Preparation method and application of metal nanocluster doped silicate catalyst
The preparation of metal nano-cluster doped zeolite catalysts through a simplified process addresses the stability and activity issues of traditional catalysts, offering high efficiency and ease of recovery, thus enhancing the treatment of toxic organic pollutants.
Patent Information
- Application Number
- CN202510471040.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-15
- Publication Date
- 2025-07-15
AI Technical Summary
Traditional advanced oxidation methods have problems such as secondary pollution and difficulty in degrading emerging organic pollutants, and traditional catalysts have poor stability, short life and limited activity.
The preparation method of metal nanocluster doped silicate catalyst is adopted to prepare a metal nanocluster doped silicate catalyst by mixing silicate minerals with metal compounds under specific conditions, achieving uniform dispersion and efficient catalysis of metals, reducing preparation costs and improving the cycle stability of the catalyst.
A catalyst with high catalytic efficiency, long life and easy recovery is achieved, which avoids secondary pollution caused by metal ions exudation, and significantly improves the degradation efficiency of organic pollutants and the stability of the catalyst.
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Figure CN120305967A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of advanced oxidation catalytic materials for sewage treatment, and particularly relates to a preparation method and application of a metal nanocluster-doped silicate catalyst. Background Art
[0002] With the acceleration of the global industrialization process, the limitations of traditional resources and raw materials have become increasingly prominent. To meet the diverse needs of the booming industry, scientific researchers have explored various new energy sources and searched for convenient and efficient raw materials from vast natural substances and cutting-edge synthetic materials, hoping to obtain ideal raw materials with excellent performance and low cost in industrial production. Silicate minerals are a class of oxygen-containing salt minerals formed by the combination of metal cations and silicate anions, and are the main minerals constituting the earth's crust and upper mantle, accounting for more than 90% of the entire earth's crust. Many silicate minerals have become excellent and inexpensive non-metallic mineral raw materials and materials, which are urgently to be developed.
[0003] The advanced oxidation method is a key technical means for treating toxic and refractory emerging organic pollutants. It is widely used because of its fast speed and remarkable effect. As an effective method to promote the generation of free radicals in the advanced oxidation degradation system, although transition metal activation is outstanding in improving the degradation efficiency, it also faces problems such as secondary pollution and difficult recycling. Summary of the Invention
[0004] Aiming at the deficiencies of the prior art, the present invention provides a preparation method and application of a metal nanocluster-doped silicate catalyst.
[0005] The preparation method provided by the present invention simplifies the preparation process of the metal-doped catalyst and reduces the preparation cost of the catalyst material. The metal nanocluster-doped silicate catalyst prepared by the present invention has the advantages of high catalytic efficiency, high cycle stability, easy recovery, long lifespan, and high specific surface area, and also avoids problems such as secondary pollution caused by the leaching of metal ions. It is applicable to various water bodies and effectively solves the problems of poor stability, short lifespan, and limited activity faced by traditional catalysts.
[0006] The technical solution of the present invention is as follows:
[0007] A preparation method of a metal nanocluster-doped silicate catalyst, comprising the following steps:
[0008] S1. Add a certain mass of silicate mineral particles to a hydrogen peroxide solution, mix evenly to obtain a mixed solution, stir and heat. After the heating is completed, cool the reaction product, and then perform water bath ultrasonic treatment, collection, drying, and sieving to obtain silicate mineral powder.
[0009] S2. Weigh a predetermined mass of the silicate mineral powder prepared in step S1, disperse it in an ethanol aqueous solution, and perform ultrasonic treatment for 0.5 - 2 h to obtain a silicate mineral mixture. Separately, dissolve a predetermined mass of the metal compound in distilled water to make a metal compound solution with a corresponding concentration, add the metal compound solution to the silicate mineral mixture to obtain a metal compound and silicate mineral mixture, stir and heat the mixture, with the reaction temperature being 50 - 150 °C and the reaction time being 5 - 15 h. After the reaction ends, collect, wash, dry, and screen the reaction product to prepare a metal nanocluster-doped silicate catalyst.
[0010] Preferably according to the present invention, in step S1, the mass fraction of the hydrogen peroxide is 20 - 40%.
[0011] Preferably according to the present invention, in step S1, the mass percentage of the silicate mineral particles in the mixture is 0.5% - 1.5%.
[0012] Preferably according to the present invention, in step S1, the heating temperature is 80 - 150 °C and the heating time is 10 min - 60 min.
[0013] Preferably according to the present invention, in step S1, the collection centrifugation time is 30 min - 120 min and the centrifugal force is 500 g - 3000 g.
[0014] Preferably according to the present invention, in step S1, the time of water bath ultrasonic treatment is 10 min - 60 min.
[0015] Preferably according to the present invention, in step S1, the silicate mineral includes any one or more of attapulgite, diatomite, kaolin, halloysite, illite, vermiculite.
[0016] Preferably according to the present invention, in step S2, the volume fraction of the ethanol aqueous solution is 85% - 95%.
[0017] Preferably according to the present invention, in step S2, the mass percentage of the silicate mineral in the silicate mineral mixture is 0.1% - 0.5%.
[0018] Preferably according to the present invention, in step S2, the metal compound includes any one or more of NiCl2, Co(AC)2, Fe(NO3)3, MnCl2.
[0019] Preferably according to the present invention, in step S2, the molar concentration of the metal compound in the metal compound aqueous solution is 0.1 - 2 mol / L.
[0020] Preferably according to the present invention, in step S2, the concentration of the metal compound in the metal compound and silicate mineral mixture is 2.5 mM / L to 30 mM / L.
[0021] Further preferably according to the present invention, in step S2, the concentration of the metal compound in the metal compound and silicate mineral mixture is 2.9 mM / L to 15 mM / L, and the mass fraction of the silicate mineral is 0.10% to 0.20%.
[0022] More preferably, in step S2, the concentration of the metal compound in the metal compound and silicate mineral mixture is 2.9 mM / L to 6 mM / L, and the mass fraction of the silicate mineral is 0.15% to 0.18%.
[0023] Preferably, in step S2, the centrifugation time for collecting the reaction product is 5 min to 10 min, and the centrifugal force is 6000 g to 7000 g.
[0024] Preferably according to the present invention, in step S2, the washing process uses distilled water for washing 3 to 5 times in sequence.
[0025] Preferably according to the present invention, in step S1 or S2, the mesh number of the sieving is 100 - 200 meshes.
[0026] Preferably according to the present invention, in step S1 or S2, the heating process includes water bath heating, oil bath heating, tube furnace heating or oven heating.
[0027] A metal nanocluster doped silicate catalyst is prepared by the above method.
[0028] Application of the metal nanocluster doped silicate catalyst prepared by the above method in the oxidative degradation of organic pollutants in wastewater treatment.
[0029] Further preferably, in the said application, the required oxidants include one or more of sodium persulfate, potassium persulfate, potassium peroxymonosulfate, sodium persulfate, potassium periodate.
[0030] Further preferably, the organic pollutants include one or more of p-nitrophenol, bisphenol A, oxytetracycline, ciprofloxacin, phenytoin.
[0031] Preferably according to the present invention, the specific method of the above application includes the following steps:
[0032] Put the metal nanocluster doped silicate catalyst and one or more of sodium persulfate, potassium persulfate, potassium peroxymonosulfate, sodium persulfate, potassium periodate into the wastewater containing organic pollutants, at a temperature of 15 - 40 °C, and continuously stir until the organic pollutants are degraded.
[0033] The beneficial effects of the present invention at least include the following aspects:
[0034] 1. A metal nanocluster-doped silicate catalyst prepared by the present invention realizes the uniform dispersion of metal nanoclusters on the silicate mineral carrier, significantly improving the reaction performance of the catalyst and the water treatment efficiency. The metal in the catalyst exists in the form of nanoscale particles, stimulating greater metal activity. Compared with traditional catalysts, the metal nanoclusters in the silicate mineral exhibit excellent catalytic performance, maximizing the utilization rate of metal atomic sites and significantly enhancing the ability to activate potassium peroxymonosulfate, thereby achieving a substantial increase in catalytic efficiency and a significant reduction in manufacturing costs.
[0035] 2. A metal nanocluster-doped silicate catalyst proposed by the present invention fully embodies the excellent stability endowed by the unique spatial structure of silicon crystals. It not only ensures that the catalyst is not easily deteriorated in sewage water and is easy to recycle, but also endows it with excellent cyclic performance. BRIEF DESCRIPTION OF THE DRAWINGS
[0036] Figure 1 Schematic diagram of the preparation method of a metal nanocluster-doped silicate catalyst provided by the present invention (taking a metal Co compound as an example and a silicate mineral as attapulgite as an example).
[0037] Figure 2 SEM image of 10:50Co@ATP prepared in Example 2 of the present invention.
[0038] Figure 3 Pore size distribution diagram and hysteresis curve of 10:50Co@ATP prepared in Example 2 of the present invention.
[0039] Figure 4 FTIR spectrum of 10:50Co@ATP prepared in Example 2 of the present invention.
[0040] Figure 5 XRD pattern of 10:50Co@ATP prepared in Example 2 of the present invention.
[0041] Figure 6 Comparison diagram of the degradation effect of 10:50Co@ATP prepared in Example 2 of the present invention and catalysts in different systems on tetracycline.
[0042] Figure 7 Comparison diagram of the degradation effect of Co@ATP prepared in Examples 1-4 of the present invention and pure attapulgite on tetracycline.
[0043] Figure 8 Comparison diagram of the degradation effect of 10:50Co@ATP prepared in Example 2 of the present invention on different pollutants.
[0044] Figure 9 Degradation effect diagram of 10:50Co@VMT prepared in Example 7 of the present invention on TC.
[0045] Figure 10 Cyclic stability effect diagram of 10:50Co@ATP prepared in Example 2 of the present invention. Specific implementation manners
[0046] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited thereto.
[0047] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods.
[0048] Unless otherwise specified, the materials, reagents, etc. used in the following examples can all be obtained from commercial channels.
[0049] The schematic diagram of the preparation method provided by the present invention can be seen in Figure 1 .
[0050] The equipment models used in the examples are shown in Table 1.
[0051] Table 1
[0052]
[0053] The experimental method for the degradation of tetracycline (TC) organic matter by the metal nanocluster-doped silicate catalyst includes the following steps:
[0054] Measure 100 ml of deionized water in a 200 ml beaker, weigh 1 mg of TC and add it to the beaker, ultrasonicate for 30 min and then stir for 30 min to fully dissolve the TC pollutant. Then, measure the C0 value in a UV-5100 ultraviolet spectrophotometer. Weigh PMS (potassium persulfate purchased from Shandong Keyuan Biochemical Co., Ltd.) to a final concentration of 1 mM and 0.01 g of the catalyst and add them to the beaker at the same time to start timing. The degradation experiment is carried out under magnetic stirring at 180 rpm. At fixed time intervals (1, 2, 4, 6, 8, 10, 15, 20, 15, 30 min), extract about 2 mL of the reacted solution with a 10 mL syringe. After filtering through a 0.22 μm filter head, immediately detect the absorbance of TC with a UV-5100 ultraviolet spectrophotometer, and record the value as C t , detect the absorbance of TC when PMS and the catalyst are not added, and record the value as C0, and set the wavelength to 357 nm. Calculate C t / C0 with the obtained data using an Excel spreadsheet, and then calculate the average C of the parallel samples t / C0, its removal rate is obtained using the following formula. In the above experiment, the TC concentration was 10 mg / L, the PMS concentration was 1 mM, and the catalyst concentration was 0.1 g / L.
[0055]
[0056] Example 1
[0057] S1. Weigh 2 g of attapulgite (Dehang Mineral Products Co., Ltd., Lingshou County) and add it to 200 mL of 30% hydrogen peroxide solution in a four-necked flask and mix evenly. Under the stirring condition at 120 °C, heat it in an oil bath (dimethyl silicone oil) for 10 min; cool the reaction product, ultrasonicate it in a water bath for 10 min, centrifuge and collect (990×g, 60 min), dry it (in an oven at 60 °C, 12 h), and sieve it through a 200-mesh sieve to obtain the silicate mineral powder.
[0058] S2. Measure 12.5 ml of distilled water and add it to 186.5 ml of ethanol to prepare an ethanol aqueous solution. Weigh 0.35 g of the silicate mineral powder and mix it in the ethanol aqueous solution, and ultrasonicate it for 1 h to promote the uniform dispersion of the mineral powder to obtain a uniform silicate mineral mixture. Weigh 0.1062 g of cobalt acetate (Shanghai Macklin Biochemical Co., Ltd.) and dissolve it in 3 ml of distilled water to obtain a 0.2 M cobalt acetate solution. Add the cobalt acetate solution to the silicate mineral mixture and stir and heat it. The reaction temperature is 80 °C and the reaction time is 10 h. After the reaction is completed, collect the reaction product, wash it three times with distilled water, centrifuge it (6000×g, 5 min), dry it (60 °C, 12 h), and sieve it through a 100-mesh sieve to obtain a metal nanocluster-doped silicate catalyst, denoted as 5:50Co@ATP (the mass ratio of Co to ATP is 5:50).
[0059] To investigate the degradation rate of tetracycline by the 5:50Co@ATP catalyst prepared in this example, the above experimental method was used for the degradation experiment. The experiment was carried out under the condition of magnetic stirring. The degradation effect of the catalyst on tetracycline was illustrated by testing the change of the ultraviolet absorption spectrum of the solution. The results showed that after 10 min of reaction, the TC degradation rate reached 100%. Under the same conditions, the degradation rate of TC by attapulgite (ATP) was 10%. This indicates that the 5:50Co@ATP catalyst prepared in this example has a significantly improved degradation rate of TC compared with pure attapulgite alone.
[0060] Example 2
[0061] Example 2 is only different from Example 1 in that: in step S2, the mass ratio of cobalt acetate to attapulgite is different. The addition process of cobalt acetate is as follows: Weigh 0.2124 g of cobalt acetate and dissolve it in 6 ml of distilled water to obtain a 0.2 M cobalt acetate solution. Finally, a metal nanocluster-doped silicate catalyst (10:50Co@ATP) is prepared. Other steps are the same as those in Example 1 and will not be described in detail here.
[0062] To explore the catalytic effect of a metal nanocluster-doped silicate catalyst prepared in Example 2 on TC, the test conditions of Example 1 were used. The results show that the degradation rate of the catalyst prepared in this example for TC is 100% at 6 min, which is a certain improvement compared to 10 min in Example 1. Figure 6 For the comparison of the degradation effects of a metal nanocluster-doped silicate catalyst prepared in Example 2 of the present invention with catalysts in different systems on tetracycline, the results show that the degradation rate of the catalyst prepared in this example for TC has been greatly improved compared to the degradation rate of the PMS autocatalytic reaction. At the same time, the reaction rate constant has also increased significantly.
[0063] The prepared metal nanocluster-doped silicate catalyst was characterized, and SEM was used to characterize the morphology of the catalyst. Figure 2 The SEM image of a metal nanocluster-doped silicate catalyst prepared in Example 2 is shown. The catalyst presents a clear layered structure, and the layers are intertwined with each other to form a dense network architecture. This unique microstructure endows the catalyst with a large specific surface area, which can significantly increase its contact area with the reaction substrate, provide sufficient active sites for subsequent catalytic reactions, and greatly improve the efficiency of catalytic reactions. Figure 3 The pore size distribution diagram of a metal nanocluster-doped silicate catalyst prepared in Example 2 of the present invention shows that the pore size of the catalyst is distributed at 4.31 nm and 7.84 nm. This is because the loading of part of the cobalt blocks part of the pore channels of ATP. Figure 4 The FTIR spectra of a metal nanocluster-doped silicate catalyst prepared in Example 2 of the present invention, the attapulgite persulfate catalyst without cobalt loading, and pure attapulgite are shown. Figure 5 The XRD pattern of a metal nanocluster-doped silicate catalyst prepared in Example 2 of the present invention is shown. From Figure 4 and Figure 5 it can be seen that with or without cobalt loading, the crystal structure of the catalyst has not changed significantly. This indicates that a metal nanocluster-doped silicate catalyst still retains excellent physicochemical properties such as abundant surface bonding, adsorption sites, and structural hydroxyl groups of attapulgite. At the same time, it also indicates the successful loading of cobalt on the surface of attapulgite.
[0064] Example 3
[0065] Example 3 is only different from Example 1 in that: in step S2, the mass ratio of cobalt acetate to attapulgite is different. The addition process of cobalt acetate is as follows: Weigh 0.5310 g of cobalt acetate and dissolve it in 15 ml of distilled water to obtain a 0.2 M cobalt acetate solution. Finally, a metal nanocluster-doped silicate catalyst (25:50Co@ATP) is prepared. Other steps are the same as those in Example 1 and will not be elaborated here.
[0066] To explore the catalytic effect of a metal nanocluster-doped silicate catalyst prepared in Example 3 on TC, the test conditions of Example 1 were adopted. The results showed that the catalyst prepared in this example had a 100% degradation rate of TC within 3 min, which was significantly improved compared with 10 min in Example 1.
[0067] Example 4
[0068] To explore the degradation effect of attapulgite without loaded cobalt on tetracycline, a catalyst of attapulgite without loaded cobalt was prepared in Example 4. Example 4 is only different from Example 1 in that: in step S2, cobalt acetate is not added. Finally, a metal nanocluster-doped silicate catalyst (0:50Co@ATP) is prepared. Other steps are the same as those in Example 1 and will not be elaborated here.
[0069] Example 5
[0070] To explore the catalytic effects of 5:50Co@ATP, 10:50Co@ATP, 25:50Co@ATP prepared in Examples 1 - 3, pure attapulgite (pure-ATP), and the catalyst of attapulgite without loaded cobalt (0:50Co@ATP) on TC, the test conditions of Example 1 were adopted. The degradation effect on TC is as Figure 7 shown. The metal nanocluster-doped silicate catalysts prepared in Examples 1 - 3 had a 100% degradation rate of TC within 10 min, 6 min, and 3 min, which was significantly improved compared with the 60% and 76% degradation rates of pure attapulgite and the catalyst of attapulgite without loaded cobalt within 30 min. It can be Figure 7 seen that 25:50Co@ATP had the best catalytic effect on TC. In actual conditions, with the increase of cobalt loading, its leaching amount may also increase, which may cause secondary pollution. By balancing the catalytic effect and leaching amount, the catalyst prepared in Example 2 had a high catalytic efficiency for TC, that is, when the mass ratio of cobalt to attapulgite in the catalyst was 10:50, the prepared catalyst could show excellent degradation performance and less environmental impact.
[0071] Example 6
[0072] To investigate the degradation effect of the Co@ATP catalyst prepared in Example 2 on different pollutants, the degradation experimental conditions in Example 1 were used to conduct degradation tests on oxytetracycline (OTC), ciprofloxacin (CPFX), ofloxacin (OFX), and norfloxacin (NFX) respectively. The test results are as Figure 8 shown. It can be seen from the figure that under the catalytic system, OTC can achieve complete degradation at 6 min. At 30 min, the catalytic efficiencies of OFX, NFX, and CPFX are 98%, 94%, and 86% respectively. The above experimental results show that the Co@ATP / PMS catalytic system can effectively remove various pollutants. During the experiment, the reaction time can be appropriately extended to improve the catalytic efficiency of OFX, NFX, and CPFX.
[0073] Example 7
[0074] To investigate the effect of metal nanocluster-doped other silicate catalysts on antibiotics, vermiculite (VMT) was selected as the source of silicate minerals, and the 10:50Co@VMT catalyst was prepared by the method of the 10:50Co@ATP catalyst prepared in Example 2. The results of the TC degradation test are shown as Figure 9 shown, which confirms that different silicate minerals loaded with metal nanoclusters have good degradation effects on antibiotics.
[0075] In terms of the antibiotic degradation effect, the two catalysts with different silicate minerals as carriers, 10:50Co@VMT and 10:50Co@ATP, show obvious performance differences. During the degradation process of tetracycline (TC), the 10:50Co@VMT catalyst requires 10 min to reach a 100% degradation rate, while the 10:50Co@ATP catalyst only requires 6 min to reach a 100% degradation rate. This data indicates that the catalytic efficiency of the 10:50Co@ATP catalyst is more excellent than that of the 10:50Co@VMT catalyst.
[0076] From a microscopic perspective, the silicate minerals loaded by the 10:50Co@ATP catalyst have a more unique crystal structure and surface properties, which promote the more uniform dispersion of cobalt nanoclusters on its surface, greatly improving the accessibility of active sites, accelerating the mass transfer and electron transfer rates of the catalytic reaction, and significantly shortening the reaction process. When treating large-scale TC-containing wastewater, the 10:50Co@ATP can improve the degradation efficiency and, with a faster degradation rate, can significantly reduce the volume of treatment equipment and lower the operation and maintenance costs, showing obvious advantages compared with 10:50Co@VMT.
[0077] Example 8
[0078] The 10:50Co@ATP catalyst prepared in Example 2 was selected for cyclic stability experiments and actual water application to verify the stability and adaptability of the catalyst.
[0079] Cyclic stability test: After catalytic degradation of TC using the above experimental method, the solution after the reaction was centrifuged for 3 minutes at a speed of 8000r / min, the supernatant was poured off, the remaining solid material was recovered, washed with distilled water for 3 times, and dried in an oven at 60°C before being reused in subsequent TC degradation tests. The experimental results are as follows Figure 10 As shown in the figure, after the third cycle, 10:50Co@ATP still maintained a high removal rate of 100%; in the fourth cycle, the removal rate was still maintained at around 95%, so the 10:50Co@ATP catalyst showed good cyclic stability.
[0080] Application in actual water bodies: When the catalyst is applied to various water bodies that are closer to the actual situation, the 10:50Co@ATP system also shows significant treatment efficiency. When tap water, Daming Lake water, and Jiazi Lake water are used to replace the deionized water in the above experimental method of TC degradation, 10:50Co@ATP can maintain excellent degradation efficiency, and the TC removal rate is 100% within 15 minutes. This result not only illustrates the wide applicability of the 10:50Co@ATP catalyst, but also highlights its potential to effectively remove pollutants under complex and changeable actual water quality conditions.
[0081] In summary, the present invention proposes a method for preparing a metal nanocluster doped silicate catalyst, especially combining attapulgite and cobalt. By combining attapulgite and cobalt, the agglomeration of metal cobalt can be hindered, the crystallization and aggregation of metal nanomaterials can be reduced, more catalytic sites of the metal can be exposed, and the contact probability and mass transfer rate between persulfate, pollutant molecules and the catalyst can be greatly improved, so that the catalytic properties of the two can be fully exerted; the catalyst finally obtained exhibits more excellent catalytic performance; the catalyst prepared by the present invention can be recycled and has high catalytic performance.
Claims
1. A preparation method of a metal nanocluster-doped silicate catalyst, characterized in that, It includes the following steps: S1. Add silicate mineral particles of a certain mass to a hydrogen peroxide solution, mix evenly to obtain a mixed solution, stir and heat. After the heating ends, cool the reaction product, then perform water bath ultrasonic treatment, collection, drying, and sieving to obtain silicate mineral powder. S2. Weigh a predetermined mass of the silicate mineral powder prepared in step S1, disperse it in an ethanol aqueous solution, perform ultrasonic treatment for 0.5 - 2 h to obtain a silicate mineral mixed solution. Separately, dissolve a predetermined mass of a metal compound in distilled water to prepare a metal compound solution with a corresponding concentration. Add the metal compound solution to the silicate mineral mixed solution to obtain a metal compound and silicate mineral mixed solution. Stir and heat the mixed solution, with the reaction temperature being 50 - 150 °C and the reaction time being 5 - 15 h. After the reaction ends, collect, wash, dry, and sieve the reaction product to obtain a metal nanocluster-doped silicate catalyst.
2. The preparation method according to claim 1, characterized in that In step S1, the mass fraction of the hydrogen peroxide solution is 20% - 40%. Preferably, in step S1, the mass percentage of silicate mineral particles in the mixed solution is 0.5% - 1.5%. Preferably, in step S1, the heating temperature is 80 - 150 °C and the heating time is 10 min - 60 min. Preferably, in step S1, the collection centrifugation time is 30 min - 120 min and the centrifugal force is 500 g - 3000 g. Preferably, in step S1, the time of water bath ultrasonic treatment is 10 min - 60 min.
3. The preparation method according to claim 1, characterized in that, In step S1, the silicate mineral includes any one or more of attapulgite, diatomite, kaolin, halloysite, illite, and vermiculite.
4. The preparation method according to claim 1, characterized in that In step S2, the volume fraction of the ethanol aqueous solution is 85% - 95%. Preferably, in step S2, the mass percentage of silicate mineral in the silicate mineral mixed solution is 0.1% - 0.5%.
5. The preparation method according to claim 1, characterized in that, In step S2, the metal compound includes any one or more of NiCl2, Co(AC)2, Fe(NO3)3, and MnCl2. Preferably, in step S2, the molar concentration of the metal compound in the metal compound aqueous solution is 0.1 - 2 mol / L.
6. The preparation method according to claim 1, characterized in that, In step S2, the concentration of the metal compound in the metal compound and silicate mineral mixed solution is 2.5 mM / L - 30 mM / L. Preferably, in step S2, the concentration of the metal compound in the metal compound and silicate mineral mixed solution is 2.9 mM / L - 15 mM / L, and the mass fraction of the silicate mineral is 0.10% - 0.20%. Preferably, in step S2, the concentration of the metal compound in the metal compound and silicate mineral mixed solution is 2.9 mM / L - 6 mM / L, and the mass fraction of the silicate mineral is 0.15% - 0.18%. Preferably, in step S2, the collection centrifugation time of the reaction product is 5 min - 10 min and the centrifugal force is 6000 g - 7000 g.
7. The preparation method according to claim 1, characterized in that, In step S2, the washing process uses distilled water to wash 3 - 5 times in sequence. Preferably, in step S1 or S2, the sieve mesh number is 100 - 200 meshes. Preferably, in step S1 or S2, the heating process includes water bath heating, oil bath heating, tube furnace heating or oven heating.
8. A metal nanocluster-doped silicate catalyst, characterized in that, Prepared according to the method described in any one of claims 1-7.
9. Use of the metal nanocluster-doped silicate catalyst prepared by the method described in any one of claims 1-7 in the oxidative degradation of organic pollutants in wastewater treatment.
10. The application according to claim 9, characterized in that, In the said use, the oxidizing agent required includes one or more of sodium persulfate, potassium persulfate, potassium peroxymonosulfate, sodium persulfate, potassium periodate; Preferably, the organic pollutants include one or more of p-nitrophenol, bisphenol A, oxytetracycline, ciprofloxacin, phenytoin; Preferably, the specific method of the said use includes the following steps: Put the metal nanocluster-doped silicate catalyst and one or more of sodium persulfate, potassium persulfate, potassium peroxymonosulfate, sodium persulfate, potassium periodate into the wastewater containing organic pollutants, at a temperature of 15-40 °C, and continuously stir until the organic pollutants are degraded.