollutants, oxidants, and metal active species in the system lacks effective control. Due to the poor dispersibility of hydrophobic pollutants in the aqueous phase, they are difficult to achieve stable enrichment in the early stage of the reaction and often need to rely on random diffusion to enter the active region, resulting in insufficient local reactant concentrations. At the same time, the mass transfer path of the oxidant near the pores or interface is discontinuous, and the activation sites are dispersed, which limits the effective contact probability between pollutants and active species. The overall reaction process is prone to shift from local interface control to bulk diffusion control, thus affecting the synergy and sustainability of the degradation process.

[0004] Furthermore, under conditions of continuous reaction or multiple cycles, the coordination environment and valence state transformation pathway of the active metal components in existing processes are not stable enough. The activation process often relies on non-directional electron transfer behavior, making it difficult to maintain a continuous and repeatable reaction path. Moreover, the hydrophobic intermediates generated during the reaction lack effective confinement and buffering mechanisms, easily detach from the active region and repeatedly migrate in the system, causing interruptions in the reaction path and fluctuations in local load. These problems are further amplified after multiple runs, manifesting as decreased degradation efficiency, inconsistent reaction behavior, and limited material recycling performance, which restricts the application of related processes under long-term stable operating conditions.

[0005] To address this technical deficiency, a solution is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a method for degrading benzo(α)pyrene in water using gamma rays, which solves the technical problem that the degradation efficiency and degree of benzo(α)pyrene in water using gamma rays need to be further improved in the prior art.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A method for degrading benzo(α)pyrene in water using gamma rays includes the following steps:

[0009] S1. Quaternized porous aromatic material, sulfonated silicon-based hybrid channel material, cross-linked β-cyclodextrin material and deionized water are added to the reaction vessel and stirred. After uniform dispersion, a complexing agent is added and the reaction vessel is heated to 30-40℃. The mixture is kept at this temperature and stirred for 3-5 hours. The iron recycling functional composite material is obtained after post-treatment.

[0010] S2. Add the iron recycling functional composite material and the activation liquid to the reaction vessel and stir. After the mixture is uniform, heat the reaction vessel to 30-40℃ and keep it at the temperature for 2-3 hours. The iron recycling-persulfate synergistic composite material is obtained by post-treatment.

[0011] The reaction principle for preparing the iron cycling-persulfate synergistic composite material is as follows:

[0012] The nitrogen-containing groups, sulfonic acid groups, and cyclodextrin structural units introduced into the multi-component organic-inorganic material system can provide a multi-site coordination environment for metal ions. The iron ions formed by the dissociation of ferric chloride in solution can form complexes with amino groups, sulfonic acid groups, and oxygen-containing functional groups through coordination bonds, thereby anchoring them in a stable form within the composite material skeleton. On this basis, persulfate anions can form a synergistic combination with the iron coordination centers and the porous skeleton surface through electrostatic interactions, hydrogen bonding, and coordination interactions, enabling the inorganic oxidant to coexist and be fixed in the organic-inorganic hybrid structure. This constructs a composite system containing iron coordination structures and persulfate species, ultimately preparing an iron-cycle-persulfate synergistic composite material.

[0013] S3. Add an iron cycle-persulfate synergistic composite material to the water body containing benzo(α)pyrene, and then treat the water body under γ-ray irradiation conditions, wherein the water body to be treated is an actual polluted water body or an artificially prepared simulated water body.

[0014] The reaction principle of benzo(α)pyrene degradation under gamma ray irradiation is as follows:

[0015] In the iron-cycle-persulfate synergistic composite material, the iron coordination structure and persulfate species coexist stably and are anchored in a porous organic-inorganic hybrid framework. Under gamma-ray irradiation, this composite system can serve as a reaction interface for radiation-induced electron transfer and free radical generation. The iron coordination center undergoes a valence state transition under the action of active electrons generated by irradiation, thereby promoting the activation reaction of persulfate and generating highly active sulfur-containing free radical species such as sulfate free radicals. The porous aromatic framework and hybrid channel structure provide an interfacial contact environment for benzo(α)pyrene molecules, making them more likely to participate in free radical-mediated addition, electron transfer, and bond breaking reactions on the material surface and in the pore region, thus constituting the basis for the irradiation chemical transformation of benzo(α)pyrene in this synergistic system.

[0016] Further, in step S1, the ratio of the quaternized porous aromatic material, sulfonated silicon-based hybrid channel functional group, cross-linked β-cyclodextrin material, deionized water and complexing agent is 3-4g:2-3g:2-3g:200mL:200mL, wherein the complexing agent is a 0.08-0.12mol / L ferric chloride aqueous solution. The post-treatment includes: cooling to room temperature after the reaction, filtering to collect the filter cake, washing and then placing it in a 60℃ drying oven for vacuum drying for 10-12h to obtain the iron recycling functional composite material.

[0017] Further, in step S2, the ratio of the iron recycling functional composite material to the activation solution is 5-8g:200mL, wherein the activation solution is a 0.08-0.12mol / L potassium persulfate aqueous solution. The post-treatment includes: cooling to room temperature after the reaction is completed, filtering to collect the filter cake, washing, and then placing it in a 60℃ drying oven for vacuum drying for 10-12h to obtain the iron recycling-persulfate synergistic composite material.

[0018] Furthermore, in step S3, the mass ratio of the iron-cycle-persulfate synergistic composite material to the benzo(α)pyrene in the water to be treated is 40-60:1, wherein the gamma ray dose rate is 2-3 kGy·h. -1 .

[0019] Furthermore, the quaternized porous aromatic material is prepared by the following method:

[0020] A1. Add the porous aromatic epoxy crosslinking polymer framework and anhydrous ethanol to the reactor and stir. After the mixture is evenly dispersed, add diethylenetriamine and heat the reactor to 60-70℃. Keep the mixture warm and stir for 8-12 hours. The resulting porous aromatic polyamine functionalized polymer framework is then obtained through post-treatment.

[0021] A2. Add the porous aromatic polyamine functionalized polymer framework and anhydrous acetonitrile to the reactor and stir. After mixing evenly, add benzyl bromide in five equal batches with an interval of 5 minutes between additions. After the addition is complete, heat the reactor to 50-60℃ and keep it at this temperature for 8-10 hours. The quaternized porous aromatic material is then obtained through post-treatment.

[0022] The reaction principle for preparing quaternized porous aromatic materials is as follows:

[0023] The residual epoxy groups in the porous aromatic epoxy crosslinking polymer backbone are prone to ring-opening reactions under nucleophilic conditions. The primary and secondary amine groups in the diethylenetriamine molecule can nucleophilically attack the epoxy ring, thereby introducing nitrogen-containing segments on the surface of the aromatic crosslinking backbone and forming a stable covalent connection structure. In the backbone after amination modification, the amino groups are distributed in a free state on the surface of the polymer network. Under the condition of haloalkanes, they can further undergo nucleophilic substitution reactions, and quaternary ammonium bonds are formed between nitrogen atoms and benzyl groups. This allows the organic cationic groups to be fixed in the porous aromatic polymer backbone in a covalent manner, and finally, quaternized porous aromatic materials are prepared.

[0024] Further, in step A1, the ratio of the porous aromatic epoxy crosslinking polymer backbone, anhydrous ethanol and diethylenetriamine is 8-12g:120-150mL:35-45mL. The post-treatment includes: cooling to room temperature after the reaction, filtering to collect the filter cake, washing and then placing it in a 60℃ drying oven for vacuum drying for 10-12h to obtain the porous aromatic polyamine functionalized polymer backbone.

[0025] Further, in step A2, the ratio of the porous aromatic polyamine functionalized polymer framework, anhydrous acetonitrile, and benzyl bromide is 8-10g:140-160mL:8-10mL. The post-treatment includes: cooling to room temperature after the reaction, filtering to collect the filter cake, washing, and then vacuum drying in a 60℃ drying oven for 10-12h to obtain the quaternized porous aromatic material.

[0026] Furthermore, the preparation method of the porous aromatic epoxy crosslinked polymer framework is as follows: the dispersed phase is added to the reaction vessel, and the organic phase is added to the dispersed phase in 10 equal batches under stirring conditions, with an addition interval of 5 min. After the addition is completed, nitrogen gas is introduced for protection and the reaction vessel is heated to 70-80℃. The mixture is kept at this temperature and stirred for 6-8 h. The porous aromatic epoxy crosslinked polymer framework is then obtained through post-treatment.

[0027] The reaction principle for preparing porous aromatic epoxy crosslinked polymer backbone is as follows:

[0028] Under free radical initiation conditions, divinylbenzene copolymerizes with the unsaturated double bonds in glycidyl methacrylate to form a cross-linked polymer network dominated by aromatic structural units. Divinylbenzene, as a multifunctional cross-linking monomer, participates in the construction of a three-dimensional covalent framework, while glycidyl methacrylate is introduced into the polymerization system through its vinyl groups. The epoxy groups are retained and embedded in the framework structure during the polymerization process. This type of free radical copolymerization reaction promotes the formation of a continuously cross-linked polymer framework of aromatic units in space, and finally prepares a porous aromatic epoxy cross-linked polymer framework.

[0029] Furthermore, in the preparation of the porous aromatic epoxy crosslinked polymer framework, the ratio of the dispersed phase to the organic phase is 300 mL: 70-80 g, wherein the dispersed phase is a 1.0-1.2 wt% polyvinyl alcohol aqueous solution, and the organic phase is composed of divinylbenzene, glycidyl methacrylate, toluene, n-heptane, and azobisisobutyronitrile in a ratio of 24-30 g: 10-12 g: 40 mL: 40 mL: 0.4-0.5 g. The post-treatment includes: cooling to room temperature after the reaction, filtering to collect the filter cake, washing, and then vacuum drying in a 60℃ drying oven for 10-12 h to obtain the porous aromatic epoxy crosslinked polymer framework.

[0030] Furthermore, the sulfonated silicon-based hybrid channel material is prepared by the following method:

[0031] B1. Add anhydrous ethanol and deionized water to the reaction vessel and stir. After mixing evenly, add tetraethyl orthosilicate and 3-mercaptopropyltrimethoxysilane in sequence, and add saturated ammonia water. Continue stirring for 40-80 minutes. Post-processing yields a mercaptosilyl hybrid channel framework.

[0032] B2. Add the mercaptosilicone hybrid channel framework and deionized water to the reactor and stir. After mixing evenly, add 30wt% hydrogen peroxide aqueous solution in 10 equal batches with an 8-minute interval between additions. After the addition is complete, heat the reactor to 40-50℃ and keep it at this temperature for 4-6 hours. Post-processing yields sulfonated silicon-based hybrid channel material.

[0033] The reaction principle for preparing sulfonated silicon-based hybrid channel materials is as follows:

[0034] Under alkaline conditions, tetraethyl orthosilicate and 3-mercaptopropyltrimethoxysilane undergo hydrolysis to generate the corresponding silanol intermediates. Subsequently, a hybrid network structure with Si-O-Si bonds as the backbone is formed through the condensation reaction between silanols. Thiol groups are introduced into the silicon-based framework in the form of organosilanes through co-condensation and are uniformly distributed. Under oxidative conditions, the thiol groups in the resulting hybrid structure undergo valence state transformation, and sulfur atoms are gradually transformed from the reduced state to high-valence oxygen-containing sulfur groups, forming a hybrid structure system with silicon-oxygen network as the main body and sulfonic acid groups covalently anchored. Finally, sulfonated silicon-based hybrid channel materials are prepared.

[0035] Further, in step B1, the ratio of anhydrous ethanol, deionized water, tetraethyl orthosilicate, 3-mercaptopropyltrimethoxysilane, and saturated ammonia is 200mL:20mL:18-24mL:8-12mL:0.8-1.0mL. The post-treatment includes: after stirring, the system is allowed to stand for aging for 24-30 hours. After aging, the filter cake is collected by filtration, washed, and then placed in a 60℃ drying oven for vacuum drying for 10-12 hours to obtain a mercaptosilicone hybrid channel framework.

[0036] Further, in step B2, the ratio of the mercaptosilicone hybrid channel framework, deionized water, and 30wt% hydrogen peroxide aqueous solution is 8-12g:200mL:35-45mL. The post-treatment includes: cooling to room temperature after the reaction, filtering to collect the filter cake, washing, and then vacuum drying in a 60℃ drying oven for 10-12h to obtain the sulfonated silicon-based hybrid channel material.

[0037] Furthermore, the preparation method of the cross-linked β-cyclodextrin material is as follows: β-cyclodextrin and deionized water are added to a reaction vessel and stirred. After dissolution, sodium hydroxide is added and stirring is continued for 10-20 minutes. The reaction vessel is then heated to 50-60°C. Epichlorohydrin is added in four equal batches with a 5-minute interval between each addition under stirring conditions. After stirring at this temperature for 6-8 hours, the cross-linked β-cyclodextrin material is obtained through post-treatment.

[0038] The reaction principle for preparing cross-linked β-cyclodextrin materials is as follows:

[0039] Under alkaline conditions, the hydroxyl groups on β-cyclodextrin molecules undergo deprotonation, forming alkoxy anions with strong nucleophilicity. The epoxy groups with high stress in epichlorohydrin molecules are easily subjected to nucleophilic attack and undergo ring-opening reactions. At the same time, its chloroalkyl structure can further participate in substitution reactions, thereby forming ether bonds between different β-cyclodextrin molecules. The combined effect of this type of nucleophilic ring-opening and substitution reaction enables β-cyclodextrin units to construct cross-linked structures through covalent bonds, ultimately preparing cross-linked β-cyclodextrin materials.

[0040] Furthermore, in the preparation of the cross-linked β-cyclodextrin material, the ratio of β-cyclodextrin, deionized water, sodium hydroxide and epichlorohydrin is 8-12g:100mL:3-4g:8-12mL. The post-treatment includes: cooling to room temperature after the reaction, filtering to collect the filter cake, washing and then placing it in a 60℃ drying oven for vacuum drying for 10-12h to obtain the cross-linked β-cyclodextrin material.

[0041] The present invention has the following beneficial effects:

[0042] 1. In the composite material used in this invention, the quaternized porous aromatic material constitutes a continuous hierarchical porous structure. Its positive surface charge generates stable interfacial adsorption and spatial enrichment of hydrophobic organic pollutants and persulfate during operation, forming a high local concentration region of reactants on the material surface. At the same time, the sulfonated silicon-based hybrid channel material, with its hydrophilic framework, runs through the porous structure, providing a continuous mass transfer pathway for persulfate and aqueous active species in the reaction system. It also participates in the electron transfer process of iron species through the local environment formed by the sulfonic acid groups. The cross-linked β-cyclodextrin material is distributed in the above structure, and its hydrophobic cavity encapsulates the target pollutants, so that the pollutants are in the active region at the beginning of the reaction. The above structural configuration forms a reaction pathway with the combined effects of enrichment, mass transfer and confinement during operation, which ultimately significantly improves the degradation efficiency.

[0043] 2. During the continuous reaction, the inorganic-organic hybrid framework constructed by the sulfonated silicon-based hybrid channel material provides a stable coordination and distribution environment for iron species, enabling the iron valence state to repeatedly participate in the activation process of persulfate. The microenvironment formed by its sulfonic acid groups on the material surface is conducive to maintaining the continuity of the above activation pathway. In addition, the quaternized porous aromatic material spatially fixes the reactants and oxidants through its pore structure, reducing the possibility of intermediate products detaching from the reaction interface. At the same time, the cross-linked β-cyclodextrin material performs secondary inclusion on the hydrophobic intermediates generated during the reaction, allowing them to remain in the active species enrichment region and participate in the subsequent oxidation process. The three materials form interconnected transformation channels during the reaction, ultimately significantly improving the degradation degree of benzo(α)pyrene.

[0044] 3. Under repeated operation conditions, the cross-linked network structure of the cross-linked β-cyclodextrin material continues to play a confinement and buffering role in the system. Its inclusion behavior of pollutants and intermediate products helps to reduce the impact of local accumulation on the material surface on the reaction pathway. Meanwhile, the sulfonated silicon-based hybrid channel material, with its structural stability of silicon-oxygen framework, maintains the distribution of iron species during repeated operation, enabling it to continue to participate in the activation process of persulfate. At the same time, the quaternized porous aromatic material regulates the spatial distribution of reactants and oxidants through its pore structure and electrical interface, reducing the imbalance of active sites during operation. The above materials form a synergistic configuration in terms of structural maintenance and reaction pathway maintenance, so that the system maintains a consistent reaction mode under repeated operation conditions, thereby significantly improving the recycling capacity of the materials. Detailed Implementation

[0045] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0046] In this application, the polyvinyl alcohol used was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with the product number P434367.

[0047] Example 1

[0048] This embodiment provides a method for preparing quaternized porous aromatic materials, including the following steps:

[0049] Step I: Preparation of a porous aromatic epoxy crosslinking polymer framework

[0050] Weigh out 24.0 g divinylbenzene, 10.0 g glycidyl methacrylate, 40.0 mL toluene, 40.0 mL n-heptane and 0.4 g azobisisobutyronitrile and mix them to obtain an organic phase;

[0051] Weigh 300.0 mL of 1.0 wt% polyvinyl alcohol aqueous solution and add it to the reactor. Under stirring conditions, add 70.0 g of organic phase in 10 equal batches to the dispersed phase at 5 min intervals. After the addition is complete, purge with nitrogen and heat the reactor to 70 °C. Keep it at this temperature and stir for 6 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. After washing, place it in a 60 °C drying oven and vacuum dry for 10 h to obtain a porous aromatic epoxy crosslinked polymer backbone.

[0052] Step II: Preparation of porous aromatic polyamine functionalized polymeric framework

[0053] Weigh 8.0 g of porous aromatic epoxy crosslinking polymer backbone and 120.0 mL of anhydrous ethanol and add them to the reaction vessel. Stir until the mixture is evenly dispersed. Then add 35.0 mL of diethylenetriamine and heat the reaction vessel to 60 °C. Keep the mixture at this temperature and stir for 8 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. Wash the cake and place it in a 60 °C drying oven for vacuum drying for 10 h to obtain the porous aromatic polyamine functionalized polymer backbone.

[0054] Step III: Preparation of Quaternized Porous Aromatic Materials

[0055] Weigh 8.0 g of porous aromatic polyamine functionalized polymer backbone and 140.0 mL of anhydrous acetonitrile and add them to the reactor and stir. After mixing evenly, add benzyl bromide in five equal batches, with a total addition of 8.0 mL and an interval of 5 min between additions. After the addition is complete, heat the reactor to 50 °C and keep it at that temperature for 8 h with stirring. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash it and place it in a 60 °C drying oven for vacuum drying for 10 h to obtain quaternized porous aromatic material.

[0056] Example 2

[0057] This embodiment provides a method for preparing quaternized porous aromatic materials, including the following steps:

[0058] Step I: Preparation of a porous aromatic epoxy crosslinking polymer framework

[0059] Weigh out 30.0 g divinylbenzene, 12.0 g glycidyl methacrylate, 40.0 mL toluene, 40.0 mL n-heptane and 0.5 g azobisisobutyronitrile and mix them to obtain an organic phase;

[0060] Weigh 300.0 mL of 1.2 wt% polyvinyl alcohol aqueous solution and add it to the reactor. Under stirring conditions, add 80.0 g of organic phase in 10 equal batches to the dispersed phase at 5 min intervals. After the addition is complete, purge with nitrogen and heat the reactor to 80 °C. Keep the temperature and stir for 8 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. After washing, place it in a 60 °C drying oven and vacuum dry for 12 h to obtain a porous aromatic epoxy crosslinked polymer backbone.

[0061] Step II: Preparation of porous aromatic polyamine functionalized polymeric framework

[0062] Weigh 12.0 g of porous aromatic epoxy crosslinking polymer backbone and 150.0 mL of anhydrous ethanol and add them to the reaction vessel. Stir until the mixture is evenly dispersed. Then add 45.0 mL of diethylenetriamine and heat the reaction vessel to 70 °C. Keep the mixture at this temperature and stir for 12 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. Wash the cake and place it in a 60 °C drying oven for vacuum drying for 12 h to obtain the porous aromatic polyamine functionalized polymer backbone.

[0063] Step III: Preparation of Quaternized Porous Aromatic Materials

[0064] Weigh 10.0 g of porous aromatic polyamine functionalized polymer backbone and 160.0 mL of anhydrous acetonitrile and add them to the reactor and stir. After mixing evenly, add benzyl bromide in five equal batches, with a total addition of 10.0 mL and an interval of 5 min between additions. After the addition is complete, heat the reactor to 60 °C and keep it at that temperature for 10 h with stirring. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash it and place it in a 60 °C drying oven for vacuum drying for 12 h to obtain quaternized porous aromatic material.

[0065] Example 3

[0066] This embodiment provides a method for preparing quaternized porous aromatic materials, including the following steps:

[0067] Step I: Preparation of a porous aromatic epoxy crosslinking polymer framework

[0068] Weigh out 27.0 g divinylbenzene, 11.0 g glycidyl methacrylate, 40.0 mL toluene, 40.0 mL n-heptane and 0.5 g azobisisobutyronitrile and mix them to obtain an organic phase;

[0069] Weigh 300.0 mL of 1.1 wt% polyvinyl alcohol aqueous solution and add it to the reactor. Under stirring conditions, add 75.0 g of organic phase in 10 equal batches to the dispersed phase at 5 min intervals. After the addition is complete, purge with nitrogen and heat the reactor to 75 °C. Keep it at this temperature and stir for 7 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. After washing, place it in a 60 °C drying oven and vacuum dry for 11 h to obtain a porous aromatic epoxy crosslinked polymer backbone.

[0070] Step II: Preparation of porous aromatic polyamine functionalized polymeric framework

[0071] Weigh 10.0 g of porous aromatic epoxy crosslinking polymer backbone and 135.0 mL of anhydrous ethanol and add them to the reaction vessel. Stir until the mixture is evenly dispersed. Then add 40.0 mL of diethylenetriamine and heat the reaction vessel to 65 °C. Keep the mixture at this temperature and stir for 10 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. Wash the cake and place it in a 60 °C drying oven for vacuum drying for 11 h to obtain the porous aromatic polyamine functionalized polymer backbone.

[0072] Step III: Preparation of Quaternized Porous Aromatic Materials

[0073] Weigh 9.0 g of porous aromatic polyamine functionalized polymer backbone and 150.0 mL of anhydrous acetonitrile and add them to the reactor and stir. After mixing evenly, add benzyl bromide in five equal batches, with a total addition of 9.0 mL and an interval of 5 min between additions. After the addition is complete, heat the reactor to 55 °C and keep it at that temperature for 9 h with stirring. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash it and place it in a 60 °C drying oven for vacuum drying for 11 h to obtain quaternized porous aromatic material.

[0074] Example 4

[0075] This embodiment provides a method for preparing a sulfonated silicon-based hybrid channel material, including the following steps:

[0076] Step ①: Preparation of a thiol-silicon hybrid channel framework

[0077] Weigh out 200.0 mL of anhydrous ethanol and 20.0 mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous. Then add 18.0 mL of tetraethyl orthosilicate and 8.0 mL of 3-mercaptopropyltrimethoxysilane, followed by 0.8 mL of saturated ammonia. Continue stirring for 40 min. After stirring, allow the system to stand for 24 h for aging. After aging, filter and collect the filter cake. Wash the cake and place it in a 60 °C drying oven for vacuum drying for 10 h to obtain the mercaptosilicone hybrid channel framework.

[0078] Step 2: Preparation of sulfonated silicon-based hybrid channel materials

[0079] Weigh 8.0 g of mercaptosilicone hybrid channel framework and 200.0 mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous. Then, add 30 wt% hydrogen peroxide aqueous solution in 10 equal batches, with a total addition of 35.0 mL and an interval of 8 min between additions. After the addition is complete, heat the reaction vessel to 40 °C and stir for 4 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. After washing, place it in a 60 °C drying oven and vacuum dry for 10 h to obtain sulfonated silicon-based hybrid channel material.

[0080] Example 5

[0081] This embodiment provides a method for preparing a sulfonated silicon-based hybrid channel material, including the following steps:

[0082] Step ①: Preparation of a thiol-silicon hybrid channel framework

[0083] Weigh out 200.0 mL of anhydrous ethanol and 20.0 mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous. Then add 24.0 mL of tetraethyl orthosilicate and 12.0 mL of 3-mercaptopropyltrimethoxysilane, and add 1.0 mL of saturated ammonia. Continue stirring for 80 min. After stirring, let the system stand for 30 h to age. After aging, filter and collect the filter cake. Wash the cake and place it in a 60 °C drying oven for vacuum drying for 12 h to obtain the mercaptosilicone hybrid channel framework.

[0084] Step 2: Preparation of sulfonated silicon-based hybrid channel materials

[0085] Weigh 12.0 g of mercaptosilicone hybrid channel framework and 200.0 mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous. Then, add 30 wt% hydrogen peroxide aqueous solution in 10 equal batches, with a total addition of 45.0 mL and an interval of 8 min between additions. After the addition is complete, heat the reaction vessel to 50 °C and keep it at that temperature for 6 h with stirring. After the reaction is complete, cool to room temperature, filter and collect the filter cake. After washing, place it in a 60 °C drying oven and vacuum dry for 12 h to obtain sulfonated silicon-based hybrid channel material.

[0086] Example 6

[0087] This embodiment provides a method for preparing a sulfonated silicon-based hybrid channel material, including the following steps:

[0088] Step ①: Preparation of a thiol-silicon hybrid channel framework

[0089] Weigh out 200.0 mL of anhydrous ethanol and 20.0 mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous. Then add 21.0 mL of tetraethyl orthosilicate and 10.0 mL of 3-mercaptopropyltrimethoxysilane, and add 0.9 mL of saturated ammonia. Continue stirring for 60 min. After stirring, let the system stand for 27 h to age. After aging, filter and collect the filter cake. Wash the cake and place it in a 60 °C drying oven for vacuum drying for 11 h to obtain the mercaptosilyl hybrid channel framework.

[0090] Step 2: Preparation of sulfonated silicon-based hybrid channel materials

[0091] Weigh 10.0g of mercaptosilicone hybrid channel framework and 200.0mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous. Then, add 30wt% hydrogen peroxide aqueous solution in 10 equal batches, with a total addition of 40.0mL and an interval of 8min between additions. After the addition is complete, heat the reaction vessel to 45℃ and keep it at that temperature for 5h. After the reaction is complete, cool it to room temperature, filter and collect the filter cake. After washing, place it in a 60℃ drying oven and vacuum dry for 11h to obtain sulfonated silicon-based hybrid channel material.

[0092] Example 7

[0093] This embodiment provides a method for preparing an iron cycling-persulfate synergistic composite material, including the following steps:

[0094] Step 1: Preparation of cross-linked β-cyclodextrin materials

[0095] Weigh 8.0 g of β-cyclodextrin and 100.0 mL of deionized water and add them to the reaction vessel. Stir until dissolved, then add 3.0 g of sodium hydroxide and continue stirring for 10 min. Heat the reaction vessel to 50 °C and add epichlorohydrin in four equal batches with a total addition of 8.0 mL under stirring. Each addition is 5 min apart. Keep the mixture warm and stir for 6 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. Wash the cake and place it in a 60 °C drying oven for vacuum drying for 10 h to obtain cross-linked β-cyclodextrin material.

[0096] Step 2: Preparation of iron recycling functional composite materials

[0097] Weigh out 3.0g of the quaternized porous aromatic material prepared in Example 1, 2.0g of the sulfonated silicon-based hybrid channel material prepared in Example 4, 2.0g of the cross-linked β-cyclodextrin material, and 200.0mL of deionized water and add them to the reaction vessel. Stir until the mixture is evenly dispersed, then add 200.0mL of 0.08mol / L ferric chloride aqueous solution and heat the reaction vessel to 30℃. Keep the mixture warm and stir for 3h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. After washing, place it in a 60℃ drying oven and vacuum dry for 10h to obtain the iron recycling functional composite material.

[0098] Step 3: Preparation of iron cycling-persulfate synergistic composite material

[0099] Weigh 5.0g of iron recycling functional composite material and 200.0mL of 0.08mol / L potassium persulfate aqueous solution and add them to the reaction vessel. Stir until the mixture is uniform, then heat the reaction vessel to 30℃ and keep it at that temperature for 2h. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash it and place it in a 60℃ drying oven for vacuum drying for 10h to obtain the iron recycling-persulfate synergistic composite material.

[0100] Example 8

[0101] This embodiment provides a method for preparing an iron cycling-persulfate synergistic composite material, including the following steps:

[0102] Step 1: Preparation of cross-linked β-cyclodextrin materials

[0103] Weigh 12.0 g of β-cyclodextrin and 100.0 mL of deionized water and add them to the reaction vessel. Stir until dissolved, then add 4.0 g of sodium hydroxide and continue stirring for 20 min. Heat the reaction vessel to 60 °C and add epichlorohydrin in four equal batches with a total addition of 12.0 mL under stirring. Each addition is 5 min apart. Keep the mixture warm and stir for 8 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. Wash the cake and place it in a 60 °C drying oven for vacuum drying for 12 h to obtain cross-linked β-cyclodextrin material.

[0104] Step 2: Preparation of iron recycling functional composite materials

[0105] Weigh out 4.0g of the quaternized porous aromatic material prepared in Example 2, 3.0g of the sulfonated silicon-based hybrid channel material prepared in Example 5, 3.0g of the cross-linked β-cyclodextrin material, and 200.0mL of deionized water and add them to the reaction vessel. Stir until the mixture is evenly dispersed, then add 200.0mL of 0.12mol / L ferric chloride aqueous solution and heat the reaction vessel to 40℃. Keep the mixture warm and stir for 5h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. After washing, place it in a 60℃ drying oven and vacuum dry for 12h to obtain the iron recycling functional composite material.

[0106] Step 3: Preparation of iron cycling-persulfate synergistic composite material

[0107] Weigh 8.0g of iron recycling functional composite material and 200.0mL of 0.12mol / L potassium persulfate aqueous solution and add them to the reaction vessel. Stir until the mixture is uniform, then heat the reaction vessel to 40℃ and keep it at that temperature for 3h. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash it and place it in a 60℃ drying oven for vacuum drying for 12h to obtain the iron recycling-persulfate synergistic composite material.

[0108] Example 9

[0109] This embodiment provides a method for preparing an iron cycling-persulfate synergistic composite material, including the following steps:

[0110] Step 1: Preparation of cross-linked β-cyclodextrin materials

[0111] Weigh 10.0 g of β-cyclodextrin and 100.0 mL of deionized water and add them to the reaction vessel. Stir until dissolved, then add 3.5 g of sodium hydroxide and continue stirring for 15 min. Heat the reaction vessel to 55 °C and add epichlorohydrin in four equal batches with a total addition of 10.0 mL under stirring. Each addition is 5 min apart. Keep the mixture warm and stir for 7 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. After washing, place it in a 60 °C drying oven and vacuum dry for 11 h to obtain cross-linked β-cyclodextrin material.

[0112] Step 2: Preparation of iron recycling functional composite materials

[0113] Weigh out 3.5g of the quaternized porous aromatic material prepared in Example 3, 2.5g of the sulfonated silicon-based hybrid channel material prepared in Example 6, 2.5g of the cross-linked β-cyclodextrin material, and 200.0mL of deionized water and add them to the reaction vessel. Stir until the mixture is evenly dispersed, then add 200.0mL of 0.10mol / L ferric chloride aqueous solution and heat the reaction vessel to 35℃. Keep the mixture warm and stir for 4h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. After washing, place it in a 60℃ drying oven and vacuum dry for 11h to obtain the iron recycling functional composite material.

[0114] Step 3: Preparation of iron cycling-persulfate synergistic composite material

[0115] Weigh 6.0 g of iron recycling functional composite material and 200.0 mL of 0.10 mol / L potassium persulfate aqueous solution and add them to the reaction vessel. Stir until the mixture is uniform, then heat the reaction vessel to 35 °C and keep it at that temperature for 3 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash it and place it in a 60 °C drying oven for vacuum drying for 11 h to obtain the iron recycling-persulfate synergistic composite material.

[0116] Comparative Example 1

[0117] The difference between this comparative example and Example 9 is that, in the preparation process of the quaternized porous aromatic material used in step two, step III is omitted, and the porous aromatic polyamine functionalized polymer framework prepared in step II is used to replace the quaternized porous aromatic material in an equal amount.

[0118] Comparative Example 2

[0119] The difference between this comparative example and Example 9 is that, in the preparation process of the sulfonated silicon-based hybrid channel material used in step 2, step ② is omitted, and the mercaptosilicone-based hybrid channel framework prepared in step ① is used to replace the sulfonated silicon-based hybrid channel material in an equal amount.

[0120] Comparative Example 3

[0121] The difference between this comparative example and Example 9 is that the cross-linked β-cyclodextrin material was omitted in step two.

[0122] Performance testing:

[0123] Dissolve 200 mg NaHCO3, 100 mg NaCl, 50 mg CaCl2·2H2O, 50 mg MgSO4·7H2O, and 5 mg humic acid in 1.0 L of deionized water in sequence, and stir in the dark until clear;

[0124] Another 1.0 mg·mL⁻¹ of benzo(α)pyrene mother liquor was prepared with methanol. 50.0 μL of the solution was added to the above water body to make the initial concentration C0 = 50 μg·L⁻¹ and the methanol volume fraction ≤ 0.1%. The solution was stirred and equilibrated in the dark for 30 min to obtain the simulated water body.

[0125] The simulated water body was irradiated in a gamma-ray field with a dose rate set at 2.5 kGy·h. -1 10.0 mL samples were taken at t1 (15 min), t2 (30 min), t3 (60 min), and t4 (120 min) for 120 min, and an endpoint sample was taken at t5 (180 min). After each sampling, the sample was immediately filtered through a 0.22 μm filter to remove solids, and methanol was added to quench the sample to a volume fraction of 10%. The sample was then stored in the dark to obtain a blank control sample.

[0126] Methods for determining the degree of degradation and degradation efficiency:

[0127] 2.50 mg of the iron cycling-persulfate synergistic composite material prepared in Examples 1-3 and Comparative Examples 1-3 was weighed and added to a reaction vessel. 1.0 L of the simulated water was added and stirred and dispersed for 10 min. The vessel was then placed in a gamma-ray field for irradiation, with the dose rate set at 2.5 kGy·h. -110.0 mL samples were taken at t1 (15 min), t2 (30 min), t3 (60 min), and t4 (120 min) for 120 min, and an endpoint sample was taken at t5 (180 min). After each sampling, the sample was immediately filtered through a 0.22 μm filter to remove solids, and methanol was added to quench the sample to a volume fraction of 10%. The sample was then stored in the dark to obtain purified water.

[0128] After sampling at the endpoint of t5 (180 min), stirring was immediately stopped and the reaction system was allowed to stand in the dark for 15 min. The precipitate was then collected by centrifugation at 4000 rpm for 5 min, washed three times with deionized water, rinsed once with anhydrous ethanol, and then washed once more with deionized water. The washed precipitate was then vacuum dried at 50 °C to constant weight to obtain the recovered iron cycling-persulfate synergistic composite materials prepared in Examples 7-9 and Comparative Examples 1-3. The weight was then added to a final volume of 2.50 mg, and the degradation degree and degradation efficiency were repeatedly measured. The 5th (n5) and 10th (n...) cycles were collected. 10 ) and the 20th (n 20 A 180-minute key sample was collected to obtain circulating purified water;

[0129] Referring to standard GB 11895-1989 "Determination of Benzo(α)pyrene in Water by Acetylated Filter Paper Chromatography Fluorescence Spectrophotometry", the concentration of benzo(α)pyrene in the purified water at various time periods was obtained after degradation using the iron cycling-persulfate synergistic composite materials prepared in Examples 7-9 and Comparative Examples 1-3, as well as the blank control sample. The degradation rate was calculated, and the specific data are shown in Table 1.

[0130] The concentration of benzo(α)pyrene in the circulating purified water obtained by cyclic degradation of the iron-persulfate synergistic composite material prepared in Examples 7-9 and Comparative Examples 1-3 was determined according to the standard GB 11895-1989 "Determination of Benzo(α)pyrene in Water by Acetylated Filter Paper Chromatography Fluorescence Spectrophotometry". The degradation rate was calculated and the specific data are shown in Table 2.

[0131] Table 1 - Degradation of benzo(α)pyrene

[0132]

[0133] Table 2 - Degradation of benzo(α)pyrene at different cycle numbers

[0134]

[0135] Data Analysis:

[0136] Comparative analysis of the data in Table 1 reveals that the simulated water body degraded using the iron cycling-persulfate synergistic composite material prepared in this invention exhibits degradation rates of 36.5% at 15 min, 55.4% at 30 min, 74.3% at 60 min, and 87.7% at 120 min, with a final degradation rate of 92.5%.

[0137] Comparative analysis of the data in Table 2 reveals that the iron recycling-persulfate synergistic composite material prepared using this invention exhibits a degradation rate of 89.3% after 5 cycles, 87.0% after 10 cycles, and 83.7% after 20 cycles. All these data are superior to the comparative example, indicating that:

[0138] In Comparative Example 1, the porous aromatic framework did not undergo quaternization modification. Its surface functional groups changed from stable quaternary ammonium salt structures to protonable groups mainly composed of amine groups. This change altered the interfacial charge state and ion distribution during material operation. The aggregation mode of persulfate near the pores and interfaces was adjusted accordingly, resulting in a decrease in the spatial coupling between the oxidant and iron species. At the same time, due to changes in interfacial polarity and the microenvironment within the pores, the residence mode of pollutants in the porous structure changed from interfacial adsorption to dynamic migration. This reduced the frequency of synchronous contact between pollutants, oxidants, and iron active sites, and the reaction system gradually shifted from local interfacial control to bulk diffusion control.

[0139] In Comparative Example 2, the silicon-based hybrid channel framework did not undergo the transformation from thiol to sulfonic acid groups. Its surface functional environment changed from strongly polar acidic sites to a distribution state of neutral or weakly polar groups. This structural change adjusted the coordination mode and valence state transformation pathway of iron species in the channel. The iron cycling process relied more on non-directional electron transfer rather than a continuous cycling pathway during operation. At the same time, the activation sites of persulfate in the channel structure tended to be dispersed, and the ability of the local microenvironment to regulate the generation of active species was weakened. This made the activation process exhibit discrete characteristics in time and space, thus affecting the reaction connection between pollutants and active sites after entering the channel.

[0140] In Comparative Example 3, no cross-linked β-cyclodextrin structure was introduced into the system. The reaction system lost the inclusion and confinement channels for hydrophobic pollutants and their reaction intermediates. During operation, pollutants were more likely to migrate in the aqueous phase and the pore-external region, rather than continuously remaining in the micro-domain of the synergistic effect of iron cycling and persulfate. At the same time, the hydrophobic intermediates generated during the reaction were more likely to detach from the active region, making the reaction path exhibit a discontinuous characteristic of multiple diffusion-re-contact. Due to the lack of buffering and spatial diversion for the organic load, the distribution state of each reaction component in the system between the pores and the interface was more likely to fluctuate, thereby changing the continuity of the overall reaction path.

[0141] Compared to the blank control sample without the introduction of functional materials, the composite material system constructed in this invention exerts a structural regulatory effect on the reaction system's operational path through the synergistic configuration of multi-level structural units. Specifically, the porous aromatic material provides a continuous solid-phase interface and pore network for the system, allowing pollutants and persulfate to no longer rely entirely on aqueous diffusion during the reaction process and instead engage in random contact. The sulfonated silicon-based hybrid channels construct a confined coordination environment for iron species, ensuring that the electron transfer process involving iron mainly occurs within a fixed microdomain. The cross-linked β-cyclodextrin structure guides pollutants and reaction intermediates to remain near the active region through hydrophobic confinement. The synergistic coupling of the above structural units in space makes the distribution mode, contact sequence, and action position of the reactants different from the bulk reaction-dominated operational state in the blank system.

[0142] Ultimately, it is demonstrated that when the reaction system lacks a synergistic structure of porous framework, functional channels, and confined units, the interactions between pollutants, persulfate, and iron species mainly rely on random diffusion and transient contact in the bulk phase. It is difficult to establish continuous, stable, and consistent interaction relationships within the solid-phase microdomain. Furthermore, due to the absence of interface regulation, acidic coordination environment, or confined structure, the reaction processes of each comparative example exhibit characteristics of dispersed interaction sites, inconsistent microenvironments, and uncontrollable reaction pathways, with the overall operating mode tending to be bulk-dominated. In contrast, this invention achieves overall regulation of the formation, maintenance, and reaction pathway organization of the reaction microdomain through the synergistic configuration of multi-level structural units. This operating mechanism cannot be naturally obtained through the introduction of a single structure or conventional material combination, clearly demonstrating the substantial difference between the technical solution of this invention and the comparative and blank control systems at the mechanistic level.

[0143] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0144] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0145] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for degrading benzo(α)pyrene in water using gamma rays, characterized in that, Includes the following steps: S1. Quaternized porous aromatic material, sulfonated silicon-based hybrid channel material, cross-linked β-cyclodextrin material and deionized water are added to the reaction vessel and stirred. After uniform dispersion, a complexing agent is added and the reaction vessel is heated to 30-40℃. The mixture is kept at this temperature and stirred for 3-5 hours. The iron recycling functional composite material is obtained after post-treatment. S2. Add the iron recycling functional composite material and the activation liquid to the reaction vessel and stir. After the mixture is uniform, heat the reaction vessel to 30-40℃ and keep it at the temperature for 2-3 hours. The iron recycling-persulfate synergistic composite material is obtained by post-treatment. S3. Add an iron cycle-persulfate synergistic composite material to the water body containing benzo(α)pyrene, and then treat the water body under γ-ray irradiation conditions, wherein the water body to be treated is an actual polluted water body or an artificially prepared simulated water body.

2. The method for degrading benzo(α)pyrene in water using gamma rays according to claim 1, characterized in that, In step S1, the ratio of the quaternized porous aromatic material, sulfonated silicon-based hybrid channel functional group, cross-linked β-cyclodextrin material, deionized water, and complexing agent is 3-4 g: 2-3 g: 2-3 g: 200 mL: 200 mL, wherein the complexing agent is a 0.08-0.12 mol / L ferric chloride aqueous solution; in step S2, the ratio of the iron-cycling functional composite material to the activation solution is 5-8 g: 200 mL, wherein the activation solution is a 0.08-0.12 mol / L potassium persulfate aqueous solution; in step S3, the mass ratio of the iron-cycling-persulfate synergistic composite material to benzo(α)pyrene in the water to be treated is 40-60:1, wherein the γ-ray dose rate is 2-3 kGy·h. -1 .

3. The method for degrading benzo(α)pyrene in water using gamma rays according to claim 1, characterized in that, The quaternized porous aromatic material was prepared by the following method: A1. Add the porous aromatic epoxy crosslinking polymer framework and anhydrous ethanol to the reactor and stir. After the mixture is evenly dispersed, add diethylenetriamine and heat the reactor to 60-70℃. Keep the mixture warm and stir for 8-12 hours. The resulting porous aromatic polyamine functionalized polymer framework is then obtained through post-treatment. A2. Add the porous aromatic polyamine functionalized polymer framework and anhydrous acetonitrile to the reactor and stir. After mixing evenly, add benzyl bromide in five equal batches with an interval of 5 minutes between additions. After the addition is complete, heat the reactor to 50-60℃ and keep it at this temperature for 8-10 hours. The quaternized porous aromatic material is then obtained through post-treatment.

4. The method for degrading benzo(α)pyrene in water using gamma rays according to claim 3, characterized in that, In step A1, the ratio of the porous aromatic epoxy crosslinking polymer backbone, anhydrous ethanol, and diethylenetriamine is 8-12g:120-150mL:35-45mL; in step A2, the ratio of the porous aromatic polyamine functionalized polymer backbone, anhydrous acetonitrile, and benzyl bromide is 8-10g:140-160mL:8-10mL.

5. The method for degrading benzo(α)pyrene in water using gamma rays according to claim 3, characterized in that, The preparation method of the porous aromatic epoxy crosslinked polymer framework is as follows: the dispersed phase is added to the reaction vessel, and the organic phase is added to the dispersed phase in 10 equal batches under stirring conditions, with an addition interval of 5 min. After the addition is completed, nitrogen gas is introduced for protection and the reaction vessel is heated to 70-80℃. The mixture is kept at this temperature and stirred for 6-8 h. After the reaction is completed, the mixture is cooled to room temperature, filtered and the filter cake is collected. After washing, the filter cake is placed in a 60℃ drying oven and vacuum dried for 10-12 h to obtain the porous aromatic epoxy crosslinked polymer framework.

6. The method for degrading benzo(α)pyrene in water using gamma rays according to claim 5, characterized in that, In the preparation of the porous aromatic epoxy crosslinked polymer backbone, the ratio of the dispersed phase to the organic phase is 300 mL: 70-80 g, wherein the dispersed phase is a 1.0-1.2 wt% polyvinyl alcohol aqueous solution, and the organic phase is prepared by mixing divinylbenzene, glycidyl methacrylate, toluene, n-heptane, and azobisisobutyronitrile in a ratio of 24-30 g: 10-12 g: 40 mL: 40 mL: 0.4-0.5 g.

7. The method for degrading benzo(α)pyrene in water using gamma rays according to claim 1, characterized in that, The sulfonated silicon-based hybrid channel material was prepared by the following method: B1. Add anhydrous ethanol and deionized water to the reaction vessel and stir. After mixing evenly, add tetraethyl orthosilicate and 3-mercaptopropyltrimethoxysilane in sequence, and add saturated ammonia water. Continue stirring for 40-80 minutes. Post-processing yields a mercaptosilyl hybrid channel framework. B2. Add the mercaptosilicone hybrid channel framework and deionized water to the reactor and stir. After mixing evenly, add 30wt% hydrogen peroxide aqueous solution in 10 equal batches with an 8-minute interval between additions. After the addition is complete, heat the reactor to 40-50℃ and keep it at this temperature for 4-6 hours. Post-processing yields sulfonated silicon-based hybrid channel material.

8. The method for degrading benzo(α)pyrene in water using gamma rays according to claim 7, characterized in that, In step B1, the ratio of anhydrous ethanol, deionized water, tetraethyl orthosilicate, 3-mercaptopropyltrimethoxysilane, and saturated ammonia is 200 mL: 20 mL: 18-24 mL: 8-12 mL: 0.8-1.0 mL; in step B2, the ratio of the mercaptosilyl hybrid channel framework, deionized water, and 30 wt% hydrogen peroxide aqueous solution is 8-12 g: 200 mL: 35-45 mL.

9. The method for degrading benzo(α)pyrene in water using gamma rays according to claim 1, characterized in that, The preparation method of the cross-linked β-cyclodextrin material is as follows: β-cyclodextrin and deionized water are added to a reaction vessel and stirred. After dissolution, sodium hydroxide is added and stirring is continued for 10-20 minutes. The reaction vessel is then heated to 50-60°C. Epichlorohydrin is added in four equal batches with a 5-minute interval between each addition under stirring conditions. After stirring at this temperature for 6-8 hours, the cross-linked β-cyclodextrin material is obtained through post-treatment.

10. A method for degrading benzo(α)pyrene in water using gamma rays according to claim 9, characterized in that, In the preparation of cross-linked β-cyclodextrin materials, the ratio of β-cyclodextrin, deionized water, sodium hydroxide and epichlorohydrin is 8-12g:100mL:3-4g:8-12mL.

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