Preparation method and application of cobalt ferrite modified mesoporous silicon catalyst

Abstract

The invention discloses a cobalt ferrite modified mesoporous silicon catalyst and a preparation method and application thereof.The preparation method comprises the steps that alkyl quaternary ammonium salt, absolute ethyl alcohol, ammonia water and a silicon source are added into water, stirred and then left to stand; separating and cleaning the white precipitate to obtain a mesoporous silicon material containing a template agent; and putting the mesoporous silicon material containing the template agent and cobalt ferrite into a mortar, fully grinding, and calcining to obtain the cobalt ferrite modified mesoporous silicon catalyst. As the mesoporous silicon material has the characteristics of large specific surface area and highly ordered mesoporous structure, the cobalt ferrite particles can be effectively dispersed, and the problems that the cobalt ferrite particles are easy to agglomerate, low in persulfate activation performance and the like are solved. The cobalt ferrite modified meso-porous silicon catalyst is synthesized through a grinding-calcining one-step method, the method has the advantages that a meso-porous silicon template agent is removed and cobalt ferrite is dispersed and fixed on meso-porous silicon at the same time, the energy consumption is reduced, the cost is saved, and the material synthesis period is shortened; the mesoporous silicon catalyst disclosed by the invention is applied to removal of sulfonamide antibiotics in a water environment.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation and application of cobalt ferrite modified mesoporous silicon catalytic materials, and specifically discloses a preparation method and application of a cobalt ferrite modified mesoporous silicon catalyst. Background Art

[0002] Sulfonamide antibiotics, as new pollutants, pose a serious threat to aquatic life and human health due to their high biological toxicity, stable properties and difficulty in degradation. The advanced oxidation process based on persulfate has a high redox potential (2.5-3.1V) and a long half-life (30-40μs), and has good oxidation ability for difficult-to-degrade organic pollutants, and has been widely used. There are many ways to activate persulfate. Among them, cobalt ferrite, as a common spinel bimetallic oxide, is often used to activate persulfate to degrade organic pollutants in the water environment because of its multiple transition metal element valence states, high electronic conductivity and good chemical stability. However, due to the disadvantage of easy agglomeration of cobalt ferrite materials, the persulfate activation efficiency and sulfonamide antibiotic degradation efficiency in its persulfate activation system are low, the catalyst and persulfate dosage are high, and other problems exist.

[0003] Although the modification method is one of the effective methods to overcome the easy agglomeration of cobalt ferrite, the commonly used modification methods such as impregnation-calcination method and co-precipitation method have problems such as complex reaction system, long reaction time, and large amount of waste liquid generated. In addition, the metal ions on the modified cobalt ferrite material are leached into water at a high concentration, which not only easily causes secondary pollution of the water environment, but also affects the regeneration and reuse efficiency of the cobalt ferrite modified material.

[0004] Mesoporous silica materials are a type of molecular sieve materials with a unique pore structure. They have large specific surface area, well-developed pores, and regular and orderly pore arrangement, making them good cobalt ferrite carriers. However, when preparing cobalt ferrite-modified mesoporous silica materials, it is usually necessary to remove the template agent on the mesoporous silica before using impregnation-calcination method, coprecipitation method and other methods to synthesize cobalt ferrite-modified mesoporous silica materials. Therefore, not only do they have the common problems of impregnation-calcination method, coprecipitation method and other methods, but they also increase the number of operating steps, making the preparation process more complicated. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a method for preparing a cobalt ferrite modified mesoporous silicon catalyst, aiming to solve the problems in the prior art that cobalt ferrite is easy to agglomerate, has low activation performance, has a large amount of catalyst and persulfate added, a large amount of metal leaching, has poor regeneration cycle performance, and the preparation method of cobalt ferrite modified mesoporous silicon material is complicated. The second purpose of the present invention is to provide an application of a cobalt ferrite modified mesoporous silicon catalyst to remove organic pollutants such as sulfonamide antibiotics.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions: A method for preparing a cobalt ferrite modified mesoporous silicon catalyst, characterized in that it comprises the following steps: 1): Add alkyl quaternary ammonium salt, anhydrous ethanol, ammonia water and silicon source into water in sequence, stir evenly and let stand; 2): Separate and wash the white precipitate after standing to obtain a mesoporous silicon material containing a template agent; 3): Put the mesoporous silicon material containing the template and cobalt ferrite into a mortar and grind for the time required by the process; 4): The ground material is calcined in an air atmosphere to obtain a cobalt ferrite modified mesoporous silicon catalyst.

[0007] Furthermore, in step 1), the mass ratio of water to alkyl quaternary ammonium salt is 200:1.30-1.80, and the water, anhydrous The volume ratio of ethanol, ammonia water and silicon source is 70~90:20~28:7~9:1.5~2.5.

[0008] Furthermore, in the step 1), the stirring time is 30 min to 120 min, and the standing time is 12-20 h.

[0009] Furthermore, in step 2), the white precipitate is washed with water 2-4 times to remove excess reagents adsorbed on the surface of the material.

[0010] Furthermore, in the step 3), the mass ratio of the mesoporous silicon material containing the template agent to cobalt ferrite is 1:0.25-0.70.

[0011] Furthermore, in step 3), the grinding time in the mortar is 20 to 60 minutes.

[0012] Furthermore, in step 4), the calcination method is a tubular furnace or a muffle furnace.

[0013] Furthermore, in the step 4), the calcination temperature is 500-600° C., the heating rate is 2-5° C. / min, and the holding time is 4-6 h.

[0014] An application of a cobalt ferrite modified mesoporous silicon catalyst prepared by the above-mentioned cobalt ferrite modified mesoporous silicon catalyst preparation method, characterized in that it is applied to remove sulfonamide antibiotics in an aquatic environment.

[0015] Furthermore, the specific steps of applying the cobalt ferrite modified mesoporous silicon catalyst to remove sulfonamide antibiotics are as follows: adding the cobalt ferrite modified mesoporous silicon catalyst to a solution containing sulfonamide antibiotics, and then adding persulfate to degrade the sulfonamide antibiotics; after the reaction is completed, separating the cobalt ferrite modified mesoporous silicon material with a magnet, washing and drying it with water, and then reusing it.

[0016] Furthermore, the persulfate is any one of sodium persulfate, potassium persulfate, potassium hydrogen persulfate, and sodium hydrogen persulfate, or any two of them are mixed in a ratio greater than 0%, or any several of them are mixed in a ratio greater than 0%, or four of them are mixed in a ratio greater than 0%.

[0017] Compared with the prior art, the present invention has the following beneficial effects: 1. The "grinding-calcination" one-step method for preparing a cobalt ferrite-modified mesoporous silicon catalyst provided by the present invention can simultaneously remove the template agent and synthesize the cobalt ferrite-modified mesoporous silicon catalyst, thereby simplifying the operating steps of the system, reducing energy consumption, saving production costs, and shortening production time.

[0018] 2. The present invention adopts a one-step "grinding-calcination" method to synthesize the cobalt ferrite modified mesoporous silicon catalyst, which can effectively overcome the disadvantage that cobalt ferrite is easy to agglomerate and deactivate, and further improve its activation efficiency for persulfate.

[0019] 3. The cobalt ferrite modified mesoporous silicon catalyst prepared by the present invention is used in the application of efficient activation of persulfate to remove sulfonamide antibiotics. The dosage of catalyst and persulfate is small, the activation of persulfate has high efficiency in degrading sulfonamide antibiotics, the leaching amount of cobalt and iron ions on the catalyst is small, no secondary pollution is caused, and it is environmentally friendly.

[0020] 4. The cobalt ferrite modified mesoporous silicon catalyst prepared by the present invention can realize material recovery by means of an external magnetic field, and can be recycled after simple water washing and drying. When recycled, it still has good efficiency in activating persulfate to remove sulfonamide antibiotics, and is a type of high-efficiency, low-energy, recyclable and reusable catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 X-ray diffraction patterns of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 of the present invention and the mesoporous silicon and cobalt ferrite prepared in the comparative example.

[0022] Figure 2 High-resolution transmission electron microscopy images of the cobalt ferrite-modified mesoporous silicon catalyst prepared in Example 1 of the present invention and the mesoporous silicon prepared in the comparative example.

[0023] Figure 3 Field emission scanning electron microscope images of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 of the present invention and the mesoporous silicon and cobalt ferrite prepared in the comparative example.

[0024] Figure 4 This is a hysteresis curve diagram of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 of the present invention.

[0025] Figure 5 This is a graph showing the removal efficiency of sulfamethoxazole by the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 of the present invention and the mesoporous silicon and cobalt ferrite prepared in the comparative example.

[0026] Figure 6 This is a graph showing the efficiency of sulfamethoxazole degradation by activating different concentrations of potassium persulfate using the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 of the present invention.

[0027] Figure 7 This is a graph showing the efficiency of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 of the present invention in activating potassium persulfate at different dosages to degrade sulfamethoxazole.

[0028] Figure 8 This is a graph showing the amount of metal ions precipitated from the cobalt ferrite-modified mesoporous silicon catalyst prepared in Example 1 of the present invention in an aqueous solution.

[0029] Fig. 9 This is a cyclic regeneration performance diagram of the degradation of sulfamethoxazole by activating potassium persulfate with the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 of the present invention.

[0030] Fig.10 The degradation efficiency of sulfamethoxazole in different actual water bodies is shown in the graph of the cobalt ferrite modified mesoporous silicon catalyst activated with potassium persulfate prepared in Example 1 of the present invention.

[0031] Fig.11 This is a graph showing the efficiency of sulfamethoxazole degradation by activating potassium persulfate with the cobalt ferrite modified mesoporous silicon catalyst prepared in Examples 6 and 7 of the present invention. DETAILED DESCRIPTION

[0032] In the following, some embodiments of the present invention are described in detail in conjunction with the accompanying drawings, and the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by ordinary technicians in this field based on the present invention belong to the scope of protection of the present invention.

[0033] The present invention provides a method for preparing a cobalt ferrite modified mesoporous silicon catalyst, comprising the following steps: Step 1): Add alkyl quaternary ammonium salt, anhydrous ethanol, ammonia water and silicon source to water in sequence, stir evenly and let stand for the time required by the process; these components will react chemically when added, and the silicon source will hydrolyze and crosslink around the template alkyl quaternary ammonium salt under the alkaline conditions created by ammonia water, thereby forming a mesoporous silicon material containing a template with a hexagonal liquid crystal phase structure. The addition of anhydrous ethanol can change the hydrolysis and crosslinking rate of the silicon source, so that the mesoporous silicon molecular sieve material forms spherical particles.

[0034] Step 2): separating and washing the white precipitate after standing to obtain a mesoporous silicon material containing a template agent; Step 1) After adding these reagents in sequence, a chemical reaction will occur to produce a white precipitate. The template agent is an alkyl quaternary ammonium salt, which acts as a template agent. After removing the template agent, an ordered pore can be obtained.

[0035] Step 3): The mesoporous silicon material containing the template and cobalt ferrite are put into a mortar and ground thoroughly; The purpose of grinding is to mix the mesoporous silicon material containing the template agent and the cobalt ferrite evenly, so that the cobalt ferrite can be evenly loaded on the mesoporous silicon after calcination.

[0036] Step 4): The ground material is fully calcined in an air atmosphere. The calcination process requires time to obtain a cobalt ferrite modified mesoporous silicon catalyst.

[0037] Furthermore, in step 1), the mass ratio of water to alkyl quaternary ammonium salt is 200:1.30-1.80, and the volume ratio of water, anhydrous ethanol, ammonia water and silicon source is 70-90:20-28:7-9:1.5-2.5.

[0038] Furthermore, in step 1), the stirring time is 30 min to 120 min, and the standing time is 12-20 h.

[0039] Furthermore, in step 2), the white precipitate is washed with water 2-4 times.

[0040] Furthermore, in step 3), the mass ratio of the mesoporous silicon material containing the template agent to cobalt ferrite is 1:0.25-0.70.

[0041] Furthermore, in step 3), the grinding time in the mortar is 20 to 60 minutes.

[0042] Furthermore, in step 4), the calcination method is calcination in any one of a tubular furnace and a muffle furnace.

[0043] Furthermore, in step 4), the calcination temperature is 500-600° C., the heating rate is 2-5° C. / min, and the holding time is 4-6 h.

[0044] The cobalt ferrite modified mesoporous silicon catalyst for highly efficient persulfate activation prepared by the above method is used in the degradation of sulfonamide antibiotics, an organic pollutant in water, to degrade sulfonamide antibiotics, an organic pollutant in water.

[0045] The specific steps of using the cobalt ferrite modified mesoporous silicon catalyst with high efficiency persulfate activation prepared by the above method in degrading sulfonamide antibiotics, an organic pollutant in water, are as follows: adding the cobalt ferrite modified mesoporous silicon catalyst to a solution containing sulfonamide antibiotics, and then adding persulfate to degrade the sulfonamide antibiotics to achieve the reaction time required by the process; after the reaction is completed, separating the cobalt ferrite modified mesoporous silicon catalyst material with a magnet, and then washing and drying it with water for repeated reuse.

[0046] Furthermore, the persulfate is any one of sodium persulfate, potassium persulfate, potassium hydrogen persulfate, and sodium hydrogen persulfate, or any two of them are mixed in a ratio greater than 0%, or any three of them are mixed in a ratio greater than 0%, or four of them are mixed in a ratio greater than 0%.

[0047] Example 1 This embodiment provides a method for preparing a cobalt ferrite modified mesoporous silicon catalyst, comprising the following steps: Step 1): 24 g of alkyl quaternary ammonium salt, 1.0 L of anhydrous ethanol, 320 mL of ammonia water and 80 mL of ethyl orthosilicate were added to 3.2 L of water in sequence, stirred evenly for 30 min and then allowed to stand for 12 h.

[0048] Step 2): The white precipitate after standing is filtered and washed with water three times to obtain a mesoporous silica material containing a template agent.

[0049] Step 3): 3 g of mesoporous silicon material containing a template and 1.2 g of cobalt ferrite were put into a mortar and ground for 30 min.

[0050] Step 4): Take out the ground material and put it into a tubular furnace, raise the temperature to 550°C at 2°C / min and calcine in air for 5 hours to obtain the cobalt ferrite modified mesoporous silicon catalyst.

[0051] Comparative Example The cobalt ferrite is obtained from commercial cobalt ferrite, and the mesoporous silicon is obtained by calcining the mesoporous silicon material containing the template in step 2) of Example 1 in the same manner and under the same calcination parameters as in step 4).

[0052] Figure 1 The X-ray diffraction patterns of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 and the mesoporous silicon material and cobalt ferrite in the comparative example are shown in FIG. Figure 1It can be seen that the diffraction peak of the mesoporous silicon material appears near 2θ=21-24°, which is the characteristic peak of mesoporous silicon. The diffraction peaks of cobalt ferrite appear at 2θ=18.4°, 30.2°, 35.5°, 43.2°, 53.6°, 57.3°, and 62.8°, corresponding to the (111), (220), (311), (400), (422), (511), and (440) crystal planes of cobalt ferrite, respectively. The X-ray diffraction pattern of the cobalt ferrite-modified mesoporous silicon catalyst prepared by the method of Example 1 shows 8 diffraction peaks, and the peak angle does not change, which is consistent with the characteristic peaks of the mesoporous silicon material and cobalt ferrite, indicating that cobalt ferrite is successfully loaded on mesoporous silicon.

[0053] Figure 2 and Figure 3 The high-resolution transmission electron microscopy and field emission scanning electron microscopy images of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 and the mesoporous silicon material in the comparative example are shown respectively. Figure 2 , 3 It can be seen that the mesoporous silicon material has ordered mesoporous channels and a spherical morphology. The cobalt ferrite modified mesoporous silicon catalyst synthesized by the method of Example 1 does not change the ordered mesoporous channels and spherical morphology characteristics of the mesoporous silicon material, and the cobalt ferrite is effectively dispersed and fixed on the mesoporous silicon.

[0054] Figure 4 is the hysteresis regression curve of the cobalt ferrite modified mesoporous silicon catalyst in Example 1. Figure 4 It can be seen that the saturation magnetization intensity (Ms) of the cobalt ferrite modified mesoporous silica catalyst is 23.05emu / g, indicating that the cobalt ferrite modified mesoporous silica catalyst has strong magnetic properties, which is conducive to rapid separation from the aqueous solution after the degradation experiment.

[0055] Sulfamethoxazole is a typical broad-spectrum sulfonamide antibiotic in life, widely present in environmental water bodies, and poses a potential threat to aquatic organisms and humans. The cobalt ferrite modified mesoporous silicon catalyst prepared in this example and the mesoporous silicon and cobalt ferrite materials of the comparative example are used to activate potassium persulfate to test their degradation performance on sulfamethoxazole, comprising the following steps: 20 mg of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 and the mesoporous silicon and cobalt ferrite in Comparative Example 1 were added to 100 mL of sulfamethoxazole solution with an initial concentration of 10 mg / L, and 0.15 mmol / L potassium persulfate (PMS) was added to initiate the degradation experiment of sulfamethoxazole; the initial pH of the solution was 7. After sampling for a certain period of time, the concentration of sulfamethoxazole remaining in the solution was determined by high performance liquid chromatography.

[0056] like Figure 5As shown, the removal rates of sulfamethoxazole by mesoporous silicon, cobalt ferrite and cobalt ferrite modified mesoporous silicon materials were less than 10% in 30 minutes, indicating that these three types of materials had almost no adsorption effect on sulfamethoxazole. The removal rate of sulfamethoxazole by potassium persulfate (0.15mmol / L) alone was 24.45% in 30 minutes. The removal efficiency of sulfamethoxazole by mesoporous silicon material and cobalt ferrite activated potassium persulfate was 24.7% and 38.8%, respectively, indicating that mesoporous silicon had almost no ability to activate potassium persulfate composite salt to degrade sulfamethoxazole. Although cobalt ferrite had the ability to activate potassium persulfate, its removal rate of sulfamethoxazole was low. The efficiency of removing sulfamethoxazole by activating potassium persulfate with the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 could reach 96.72%, indicating that the cobalt ferrite modified mesoporous silicon catalyst prepared in the present invention could efficiently activate potassium persulfate to degrade and remove sulfamethoxazole.

[0057] Example 2 This application example provides an application of a cobalt ferrite-modified mesoporous silicon catalyst, comprising the following steps: 20 mg of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 was added to 100 mL of a sulfamethoxazole solution with an initial concentration of 10 mg / L. 0.15 mmol / L, 0.2 mmol / L and 0.3 mmol / L of potassium persulfate were added to different beakers under the same conditions to initiate a degradation experiment of sulfamethoxazole. The initial pH of the solution was 7, and the concentration of sulfamethoxazole remaining in the solution was determined by high performance liquid chromatography after sampling at a certain time.

[0058] like Figure 6 It can be seen that when the concentration of potassium persulfate is 0.15 mmol / L, 0.2 mmol / L and 0.3 mmol / L, the removal efficiency of the cobalt ferrite modified mesoporous silicon catalyst in Example 1 for sulfamethoxazole is 96.82%, 95.82% and 97.89%, respectively, indicating that at a lower concentration of potassium persulfate, the cobalt ferrite modified mesoporous silicon catalyst in Example 1 can efficiently remove sulfamethoxazole.

[0059] Example 3 This embodiment provides an application of a cobalt ferrite modified mesoporous silicon catalyst, comprising the following steps: 20 mg, 30 mg and 40 mg of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 were added to 100 mL of a sulfamethoxazole solution with an initial concentration of 10 mg / L, and then 0.15 mmol / L of potassium persulfate was added to initiate the degradation experiment of sulfamethoxazole. The initial pH of the solution was 7. After sampling at a certain time, the concentration of sulfamethoxazole remaining in the solution was determined by high performance liquid chromatography.

[0060] like Figure 7It can be seen that at dosages of 0.2 g / L, 0.3 g / L and 0.4 g / L, the removal efficiency of sulfamethoxazole by the cobalt ferrite modified mesoporous silicon catalyst activated with potassium persulfate prepared in Example 1 was 96.82%, 96.60% and 96.92%, respectively, indicating that at a lower dosage, the cobalt ferrite modified mesoporous silicon catalyst still has a significant effect on the degradation of sulfamethoxazole.

[0061] Example 4 This embodiment provides an application of a cobalt ferrite modified mesoporous silicon catalyst, comprising the following steps: Take 20 mg of the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 and add it to 100 mL of sulfamethoxazole solution with an initial concentration of 10 mg / L, and add 0.15 mmol / L of potassium persulfate to initiate the degradation experiment of sulfamethoxazole. The initial pH of the solution is 7. After sampling for a certain period of time, the concentration of sulfamethoxazole remaining in the solution is determined by high performance liquid chromatography. After the degradation is completed, the metal ion content leached in the solution after the reaction is determined by an inductively coupled plasma spectrometer, and the cobalt ferrite modified mesoporous silicon catalyst is separated by a magnet, washed with water and dried, and the above degradation experiment process is repeated. like Figure 8 As shown in the figure, the amount of cobalt ions and iron ions leached from the cobalt ferrite modified mesoporous silicon catalyst is 0.080 mg / L and 0.061 mg / L, respectively, indicating that mesoporous silicon can not only effectively disperse the cobalt ferrite particles, but also fix the cobalt ferrite particles, reduce the amount of cobalt ions and iron ions leached, and avoid secondary pollution. After 5 experiments, the removal efficiency of sulfamethoxazole by the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 is still 81.57% (such as Fig. 9 As shown), it shows that the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 1 is relatively stable, can achieve the goal of long-term repeated use, and reduce operating costs.

[0062] Example 5 This embodiment provides an application of a cobalt ferrite modified mesoporous silicon catalyst, comprising the following steps: 20 mg of the cobalt ferrite modified mesoporous silicon catalyst obtained in Example 1 was added to 100 mL of tap water, lake water and secondary effluent from a sewage treatment plant containing 10 mg / L sulfamethoxazole solution, and 0.15 mmol / L potassium persulfate was added to initiate the degradation experiment of sulfamethoxazole. After sampling at a certain time, the concentration of sulfamethoxazole remaining in the solution was determined by high performance liquid chromatography.

[0063] like Fig.10 As shown, the removal efficiency of sulfamethoxazole in different actual water bodies by cobalt ferrite modified mesoporous silica catalyst activated with potassium persulfate is still above 77%, indicating that cobalt ferrite modified mesoporous silica catalyst still has a significant removal effect on sulfamethoxazole in actual water bodies.

[0064] Example 6 The masses of the mesoporous silicon material and cobalt ferrite containing the template in step 3) of Example 1 were adjusted to 2.52 g and 1.68 g, respectively, and the parameters and order of other steps were kept unchanged. 20 mg of the obtained cobalt ferrite-modified mesoporous silicon catalyst was added to 100 mL of sulfamethoxazole solution with an initial concentration of 10 mg / L, and 0.15 mmol / L of potassium persulfate was added to initiate the degradation of sulfamethoxazole. The initial pH of the solution was 7. After sampling at a certain time, the concentration of sulfamethoxazole remaining in the solution was determined using high performance liquid chromatography. Fig.11 As shown, the removal efficiency of sulfamethoxazole by potassium persulfate activated with the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 6 can reach 86.38%.

[0065] Example 7 The masses of the mesoporous silicon material and cobalt ferrite containing the template in step 3) of Example 1 were adjusted to 3.36 g and 0.84 g, respectively, and the parameters and order of other steps were kept unchanged. 20 mg of the obtained cobalt ferrite-modified mesoporous silicon catalyst was added to 100 mL of sulfamethoxazole solution with an initial concentration of 10 mg / L, and 0.15 mmol / L of potassium persulfate was added to initiate the degradation of sulfamethoxazole. The initial pH of the solution was 7. After sampling at a certain time, the concentration of sulfamethoxazole remaining in the solution was determined using high performance liquid chromatography. Fig.11 As shown, the removal efficiency of sulfamethoxazole by potassium persulfate activated by the cobalt ferrite modified mesoporous silicon catalyst prepared in Example 7 is 73.60%.

[0066] The above are only several embodiments of the present invention, which cannot be used to limit the scope of the present invention in any form. Any technician familiar with the field, without departing from the scope of the technical rights of the present invention, using all or part of the processes of the above-described embodiments to make changes or modifications are equivalent to equivalent implementation cases and fall within the protection scope of the present invention.

Claims

1. A method for preparing a cobalt ferrite modified mesoporous silicon catalyst, characterized in that: The following steps are involved: 1): Add alkyl quaternary ammonium salt, anhydrous ethanol, ammonia water and silicon source into water in sequence, stir evenly and let stand; : separating and washing the white precipitate after standing to obtain a mesoporous silicon material containing a template agent; 3): Put the mesoporous silicon material containing the template and cobalt ferrite into a mortar and grind for the time required by the process; 4): The ground material is calcined in an air atmosphere to obtain a cobalt ferrite modified mesoporous silicon catalyst.

2. The method for preparing the cobalt ferrite modified mesoporous silicon catalyst according to claim 1, characterized in that: In the step 1), the mass ratio of water to alkyl quaternary ammonium salt is 200:1.30-1.80, and the volume ratio of water, anhydrous ethanol, ammonia water and silicon source is 70-90:20-28:7-9:1.5-2.

5.

3. The method for preparing a cobalt ferrite modified mesoporous silicon catalyst according to claim 1, wherein The characteristic is that in the step 1), the stirring time is 30 min to 120 min, and the standing time is 12-20 h.

4. The method for preparing a cobalt ferrite modified mesoporous silicon catalyst according to claim 1, wherein The method is characterized in that the white precipitate is washed with water 2-4 times to remove excess reagent adsorbed on the surface of the material.

5. The method for preparing a cobalt ferrite modified mesoporous silicon catalyst according to claim 1, wherein The invention is characterized in that the mass ratio of the mesoporous silicon material containing the template agent to the cobalt ferrite in the step 3) is 1:0.25-0.

70.

6. The method for preparing a cobalt ferrite modified mesoporous silicon catalyst according to claim 1, characterized in that: The grinding time in the mortar in step 3) is 20 to 60 minutes.

7. The method for preparing a cobalt ferrite modified mesoporous silicon catalyst according to claim 1, characterized in that: The calcination method in step 4) is a tubular furnace or a muffle furnace.

8. The method for preparing a cobalt ferrite modified mesoporous silicon catalyst according to claim 1, characterized in that: In the step 4), the calcination temperature is 500-600° C., the heating rate is 2-5° C. / min, and the holding time is 4-6 hours.

9. An application of a cobalt ferrite modified mesoporous silicon catalyst prepared by the method for preparing a cobalt ferrite modified mesoporous silicon catalyst according to any one of claims 1 to 8, characterized in that: Used to remove sulfonamide antibiotics in water environments.

10. Use of the cobalt ferrite modified mesoporous silicon catalyst prepared by the method for preparing the cobalt ferrite modified mesoporous silicon catalyst according to claim 9, characterized in that: The specific steps of applying the cobalt ferrite modified mesoporous silicon catalyst to remove sulfonamide antibiotics are as follows: adding the cobalt ferrite modified mesoporous silicon catalyst to a solution containing sulfonamide antibiotics, and then adding persulfate to degrade the sulfonamide antibiotics; after the reaction is completed, separating the cobalt ferrite modified mesoporous silicon material with a magnet, washing and drying it with water, and then reusing it.

11. Use of the cobalt ferrite modified mesoporous silicon catalyst prepared by the method for preparing the cobalt ferrite modified mesoporous silicon catalyst according to claim 10, characterized in that: The persulfate is any one of sodium persulfate, potassium persulfate, potassium hydrogen persulfate, and sodium hydrogen persulfate, or any two of them are mixed in a ratio greater than 0%, or any several of them are mixed in a ratio greater than 0%, or four of them are mixed in a ratio greater than 0%.

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