A (CaMn)SiOx (x=4~6) material, a preparation method thereof and application thereof in ozone catalytic water purification process

Abstract

This invention discloses a (CaMn)SiOx (x=4~6) material, its preparation method, and its application in ozone catalytic water purification. This material simultaneously degrades organophosphorus compounds and recovers phosphate ions during ozone catalytic water purification. The preparation process involves first preparing an organic ligand precursor, which is then mixed with Ca(NO3)2, Mn(CH3COO)2·4H2O, and (3-chloropropyl)trimethoxysilane in a specific ratio and subjected to a hydrothermal reaction to generate the precursor, followed by calcination in a high-temperature tube furnace. The (CaMn)SiOx (x=4~6) prepared by this invention is highly dispersed and porous, fully exposing active sites. Different sites exhibit catalytic ozone degradation of organophosphorus pollutants and phosphate adsorption. Using phenylphosphonic acid as the organophosphorus pollutant, this invention not only efficiently catalyzes the ozone degradation of phenylphosphonic acid to HPO4, but also... 2‑ It can also degrade the water by producing HPO4. 2‑ Recycling and adsorption. Through experiments and characterization, it was found that the main catalytic site of the material is oxygen vacancy, and the main adsorption site is surface hydroxyl groups.

Description

Technical Field

[0001] This invention belongs to the field of nanomaterials and water treatment technology, and relates to a (CaMn)SiOx (x=4~6) (i.e., a mixture of CaMnSiO4 and CaMnSi2O6) material, its preparation method, and its application in the ozone catalytic water purification process. Background Technology

[0002] Organophosphorus compounds are widely used in pesticides, scale inhibitors, corrosion inhibitors, detergents, flame retardants, and plasticizers. Due to the direct or indirect discharge of agricultural and urban wastewater, organophosphorus compounds are frequently detected in surface water and groundwater, leading to algal blooms and eutrophication. Some organophosphorus compounds can cause mutagenicity, teratogenicity, carcinogenicity, and nervous system disorders in humans by inhibiting acetylcholinesterase activity. Furthermore, the phosphate generated from the decomposition of organophosphorus compounds leads to abnormal growth of algae and aquatic plants. Many aquatic species rot and die due to reduced dissolved oxygen levels, forming harmful algal toxins that can pose a fatal threat to human health. This gradual deterioration of water quality ultimately results in the complete destruction of the entire ecological balance.

[0003] Ozone catalytic oxidation is a green and highly efficient advanced oxidation technology commonly used to remove recalcitrant organic pollutants from water. By utilizing a catalyst to catalyze ozone to generate abundant reactive oxygen species, it can efficiently degrade the vast majority of emerging organic pollutants in water.

[0004] In recent years, materials capable of efficiently catalyzing ozone and materials for recovering phosphate from water have attracted widespread attention from researchers. However, these two types of materials commonly found do not overlap; they only respectively catalyze ozone degradation of pollutants or recover adsorbed phosphate. When the pollutant is organophosphate, it is usually impossible to meet the application requirements of degrading organophosphate and recovering phosphate in the same process stage. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a simple and easy-to-operate method for preparing (CaMn)SiOx (x=4~6) materials, which is then applied to ozone catalytic water purification processes to simultaneously degrade organophosphorus compounds and recover phosphate ions. The prepared catalyst exhibits excellent performance in ozone catalysis and phosphate adsorption, and can be used to catalyze the ozone degradation of organophosphorus pollutants while simultaneously removing and recovering phosphate ions from wastewater.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention proposes a method for preparing (CaMn)SiOx (x=4~6) material, which can simultaneously catalyze the degradation of organic phosphorus and recover phosphate ions by ozone during ozone catalytic water purification. The preparation process is as follows: firstly, an organic ligand precursor is prepared by reacting 5-tert-butylisophthalic acid, sodium tert-butoxide and sodium citrate solution; then, it is mixed with Ca(NO3)2, Mn(CH3COO)2·4 H2O and (3-chloropropyl)trimethoxysilane and preliminarily synthesized by hydrothermal reaction; and then calcined in a tube furnace to obtain the precursor.

[0008] Preferably, the preparation method specifically includes the following steps:

[0009] S1: Add 5-tert-butylisophthalic acid powder to sodium tert-butoxide solution and stir in a high-temperature water bath;

[0010] S2: Slowly add sodium citrate solution to the above solution and continue stirring until a yellow flocculent substance is formed. Filter to obtain a yellow solid.

[0011] S3: Dissolve the yellow solid obtained in S2 in water, slowly add glacial acetic acid to adjust the pH of the solution, stir at room temperature and filter, dry the solid under vacuum to obtain the organic ligand precursor;

[0012] S4: Ca(NO3)2, Mn(CH3COO)2·4H2O, organic ligand precursor and (3-chloropropyl)trimethoxysilane are mixed evenly in proportion, stirred and transferred into a hydrothermal reactor for high-temperature hydrothermal reaction to obtain silane-coupled CaMn bimetallic MOFs material.

[0013] S5: The silane-coupled CaMn bimetallic MOFs material was filtered and separated, then dried under vacuum, and then transferred to a tube furnace for high-temperature calcination under an argon atmosphere to finally obtain highly dispersed (CaMn)SiOx (x=4~6) material.

[0014] Preferably, the precursor of the organic ligand is obtained by reacting 5-tert-butylisophthalic acid, sodium tert-butoxide, and sodium citrate solution; during the synthesis of the organic ligand precursor, glacial acetic acid is used to adjust the pH; Ca(NO3)2, Mn(CH3COO)2·4H2O, the organic ligand precursor, and (3-chloropropyl)trimethoxysilane are mixed in different proportions and subjected to hydrothermal reaction in a high-pressure reactor; the silane-coupled CaMn bimetallic MOFs material needs to be calcined at high temperature in a tube furnace.

[0015] Preferably, in step S1, the 5-tert-butylisophthalic acid powder and sodium tert-butoxide are added to 400 ml of deionized water at a molar ratio of 1:5; the temperature is 50–80 °C; and the stirring time is 1–10 h.

[0016] Preferably, in step S2, the concentration of sodium citrate solution is 0.01–2 M; and the stirring time is 1–10 h.

[0017] Preferably, in step S3, the concentration of glacial acetic acid is 0.01–2 M; the pH is adjusted to 3–5; the stirring time is 1–10 h; and the temperature of the vacuum drying oven is 60–150°C.

[0018] Preferably, in step S4, Ca(NO3)2, Mn(CH3COO)2·4H2O, the organic ligand precursor, and (3-chloropropyl)trimethoxysilane are mixed evenly in a molar ratio of (0.1-1):1:2:100; the stirring time is 1-10 h; the hydrothermal reaction temperature is 120-200°C; and the hydrothermal reaction time is 10-20 h.

[0019] Preferably, in step S5, the vacuum drying temperature is 60–150°C; the tube furnace calcination temperature is 300–700°C; and the calcination time is 1–10 hours.

[0020] Secondly, the present invention also proposes (CaMn)SiOx (x=4~6) materials prepared by the above preparation method.

[0021] Thirdly, the present invention also proposes the application of the (CaMn)SiOx (x=4~6) material as a catalyst in the ozone catalytic water purification process. Preferably, the material can simultaneously adsorb and degrade the product phosphate during the catalytic ozone degradation of organic phosphorus pollutants in water.

[0022] Furthermore, the water body mentioned is agricultural wastewater or industrial wastewater containing organophosphorus compounds.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] 1. Compared with the traditional highly dense and hard CaMnSiO4 or CaMnSi2O6, the (CaMn)SiOx (x=4~6) prepared by this method is highly dispersed and loose, which can fully expose active sites. Different sites can exhibit adsorption and catalytic effects.

[0025] 2. Different sites on the catalyst of this invention can each exhibit catalytic ozone formation and phosphate adsorption effects;

[0026] 3. The present invention enables metal ions to have a certain degree of conformational freedom and bring about diversified coordination orientations by introducing organic ligand precursors; the introduction of second ligands can increase the coordination mode of metal center and change the structure, and the introduction of functional groups brings about performance improvement.

[0027] 4. The (CaMn)SiOx (x=4~6) material prepared by this invention contains abundant oxygen vacancies. These oxygen vacancies can catalyze the production of reactive oxygen species from ozone, thereby degrading phenylphosphonic acid to generate phosphate. The hydroxyl groups attached to the oxygen vacancies can undergo ion exchange with the phosphate, resulting in the adsorption of phosphate. Attached Figure Description

[0028] Figure 1 Scanning electron microscope image of (CaMn)SiOx (x=4~6) material prepared for this invention, which can simultaneously catalyze ozone degradation of organophosphorus and recover phosphate ions;

[0029] Figure 2 X-ray diffraction image of the (CaMn)SiOx (x=4~6) material prepared in this invention, which can simultaneously catalyze ozone degradation of organophosphorus and recover phosphate ions;

[0030] Figure 3 Electron paramagnetic resonance images of (CaMn)SiOx (x=4~6) materials prepared in this invention that can simultaneously catalyze ozone degradation of organophosphorus and recover phosphate ions;

[0031] Figure 4 A comparison of the performance of the (CaMn)SiOx (x=4~6) material prepared in this invention, which can simultaneously catalyze the degradation of organophosphorus compounds by ozone and recover phosphate ions, as a catalyst for the degradation of organophosphorus pollutant phenylphosphonic acid.

[0032] Figure 5 The diagram shows a comparison of the performance of the (CaMn)SiOx (x=4~6) material prepared in this invention, which can simultaneously catalyze the degradation of organic phosphorus by ozone and recover phosphate, as a catalyst for removing phosphate from wastewater. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0034] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0035] Example 1

[0036] A (CaMn)SiOx (x=4~6) material that can simultaneously catalyze the degradation of organophosphorus compounds by ozone and recover phosphate ions is prepared by high-temperature hydrothermal calcination of Ca(NO3)2, Mn(CH3COO)2·4H2O, organic ligand precursor and (3-chloropropyl)trimethoxysilane;

[0037] Example 2

[0038] A method for preparing (CaMn)SiOx (x=4~6) material that can simultaneously catalyze ozone degradation of organophosphorus compounds and recover phosphate ions is described below:

[0039] Step 1: Add 100 mmol of 5-tert-butylisophthalic acid powder to 500 mmol of sodium tert-butoxide solution dissolved in 400 mL, and stir in a 50°C water bath for 1 h.

[0040] Step 2: Slowly add 100 mL of 0.05 M sodium citrate solution to the above solution and continue stirring for 1 hour until a yellow flocculent substance is formed. Filter to obtain a yellow solid. Dissolve the yellow solid in 250 mL of water, slowly add glacial acetic acid to adjust the pH of the solution to 3, and the concentration of glacial acetic acid is 0.01 M. After stirring, filter and vacuum dry the solid at 60 °C to obtain the organic ligand precursor.

[0041] Step 3: Mix Ca(NO3)2, Mn(CH3COO)2·4H2O, organic ligand precursor and (3-chloropropyl)trimethoxysilane in a molar ratio of 0.3:1:2:100 until homogeneous. After stirring, transfer the mixture to a hydrothermal reactor and perform high-temperature hydrothermal reaction for 10 hours at a temperature of 120℃ to obtain silane-coupled CaMn bimetallic MOFs material.

[0042] Step 4: After filtering and separating the silane-coupled CaMn bimetallic MOFs material, vacuum dry it at a temperature of 60°C. Then transfer it to a tube furnace and calcine it at a high temperature of 300°C for 2 hours under an argon atmosphere to finally obtain highly dispersed (CaMn)SiOx (x=4~6).

[0043] Example 3

[0044] The difference between this embodiment and Embodiment 2 is that the temperature of the water bath in step one is limited to 70°C.

[0045] Example 4

[0046] The difference between this embodiment and Embodiment 2 is that the stirring time in step one is limited to 10 hours.

[0047] Example 5

[0048] The difference between this embodiment and Embodiment 2 is that the stirring time in step two is limited to 10 hours.

[0049] Example 6

[0050] The difference between this embodiment and Embodiment 2 is that the concentration of glacial acetic acid in step two is 2M.

[0051] Example 7

[0052] The difference between this embodiment and Embodiment 2 is that the pH in step two is limited to 5.

[0053] Example 8

[0054] The difference between this embodiment and Embodiment 2 is that the temperature of the vacuum drying oven described in step two is limited to 150°C.

[0055] Example 9

[0056] The difference between this embodiment and Embodiment 2 is that the ratio of Ca(NO3)2, Mn(CH3COO)2·4H2O, organic ligand precursor and (3-chloropropyl)trimethoxysilane in step three is limited to 0.1:1:2:100.

[0057] Example 10

[0058] The difference between this embodiment and Embodiment 2 is that the ratio of Ca(NO3)2, Mn(CH3COO)2·4H2O, organic ligand precursor and (3-chloropropyl)trimethoxysilane in step three is limited to 0.5:1:2:100.

[0059] Example 11

[0060] The difference between this embodiment and Embodiment 2 is that the ratio of Ca(NO3)2, Mn(CH3COO)2·4H2O, organic ligand precursor and (3-chloropropyl)trimethoxysilane in step three is limited to 1:1:2:100.

[0061] Example 12

[0062] The difference between this embodiment and Embodiment 2 is that the hydrothermal reaction temperature in step three is limited to 200°C.

[0063] Example 13

[0064] The difference between this embodiment and Embodiment 2 is that the hydrothermal reaction time in step three is limited to 20 hours.

[0065] Example 14

[0066] The difference between this embodiment and Embodiment 2 is that the vacuum drying temperature in step four is limited to 150°C.

[0067] Example 15

[0068] The difference between this embodiment and embodiment 2 is that the calcination temperature of the tubular furnace in step four is limited to 700°C.

[0069] Comparative Example 1

[0070] This comparative example uses directly purchased natural calcium manganese olivine powder (CaMnSiO4).

[0071] Comparative Example 2

[0072] This comparative example uses directly purchased natural manganese calcium pyroxene powder (CaMnSi2O6).

[0073] The effectiveness of the present invention was verified by the following experiments:

[0074] Experiment 1: This experiment is a preparation experiment of a (CaMn)SiOx (x=4~6) material that can simultaneously catalyze the degradation of organophosphorus compounds by ozone and recover phosphate ions. The specific steps are as follows:

[0075] First, the organic ligand precursor was prepared: 100 mmol of 5-tert-butylisophthalic acid powder was added to 500 mmol of sodium tert-butoxide solution in 400 mL of solution, and stirred at 70°C for 1 h. 100 mL of 0.05 M sodium citrate solution was slowly added to the above solution, and stirring continued for 2 h until a yellow flocculent substance was formed. The solid was filtered to obtain a yellow solid. The yellow solid was dissolved in 250 mL of water, and 1 M glacial acetic acid was slowly added dropwise to adjust the pH to 3. After stirring at room temperature for 2 h, the solution was filtered, and the solid was dried under vacuum at 105°C to obtain the organic ligand precursor.

[0076] Ca(NO3)2, Mn(CH3COO)2·4H2O, an organic ligand precursor, and (3-chloropropyl)trimethoxysilane were mixed uniformly in a molar ratio of 1:1:2:100. After stirring for 1 h, the mixture was transferred to a hydrothermal reactor and hydrothermally heated at 180°C for 18 h to obtain silane-coupled CaMn bimetallic MOFs materials. The silane-coupled CaMn bimetallic MOFs materials were filtered and separated, then vacuum dried at 105°C, and subsequently transferred to a tube furnace and calcined at 500°C for 2 h under an argon atmosphere to finally obtain highly dispersed (CaMn)SiOx (x=4~6).

[0077] Experiment 2: Simulation of the application of (CaMn)SiOx (x=4~6) materials capable of simultaneously catalyzing ozone degradation of organophosphorus compounds and recovering phosphate ions in the efficient catalytic degradation of organophosphorus pollutant phenylphosphonic acid and degradation product HPO4 by ozone. 2- Adsorption test. Phenylphosphonic acid was dissolved in 1 L of deionized water to a concentration of 10 mg / L. The resulting solution was loaded into an ozone catalytic reactor. The (CaMn)SiOx (x=4~6) material prepared in Experiment 1, capable of simultaneously catalyzing ozone degradation of organophosphorus compounds and recovering phosphate ions, was then added to the solution in the ozone catalytic reactor at a catalyst dosage of 0.1 g / L. Ozone was continuously introduced into the reactor, and samples of phenylphosphonic acid and HPO4 in the simulated wastewater were taken at regular intervals for monitoring.2- The concentration of was used as the experimental group.

[0078] Six control groups were set up. The difference between control group 1 and the experimental group was that no catalyst was added; the difference between control group 2 and the experimental group was that the (CaMn)SiOx (x=4~6) material that can simultaneously catalyze the degradation of organophosphorus compounds by ozone and recover phosphate was replaced with the material prepared in Comparative Example 1 (directly purchased natural calcium manganese olivine powder CaMnSiO4); the difference between control group 3 and the experimental group was that (CaMn)SiOx material that can simultaneously catalyze the degradation of organophosphorus compounds by ozone and recover phosphate was added. The materials (x=4~6) were replaced with the materials prepared in Comparative Example 2 (directly purchased natural manganese calcium pyroxene powder CaMnSi2O6); the difference between control groups 4 and 5 and the experimental group was that the (CaMn)SiOx (x=4~6) material that could simultaneously catalyze the degradation of organophosphorus by ozone and recover phosphate was replaced with the materials prepared in Examples 9 and 10 (the ratio of Ca(NO3)2:Mn(CH3COO)2·4H2O:organic ligand precursor:(3-chloropropyl)trimethoxysilane was 0.1:1:2:100 and 0.5:1:2:100); the difference between control group 6 and the experimental group was that the (CaMn)SiOx (x=4~6) material that could simultaneously catalyze the degradation of organophosphorus by ozone and recover phosphate was replaced with a mixture of CaMnSiO4 and CaMnSi2O6 (1:1).

[0079] Figure 2 This indicates that the present invention is a mixture of CaMnSiO4 and CaMnSi2O6.

[0080] Figure 3 This indicates that the catalyst of the present invention contains abundant oxygen vacancies, which are essential for the degradation of phenylphosphonic acid and the adsorption of HPO4. 2- The main active site.

[0081] The experimental group and six control groups degraded phenylphosphonic acid and adsorbed HPO4. 2- The test results are as follows Figure 4 and 5 As shown.

[0082] Figure 4The results showed that after a reaction time of 30 minutes, in control group 1 without catalyst, the degradation rate of phenylphosphonic acid by pure ozone oxidation was 47.0%; in control group 2, the degradation rate of phenylphosphonic acid by catalytic ozone oxidation was 88.3%; in control group 3, the degradation rate of phenylphosphonic acid by catalytic ozone oxidation was 85.0%; in control groups 4 and 5, materials prepared under different ratios of Ca(NO3)2:Mn(CH3COO)2·4H2O:organic ligand precursor:(3-chloropropyl)trimethoxysilane (0.1:1:2:100 and 0.5:1:2:100), the degradation rates of phenylphosphonic acid by catalytic ozone oxidation were 93.1% and 95.6%, respectively; in control group 6, a mixture of CaMnSiO4 and CaMnSi2O6 (1:1), the degradation rate of phenylphosphonic acid by catalytic ozone oxidation was 86.0%. In the experimental group using (CaMn)SiOx (x=4~6) prepared in Experiment 1, which can simultaneously catalyze the degradation of organic phosphorus by ozone and recover phosphate, phenylphosphonic acid was almost completely degraded, and more than 95.0% of phenylphosphonic acid was catalytically oxidized within 1 minute.

[0083] Figure 5 This indicates that after a reaction time of 30 minutes, in control group 1 without catalyst, HPO4... 2- The continuous accumulation is due to the insufficient degradation of phenylphosphonic acid by pure ozone; in control group 2 of the purchased natural calcium manganese olivine powder CaMnSiO4, HPO4 2- The concentration initially rose to 0.37 mg / PL and then decreased to 0.2 mg / PL. This is because the catalyst was primarily used to degrade phenylphosphonic acid in the first ten minutes, and then to degrade HPO4 in the following 20 minutes. 2- Adsorption of HPO4 2- The active sites; in control group 3, which was directly purchased natural manganese calcium pyroxene powder CaMnSi2O6, HPO4 2- The concentration continued to accumulate to 0.73 mg / PL, indicating that the catalyst had no adsorption sites. In control group 4, materials prepared under different Ca(NO3)2:Mn(CH3COO)2·4H2O:organic ligand precursor:(3-chloropropyl)trimethoxysilane ratios (0.1:1:2:100) showed that HPO4... 2- The content initially accumulated to 0.52 mg / PL, then decreased to 0.43 mg / PL. In control group 5, materials prepared under different Ca(NO3)2:Mn(CH3COO)2·4H2O:organic ligand precursor:(3-chloropropyl)trimethoxysilane ratios (0.5:1:2:100) showed HPO4 content... 2- Continuously accumulating to 0.71 mg / PL; in control group 6, a mixture of CaMnSiO4 and CaMnSi2O6 (1:1), HPO4 2-The concentration initially accumulated to 0.41 mg / PL, then decreased to 0.27 mg / PL. In the experimental group using the (CaMn)SiOx (x=4~6) material prepared in Experiment 1, which can simultaneously catalyze ozone degradation of organophosphorus compounds and recover phosphate, HPO4 content was [data missing] at 5 minutes. 2- The concentration was increased to 0.14 mg / PL, after which it was almost completely adsorbed by the catalyst.

[0084] Using phenylphosphonic acid as an organophosphorus pollutant, this invention can not only efficiently catalyze the ozone degradation of phenylphosphonic acid into HPO4. 2- It can also degrade the water by producing HPO4. 2- Recycling and adsorption. Through experiments and characterization, it was found that the main catalytic site of the material is oxygen vacancy, and the main adsorption site is surface hydroxyl groups.

[0085] The (CaMn)SiOx (x=4~6) material prepared by this invention contains abundant oxygen vacancies. These oxygen vacancies can catalyze the production of reactive oxygen species from ozone, thereby degrading phenylphosphonic acid to generate phosphate. Furthermore, the hydroxyl groups attached to the oxygen vacancies can undergo ion exchange with the phosphate, resulting in the adsorption of the phosphate.

[0086] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing (CaMn)SiOx material, characterized in that, The process is as follows: First, an organic ligand precursor is prepared by reacting 5-tert-butylisophthalic acid, sodium tert-butoxide, and sodium citrate solution. Then, the prepared organic ligand precursor is mixed with Ca(NO3)2, Mn(CH3COO)2·4H2O, and (3-chloropropyl)trimethoxysilane and subjected to a hydrothermal reaction to preliminarily synthesize the precursor. Finally, it is calcined in a tube furnace to obtain the final product. The (CaMn)SiOx is a mixture of CaMnSiO4 and CaMnSi2O6.

2. The method for preparing (CaMn)SiOx material according to claim 1, characterized in that, Specifically, the steps include the following: S1: Add 5-tert-butylisophthalic acid powder to sodium tert-butoxide solution and stir in a high-temperature water bath; S2: Slowly add sodium citrate solution to the above solution and continue stirring until a yellow flocculent substance is formed. Filter to obtain a yellow solid. S3: Dissolve the yellow solid obtained in S2 in water, slowly add glacial acetic acid to adjust the pH of the solution, stir at room temperature and filter, dry the solid under vacuum to obtain the organic ligand precursor; S4: Ca(NO3)2, Mn(CH3COO)2·4H2O, organic ligand precursor and (3-chloropropyl)trimethoxysilane are mixed evenly in proportion, stirred and transferred into a hydrothermal reactor for high-temperature hydrothermal reaction to obtain silane-coupled CaMn bimetallic MOFs material. S5: The silane-coupled CaMn bimetallic MOFs material was filtered and separated, then dried under vacuum, and then transferred to a tube furnace for high-temperature calcination under an argon atmosphere to finally obtain a highly dispersed (CaMn)SiOx material.

3. The method for preparing (CaMn)SiOx material according to claim 2, characterized in that, In step S1, the molar ratio of 5-tert-butylisophthalic acid powder to sodium tert-butoxide is 1:5; the high temperature is 50-80℃; and the stirring time is 1-10h.

4. The method for preparing (CaMn)SiOx material according to claim 2, characterized in that, In step S2, the concentration of sodium citrate solution is 0.01–2 M; the stirring time is 1–10 h.

5. The method for preparing (CaMn)SiOx material according to claim 2, characterized in that, In step S3, the concentration of glacial acetic acid is 0.01–2 M; the pH is adjusted to 3–5; the stirring time is 1–10 h; and the temperature of the vacuum drying oven is 60–150°C.

6. The method for preparing (CaMn)SiOx material according to claim 2, characterized in that, In step S4, Ca(NO3)2, Mn(CH3COO)2·4H2O, organic ligand precursor, and (3-chloropropyl)trimethoxysilane are mixed evenly in a molar ratio of (0.1-1):1:2:100; the stirring time is 1-10 h; the hydrothermal reaction temperature is 120-200°C; and the hydrothermal reaction time is 10-20 h.

7. The method for preparing (CaMn)SiOx material according to claim 2, characterized in that, In step S5, the vacuum drying temperature is 60–150°C; the tube furnace calcination temperature is 300–700°C; and the calcination time is 1–10 hours.

8. (CaMn)SiOx material prepared by the preparation method according to any one of claims 1-7.

9. The application of the (CaMn)SiOx material as a catalyst in the ozone catalytic water purification process as described in claim 8, characterized in that, The material can simultaneously adsorb and degrade phosphate ions, a product of catalytic ozone degradation of organic phosphorus pollutants in water.

10. The application of the (CaMn)SiOx material as a catalyst in the ozone catalytic water purification process according to claim 9, characterized in that, The water body in question is agricultural or industrial wastewater containing organophosphorus compounds.

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