Catalytic material, method for preparing the same and use thereof

Abstract

The application relates to the technical field of MOF materials, and provides a kind of catalytic material and its preparation method and application, including the following steps: dissolving Ni salt, Co salt, Ce salt and trimesic acid in mixed solvent to obtain a reaction solution, carrying out hydrothermal reaction on the reaction solution, and obtaining MOF material through centrifugation and drying; mixing the MOF material with water, standing to obtain a wet precursor, placing the wet precursor in a closed environment for heating reaction, and obtaining the catalytic material through washing and drying. The application mixes the MOF material with water, and then carries out heating reaction in a closed environment to obtain the catalytic material, forms a self-generated micro-pressure hydrothermal environment under the premise of retaining the internal delocalized porous network and skeleton of the MOF material, constructs high-density coordination unsaturated metal active centers, and drives micropore fusion to create micro-mesoporous hierarchical pores, which greatly improves the catalytic effect of the MOF material.

Description

Technical Field

[0001] This invention relates to the field of MOF materials technology, specifically to a catalytic material, its preparation method, and its application. Background Technology

[0002] The widespread use of antibiotics results in a continuous influx of unmetabolized antibiotics into aquatic environments through medical wastewater, pharmaceutical wastewater, and aquaculture wastewater. This not only has toxic effects on aquatic organisms but also seriously induces antibiotic resistance genes in bacteria, threatening global public health security. Advanced oxidation technologies based on sulfate radicals have become an effective means of treating antibiotic wastewater due to their strong oxidizing power and wide pH applicability. Persulfate can be activated to generate sulfate radicals through electron transfer from transition metal ions. However, homogeneous catalysis suffers from problems such as difficulty in recovering metal ions and the potential for secondary pollution. Therefore, there is a need to develop efficient, stable, and recyclable heterogeneous catalysts.

[0003] Metal-organic frameworks (MOFs) exhibit significant advantages in heterogeneous catalytic activation of phosphoric acid (PMS) due to their high-density, atomically dispersed active sites and well-ordered pore structures. Combining transition metals with rare-earth metals to construct multi-metal MOF materials, utilizing the synergistic effect of 3d and 4f electrons, can further enhance catalytic activity. However, in MOF materials, the metal nodes are fully coordinated with the organic ligands, and the active sites are "wrapped" in the coordination network. Electrons are highly delocalized through metal-ligand-metal bridging pathways, resulting in weak single-point reducibility. Simultaneously, the microporous pore structure of MOF materials restricts pollutant mass transfer and diffusion, thus limiting the catalytic performance of MOF materials. Summary of the Invention

[0004] The technical problem to be solved by this invention is how to improve the catalytic performance of MOF materials.

[0005] The present invention solves the above-mentioned technical problems through the following technical means: The first aspect of this invention provides a method for preparing a catalytic material, comprising the following steps: S1. Ni salt, Co salt, Ce salt and pyromellitic acid are dissolved in a mixed solvent to obtain a reaction solution. The reaction solution is subjected to a hydrothermal reaction, and the MOF material is obtained by centrifugation and drying. S2. Mix MOF material with water at a mass-volume ratio of 0.1g:30~100μL, let stand to obtain a moist precursor, place the moist precursor in a closed environment for heating reaction at 100~150℃, and obtain the catalyst material after washing, centrifugation and drying.

[0006] Preferably, the heating reaction time is 1 to 4 hours.

[0007] Preferably, the molar ratio of Ni salt, Co salt, Ce salt, and pyromellitic acid is 1:1:0.1:2.

[0008] More preferably, the Ni salt is nickel nitrate; the Co salt is cobalt nitrate; and the Ce salt is cerium nitrate.

[0009] Preferably, the hydrothermal reaction temperature is 120~180℃ and the reaction time is 18~22h.

[0010] Preferably, the mixed solvent is obtained by mixing dimethylformamide, anhydrous ethanol and water in a volume ratio of 4:1:1.

[0011] Preferably, the settling time is 15-30 minutes.

[0012] Preferably, the heating reaction time in S2 is 1 to 4 hours.

[0013] The second aspect of the present invention provides a method for preparing the above-mentioned catalytic material.

[0014] The third aspect of this invention provides the application of the above-mentioned catalytic material in the degradation of organic pollutants in water.

[0015] Preferably, the organic pollutant includes at least one of tetracycline, oxytetracycline hydrochloride, sulfadiazine, chlortetracycline hydrochloride, doxycycline, methylene blue, and bisphenol A.

[0016] Preferably, the catalytic material is added to water and ultrasonically dispersed; then peroxide is added to carry out a catalytic degradation reaction to remove organic pollutants from the water.

[0017] Preferably, the peroxide is one of hydrogen peroxide, persulfate, or peracetic acid.

[0018] Preferably, the dosage of the catalyst is 0.02 g / L to 0.15 g / L, and the concentration of persulfate is 0.05 to 0.5 mM.

[0019] Preferably, the catalytic degradation reaction is carried out under stirring at 300~600 rpm / min, and the reaction time is 20~60 min.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: Firstly, at the structural level, this invention constructs a three-in-one synergistic structure of "internal delocalized porous network + surface localized activation centers + hierarchical channels" through the synergistic effect of MOF material mixing with water and heating reaction in a closed environment. The internal delocalized porous network is fully preserved, continuing to perform its functions of long-range electron transport and structural support; the surface localized activation centers are composed of coordinated unsaturated metal sites, where metal d / f electrons transition from delocalized to localized states, significantly enhancing single-point reducibility; the hierarchical channels are composed of micropores and mesopores, with mesopores providing rapid mass transfer channels and micropores providing enrichment sites for contaminants and PMS. These three structural units work synergistically in a spatially partitioned manner, simultaneously achieving a qualitative leap in catalytic performance across three dimensions: electron transport, active site exposure, and mass transfer. This overcomes the inherent limitations of traditional high-temperature calcination methods, which lead to framework collapse, or impregnation methods, which only allow for surface loading.

[0021] Secondly, at the methodological level, this invention achieves hierarchical reconstruction of the MOF framework under mild conditions of 100-150°C by precisely controlling only two parameters: the moisture content of the wetted precursor and the closed heating temperature. Compared with traditional methods that require high-temperature calcination at 300-500°C, this invention does not involve high-temperature treatment throughout the process, significantly reducing energy consumption. Compared with impregnation methods that require the addition of external metal salt solutions and complex post-treatment, this invention does not require the introduction of any external reagents, utilizing only the material's own moisture as the driving medium. The process is simple, environmentally friendly, and easy to scale up.

[0022] Finally, in terms of performance, the catalytic material prepared by the method of this invention exhibits significantly higher PMS activation efficiency than the original MOF material, the comparative MOF material treated by traditional high-temperature calcination, and the MOF material treated by impregnation loading. The high-density exposure of surface-coordinated unsaturated metal sites greatly enhances the PMS activation rate, the construction of hierarchical channels accelerates the mass transfer and diffusion between pollutants and PMS, and the retention of the internal delocalized porous network ensures electron transport and structural stability. The synergistic effect of these three factors enables the catalytic material to demonstrate excellent activity and stability in the degradation of antibiotic pollutants such as tetracycline and bisphenol A, showing broad prospects for practical applications. Attached Figure Description

[0023] Figure 1 These are electron microscope images of the NiCoCe-MOF catalytic material in Comparative Example 2 of this invention; where image a is the overall morphology and image b is a microscopic detail image. Figure 2 These are electron microscope images of the WR-NiCoCe-MOF-1 catalytic material in Example 1 of this invention; where image a is the overall morphology and image b is a microscopic detail image. Figure 3 These are the XRD patterns of the WR-NiCoCe-MOF-1 catalytic material, the NiCo-MOF-imp-Ce catalytic material, and the NiCoCe-MOF catalytic material in this invention; Figure 4 This is a degradation curve of tetracycline by the catalytic materials prepared in Examples 1-5 of this invention; Figure 5 This is a degradation curve of tetracycline by the catalytic materials prepared in Example 1 and Comparative Examples 1-5 of this invention; Figure 6 This is a degradation curve of bisphenol A by the catalytic material prepared in Example 1 of this invention. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, 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.

[0025] Unless otherwise specified, all test materials and reagents used in the following examples are commercially available.

[0026] Unless otherwise specified in the embodiments, the techniques or conditions described in the literature in this field or in accordance with the product manual may be followed.

[0027] Example 1 This embodiment provides a method for preparing a catalytic material, specifically including the following steps: Preparation of S1 and MOF materials 2 mmol Ni(NO3)2·6H2O, 2 mmol Co(NO3)2·6H2O, 0.2 mmol Ce(NO3)3·6H2O, and 4 mmol trimesic acid were added to a mixed solvent consisting of 40 mL dimethylformamide, 10 mL anhydrous ethanol, and 10 mL ultrapure water. The mixture was ultrasonically dispersed for 10 minutes and magnetically stirred for 20 minutes to obtain a homogeneous reaction solution. The reaction solution was transferred to a 100 mL polytetrafluoroethylene-lined autoclave, sealed, and placed in an oven for hydrothermal reaction at 150°C for 20 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0028] Open the autoclave, discard the supernatant, and wash the obtained solid three times each with dimethylformamide, anhydrous ethanol, and ultrapure water in sequence by centrifugation. Then, dry it under vacuum at 60°C for 12 hours to obtain completely dry NiCoCe-MOF material powder.

[0029] S2, Preparation of catalytic materials 0.10 g of NiCoCe-MOF material powder was placed in a 5 mL centrifuge tube. 60 μL of deionized water was added to the tube using a pipette. The tube was then capped and vortexed for 3 min to ensure sufficient contact and initial dispersion of the deionized water with the NiCoCe-MOF material. After vortexing, the tube was allowed to stand at room temperature for 20 min to allow the water to fully penetrate between the NiCoCe-MOF particles, resulting in a uniformly moist precursor. The moist solid was transferred to a covered ceramic crucible, which was then sealed. The crucible was placed in a muffle furnace and heated to 120°C at a rate of 5°C / min, and the reaction was maintained at this temperature for 2 h.

[0030] The solid after the reaction was removed, washed with deionized water and centrifuged three times, and then washed with anhydrous ethanol and centrifuged twice. It was then placed in a vacuum drying oven and dried under vacuum at 60°C for 12 hours. After being ground evenly with an agate mortar, WR-NiCoCe-MOF-1 catalyst material was obtained.

[0031] Example 2 This embodiment provides a method for preparing a catalytic material. The difference between this embodiment and Example 1 is that 60 μL of deionized water in S2 is replaced with 30 μL to obtain the WR-NiCoCe-MOF-2 catalytic material.

[0032] Example 3 This embodiment provides a method for preparing a catalytic material. The difference between this embodiment and Example 1 is that 60 μL of deionized water in S2 is replaced with 100 μL to obtain the WR-NiCoCe-MOF-3 catalytic material.

[0033] Example 4 This embodiment provides a method for preparing a catalytic material. The difference between this embodiment and Example 1 is that the temperature in S2 is increased to 100°C instead of 120°C, resulting in WR-NiCoCe-MOF-4 catalytic material.

[0034] Example 5 This embodiment provides a method for preparing a catalytic material. The difference between this embodiment and Example 1 is that the temperature in S2 is increased to 150°C instead of 120°C, to obtain the WR-NiCoCe-MOF-5 catalytic material.

[0035] Comparative Example 1 This comparative example provides a method for preparing catalytic materials by impregnation and calcination, with the specific steps as follows: 2 mmol Ni(NO3)2·6H2O, 2 mmol Co(NO3)2·6H2O, and 4 mmol trimesic acid were added to a mixed solvent consisting of 40 mL dimethylformamide, 10 mL anhydrous ethanol, and 10 mL ultrapure water. The mixture was ultrasonically dispersed for 10 minutes and magnetically stirred for 20 minutes to obtain a homogeneous reaction solution. The reaction solution was transferred to a 100 mL polytetrafluoroethylene-lined autoclave, sealed, and placed in an oven for hydrothermal reaction at 150°C for 20 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0036] Open the autoclave, discard the supernatant, and wash the obtained solid three times each with dimethylformamide, anhydrous ethanol, and ultrapure water in sequence by centrifugation. Then place it in a vacuum drying oven and dry it under vacuum at 60°C for 12 hours. After grinding, NiCo-MOF material is obtained.

[0037] 0.6 g of NiCo-MOF material was added to 15 mL of anhydrous ethanol solution containing 0.2 mmol Ce(NO3)3·6H2O. The mixture was magnetically stirred at room temperature until the ethanol was completely evaporated and the mixture became a dry solid.

[0038] The dried solid was transferred to a porcelain boat and placed in a tube furnace, which was open at both ends to maintain an air atmosphere. The furnace was heated from room temperature to 350°C at a heating rate of 5°C / min and held at 350°C for 2 hours. After calcination, the furnace was allowed to cool naturally to room temperature.

[0039] The calcined solid was washed 4-5 times with ultrapure water to remove unreacted cerium nitrate decomposition products and residual ions, and then washed twice with anhydrous ethanol. The washed solid was placed in a vacuum drying oven and dried under vacuum at 60°C for 12 hours. After grinding, it was labeled as NiCo-MOF-imp-Ce catalyst material.

[0040] Comparative Example 2 This comparative example provides a method for preparing NiCoCe-MOF catalytic materials, the specific steps of which are as follows: The NiCoCe-MOF material prepared in Example 1 was ground to obtain the NiCoCe-MOF catalytic material.

[0041] Comparative Example 3 This comparative example provides a method for preparing a catalytic material, the specific steps of which are as follows: The NiCoCe-MOF material prepared in Example 1 was transferred to a covered porcelain crucible, and the crucible was sealed. The crucible was placed in a muffle furnace, and the temperature was increased to 120°C at a rate of 5°C / min, and the reaction was maintained at this temperature for 2 hours. The reacted solid was removed, washed with deionized water and centrifuged three times, and then washed with anhydrous ethanol and centrifuged twice. It was then placed in a vacuum drying oven and dried under vacuum at 60°C for 12 hours. Finally, it was ground uniformly using an agate mortar to obtain the D-NiCoCe-MOF catalyst material.

[0042] Comparative Example 4 This comparative example provides a method for preparing a catalytic material. The difference between this comparative example and Example 1 is that the dispersion was directly subjected to a closed heating reaction without standing for 20 minutes in S2 to obtain the catalytic material, which is denoted as NiCoCe-MOF-NS catalytic material.

[0043] Experimental Example The catalytic materials prepared in the examples and comparative examples were characterized and tested as follows: Electron microscopy image of the NiCoCe-MOF catalyst prepared in Comparative Example 2 is shown below. Figure 1 As shown in Figure a, the low-magnification overall morphology of the NiCoCe-MOF catalytic material reveals a coexistence of layered crystals and spherical aggregates. The layered structure exhibits significant two-dimensional extension and clear edges, while the spherical aggregates have relatively dense surfaces. This coexistence of multiple morphologies is attributed to the introduction of cerium ions during hydrothermal synthesis, which modulates the local coordination environment, leading to competition between anisotropic growth (layered) and isotropic nucleation and aggregation (spherical) in the metal-organic coordination assembly. This indicates that the rare earth element cerium has been successfully incorporated into the MOF system, and the MOF framework remains intact. Figure b, a high-magnification image, further reveals the microscopic details of the NiCoCe-MOF catalytic material. The edges and surfaces of the layered crystals are adhered with numerous nanoscale particles or flocculent products, resulting in a noticeable roughness. Simultaneously, the spherical aggregates are composed of tightly packed, even finer nanoparticles with clearly defined boundaries between them. This surface roughening and nanoparticle adhesion phenomenon confirms the successful doping of cerium and also suggests that although the MOF material has a complete framework under hydrothermal conditions, the surface has begun to undergo slight reconstruction or exposure of active sites, providing a potential active interface for subsequent catalytic reactions.

[0044] The electron micrograph of the WR-NiCoCe-MOF-1 catalyst prepared in Example 1 is shown below. Figure 2As shown in Figure a, the overall morphology of the material is illustrated. It can be seen that the reconstructed material retains its original layered stacked structure, with clear lamellar edges and no overall collapse or fusion, indicating that the closed-loop heating process has an excellent skeletal protection effect. Figure b clearly shows that the layered surface is in a "transitional state"—that is, some areas have a large number of nanoscale fibers / flocculent reconstruction products attached, while adjacent areas still show a relatively flat layered matrix. This transitional state characteristic indicates that, under closed-loop heating conditions, the self-generated micro-pressure hydrothermal environment formed by quantitative moisture selectively induces the controlled breakage of metal-carboxyl coordination bonds on the lamellar surface, rather than overall destruction. This process, while preserving the internal layered delocalized porous network, gradually constructs high-density coordinated unsaturated metal active centers and drives the controlled collapse and fusion of the interlayer micropore walls, ultimately forming a hierarchical pore structure with interconnected micropores and mesopores, achieving a three-in-one synergistic structure of "internal delocalized porous network + surface localized activation centers + hierarchical pores".

[0045] The XRD patterns of the WR-NiCoCe-MOF-1 catalyst prepared in Example 1, the NiCo-MOF-imp-Ce catalyst prepared in Comparative Example 1, and the NiCoCe-MOF catalyst prepared in Comparative Example 2 are shown below. Figure 3 As shown, the XRD pattern of the NiCoCe-MOF catalyst exhibits clear and sharp characteristic diffraction peaks, indicating its high crystallinity. In contrast, the NiCo-MOF-imp-Ce catalyst prepared by the impregnation-calcination method has a flat baseline and almost no obvious diffraction peaks, indicating that the high-temperature treatment caused its framework to completely collapse and transform into an amorphous state. The WR-NiCoCe-MOF-1 catalyst prepared in Example 1 shows a significant decrease in overall peak intensity, with the originally sharp diffraction peaks becoming relatively broad, directly indicating that its crystallinity is lower than that of the NiCoCe-MOF catalyst. This characteristic of reduced but not completely disappeared crystallinity is direct structural evidence for the "retention of internal delocalized porous network + construction of surface localized activation centers" of this invention: while maintaining the basic integrity of the MOF bulk framework (ensuring electron transport and structural support), selective breakage of surface coordination bonds is induced, forming high-density coordinated unsaturated metal active sites, thereby achieving a synergistic improvement in structural stability and catalytic activity.

[0046] The catalytic materials prepared in Examples 1-5 and Comparative Examples 1-4 were tested for their degradation effect on tetracycline, as detailed below: Eleven 100 mL tetracycline solutions were prepared, with a tetracycline concentration of 20 mg / L. The accurate initial concentration of tetracycline in each solution was determined using an Agilent 1220 high-performance liquid chromatograph and denoted as C0. 0.01 g of the catalyst material prepared in Examples 1-5 and Comparative Examples 1-5, with a catalyst addition amount of 0.1 g / L, was weighed and added sequentially to the eleven tetracycline solutions. The catalyst material was sonicated for 5 s to ensure uniform dispersion. The solutions were placed on a magnetic stirrer (500 rpm / min), and 0.1 mM potassium peroxymonosulfate was added at 25°C, with timing started immediately. The pH during the reaction was approximately 6.5, requiring no additional adjustment. Samples were taken at 2, 5, 10, 20, and 30 min of the reaction, and the tetracycline concentration at each time point was determined using an Agilent 1220 high-performance liquid chromatograph and denoted as C. To eliminate experimental contingencies and ensure data reliability, the above steps were performed in triplicate.

[0047] The degradation curves of tetracycline by the catalyst materials prepared in Examples 1-5 are shown below. Figure 4 As shown, according to Figure 4 It can be seen that the WR-NiCoCe-MOF-1 catalytic material has the best performance, with the C / C0 dropping to near 0 within 2-3 minutes, achieving almost complete degradation; WR-NiCoCe-MOF-2, 3, and 4 are next, with the C / C0 between 0.05 and 0.10 at 30 minutes; WR-NiCoCe-MOF-5 is the slowest, with the C / C0 still above 0.10 at 30 minutes.

[0048] The above differences stem from the control of treatment conditions on the degree of hierarchical reconstruction of the MOF material framework: First, the mass-to-volume ratio of MOF material to water varies. When the mass-to-volume ratio of MOF material to water is 0.1g:60uL, the optimal balance between hydrolysis activation and framework stability is achieved. When the mass-to-volume ratio of MOF material to water is 0.1g:30uL, hydrolysis may be insufficient, and when the mass-to-volume ratio of MOF material to water is 0.1g:100uL, hydrolysis may be excessive and damage the framework. Second, temperature affects hydrolysis kinetics. At 100℃, the hydrolysis driving force is insufficient, and at 150℃, the pore walls collapse excessively and the vapor pressure is too high, damaging the framework.

[0049] Therefore, the WR-NiCoCe-MOF-1 catalytic material prepared in Example 1 precisely constructed a three-in-one synergistic structure with "fully exposed surface localized activation centers, moderately constructed hierarchical channels, and complete preservation of internal delocalized porous network" through the optimal combination of MOF material to water mass-volume ratio of 0.1g:60uL and 120℃, thus achieving the best degradation performance.

[0050] The degradation curves of tetracycline by the catalysts prepared in Examples 1 and Comparative Examples 1-4 are shown below. Figure 5 As shown, according to Figure 5It can be seen that the WR-NiCoCe-MOF-1 catalyst exhibits the best performance. Among them, the D-NiCoCe-MOF and NiCoCe-MOF catalysts, due to the lack of water molecule involvement in the hydrolysis process and insufficient exposure of coordination unsaturated sites, have moderate performance. The NiCo-MOF-imp-Ce catalyst performs the worst because its CeO2 particles cover the Ni / Co active sites, and high-temperature calcination destroys the MOF framework, resulting in the loss of the structural advantages of porous networks and regular channels. Notably, the NiCoCe-MOF-NS catalyst has a degradation rate of 75% after 30 minutes, lower than the untreated NiCoCe-MOF catalyst. This anomaly profoundly reveals the necessity of the settling step: when the settling step is omitted, although subsequent closed heating is performed, moisture fails to fully penetrate into the MOF interlayer and micropore interior at room temperature, only adhering to the particle surface. This leads to rapid vaporization and escape of surface moisture during heating, preventing the formation of an effective self-generated micro-pressure hydrothermal environment in the interlayer. As a result, the MOF layered framework failed to undergo the expected selective reconstruction of the "transition state," and the surface metal-carboxyl coordination bonds were not broken sufficiently, making it impossible to construct high-density coordinated unsaturated metal active centers and hierarchical channels. The rapid vaporization of surface moisture may cause local thermal stress, leading to blockage of some channels or passivation of active sites, thus making the degradation effect lower than that of the original material.

[0051] The degradation effect of the WR-NiCoCe-MOF-1 catalyst material prepared in Example 1 on bisphenol A was tested, as follows: Prepare a 100 mL bisphenol A solution with a concentration of 20 mg / L. The accurate initial concentration of bisphenol A in the solution was determined using an Agilent 1220 high-performance liquid chromatograph and denoted as C0. Weigh 0.01 g of the WR-NiCoCe-MOF-1 catalyst prepared in Example 1 and add it to the bisphenol A solution. The catalyst addition was 0.1 g / L, and the solution was sonicated for 5 s to ensure uniform dispersion. Place the solution on a magnetic stirrer (500 rpm / min), add 0.1 mM potassium peroxymonosulfate at 25°C, and start timing immediately. The pH during the reaction was approximately 6 and no additional adjustment was required. Samples were taken at 2, 5, 10, 20, and 30 min of the reaction, and the bisphenol A concentration at each time point was determined using an Agilent 1220 high-performance liquid chromatograph and denoted as C. To eliminate experimental contingencies and ensure data reliability, the above steps were performed in triplicate.

[0052] according to Figure 6 It can be seen that the WR-NiCoCe-MOF-1 catalytic material also exhibits excellent degradation effect on bisphenol A, indicating that the catalytic material prepared in this invention is not only highly efficient for tetracycline antibiotics, but also has a broad-spectrum degradation ability for other organic pollutants.

[0053] The above comparison fully demonstrates that the three-in-one synergistic structure constructed by uniformly introducing Ce through hydrothermal method and closed heating is the fundamental reason for the excellent catalytic performance of this invention.

[0054] The above embodiments and comparative examples are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a catalytic material, characterized in that, Includes the following steps: S1. Ni salt, Co salt, Ce salt and pyromellitic acid are dissolved in a mixed solvent to obtain a reaction solution. The reaction solution is subjected to a hydrothermal reaction, and the MOF material is obtained by centrifugation and drying. S2. Mix MOF material with water at a mass-volume ratio of 0.1g:30~100μL, let stand to obtain a moist precursor, place the moist precursor in a closed environment for heating reaction at 100~150℃, and obtain the catalyst material after washing, centrifugation and drying.

2. The method for preparing the catalytic material according to claim 1, characterized in that, The heating reaction time is 1 to 4 hours.

3. The method for preparing the catalytic material according to claim 1, characterized in that, The molar ratio of Ni salt, Co salt, Ce salt, and pyromellitic acid is 1:1:0.1:

2.

4. The method for preparing the catalytic material according to claim 1, characterized in that, The hydrothermal reaction temperature is 120~180℃, and the reaction time is 18~22h.

5. The method for preparing the catalytic material according to claim 1, characterized in that, The mixed solvent is obtained by mixing dimethylformamide, anhydrous ethanol and water in a volume ratio of 4:1:

1.

6. The method for preparing the catalytic material according to claim 1, characterized in that, Let it stand for 15 to 30 minutes.

7. A method for preparing a catalytic material according to any one of claims 1-6.

8. The application of the catalytic material as described in claim 7 in the degradation of organic pollutants in water.

9. The application of the catalytic material according to claim 8 in the degradation of organic pollutants in water, characterized in that, Organic pollutants include at least one of tetracycline, oxytetracycline hydrochloride, sulfadiazine, chlortetracycline hydrochloride, doxycycline, methylene blue, and bisphenol A.

10. The application of the catalytic material according to claim 8 in the degradation of organic pollutants in water, characterized in that, The catalytic material is added to water and ultrasonically dispersed; then peroxide is added to carry out a catalytic degradation reaction to remove organic pollutants from the water.

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