A method for preparing a catalytic material for removing new pollutants in complex water environments

Abstract

The present invention provides a method for preparing a catalytic material for removing new pollutants from complex water environments, comprising the following steps: Step 10, preparing a metal-organic framework material; Step 20, preparing iron oxide particles within the metal-organic framework material to obtain a confined iron nanomaterial; and Step 30, vertically growing molybdenum disulfide nanosheets on the surface of the confined iron nanomaterial to obtain a catalytic material. The present invention provides a method for preparing a catalytic material for removing new pollutants from complex water environments. The prepared catalytic material exhibits excellent anti-interference capabilities and enhanced reaction activity in complex water environments.

Description

Technical Field

[0001] The present invention belongs to the technical field of water treatment, and in particular relates to a method for preparing a catalytic material for removing new pollutants in a complex water environment. Background Art

[0002] With the widespread use of recycled water in urban and rural ecological replenishment, agricultural irrigation, and other fields, its reuse safety has attracted widespread attention. Various emerging pollutants (such as antibiotics, antiepileptic drugs, hormones, and perfluoroalkyl substances) contained in recycled water can migrate into receiving water bodies during reuse and accumulate and transform through the water-soil-plant continuum, posing a potential threat to ecological safety and human health. Advanced oxidation technologies, due to their powerful oxidative capacity, have shown potential for treating complex emerging pollutants.

[0003] However, influenced by living habits and seasonal agricultural production, water treatment in urban and rural areas faces difficulties such as large fluctuations in water quality and small water volume. Complex water environments contain inorganic ions, heavy metals, and natural organic matter, which pose a challenge to advanced oxidation systems. Studies have shown that inorganic ions and natural organic matter (NOM) will compete with the peroxide bonds in the oxidant for adsorption at the active sites of the catalytic material, while quenching the generated oxidative reactive species (ROS), thereby reducing the effective reaction between free radicals and pollutants, resulting in a decrease in catalytic efficiency. At the same time, the small water volume will lead to a decrease in the driving force for mass transfer of trace new pollutants in reclaimed water, making it difficult to compete with other substances for reaction sites, further exacerbating the difficulty of removing new pollutants. Therefore, there is an urgent need to develop advanced oxidation systems with excellent degradation selectivity and stability to meet the challenges of removing new pollutants in complex water environments. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for preparing a catalytic material for removing new pollutants in a complex water environment. The prepared catalytic material has excellent anti-interference ability in a complex water environment and improves reaction activity.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] The present invention provides a method for preparing a catalytic material for removing new pollutants in a complex water environment, comprising the following steps:

[0007] Step 10, preparing a metal organic framework material;

[0008] Step 20, preparing iron oxide particles inside the metal organic framework material to obtain confined iron nanomaterials;

[0009] Step 30: vertically growing molybdenum disulfide nanosheets on the surface of the confined iron nanomaterial to obtain a catalytic material.

[0010] As a further improvement of the present invention, the step 20 specifically includes:

[0011] Step 201, using ether solution as solvent and 2-tert-butyl-p-cresol as solute to prepare 2-tert-butyl-p-cresol ether solution, and mixing the 2-tert-butyl-p-cresol ether solution with a metal-organic framework material under closed conditions to obtain a mixed solution;

[0012] Step 202, heating the mixed solution obtained in step 201 to a constant weight;

[0013] Step 203, dispersing the mixed solution treated in step 202 in a FeCl2·4H2O aqueous solution and performing a shaking reaction at room temperature;

[0014] Step 204 , collecting the precipitated product obtained in step 203 by centrifugation, repeatedly washing the product with an ethanol solution and deionized water, and then aging the product in an oven to obtain a confined iron nanomaterial.

[0015] As a further improvement of the present invention, in step 201, the mass ratio of 2-tert-butyl-p-cresol to the metal organic framework material is 1:3-7;

[0016] In step 202, the mixed solution obtained in step 201 is heated to a constant weight using an inert gas flow at 100-120°C.

[0017] As a further improvement of the present invention, in step 203, during the reaction, the pH of the reaction solution is controlled within the range of 5 to 10.

[0018] As a further improvement of the present invention, in step 204, the temperature in the oven is 130-140°C.

[0019] As a further improvement of the present invention, step 30 specifically includes:

[0020] Step 301, dispersing confined iron nanomaterials in deionized water to obtain a confined iron nanoparticle dispersion;

[0021] Step 302, adding ammonium molybdate and thiourea to the confined iron nanoparticle dispersion and stirring;

[0022] Step 303, transferring the mixed solution obtained in step 302 to a high-pressure reactor equipped with a polytetrafluoroethylene liner, and placing it in an oven for reaction;

[0023] Step 304 , collecting the precipitated product in the autoclave in step 303 by centrifugation, repeatedly washing the product with deionized water and ethanol solution, and then drying the product in a vacuum oven to obtain a catalytic material.

[0024] As a further improvement of the present invention, in step 30, the mass ratio of ammonium molybdate, thiourea, and confined iron nanomaterial is 1:1 to 2:2 to 3.

[0025] As a further improvement of the present invention, in step 303, the temperature in the oven is 185-195°C; in step 304, the temperature in the oven is 40-60°C.

[0026] As a further improvement of the present invention, the metal organic framework material is a zeolite imidazolate framework material coordinated with metal Co.

[0027] As a further improvement of the present invention, step 10 specifically includes:

[0028] Step 101: dissolving cobalt nitrate hexahydrate in a methanol solution to obtain a cobalt nitrate hexahydrate methanol solution; dissolving 2-methylimidazole in a methanol solution to obtain a 2-methylimidazole methanol solution;

[0029] Step 102, adding the cobalt nitrate hexahydrate methanol solution dropwise to the 2-methylimidazole methanol solution, stirring, and then allowing to stand for aging;

[0030] Step 103, collecting the precipitated product obtained in step 102 by centrifugation, repeatedly washing the product with an ethanol solution, and drying it in an oven to obtain a zeolite imidazolate framework material containing metal Co coordination.

[0031] Compared with the prior art, the technical solution of the present invention has the following beneficial effects: the present invention provides a method for preparing a catalytic material for removing new pollutants in a complex water environment, first preparing a metal organic framework material; then preparing iron oxide particles inside the metal organic framework material to obtain a confined iron nanomaterial; finally, vertically growing MoS2 nanosheets on the surface of the confined iron nanomaterial to obtain a catalytic material. The prepared catalytic material has a confined structure, which can protect the Fe reaction sites inside the nanospace, exclude most natural organic matter from the reaction space, reduce the interference of competitive adsorption of coexisting substances near the active sites, thereby providing a more superior catalytic environment for the target pollutants, and has excellent anti-interference ability in complex water environments, thereby improving reaction activity. Nano-confined Fe and loaded surface MoS2 increase the number of active sites in the catalytic material, can regulate the energy level structure of the catalytic material, significantly improve carrier mobility, and enhance the reaction activity of the catalytic material. MoS2 nanosheets are vertically grown on the surface of the confined iron nanomaterial. The active sites of MoS2 are mostly concentrated at the edges of the nanosheets. This vertical growth pattern can maximize the exposure of the edge active sites of MoS2, which is conducive to the occurrence of catalytic reactions. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1A flow chart of the method for preparing a catalytic material for removing new pollutants in a complex water environment provided by the present invention;

[0033] Figure 2 Schematic diagram of the synthesis of the catalytic material in the method of the present invention;

[0034] Figure 3 SEM images of the materials obtained in Example 1 and Comparative Example 1, wherein (a) is a SEM image of the ZIF obtained in Example 1, (b) is a SEM image of the ZF obtained in Example 1, (c) is a SEM image of the ZFM obtained in Example 1, and (d) is a SEM image of the ZF-OUT obtained in Comparative Example 1;

[0035] Figure 4 It is a radar chart showing the effect of different inorganic anion interferences on the degradation kinetic constants of SMX using the ZFM obtained in Example 1 and the ZFM-OUT obtained in Comparative Example 1;

[0036] Figure 5 The figure is a bar graph showing the SMX removal rate at different initial pH values ​​using the ZFM obtained in Example 1 and the ZFM-OUT obtained in Comparative Example 1;

[0037] Figure 6 The figure is a bar graph showing the SMX removal rate using the ZFM obtained in Example 1 and the ZFM-OUT obtained in Comparative Example 1 at different initial humic acid concentrations. DETAILED DESCRIPTION

[0038] The technical solution of the present invention is described in detail below.

[0039] The present invention provides a method for preparing a catalytic material for removing new pollutants in complex water environments, such as Figure 1 As shown, the following steps are included:

[0040] Step 10, preparing a metal organic framework material;

[0041] Step 20, preparing iron oxide particles inside the metal organic framework material to obtain confined iron nanomaterials;

[0042] Step 30: vertically growing molybdenum disulfide nanosheets on the surface of the confined iron nanomaterial to obtain a catalytic material.

[0043] The method of the present invention first prepares a metal-organic framework material; then, iron oxide particles are prepared inside the metal-organic framework material to obtain a confined iron nanomaterial; finally, MoS2 nanosheets are vertically grown on the surface of the confined iron nanomaterial to obtain a catalytic material. The prepared catalytic material has a confined structure, and the Fe reaction site is located inside the nanospace. Due to the large size of most natural organic matter, it cannot enter the nanospace, while new pollutants can enter and react with the Fe reaction sites, thereby excluding most natural organic matter from the reaction space, reducing the interference of competitive adsorption of coexisting substances near the active site, thereby providing a more superior catalytic environment for new pollutants, having excellent anti-interference ability in complex water environments, and improving reaction activity. Nano-confined Fe and loaded surface MoS2 increase the number of active sites in the catalytic material, can regulate the energy level structure of the catalytic material, significantly improve carrier mobility, and enhance the reaction activity of the catalytic material. MoS2 nanosheets are vertically grown on the surface of the confined iron nanomaterial. The active sites of MoS2 are mostly concentrated at the edges of the nanosheets. This vertical growth pattern can maximize the exposure of the edge active sites of MoS2, which is conducive to the occurrence of catalytic reactions.

[0044] Preferably, the metal organic framework material is a zeolite imidazolate framework material containing metal Co coordination.

[0045] Step 10 specifically includes:

[0046] In step 101, cobalt nitrate hexahydrate is dissolved in a methanol solution to obtain a cobalt nitrate hexahydrate methanol solution; and 2-methylimidazole is dissolved in a methanol solution to obtain a 2-methylimidazole methanol solution. Methanol is used as the solvent. Preferably, the ratio of the mass (mg) of cobalt nitrate hexahydrate to the volume (mL) of the methanol solution is 15-19:1, and the ratio of the mass (mg) of 2-methylimidazole to the volume (mL) of the methanol solution is 13-17:1. During preparation, the cobalt nitrate hexahydrate methanol solution and the 2-methylimidazole methanol solution have the same volume of methanol solution.

[0047] Step 102: add all the cobalt nitrate hexahydrate methanol solution dropwise into the 2-methylimidazole methanol solution, stir, and then allow to stand for aging.

[0048] In step 103, the precipitated product obtained in step 102 is collected by centrifugation, repeatedly washed with an ethanol solution, and then dried in an oven to obtain a zeolitic imidazolate framework (ZIF) containing metal Co coordination. Preferably, the temperature in the oven is 40-60°C.

[0049] Preferably, step 20 specifically includes:

[0050] Step 201, using ether solution as solvent and 2-tert-butyl-p-cresol as solute, prepare 2-tert-butyl-p-cresol ether solution, and mix the 2-tert-butyl-p-cresol ether solution with the metal organic framework material under closed conditions to obtain a mixed solution. In this process, under the action of ether, 2-tert-butyl-p-cresol (tBMP) is introduced into the cavity of the metal organic framework material, such as Figure 2 Preferably, the mass ratio of 2-tert-butyl-p-cresol (mg) to the volume ratio of ether solution (mL) is 5-15:1. The mass ratio of 2-tert-butyl-p-cresol to the metal organic framework material is 1:3-7.

[0051] Step 202 : heating the mixed solution obtained in step 201 to a constant weight to remove the ether and tBMP outside the metal organic framework material.

[0052] Step 203: Disperse the mixed solution treated in step 202 in an excess of FeCl2·4H2O aqueous solution and conduct a shaking reaction at room temperature to generate FeO inside the metal organic framework material. x Hydrates, such as Figure 2 Preferably, the concentration of the FeCl2·4H2O aqueous solution is 15-25 mM.

[0053] In step 204, the precipitated product obtained in step 203 is collected by centrifugation, and the product is repeatedly washed with ethanol solution and deionized water to remove residual organic reagents. The product is aged in an oven to obtain a confined iron nanomaterial.

[0054] Preferably, in step 202, the mixed solution obtained in step 201 is heated to a constant weight using an inert gas flow at 100-120°C. The mixed solution is heated using an inert gas flow to isolate oxygen, so that the FeCl2·4H2O in the cavity of the metal organic framework material is converted into FeO under the action of 2-tert-butyl-p-cresol. x The inert gas flow may be nitrogen flow, argon flow, etc. The temperature of the inert gas flow is 100-120° C., which can maintain the structural stability of the metal organic framework material.

[0055] Preferably, in step 203, during the reaction, the pH of the reaction solution is controlled within the range of 5 to 10. Controlling the pH within the range of 5 to 10 regulates the redox potential, thereby driving the reduction reaction, which is beneficial to the synthesis of FeO x .

[0056] Preferably, in step 204, the temperature in the oven is 130-140° C. to facilitate curing of the material.

[0057] In step 20 of the method of the present invention, based on the differences in redox sites and pH values ​​between the compounds, 2-tert-butyl-p-cresol (tBMP) is introduced into the cavity of the metal organic framework material using ether, thereby preparing FeO inside the metal organic framework material. x Particles, synthesized nanomaterials with confined iron structure. x Nanoparticles mainly grow in the pores of metal organic framework materials rather than gathering outside the pores, thus not hindering the channel formation of catalytic materials and ensuring effective mass transfer during the catalytic process. x Nanoparticles increase the specific surface area within the micropores, providing more adsorption sites for reactants and promoting their adsorption and reaction within the catalytic material. The confined structure protects the Fe reaction sites within the nanopores, excluding most natural organic matter from the reaction space. This reduces interference from competitive adsorption of coexisting substances near the active sites, thereby providing a more favorable catalytic environment for the target pollutants. The catalyst exhibits excellent anti-interference capabilities in complex aqueous environments, enhancing reaction activity.

[0058] Preferably, step 30 specifically includes:

[0059] Step 301: Disperse the confined iron nanomaterial in deionized water to obtain a confined iron nanoparticle dispersion. Preferably, the ratio of the mass (mg) of the confined iron nanomaterial to the volume (mL) of deionized water is 1.5-1.8:1.

[0060] Step 302: Add ammonium molybdate and thiourea to the confined iron nanoparticle dispersion and stir. Preferably, the mass ratio of ammonium molybdate, thiourea, and confined iron nanoparticles is 1:1 to 2:2 to 3.

[0061] Step 303: transfer the mixed solution obtained in step 302 to a high-pressure reactor equipped with a polytetrafluoroethylene liner, and place the high-pressure reactor in an oven for reaction, as shown in FIG. Figure 2 shown.

[0062] Step 304 , collecting the precipitated product in the autoclave of step 303 by centrifugation, repeatedly washing the product with deionized water and ethanol solution, and then drying the product in a vacuum oven to obtain a catalytic material.

[0063] Preferably, in step 303, the temperature in the oven is 185-195° C. A temperature that is too low can easily lead to thick MoS2 nanosheets, affecting the photoelectric conversion efficiency, while a temperature that is too high can cause the MoS2 nanosheets to break up. Carrying out the reaction within the above temperature range can ensure the successful formation of MoS2 nanosheets.

[0064] Preferably, in step 303, the reaction time is 9 to 24 hours. A shorter reaction time may only form simple structures such as nanosheets or nanorods, while as the reaction time increases, these nanosheets will gradually assemble into flower-like structures. However, a long reaction time will affect the stability of the confined iron nanomaterial.

[0065] Preferably, in step 304, the temperature in the oven is 40-60°C.

[0066] Step 30 in the method of the present invention, such as Figure 2 As shown, the hydrothermal method is used to control the reaction temperature, reaction time and mass ratio of reactants to vertically grow MoS2 nanosheets on the surface of confined iron nanomaterials. The active sites of MoS2 are mostly concentrated at the edges of the nanosheets. This vertical growth pattern can maximize the exposure of the edge active sites of MoS2, which is conducive to the occurrence of catalytic reactions.

[0067] Three examples and one comparative example are provided below to verify the performance of the catalytic material prepared by the method of the present invention.

[0068] In the following examples and comparative examples, the methanol solution used is anhydrous methanol, the ethanol solution is anhydrous ethanol, and the ether solution is anhydrous ether.

[0069] Example 1

[0070] Step 1: Preparation of a Co-coordinated Zeolitic Imidazole Framework (ZIF)

[0071] 837 mg of cobalt nitrate hexahydrate was dissolved in 50 mL of methanol solution to prepare cobalt nitrate hexahydrate methanol solution. 730 mg of 2-methylimidazole was dissolved in 50 mL of methanol solution to prepare 2-methylimidazole methanol solution.

[0072] A methanolic solution of cobalt nitrate hexahydrate was added dropwise to a methanolic solution of 2-methylimidazole. After stirring for 5 minutes, the mixture was allowed to stand for 24 hours to allow for aging and precipitation. The precipitated product was collected by centrifugation, repeatedly washed with ethanol to remove any residual organic reagents, and then dried in a 60°C oven for 12 hours to yield a purple ZIF product.

[0073] Step 2: Preparation of nanomaterial ZIF-FeO with confined structure x (abbreviated as ZF)

[0074] 2-tert-Butyl-p-cresol etherate solution (tBMP / DE) was prepared by adding 10 mg of 2-tert-Butyl-p-cresol to 1 mL of ether. Under sealed conditions, the etherate solution was mixed with 50 mg of ZIF and heated to a constant weight at 120°C under a nitrogen stream. The treated tBMP@ZIF solution was dispersed in an excess of 20 mM FeCl2·4H2O aqueous solution and allowed to react at room temperature for 4 hours with shaking, maintaining a pH of 8. The product was collected by centrifugation, repeatedly washed with ethanol and deionized water to remove residual organic reagents, and aged in an oven at 140°C for 2 hours to obtain ZF.

[0075] Step 3: Preparation of catalytic material ZIF-FeO x @MoS2 (abbreviated as ZFM)

[0076] 50 mg of ZF was added to 30 mL of deionized water to obtain a ZF nanoparticle dispersion. 20 mg of ammonium molybdate and 34.5 mg of thiourea were added to the ZF nanoparticle dispersion and stirred for 30 minutes. The mixture was transferred to a 100 mL polytetrafluoroethylene-lined autoclave and placed in a 190°C oven for 15 hours. After the reaction, the precipitated product was collected by centrifugation and repeatedly washed with deionized water and ethanol to remove any residual organic reagents on the surface. The resulting product was dried in a vacuum oven at 60°C for 6 hours to obtain the black nanomaterial ZFM.

[0077] Example 2

[0078] Step 1: Preparation of a Co-coordinated Zeolitic Imidazole Framework (ZIF)

[0079] Dissolve 750 mg of cobalt nitrate hexahydrate in 50 mL of methanol to prepare a cobalt nitrate hexahydrate methanol solution. Dissolve 650 mg of 2-methylimidazole in 50 mL of methanol to prepare a 2-methylimidazole methanol solution.

[0080] A methanolic solution of cobalt nitrate hexahydrate was added dropwise to a methanolic solution of 2-methylimidazole. After stirring for 5 minutes, the mixture was allowed to stand for 24 hours to allow for aging and precipitation. The precipitated product was collected by centrifugation, repeatedly washed with ethanol to remove any residual organic reagents, and then dried in a 40°C oven for 12 hours to yield a purple ZIF product.

[0081] Step 2: Preparation of nanomaterial ZIF-FeO with confined structure x (abbreviated as ZF)

[0082] 2-tert-Butyl-p-cresol etherate solution tBMP / DE was prepared by adding 5 mg of 2-tert-Butyl-p-cresol to 1 mL of ether. Under sealed conditions, the etherate solution was mixed with 15 mg of ZIF and heated to constant weight at 100°C under an argon stream. The treated tBMP@ZIF solution was dispersed in an excess of 15 mM FeCl2·4H2O aqueous solution and allowed to react at room temperature for 4 hours with shaking, maintaining a pH of 5. The product was collected by centrifugation, repeatedly washed with ethanol and deionized water to remove residual organic reagents, and aged in an oven at 130°C for 2 hours to obtain ZF.

[0083] Step 3: Preparation of catalytic material ZIF-FeO x @MoS2 (abbreviated as ZFM)

[0084] 45 mg of ZF was added to 30 mL of deionized water to obtain a ZF nanoparticle dispersion. 27.5 mg of ammonium molybdate and 27.5 mg of thiourea were added to the ZF nanoparticle dispersion and stirred for 30 minutes. The mixture was transferred to a 100 mL polytetrafluoroethylene-lined autoclave and placed in an 185°C oven for 9 hours. After the reaction, the precipitated product was collected by centrifugation and repeatedly washed with deionized water and ethanol to remove any residual organic reagents on the surface. The resulting product was dried in a vacuum oven at 40°C for 6 hours to obtain the black nanomaterial ZFM.

[0085] Example 3

[0086] Step 1: Preparation of a Co-coordinated Zeolitic Imidazole Framework (ZIF)

[0087] Dissolve 950 mg of cobalt nitrate hexahydrate in 50 mL of methanol to prepare a cobalt nitrate hexahydrate methanol solution. Dissolve 850 mg of 2-methylimidazole in 50 mL of methanol to prepare a 2-methylimidazole methanol solution.

[0088] A methanolic solution of cobalt nitrate hexahydrate was added dropwise to a methanolic solution of 2-methylimidazole. After stirring for 5 minutes, the mixture was allowed to stand for 24 hours to allow for aging and precipitation. The precipitated product was collected by centrifugation, repeatedly washed with ethanol to remove any residual organic reagents, and then dried in a 50°C oven for 12 hours to yield a purple ZIF product.

[0089] Step 2: Preparation of nanomaterial ZIF-FeO with confined structure x (abbreviated as ZF)

[0090] 2-tert-Butyl-p-cresol etherate solution (tBMP / DE) was prepared by adding 15 mg of 2-tert-Butyl-p-cresol to 1 mL of ether. Under sealed conditions, the etherate solution was mixed with 105 mg of ZIF and heated to a constant weight at 110°C under a nitrogen stream. The treated tBMP@ZIF solution was dispersed in an excess of 25 mM FeCl2·4H2O aqueous solution and allowed to react at room temperature for 4 hours with shaking at a pH of 10. The product was collected by centrifugation, repeatedly washed with ethanol and deionized water to remove residual organic reagents, and aged in an oven at 130°C for 2 hours to obtain ZF.

[0091] Step 3: Preparation of catalytic material ZIF-FeO x @MoS2 (abbreviated as ZFM)

[0092] 54 mg of ZF was added to 30 mL of deionized water to obtain a ZF nanoparticle dispersion. 19 mg of ammonium molybdate and 38 mg of thiourea were added to the ZF nanoparticle dispersion and stirred for 30 minutes. The mixture was transferred to a 100 mL polytetrafluoroethylene-lined autoclave and placed in a 195°C oven for 24 hours. After the reaction, the precipitated product was collected by centrifugation and repeatedly washed with deionized water and ethanol to remove any residual organic reagents on the surface. The resulting product was dried in a vacuum oven at 50°C for 6 hours to obtain the black nanomaterial ZFM.

[0093] Comparative Example 1

[0094] Step 1, preparation of ZIF: The same as step 1 of Example 1, ZIF was obtained.

[0095] Step 2: Preparation of nanomaterial ZF-OUT without confined structure: Replace the ether solution in step 2 of Example 1 with deionized water, and proceed in the same manner as above to obtain ZF-OUT.

[0096] Step 3, preparing the catalytic material ZFM-OUT. Replace ZF in step 3 of Example 1 with ZF-OUT, and proceed in the same manner as above to obtain ZFM-OUT.

[0097] The ZIF, ZF, ZFM obtained in Example 1 and the ZF-OUT obtained in Comparative Example 1 were scanned using a scanning electron microscope (SEM, S-4800, Hitachi) to obtain their surface morphologies. Figure 3 As shown in (a), the zeolitic imidazolate framework material ZIF prepared in Example 1 presents a regular dodecahedral morphology with a size ranging from 1.5 to 2.0 μm. Figure 3 (b) No obvious aggregation of FeO was observed on the ZF surface. x Crystal, Example 1 FeOx The ZFM sample shown in Figure 3(c) shows MoS2 nanosheets with a three-dimensional structure growing vertically on the ZF surface. Figure 3 (d) The ZF-OUT sample shows that the outer surface of the ZIF is obviously scattered with FeO x Nanoparticles, as indicated by yellow circles in the figure.

[0098] Change the concentration of coexisting ions respectively (regulate the initial coexisting ion concentration in the solution so that [Cl - ]0, [PO4 3- ]0, [HPO4 2- ]0, [NO3 - ]0 to 5 mM), solution pH (initial pH controlled at 3.2, 5.1, 7.2, and 10.4), and NOM concentration, represented by humic acid (HA), (initial HA concentration controlled at 0, 10, 20, and 50 mg / L), to simulate the complex water environment of secondary effluent. Sulfamethoxazole (SMX) was degraded using ZFM and ZFM-OUT as catalysts, respectively.

[0099] The experimental procedure was as follows: 10 mg of catalyst and 50 mL of a 10 mg / L SMX solution were mixed and stirred in the dark for 30 minutes until the reaction system reached adsorption-desorption equilibrium. Permonosulfate (PMS) was then added to the solution, and the catalytic reaction was initiated under a light source. A circulating water system with a jacketed beaker was used to control the reaction temperature to eliminate thermal effects. The reaction time for each catalytic system was set to 40 minutes, with a sampling interval of 5 minutes and a sample volume of 0.7 mL. The initial PMS concentration in the system was 0.04 mM / L. After terminating the reaction with 0.3 mL of ascorbic acid methanol solution, all samples were centrifuged to remove catalyst particles, and the supernatant was filtered through a 0.22 μm aqueous filter. SMX concentration was determined using high-performance liquid chromatography (HPLC, 1290, Aglient). The chromatograph parameters were set as follows: detection wavelength 254 nm, chromatographic column reversed phase C18 (4.6×150 mm, 5 μm), column temperature set to 25°C, mobile phase acetonitrile and pure water in a ratio of 2:3, flow rate 1.0 mL / min, injection volume 10 μL. Figure 4 、 Figure 5 and Figure 6 .

[0100] from Figure 4As can be seen in the figure, ZFM-OUT exhibited a higher initial reaction rate constant (0.1432 / min) compared to the blank control, attributed to its exposed Fe reactive sites being more accessible to reactants in the solution. However, at the end of the reaction, the SMX degradation efficiency of ZFM (96.2%) was significantly superior to that of ZFM-OUT (84.8%). This indicates that the unique spatial confinement effect of ZFM shortens the diffusion distance between free radicals and pollutants, reducing ineffective radical quenching and thereby enhancing its catalytic reactivity. Under the stress of coexisting ions, ZFM exhibited slight inhibition, while the K value of ZFM-OUT decreased by over 50%. As the inorganic ion concentration in the system increased, the exposed Fe active sites of ZFM-OUT adsorbed a large number of inorganic anions, thereby inhibiting the reaction. However, the confined structure of ZFM protected the reactive sites within the nanospace, mitigating the adverse effects of ion concentration fluctuations and promoting the continued progress of the catalytic reaction.

[0101] from Figure 5 It can be seen that under alkaline conditions, the catalytic efficiency of ZFM-OUT decreased significantly (61.4%), while ZFM showed a stable SMX removal effect in a wider pH range. This is because in alkaline environments, OH- interacts with the Fe 3+ The confined space in ZFM reduces the direct contact between OH- and internal active sites, allowing ZFM to maintain an SMX removal rate of over 90% at pH 10.4, greatly expanding the application range of the catalyst under alkaline conditions.

[0102] Complex NOM (such as HA) in the secondary effluent interacts with the catalyst through chelation and competitive adsorption, thereby affecting the catalytic reaction. Figure 6 It can be seen that with the increase of HA concentration, the degradation efficiency of ZFM-OUT showed a downward trend, while ZFM showed a stable degradation efficiency.

[0103] The experiments revealed that the size exclusion effect of the ZFM confined structure protects the reaction sites within the nanospace, excluding most natural organic matter from the reaction space. This reduces interference from competitive adsorption of coexisting substances near the active sites, thereby providing a superior catalytic environment for the target pollutants. Advanced oxidation systems based on ZFM exhibit excellent resistance to interference when exposed to complex environmental matrices.

[0104] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art will appreciate that the present invention is not limited to the specific embodiments described above. The specific embodiments and descriptions in the specification are intended only to further illustrate the principles of the present invention. The basic principles, main features, and advantages of the present invention are shown and described above without departing from the spirit and scope of the present invention. Those skilled in the art will appreciate that various changes and modifications may be made, and such changes and modifications are intended to fall within the scope of the invention as claimed.

Claims

1. A method for preparing a catalytic material for removing new pollutants in a complex water environment, characterized in that: The following steps are involved: Step 10, preparing a metal organic framework material; the metal organic framework material is a zeolite imidazolate framework material containing metal Co coordination; Step 20, preparing iron oxide particles inside the metal organic framework material to obtain confined iron nanomaterials; Step 30, vertically growing molybdenum disulfide nanosheets on the surface of the confined iron nanomaterial to obtain a catalytic material; The step 20 specifically includes: Step 201, using anhydrous ether as a solvent and 2-tert-butyl-p-cresol as a solute to prepare a 2-tert-butyl-p-cresol ether solution, and mixing the 2-tert-butyl-p-cresol ether solution with a metal-organic framework material under a closed condition to obtain a mixed solution; Step 202, heating the mixed solution obtained in step 201 to a constant weight; Step 203, dispersing the mixed solution treated in step 202 in a FeCl2·4H2O aqueous solution and performing a shaking reaction at room temperature; Step 204 , collecting the precipitated product obtained in step 203 by centrifugation, repeatedly washing the product with an ethanol solution and deionized water, and then aging the product in an oven to obtain a confined iron nanomaterial.

2. The method for preparing a catalytic material for removing new pollutants in a complex water environment according to claim 1, characterized in that: In step 201, the mass ratio of 2-tert-butyl-p-cresol to the metal organic framework material is 1:3-7; In step 202, the mixed solution obtained in step 201 is heated to a constant weight using an inert gas flow at 100-120°C.

3. The method for preparing a catalytic material for removing new pollutants in a complex water environment according to claim 1, characterized in that: In step 203, during the reaction, the pH of the reaction solution is controlled within the range of 5 to 10.

4. The method for preparing a catalytic material for removing new pollutants in a complex water environment according to claim 1, characterized in that: In step 204, the temperature in the oven is 130-140°C.

5. The method for preparing a catalytic material for removing new pollutants in a complex water environment according to claim 1, characterized in that: The step 30 specifically includes: Step 301, dispersing confined iron nanomaterials in deionized water to obtain a confined iron nanoparticle dispersion; Step 302, adding ammonium molybdate and thiourea to the confined iron nanoparticle dispersion and stirring; Step 303, transferring the mixed solution obtained in step 302 to a high-pressure reactor equipped with a polytetrafluoroethylene liner, and placing it in an oven for reaction; Step 304 , collecting the precipitated product in the autoclave in step 303 by centrifugation, repeatedly washing the product with deionized water and ethanol solution, and then drying the product in a vacuum oven to obtain a catalytic material.

6. The method for preparing a catalytic material for removing new pollutants in a complex water environment according to claim 5, characterized in that: In step 30, the mass ratio of ammonium molybdate, thiourea, and confined iron nanomaterial is 1:1 to 2:2 to 3.

7. The method for preparing a catalytic material for removing new pollutants in a complex water environment according to claim 5, characterized in that: In step 303, the temperature in the oven is 185-195°C; in step 304, the temperature in the oven is 40-60°C.

8. The method for preparing a catalytic material for removing new pollutants in a complex water environment according to claim 1, characterized in that: The step 10 specifically includes: Step 101: dissolving cobalt nitrate hexahydrate in anhydrous methanol to obtain a cobalt nitrate hexahydrate methanol solution; dissolving 2-methylimidazole in anhydrous methanol to obtain a 2-methylimidazole methanol solution; Step 102, adding the cobalt nitrate hexahydrate methanol solution dropwise to the 2-methylimidazole methanol solution, stirring, and then allowing to stand for aging; Step 103, collecting the precipitated product obtained in step 102 by centrifugation, repeatedly washing the product with an ethanol solution, and drying it in an oven to obtain a zeolite imidazolate framework material containing metal Co coordination.

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