Heterogeneous Fenton-like catalyst as well as preparation method and application thereof

Abstract

The invention discloses a heterogeneous Fenton-like catalyst as well as a preparation method and application thereof, and belongs to the technical field of nano catalytic materials. The preparation method disclosed by the invention comprises the following steps: dissolving zirconium chloride and terephthalic acid in a solvent A to obtain a mixed solution A; reacting the mixed solution to obtain a reaction product; and carrying out post-treatment on the reaction product to obtain the zirconium-based metal organic framework material. Cobalt nitrate hexahydrate and ferric nitrate hexahydrate are mixed and dispersed in water to be stirred, and after the pH value is adjusted, a mixed solution B is obtained; dissolving a zirconium-based metal organic framework material in a solvent B, and then adding the mixed solution B to obtain a mixed solution C; and carrying out suction filtration on the mixed solution C to obtain a solid, and calcining the solid to obtain the heterogeneous Fenton-like catalyst. The technical problem that an existing MOFs material is low in catalytic efficiency is solved.

Description

Technical Field

[0001] The invention belongs to the technical field of nanocatalytic materials, and specifically relates to a heterogeneous Fenton-type catalyst and a preparation method and application thereof. Background Art

[0002] Bisphenol compounds are the most common and most numerous type of endocrine disruptors, with bisphenol A (BPA) being the most typical. Since BPA is widely used in the fields of plastic production, electronic equipment, food packaging, and medical equipment, BPA will inevitably migrate into the environmental medium during the large-scale production, use, and disposal of related products. Disorderly emissions during the production or use of related chemical industries are the main source of BPA pollution in the environment. BPA is a typical environmental estrogen substance that can bind to estrogen receptors or interfere with the normal functional expression of cells through androgen antagonists after entering the human body, thereby causing harm to human health. BPA is believed to have an impact on fetal development and is carcinogenic, especially breast cancer. Due to its estrogenic activity, BPA has also been shown to lead to a decrease in sperm count and activity.

[0003] Traditional advanced oxidation technologies (AOPs) mainly rely on a variety of activation mechanisms to induce classic oxidants such as hydrogen peroxide (H2O2), molecular oxygen (O2) and ozone (O3) to generate highly reactive hydroxyl radicals (·OH). With its redox potential of about 2.8V, ·OH exhibits excellent oxidizing ability and can effectively act on organic pollutants to trigger oxidative decomposition reactions. This process causes pollutants to gradually degrade into small molecules with low or even non-toxic toxicity, and eventually achieve complete mineralization, that is, decomposition into water and carbon dioxide (CO2). In view of the significant advantages of AOPs, they have attracted much attention in the field of treating difficult-to-degrade emerging pollutants in recent years. Among them, Fenton and Fenton-like systems, ozone oxidation, photocatalytic oxidation, and persulfate-catalyzed oxidation technologies, as important branches of AOPs, each exhibits a unique reaction mechanism and broad application prospects, providing strong technical support for the fields of environmental remediation and water treatment.

[0004] Metal-organic frameworks (MOFs), also known as porous coordination networks or porous coordination polymers, are a special type of material. They are formed by self-assembly of metal ions (or metal chalcogens) as metal nodes and organic ligands through coordination interactions, resulting in a three-dimensional networked porous organic-inorganic hybrid crystalline material. MOFs materials have many significant advantages. For example, they have an extremely high specific surface area, which can provide more active sites. At the same time, by carefully selecting metal nodes and rationally designing organic ligands, the pore size of MOFs materials can be continuously regulated between micropores and mesopores, greatly enhancing their adaptability to different substances. In addition, MOFs also have characteristics such as diverse structures, good designability, and strong tailoring ability, which make them show broad application prospects in many fields such as gas adsorption and separation, biomedicine, chemical sensing, and catalysis.

[0005] However, when using metal-organic frameworks (MOFs) materials to treat endocrine disrupting chemicals (EDCs) in water, several significant defects and limitations are still faced. The primary problem is that in a complex water quality environment, the framework structure of MOFs materials is easily damaged by multiple factors such as ionic strength, pH, and organic matter in water, resulting in a significant reduction in active sites, thereby weakening the adsorption and catalytic degradation efficiency of EDCs. Secondly, the synthesis cost of MOFs materials is relatively high, mainly due to expensive raw materials and cumbersome preparation processes, involving solvent selection, precise regulation of reaction conditions, and subsequent complex purification steps, which not only increase the production time cost but also limit the large-scale application and commercial promotion of MOFs materials in the water treatment field. Therefore, exploring low-cost, high-efficiency, and structurally stable MOFs materials and their synthesis methods is of great significance for improving the removal efficiency of EDCs and promoting the application of MOFs materials in the water treatment field. Summary of the Invention

[0006] The purpose of the present invention is to provide a heterogeneous Fenton-like catalyst, its preparation method, and application to solve the technical problem of low catalytic efficiency of MOFs materials.

[0007] To achieve the above purpose, the present invention adopts the following technical solutions:

[0008] The present invention discloses a preparation method of a heterogeneous Fenton-like catalyst, including the following steps:

[0009] Dissolve zirconium chloride and terephthalic acid in solvent A to obtain a mixed solution A; react the mixed solution to obtain a reaction product;

[0010] Post-treat the reaction product to obtain a zirconium-based metal-organic framework material;

[0011] Cobalt nitrate hexahydrate and iron nitrate hexahydrate were mixed and dispersed in water and stirred. After adjusting the pH value, a mixed solution B was obtained;

[0012] The zirconium-based metal-organic framework material was dissolved in solvent B, and then the mixed solution B was added to obtain a mixed solution C;

[0013] The solid obtained by suction filtration of the mixed solution C was calcined to obtain a heterogeneous Fenton-like catalyst.

[0014] Furthermore, the molar ratio of zirconium chloride to terephthalic acid is 1:(1-5);

[0015] The solvent A is N,N-dimethylformamide or dimethyl sulfoxide;

[0016] The dosage ratio of zirconium chloride to solvent A is 1 mmol:(30-50) mL.

[0017] Furthermore, the mixed solution A was ultrasonically treated for 30-60 min and then reacted;

[0018] The reaction was carried out in a reaction kettle; the temperature of the reaction was 120-160 °C and the time was 12-24 h.

[0019] Furthermore, the post-treatment of the reaction product was to centrifugate, wash, dry and grind the reaction product in sequence; the washing was to wash three times with anhydrous methanol and N,N-dimethylformamide respectively, and then wash centrifugally with a methanol solution under the conditions of a centrifugal speed of 5000 revolutions per minute and a centrifugal time of 5 min for more than 3 times; the drying treatment was to dry in a vacuum drying oven.

[0020] Furthermore, the molar ratio of cobalt nitrate hexahydrate to iron nitrate hexahydrate is 1:3-3:1; the pH value was adjusted to neutral; the dosage ratio of zirconium chloride to water is 1 mmol:(30-50) mL.

[0021] Furthermore, the dosage ratio of the zirconium-based metal-organic framework material to solvent B is 1 mmol:(5-10) mL;

[0022] The solvent B is ultrapure water; the stirring time is 30 min-1 h.

[0023] Furthermore, the temperature of the calcination treatment is 200-300 °C and the time is 2 h.

[0024] The present invention also discloses a heterogeneous Fenton-like catalyst prepared by the above preparation method.

[0025] The present invention also discloses the application of the above heterogeneous Fenton-like catalyst in the catalytic degradation of endocrine disruptors.

[0026] Furthermore, the endocrine disruptors include natural or synthetic animal and plant hormones, detergents, azo dyes or organochlorine pesticides.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention discloses a preparation method of a heterogeneous Fenton-like catalyst. By adjusting the pH of the solution obtained after mixing cobalt nitrate hexahydrate and iron nitrate hexahydrate in water, and then mixing the zirconium-based metal-organic framework material obtained by combining with the solution made of zirconium chloride and terephthalic acid with this solution for calcination treatment. During the calcination process, the MOFs structure undergoes a thermal transformation to form a metal oxide-metal framework composite material. This new structure enables the retention of the activity of metals such as iron and cobalt, and the original porous material further increases the contact area between metal ions and reactants, improving the utilization rate of the material, and solving the technical problems of low catalytic efficiency and few active sites of existing MOFs materials.

[0029] The present invention also discloses a heterogeneous Fenton-like catalyst prepared by the above preparation method. It can be seen from the transmission electron microscope image that the loading method of this method enables the vast majority of metal nanoparticles to enter the pores of the MOF, further improving the stability of the material; this catalyst has a better crystal state, better dispersibility, a higher specific surface area, and reduces the dosage of transition metals, and has a high catalytic activity.

[0030] The present invention also discloses the application of the above heterogeneous Fenton-like catalyst in the catalytic degradation of endocrine disruptors, which has the characteristics of environmental friendliness, no secondary pollution, high reaction rate, high removal rate, etc., and has good application prospects in the environmental field. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Scanning electron microscope image of the heterogeneous Fenton-like catalyst (bimetallic oxide Co-Fe / UiO-66 catalyst) prepared in Example 1 of the present invention;

[0032] Figure 2 X-ray powder diffraction pattern of the heterogeneous Fenton-like catalyst prepared in Example 1 of the present invention;

[0033] Figure 3 Fourier transform infrared spectrometer spectrum of the heterogeneous Fenton-like catalyst prepared in Example 1 of the present invention;

[0034] Figure 4 Degradation efficiency diagram of the heterogeneous Fenton-like catalyst prepared in Example 1 of the present invention for BPA. DETAILED DESCRIPTION OF THE INVENTION

[0035] To enable those skilled in the art to understand the features and effects of the present invention, the following provides a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meaning understood by those skilled in the art with respect to the present invention. In case of conflict, the definition in this specification shall prevail.

[0036] The theories or mechanisms described and disclosed herein, whether correct or incorrect, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0037] In this article, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are only for the sake of simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values (including integers and fractions) within the ranges.

[0038] In this article, unless otherwise specified, the terms "comprising", "including", "containing", "having", or similar terms cover the meanings of "consisting of" and "consisting essentially of". For example, "A comprises a" covers the meanings of "A comprises a and others" and "A only comprises a".

[0039] In this article, for the sake of brevity of description, all possible combinations of all technical features in each embodiment or example are not described. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered as within the scope described in this specification.

[0040] The present invention provides a method for preparing a heterogeneous Fenton-like catalyst, comprising the following steps:

[0041] S1. Dissolve zirconium chloride and terephthalic acid in N,N-dimethylformamide to obtain a mixed solution.

[0042] S2. Thoroughly mix the mixed solution, ultrasonicate for 30 minutes to obtain a mixed solution A, and then add it to a reaction kettle for reaction to obtain a reaction product.

[0043] S3. Take out the reaction product, centrifuge and wash it thoroughly, and dry it to obtain zirconium-based metal-organic framework (UiO-66).

[0044] S4. Mix cobalt nitrate hexahydrate and iron nitrate hexahydrate and disperse them in ultrapure water to adjust the pH to neutral to obtain a mixed solution B.

[0045] S5. Dissolve the UiO-66 obtained in S3 in ultrapure water, add the solution B obtained in S4, and stir until a mixed state is achieved to obtain a mixed solution C.

[0046] S6. Filter the mixed solution C to obtain a solid mixture, and place it in a muffle furnace for reaction to obtain a heterogeneous Fenton-like catalyst.

[0047] Preferably, in S1, the molar ratio of zirconium chloride to terephthalic acid is 1:(1 - 5); the dosage ratio of N,N-dimethylformamide to zirconium chloride is 1 mmol: 30 - 50 m.

[0048] Preferably, in S2, the reaction temperature is 120 - 160 °C, and the reaction time is 12 - 24 h.

[0049] Preferably, in S3, the centrifugation and washing are specifically as follows: after the reaction is complete, cool to room temperature to obtain a white condensate, and wash it three times with anhydrous methanol and N,N-dimethylformamide respectively.

[0050] Preferably, in S4, the molar ratio of cobalt nitrate hexahydrate to iron nitrate hexahydrate is preferably 1:3 - 3:1; the dosage ratio of ultrapure water to zirconium chloride is 1 mmol: 30 - 50 mL.

[0051] Preferably, in S6, the temperature is 80 °C, stir, and dry to constant weight.

[0052] Preferably, in S4, both cobalt nitrate hexahydrate and iron nitrate hexahydrate are purchased chemical reagents; the stirring time is 30 min - 1 h.

[0053] Preferably, in step S3, the centrifugation and washing are to wash the complex with a methanol solution and N,N-dimethylformamide, and then centrifuge and wash it more than 3 times at a centrifugation speed of 5000 revolutions per minute and a centrifugation time of 5 minutes with a methanol solution; the drying is carried out at room temperature.

[0054] The present invention also discloses a heterogeneous Fenton-like catalyst prepared by the above preparation method.

[0055] The present invention also discloses that the above heterogeneous Fenton-like catalyst has good application in the catalytic degradation of novel endocrine disruptors; endocrine disruptors include natural or synthetic animal and plant hormones, detergents, azo dyes, organochlorine pesticides, and other industrial chemicals, etc.

[0056] The following further elaborates the present invention in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0057] Conventional instruments and equipment in the art are used in the following examples. For the experimental methods without specific conditions noted in the following examples, they are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer. Various raw materials are used in the following examples. Unless otherwise stated, commercially available products are used, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" represents weight percentage, "parts" represents weight parts, and the ratio represents weight ratio.

[0058] Example 1

[0059] A preparation method of a heterogeneous Fenton-like catalyst, comprising the following steps:

[0060] S1. Dissolve 0.466 g of zirconium chloride and 0.644 g of terephthalic acid in 45 mL of N,N-dimethylformamide, mix well and ultrasonicate for 30 min to obtain a mixed solution A;

[0061] S2. Transfer the mixed solution A to a 100 mL polytetrafluoroethylene-lined autoclave, heat at 160 °C for 24 h, cool to room temperature after complete reaction, wash the obtained white condensate with anhydrous methanol and N,N-dimethylformamide three times each, and centrifuge and wash three times with a methanol solution under the conditions of a centrifugal speed of 5000 revolutions per minute and a centrifugal time of 5 min. Finally, dry in a vacuum drying oven at 80 °C for 6 h and then grind to obtain a zirconium-based metal-organic framework material (UiO-66);

[0062] S3. Place 0.3 g of UiO-66 in a beaker and ultrasonically dissolve it in 20 mL of ultrapure water solution to obtain a solution of UiO-66; at the same time, take cobalt nitrate and iron nitrate in an equimolar ratio and place them in another 30 mL of ultrapure water solution. Ultrasonically mix the two solutions for 10 min, adjust the pH to neutral to obtain a mixed solution B; add the mixed solution B to the solution of UiO-66, place it in a water bath and ultrasonically disperse for 30 min, and then stir at room temperature for 1 h to obtain a mixed solution C;

[0063] S4. Filter the mixed solution C to obtain a solid catalyst; dry the obtained solid catalyst in a vacuum oven at 80 °C for 12 h until the water volatilizes, wash the dried solid with a methanol solution more than three times, and then calcine at 300 °C for 2 h to stabilize the structure, and then store it sealed to obtain a highly active and high specific surface area bimetallic oxide Co-Fe / UiO-66 catalyst (heterogeneous Fenton-like catalyst);

[0064] The scanning electron micrograph of the bimetallic oxide Co-Fe / UiO-66 catalyst prepared in this example is as Figure 1 shown. It can be seen that due to the increase in the amount of terephthalic acid used and the extension of the reaction time, it can be seen that the original single catalysts adhere together and undergo excessive aggregation.

[0065] Example 2

[0066] This example is about bimetallic oxide catalysts with different ratios. The purpose is to compare the catalytic efficiencies between different supported metals and select the optimal catalyst. The loading steps are the same as in Example 1, with the difference being that the prepared UiO-66 is loaded with cobalt-iron oxides with different ratios. Take 0.3 g of UiO-66 and place it in a beaker, and ultrasonically dissolve it in 40 mL of ultrapure aqueous solution to obtain an ultrapure aqueous solution of UiO-66. At the same time, take nitrides of cobalt and iron elements with different molar ratios, add them to 40 mL of ultrapure water respectively, place the well-dispersed mixture under normal temperature and stir for 1 h. After stirring, the sample is dried in a vacuum oven at 80 °C for 8 h until the water volatilizes. After washing the obtained powder three times, it is dried in a normal temperature environment overnight, collected and stored in a sealed environment to obtain UiO-66 loaded with metals with different ratios, and the ratios are Fe:Co = 1:1, 2:1, 3:1, 3:2, etc.; Figure 2 From the XRD characterization diagram with an iron-cobalt ratio of 2:1, it can be seen that iron and cobalt are loaded on the catalyst surface in different valence states; Figure 3 From the FTIR of catalysts with different iron-cobalt ratios, the oxidation state functional groups of cobalt and the stretching C-H bonds of terephthalic acid can be seen; Figure 4 It is a comparison of the degradation of bisphenol A in water by peroxymonosulfate catalyzed by catalysts with different iron-cobalt ratios.

[0067] Example 3

[0068] A preparation method of a heterogeneous Fenton-like catalyst includes the following steps:

[0069] S1. Dissolve 0.233 g of zirconium chloride and 0.166 g of terephthalic acid in 10 mL of N,N-dimethylformamide, mix well and ultrasonically for 30 min to obtain a mixed solution A;

[0070] S2. Transfer the mixed solution A to a 50 mL polytetrafluoroethylene-lined autoclave, heat it at 120 °C for 12 h, cool it to room temperature after complete reaction, wash the obtained white condensate with anhydrous methanol and N,N-dimethylformamide 3 times respectively, and finally dry it in a vacuum drying oven at 80 °C for 6 h and then grind it to obtain zirconium-based metal-organic framework (UiO-66);

[0071] S3. Place 0.3 g of UiO-66 in a beaker and ultrasonically dissolve it in 50 mL of ultrapure aqueous solution to obtain a solution of UiO-66. At the same time, take cobalt nitrate and iron nitrate in equimolar ratio and place them in another 50 mL of ultrapure water. Ultrasonically mix the two solutions for 10 min, adjust the pH to neutral to obtain a mixed solution B. Add the mixed solution B to the solution of UiO-66, place it in a water bath and ultrasonically disperse for 30 min, and then stir at room temperature for 1 h to obtain a mixed solution C.

[0072] S4. Filter the mixed solution C to obtain a solid catalyst. Place the obtained solid catalyst in a vacuum oven and dry it at 80 °C for 12 hours until the water volatilizes. Wash the dried solid with methanol solution more than 3 times and then calcine it at 200 °C for 2 hours to make the structure stable, and then store it sealed. A bimetallic oxide Co-Fe / UiO-66 catalyst with a specific crystal phase structure, high activity and high specific surface area is obtained.

[0073] The scanning electron micrograph of the bimetallic oxide Co-Fe / UiO-66 catalyst prepared in this example is as Figure 2 shown, and it can be seen that it has a good cubic crystal structure, greatly reducing the excessive aggregation phenomenon in Example 1.

[0074] The preparation method disclosed by the present invention can ensure that the reactants are fully dissolved and the expected chemical reaction occurs by precisely controlling the molar ratio of zirconium chloride to terephthalic acid (1:1 to 5) and the dosage ratio of zirconium chloride to solvent A, thereby obtaining a high-quality zirconium-based metal-organic framework material. At the same time, the reaction is carried out in a reaction kettle, and the reaction temperature and time are strictly controlled (120 to 160 °C, 12 to 24 h), which helps to form a stable crystal structure and improve the activity of the catalyst. Subsequently, the reaction product is post-treated through steps such as centrifugation, washing, drying, and grinding to remove impurities, improve the purity of the catalyst, and make it have better dispersibility and catalytic performance. Furthermore, by introducing cobalt nitrate hexahydrate and iron nitrate hexahydrate and precisely controlling their molar ratio (1:3 to 3:1), a composite catalyst with excellent catalytic performance can be formed. Selecting ultrapure water as solvent B helps the uniform dispersion of metal ions and their full combination with the zirconium-based metal-organic framework material. Finally, through calcination treatment (200 to 300 °C, 2 h), the crystallinity and activity of the catalyst can be further improved, making it have better catalytic degradation performance. The heterogeneous Fenton-like catalyst has higher stability and recyclability and is suitable for continuous flow reactions and large-scale applications. This catalyst has potential application value in the catalytic degradation of endocrine disruptors, including natural or synthetic animal and plant hormones, detergents, azo dyes, and organochlorine pesticides, which helps environmental protection and pollution control. This technical solution proposes a new preparation method for a heterogeneous Fenton-like catalyst, which is innovative and practical. The preparation and application processes of the catalyst are relatively environmentally friendly and will not cause secondary pollution to the environment.

[0075] The above content is only for explaining the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a heterogeneous Fenton-type catalyst, characterized in that: The following steps are involved: Dissolving zirconium chloride and terephthalic acid in solvent A to obtain a mixed solution A; reacting the mixed solution to obtain a reaction product; post-treating the reaction product to obtain a zirconium-based metal-organic framework material; Cobalt nitrate hexahydrate and ferric nitrate hexahydrate are mixed and dispersed in water, stirred, and the pH value is adjusted to obtain a mixed solution B; Dissolving the zirconium-based metal organic framework material in solvent B, and then adding mixed solution B to obtain mixed solution C; The solid obtained by filtering the mixed solution C is calcined to obtain a heterogeneous Fenton-type catalyst.

2. The method for preparing a heterogeneous Fenton-type catalyst according to claim 1, characterized in that: The molar ratio of zirconium chloride to terephthalic acid is 1:(1-5); The solvent A is N,N-dimethylformamide or dimethyl sulfoxide; The dosage ratio of the zirconium chloride to the solvent A is 1 mmol: (30-50) mL.

3. The method for preparing a heterogeneous Fenton-type catalyst according to claim 1, characterized in that: Mixed solution A was subjected to ultrasound for 30 to 60 minutes before reacting; The reaction is carried out in a reactor; the reaction temperature is 120-160° C. and the reaction time is 12-24 hours.

4. The method for preparing a heterogeneous Fenton-type catalyst according to claim 1, characterized in that: The post-treatment of the reaction product is to centrifuge, wash, dry and grind the reaction product in sequence; the washing is to use anhydrous methanol and N,N-dimethylformamide to wash three times respectively, and then use methanol solution to centrifuge and wash more than three times under the conditions of a centrifugal speed of 5000 rpm and a centrifugal time of 5 minutes; the drying treatment is drying in a vacuum drying oven.

5. The method for preparing a heterogeneous Fenton-type catalyst according to claim 1, characterized in that: The molar ratio of the cobalt nitrate hexahydrate to the ferric nitrate hexahydrate is 1:3 to 3:1; the pH value is adjusted to be neutral; and the molar ratio of the zirconium chloride to water is 1 mmol:30 to 50 mL.

6. The method for preparing a heterogeneous Fenton-type catalyst according to claim 1, characterized in that: The amount ratio of the zirconium-based metal organic framework material and the solvent B is 1 mmol: (5-10) mL; The solvent B is ultrapure water; the stirring time is 30 min to 1 h.

7. The method for preparing a heterogeneous Fenton-type catalyst according to claim 1, characterized in that: The calcination treatment is carried out at a temperature of 200-300° C. and for a time of 2 hours.

8. A heterogeneous Fenton-type catalyst, characterized in that: The preparation method is described in any one of claims 1 to 7.

9. Use of a heterogeneous Fenton-type catalyst as claimed in claim 8 in the catalytic degradation of endocrine disruptors.

10. Use of a heterogeneous Fenton-type catalyst in catalytic degradation of endocrine disruptors according to claim 9, characterized in that: The endocrine disruptors include natural or synthetic plant and animal hormones, detergents, azo dyes or organochlorine pesticides.

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