SiO2@C@MnOx nanomaterial, and preparation method and application thereof

Abstract

The application belongs to the technical field of catalyst materials, and particularly relates to SiO2@Graphitized carbon@MnO x (abbreviated as SiO2@C@MnO x ) nanomaterial, a preparation method and application thereof. The nanomaterial takes silica inert material as an initial carrier, and can be prepared into the SiO2@C@MnO x nanomaterial through simple hydrothermal-heat treatment by adjusting glucose solution concentration, manganese ion concentration of a manganese salt solution, hydrothermal reaction and heat treatment temperature. The material disclosed by the application weakens the strong interaction of Si-O-Mn bonds between manganese oxide and silica on the surface of silica by introducing graphitized carbon layers, improves the abundance of low-valence Mn, promotes the interface catalytic activity of the material, in addition, the carbon layer can also improve the local hydrophobic property and electron transport efficiency of the material as a catalyst, and has the ability of efficiently catalyzing ozone oxidation degradation of organic pollutants in water.

Description

Technical Field

[0001] This invention belongs to the field of catalyst materials technology. More specifically, it relates to a SiO2@C@MnOx nanomaterial, its preparation method, and its applications. Background Technology

[0002] With the rapid development of industry, agriculture, and the economy, water pollution has become increasingly severe worldwide. Various toxic and harmful substances discharged into water bodies seriously threaten the ecological environment and human health. Ozone catalytic oxidation technology is an advanced oxidation method that combines ozone oxidation with a catalyst. It has advantages such as wide adaptability to pollutant types and concentrations, high oxidation efficiency, and simple reaction operation conditions. During catalytic ozone oxidation, the catalyst promotes the rapid decomposition of ozone to generate various reactive oxygen species (such as hydroxyl radicals, singlet oxygen, and surface oxygen atoms). This can be used to effectively degrade highly stable and recalcitrant organic pollutants that are difficult to oxidize with ozone alone, thereby achieving deep oxidation and maximizing the removal of organic pollutants.

[0003] Silicon, as an inorganic substance widely found in nature, comprises a rich variety of compounds with diverse morphologies, such as silica spheres and porous silica of various pore sizes. Due to its low cost, availability, relatively stable chemical properties, ability to create unique pore structures, tunable acidity, and low production cost, it has gradually become one of the most important solid catalysts in modern industry. In the field of ozone catalytic oxidation, the abundant Si-OH groups on the silicon surface can serve as anchoring sites for metal Mn ions. The resulting Si-O-Mn bonds exhibit strong metal-support interactions, significantly regulating and stabilizing the electronic structure of Mn. This has led to numerous studies using silicon as a support for supported manganese oxides. For example, Chinese patent application CN112354543A discloses an adsorption-catalytic ozonation catalyst and its preparation method and application, which uses copper and manganese supported on macroporous spherical silica to improve the insufficient ozone catalytic activity of single metal oxides. However, this method requires two metal oxides to achieve good catalytic activity, and the strong metal-support interactions of the formed Si-O-Mn bonds result in a low degree of Mn reduction on the catalyst, failing to fully utilize the catalytic activity of the abundant low-valence Mn. Therefore, there is an urgent need to develop a Mn-based catalytic material with a high degree of Mn reduction and that can fully utilize the catalytic activity of abundant low-valence Mn. Summary of the Invention

[0004] The technical problem to be solved by this invention is to overcome the defects and shortcomings of the low reduction degree of Mn in existing silicon-supported Mn-based nanomaterials, and to provide a SiO2@C@MnO material with a high reduction degree of Mn and full utilization of the catalytic activity of abundant low-valence Mn. x Nanomaterial, SiO2@C@MnOx Nanomaterials containing weak Si-O-Mn bond interactions, abundant low-valence Mn, and exhibiting local hydrophobicity and high electron transport efficiency, along with simple preparation processes and low costs, can be used as ozone catalysts to efficiently catalyze the ozone oxidation and degradation of organic pollutants.

[0005] The purpose of this invention is to provide a SiO2@C@MnO x Preparation methods of nanomaterials.

[0006] Another object of the present invention is to provide a SiO2@C@MnO x Applications of nanomaterials.

[0007] The above-mentioned objective of this invention is achieved through the following technical solution:

[0008] A SiO2@C@MnO x The preparation method of nanomaterials specifically includes the following steps:

[0009] A silica inert support was placed in a mixed solution of glucose and manganese salt to form a suspension. A hydrothermal reaction was then carried out at 120–220 °C, followed by post-treatment to obtain a core-shell structured SiO2@C@MnO. x Precursor; SiO2@C@MnO x The precursor was heat-treated at 500–900 °C in an inert atmosphere, and after cooling, SiO2@C@MnO was obtained. x Nanomaterials;

[0010] The glucose concentration in the mixed solution is 0.02–0.2 mol / L; the manganese ion molar concentration in the mixed solution is 0.01–0.1 mol / L; and the post-treatment is conventional filtration, washing, and drying.

[0011] In existing methods for preparing silicon-supported manganese oxide nanomaterials, the Si-O-Mn bonds formed by the Si-OH groups on the surface anchoring Mn ions exhibit strong metal-support interactions, resulting in a relatively low degree of Mn reduction on the catalyst. To overcome this deficiency, this invention proposes a SiO2@C@MnO... x Nanomaterials, through a simple hydrothermal-thermal treatment process, introduce a graphitized carbon layer between the support and manganese oxide, which modulates interfacial forces, improves local hydrophobicity of the surface, and promotes electron transport. When applied to the field of ozone catalysis, they can achieve better catalytic activity.

[0012] In a hydrothermal-thermal treatment process, an inert support of silica was uniformly mixed with solutions containing different amounts of glucose and manganese salts. After hydrothermal reaction at a certain temperature for a certain time, the mixture was cooled to room temperature, filtered, washed, and dried to obtain core-shell SiO2@C@MnO with different carbon contents. x The precursor is then heat-treated in an inert atmosphere at a certain temperature for a certain time, and after cooling, SiO2@C@MnO is obtained. x The final product of nanomaterials.

[0013] The hydrothermal reaction process aims to form a core-shell structure. If the glucose concentration in the mixed solution is too low, the carbon content generated will be insufficient, resulting in inadequate carbon modification of the support surface and an inability to reduce the amount of surface Si-OH groups, which is detrimental to subsequent control of the Si-Mn bonding mode. Conversely, if the concentration is too high, the carbon content on the support surface will be excessive, leading to the formation of additional, redundant carbon particles, wasting carbon source, and resulting in insufficient surface Si-OH groups, which is detrimental to Mn ion anchoring. Furthermore, if the molar concentration of manganese ions in the mixed solution is too low, the manganese oxide loading will be insufficient; if the molar concentration is too high, the manganese oxide will agglomerate into large particles, both resulting in low catalytic ozone oxidation performance. Simultaneously, glucose hydrothermal carbonization is a thermochemical reaction that requires a certain temperature to begin, generating carbon, water, and some gases; therefore, controlling the hydrothermal temperature is crucial. Thus, the hydrothermal reaction process requires appropriate glucose solution concentration, manganese ion molar concentration, and hydrothermal reaction temperature to ensure the subsequent preparation of highly active SiO2@C@MnO. x Nanomaterials.

[0014] Preferably, the silica inert carrier is silica spheres or porous silica.

[0015] Preferably, the glucose concentration in the mixed solution is 0.02–0.15 mol / L.

[0016] Furthermore, the manganese salt in the mixed solution is manganese nitrate, manganese acetate, manganese chloride, or manganese sulfate.

[0017] Preferably, the molar concentration of manganese ions in the mixed solution is 0.01 to 0.05 mol / L.

[0018] Preferably, the temperature of the hydrothermal reaction is 160–200°C.

[0019] Preferably, the hydrothermal reaction time is 2 to 24 hours; more preferably, the hydrothermal reaction time is 8 to 12 hours.

[0020] During heat treatment, the presence of silicon and manganese, both elements that influence the graphitization of carbon, at high temperatures facilitates the graphitization of amorphous carbon. The heat treatment temperature affects the degree of carbon graphitization, the bonding mode between Si and Mn, and the formation of MnO. x The particle size and other factors affect the reduction degree of Mn in the catalyst, the content of low-valence Mn, the hydrophobicity of the material, and the electron transfer efficiency, further influencing the ozone catalytic oxidation activity of the material. Therefore, a suitable heat treatment temperature is required to ensure the subsequent preparation of highly active SiO2@C@MnO x Nanomaterials.

[0021] Furthermore, the inert atmosphere for the heat treatment is nitrogen or argon.

[0022] Preferably, the temperature of the heat treatment is 600-900℃.

[0023] Furthermore, the heat treatment time is 1 to 10 hours; preferably, the heat treatment time is 2 to 6 hours.

[0024] Furthermore, this invention also protects the SiO2@C@MnO obtained by the preparation method described above. x Nanomaterials.

[0025] Meanwhile, the present invention also provides the SiO2@C@MnO x Application of nanomaterials as ozone catalysts.

[0026] Specifically, the SiO2@C@MnO x Nanomaterials act as ozone catalysts, catalyzing the degradation of organic pollutants by ozone.

[0027] Preferably, the organic pollutant is a recalcitrant organic compound, including but not limited to antibiotics, endocrine disruptors, and other similar substances.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] This invention uses inert silicon dioxide as the initial carrier and can prepare SiO2@C@MnO through a hydrothermal-thermal treatment process. x Nanomaterials. The material described in this invention, due to the weakening of the Si-O-Mn bond interaction between the manganese oxide and the support by the graphitized thin carbon layer, can easily increase the abundance of low-valence Mn and promote the interfacial catalytic activity of the material; in addition, the introduction of the carbon layer is beneficial to improving its local hydrophobic properties and electron transport efficiency as a catalyst. Therefore, as a catalyst, it can efficiently catalyze the degradation of organic pollutants in water by ozone.

[0030] Meanwhile, the SiO2@C@MnOx The preparation process of nanomaterials is simple and inexpensive. Furthermore, SiO2@C@MnO can be prepared by controlling the concentration of glucose solution, the manganese ion concentration of manganese salt solution, the temperature of the hydrothermal reaction, and the temperature of heat treatment. x Nanomaterials. The physicochemical properties of these materials can be flexibly controlled using simple methods. Compared to ordinary manganese oxides, they exhibit a more efficient ability to catalyze the oxidation and degradation of organic pollutants by ozone, making them worthy of widespread application. Attached Figure Description

[0031] Figure 1 The X-ray diffraction (XRD) patterns of the three nanomaterials prepared in Example 1, Comparative Example 1, and Comparative Example 2 are shown.

[0032] Figure 2 Raman spectra of the two nanomaterials prepared in Example 1 and Comparative Example 1. Detailed Implementation

[0033] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

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

[0035] Example 1

[0036] A SiO2@C@MnO x The specific preparation process of nanomaterials is as follows:

[0037] Two g of 500 nm SiO2 nanospheres were dispersed in 80 mL of a mixed solution containing 0.06 mol / L glucose and 0.024 mol / L manganese acetate. The dispersion was ultrasonicated to form a uniform suspension. The suspension was transferred to a Teflon autoclave and subjected to hydrothermal reaction at 160 °C for 12 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a core-shell structured SiO2@C@MnO. x Precursor. SiO2@C@MnO x The precursor was heat-treated in an Ar atmosphere at a heating rate of 2 °C / min to 650 °C for 4 h, and after cooling, SiO2@C@MnO was obtained. x Nanomaterials.

[0038] Catalyst performance evaluation: The simulated pollutant was acetaminophen (PCM) (but treatable organic pollutants are not limited to PCM). 100 mL of 40 mg / L PCM wastewater and 0.3 g / L SiO2@C@MnO were added to a cylindrical reactor.x Nanomaterial ozone catalysts were used to evaluate the ozone catalytic oxidation activity of acetaminophen removal rate by testing the ozone concentration of 1.2 mg / L and the flow rate of 200 mL / min. Unreacted ozone at the reactor outlet was quenched with potassium iodide solution. Samples were taken periodically, and the ozone in the solution was stripped with N2 and filtered. The concentration was determined by HPLC. After 30 min of reaction, the PCM removal rate reached 91.06%.

[0039] The XRD pattern of the prepared material is shown below. Figure 1 As shown. From Figure 1 It can be observed that, apart from the broad diffraction peaks of silica, no other impurity peaks appear, indicating that the carbon formed during the hydrothermal process is not crystalline. Meanwhile, no diffraction peaks related to manganese oxides appear in the XRD pattern, suggesting good dispersion of manganese oxides on the support surface and greater exposure of ozone catalytic active sites.

[0040] Example 2

[0041] A SiO2@C@MnO x The preparation process of nanomaterials is as follows:

[0042] Two g of 500 nm SiO2 nanospheres were dispersed in 80 mL of a mixed solution containing 0.12 mol / L glucose and 0.05 mol / L manganese acetate. The dispersion was ultrasonicated to form a uniform suspension. The suspension was transferred to a Teflon autoclave and hydrothermally reacted at 200 °C for 12 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a core-shell structured SiO2@C@MnO. x Precursor. SiO2@C@MnO x The precursor was heat-treated in an Ar atmosphere at a heating rate of 2 °C / min to 900 °C for 4 h, and after cooling, SiO2@C@MnO was obtained. x Nanomaterials.

[0043] Catalyst performance evaluation: The simulated pollutant was acetaminophen (PCM) (but treatable organic pollutants are not limited to PCM). 100 mL of 40 mg / L PCM wastewater and 0.3 g / L SiO2@C@MnO were added to a cylindrical reactor. x Nanomaterial ozone catalysts were used to evaluate the ozone catalytic oxidation activity of acetaminophen removal rate by testing the ozone concentration of 1.2 mg / L and the flow rate of 200 mL / min. Unreacted ozone at the reactor outlet was quenched with potassium iodide solution. Samples were taken periodically, and the ozone in the solution was stripped with N2 and filtered. The concentration was determined by HPLC. After 30 min of reaction, the PCM removal rate reached 88.37%.

[0044] Example 3

[0045] A SiO2@C@MnO x The preparation process of nanomaterials is as follows:

[0046] Two g of 500 nm SiO2 nanospheres were dispersed in 80 mL of a mixed solution containing 0.02 mol / L glucose and 0.012 mol / L manganese acetate. The dispersion was ultrasonicated to form a uniform suspension. The suspension was transferred to a Teflon autoclave and subjected to hydrothermal reaction at 160 °C for 10 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a core-shell structured SiO2@C@MnO. x Precursor. SiO2@C@MnO x The precursor was heat-treated in an Ar atmosphere at a heating rate of 2 °C / min to 650 °C for 3 h, and then cooled to obtain SiO2@C@MnO. x Nanomaterials.

[0047] Catalyst performance evaluation: The simulated pollutant was acetaminophen (PCM) (but treatable organic pollutants are not limited to PCM). 100 mL of 40 mg / L PCM wastewater and 0.3 g / L SiO2@C@MnO were added to a cylindrical reactor. x Nanomaterial ozone catalysts were used to evaluate the ozone catalytic oxidation activity of acetaminophen removal rate by testing the ozone concentration of 1.2 mg / L and the flow rate of 200 mL / min. Unreacted ozone at the reactor outlet was quenched with potassium iodide solution. Samples were taken periodically, and the ozone in the solution was stripped with N2 and filtered. The concentration was determined by HPLC. After 30 min of reaction, the PCM removal rate reached 83.27%.

[0048] Comparative Example 1

[0049] A SiO2@MnO x The preparation process of nanomaterials is as follows:

[0050] Two g of 500 nm SiO2 nanospheres were dispersed in 80 mL of a mixed solution containing 0 mol / L glucose and 0.024 mol / L manganese acetate. The mixture was ultrasonically dispersed to form a uniform suspension. The suspension was transferred to a Teflon autoclave and hydrothermally reacted at 160 °C for 12 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a core-shell structured SiO2@MnO2 nanosphere. x Precursor. SiO2@MnO x The precursor was heat-treated in an Ar atmosphere at a heating rate of 2 °C / min to 650 °C for 4 h, and then cooled to obtain SiO2@MnO. x Nanomaterials.

[0051] Catalyst performance evaluation: The simulated pollutant was acetaminophen (PCM) (but treatable organic pollutants are not limited to PCM). 100 mL of 40 mg / L PCM wastewater and 0.3 g / L SiO2@C@MnO were added to a cylindrical reactor. x Nanomaterial ozone catalysts were used to evaluate the ozone catalytic oxidation activity of acetaminophen removal rate by testing the ozone concentration of 1.2 mg / L and the flow rate of 200 mL / min. Unreacted ozone at the reactor outlet was quenched with potassium iodide solution. Samples were taken periodically, and the ozone in the solution was stripped with N2 and filtered. The concentration was determined by HPLC. After 30 min of reaction, the PCM removal rate reached 64.45%.

[0052] The solution selected during the hydrothermal-heat treatment of the above materials did not contain glucose, resulting in the failure to form a graphitized thin carbon layer. Figure 2 It can also be seen that the characteristic peak G band of carbon (1600 cm⁻¹) -1 (location) and D-band (1345cm) -1 The presence of carbon at (location 338 cm⁻¹) indicates its absence. Simultaneously, the Raman spectrum shows a carbon atom located at 338 cm⁻¹. -1 and 489cm -1 Location, 637cm -1 At approximately 990cm -1 The bending vibration peak of the O-Mn-O bond, the breathing vibration peak of the Mn-O-Mn bond, and the characteristic peak intensity of the Si-O-Mn bond are all greater than those in Example 1, indicating that the SiO2 and MnO bonds are more reactive than those in Example 1. x The interaction of the Si-O-Mn bonds formed between them was not weakened. The XRD pattern of the prepared material is shown below. Figure 1 As shown, from Figure 1 The diffraction peaks of manganese oxides appearing in the sample indicate that large particles of Mn3O4 were formed during the preparation process. The manganese loaded on the sample was poorly dispersed, and the material lacked both local hydrophobic properties and the ability of carbon to accelerate electron transport, resulting in low ozone catalytic oxidation activity.

[0053] Comparative Example 2

[0054] The preparation process of a SiO2@C nanomaterial is as follows:

[0055] Two g of 500 nm SiO2 nanospheres were dispersed in 80 ml of a mixed solution containing 0.06 mol / L glucose and 0 mol / L manganese acetate. The mixture was ultrasonically dispersed to form a uniform suspension. The suspension was transferred to a Teflon autoclave and hydrothermally reacted at 160 °C for 12 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a core-shell structured SiO2@C precursor. The SiO2@C precursor was then heat-treated in an Ar atmosphere at a heating rate of 2 °C / min to 650 °C for 4 h. After cooling, SiO2@C nanomaterials were obtained.

[0056] Catalyst performance evaluation: The simulated pollutant was acetaminophen (PCM) (but treatable organic pollutants are not limited to PCM). 100 mL of 40 mg / L PCM wastewater and 0.3 g / L SiO2@C@MnO were added to a cylindrical reactor. x Nanomaterial ozone catalysts were used to evaluate the ozone catalytic oxidation activity of acetaminophen removal rate by testing the ozone concentration of 1.2 m³ / L and the flow rate of 200 mL / min. Unreacted ozone at the reactor outlet was quenched with potassium iodide solution. Samples were taken periodically, and the ozone in the solution was stripped with N₂ and filtered. The concentration was determined by HPLC. After 30 min of reaction, the PCM removal rate reached 54.98%.

[0057] The mixed solution used in the hydrothermal-heat treatment process of the above materials does not contain manganese ions, and the XRD pattern of the prepared materials is shown in the figure. Figure 1 As shown, from Figure 1 It can be seen that no other impurity peaks appear except for the broad diffraction peak of silica, indicating that the carbon formed during the hydrothermal process has no XRD diffraction peaks and is amorphous. Furthermore, the material surface lacks manganese oxides as active sites for ozone activation, thus exhibiting low ozone catalytic oxidation activity.

[0058] Comparative Example 3

[0059] A SiO2@C@MnO x The preparation process of nanomaterials is as follows:

[0060] Two g of 500 nm SiO2 nanospheres were dispersed in 80 mL of a mixed solution containing 0.06 mol / L glucose and 0.024 mol / L manganese acetate. The dispersion was ultrasonicated to form a uniform suspension. The suspension was transferred to a Teflon autoclave and subjected to hydrothermal reaction at 90 °C for 12 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a core-shell structured SiO2@C@MnO. x Precursor. SiO2@C@MnO xThe precursor was heat-treated in an Ar atmosphere at a heating rate of 2 °C / min to 650 °C for 4 h, and after cooling, SiO2@C@MnO was obtained. x Nanomaterials

[0061] Catalyst performance evaluation: The simulated pollutant was acetaminophen (PCM) (but treatable organic pollutants are not limited to PCM). 100 mL of 40 mg / L PCM wastewater and 0.3 g / L SiO2@C@MnO were added to a cylindrical reactor. x Nanomaterial ozone catalysts were used to evaluate the ozone catalytic oxidation activity of acetaminophen removal rate by testing the ozone concentration of 1.2 mg / L and the flow rate of 200 m³ / min. Unreacted ozone at the reactor outlet was quenched with potassium iodide solution. Samples were taken periodically, and the ozone in the solution was stripped with N₂ and filtered. The concentration was determined by HPLC. After 30 min of reaction, the PCM removal rate reached 70.12%.

[0062] The temperature selected for the above materials during the hydrothermal reaction was too low, below the temperature at which glucose just begins to undergo hydrothermal carbonization (100℃), resulting in incomplete hydrothermal carbonization and insufficient carbon production. This leads to insufficient weakening of the Si-O-Mn bond interaction, thus exhibiting low ozone catalytic oxidation activity.

[0063] Comparative Example 4

[0064] A SiO2@C@MnO x The preparation process of nanomaterials is as follows:

[0065] Two g of 500 nm SiO2 nanospheres were dispersed in 80 mL of a mixed solution containing 0.06 mol / L glucose and 0.024 mol / L manganese acetate. The dispersion was ultrasonicated to form a uniform suspension. The suspension was transferred to a Teflon autoclave and subjected to hydrothermal reaction at 160 °C for 12 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a core-shell structured SiO2@C@MnO. x Precursor. SiO2@C@MnO x The precursor was heat-treated in an Ar atmosphere at a heating rate of 2 °C / min to 1400 °C for 4 h, and then cooled to obtain SiO2@C@MnO. x Nanomaterials

[0066] Catalyst performance evaluation: The simulated pollutant was acetaminophen (PCM) (but treatable organic pollutants are not limited to PCM). 100 mL of 40 mg / L PCM wastewater and 0.3 g / L SiO2@C@MnO were added to a cylindrical reactor. xNanomaterial ozone catalysts were used to evaluate the ozone catalytic oxidation activity of acetaminophen removal rate by testing the ozone concentration of 1.2 mg / L and the flow rate of 200 mL / min. Unreacted ozone at the reactor outlet was quenched with potassium iodide solution. Samples were taken periodically, and the ozone in the solution was stripped with N2 and filtered. The concentration was determined by HPLC. After 30 min of reaction, the PCM removal rate reached 67.12%.

[0067] The above-mentioned materials were subjected to excessively high temperatures during heat treatment, which led to the agglomeration of manganese particles and an increase in the average valence state of manganese after heat treatment. This resulted in fewer active sites for activating ozone, thus exhibiting lower ozone catalytic oxidation activity.

[0068] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A SiO2@C@MnO x The application of nanomaterials as ozone catalysts in the catalytic degradation of organic pollutants by ozone is characterized by, SiO2@C@MnO x The preparation method of nanomaterials specifically includes the following steps: A silica inert support was placed in a mixed solution of glucose and manganese salt to form a suspension, which was then subjected to a hydrothermal reaction at 120–220 °C. Following post-treatment, a core-shell structured SiO2@C@MnO was obtained. x Precursor; SiO2@C@MnO x The precursor was heat-treated at 500–900 °C in an inert atmosphere, and after cooling, SiO2@C@MnO was obtained. x Nanomaterials; The glucose concentration in the mixed solution is 0.02~0.2 mol / L; the manganese ion molar concentration in the mixed solution is 0.01~0.1 mol / L. The molar concentration of manganese ions in the mixed solution is 0.01~0.05 mol / L; The heat treatment time is 1~10 h; The organic pollutant is acetaminophen.

2. The application according to claim 1, characterized in that, The silica inert carrier is silica spheres or porous silica.

3. The application according to claim 1, characterized in that, The manganese salt in the mixed solution is manganese nitrate, manganese acetate, manganese chloride, or manganese sulfate.

4. The application according to claim 1, characterized in that, The reaction time for the hydrothermal reaction is 2 to 24 hours.

5. The application according to claim 1, characterized in that, The inert atmosphere is nitrogen or argon.

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