Manganese-based composite material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of water pollution control, in particular to a manganese-based composite material and a preparation method and application thereof. The manganese-based composite material comprises a manganese sesquioxide base material and acid radical ions bonded on the surface of the manganese sesquioxide base material. The invention also provides a preparation method of the manganese-based composite material, which comprises the following steps: dissolving an inorganic manganese salt in an inorganic solvent to obtain a solution A; dissolving oxalate in an inorganic solvent to obtain a solution B; adding the solution A into the solution B, carrying out stirring reaction, and carrying out solid-liquid separation to obtain a manganese oxalate precursor; and calcining the manganese oxalate precursor to obtain porous manganese sesquioxide, immersing the porous manganese sesquioxide into an ammonium salt solution, stirring at normal temperature, standing to obtain manganese sesquioxide impregnated with ammonium salt, and calcining to obtain the manganese-based composite material. The invention also provides an application of the manganese-based composite material prepared by the preparation method as a catalyst. The problem that the oxidative degradation capacity of periodate on organic pollutants is limited when periodate is directly used as an oxidizing agent is solved.

Description

Technical Field

[0001] This invention relates to the field of water pollution control technology, specifically to a manganese-based composite material, its preparation method, and its application. Background Technology

[0002] With the rapid development of the economy and society, the market demand for fine organic chemical products such as pesticides, dyes, antibiotics, and coatings is increasing daily. However, at the same time, the amount of organic wastewater generated during the production and use of these products is also increasing year by year. These organic compounds in the wastewater are mostly chemically stable, highly biotoxic, highly cumulative, and have a lasting impact; if they enter water bodies, they will cause serious harm to the ecological environment and human health. Advanced oxidation technologies, by generating highly reactive oxidizing species (such as SO42-), can address this issue. - Free radicals such as •OH, •O2- and 1 O2 (non-free radicals, etc.) can effectively detoxify organic pollutants and even completely mineralize them into small molecule products such as water and carbon dioxide, making it a preferred technology for the deep treatment of recalcitrant organic waste liquid.

[0003] Oxidants commonly used in advanced oxidation technologies include hydrogen peroxide (H2O2), peracetic acid (PAA), ozone (O3), and persulfate (PDS / PMS). However, these oxidants have inherent drawbacks: liquid oxidants such as H2O2 and PAA are difficult to store and transport and pose an explosion risk; O3 has low water solubility, limited mass transfer efficiency, and is prone to self-decomposition; persulfate systems have weak resistance to matrix interference and poor compatibility with high-salt water bodies.

[0004] In recent years, based on periodate (IO4) - The advanced oxidation techniques for periodate (IO4) have attracted considerable attention. This is because periodate (IO4) - As a novel oxidant, it possesses good chemical stability, is in solid form for easy transport and storage, and produces environmentally friendly byproducts (mainly IO3). - It has advantages such as a wide pH range and strong resistance to matrix interference, making it highly promising for practical applications.

[0005] However, periodate has a high redox potential (E0). o (IO4) - / IO3 - (e.g., ⇌ +1.7VNHE), but when used directly as an oxidant, its ability to oxidize and degrade organic pollutants is limited, exhibiting a slow kinetic reaction rate. Therefore, how to effectively improve the utilization efficiency of periodate is an urgent problem to be solved. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to provide a manganese-based composite material, its preparation method and application, so as to solve the problem that periodate has limited ability to oxidize and degrade organic pollutants when used directly as an oxidant.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A manganese-based composite material includes a manganese trioxide (Mn2O3) matrix material and anions bonded to the surface of the manganese trioxide (Mn2O3) matrix material.

[0008] Based on the aforementioned technical methods, by chemically bonding acid radicals to the surface of a manganese trioxide (Mn2O3) matrix material, the manganese-based composite material, acting as a catalyst, can significantly enhance the oxidation efficiency of periodate (PI) through a synergistic mechanism of heterogeneous catalysis and surface modification. This effectively solves the problem of limited oxidative degradation capacity of periodate for organic pollutants when used directly as an oxidant.

[0009] Among them, Mn2O3 is used as a transition metal oxide catalyst, utilizing the Mn on its surface. 3+ / Mn 4+ The periodate adsorbed by the variable valence state is activated to generate strong oxidizing active species such as •IO3 and •OH. At the same time, the acid radical ions bonded to the surface not only provide acidic sites to promote the interfacial enrichment and electron transfer of PI, but also stabilize the manganese active center and regulate the surface charge distribution through coordination. This inhibits metal dissolution and optimizes the selective adsorption of organic pollutants, thereby significantly improving the oxidative degradation rate and catalyst stability. This solves the problem of insufficient degradation capacity caused by low yield of active species and limited mass transfer when PI is directly oxidized.

[0010] Preferably, the anion is selected from SO4. 2- and PO4 3- One or two of the acid radicals are chemically bonded to the surface of the manganese trioxide (Mn2O3) matrix material.

[0011] This invention also provides a method for preparing a manganese-based composite material, comprising the following steps: S1. Dissolve a soluble inorganic manganese salt in an inorganic solvent to obtain solution A; dissolve a soluble oxalate in an inorganic solvent to obtain solution B; S2. Add solution A to solution B, stir to react, and separate the solid and liquid to obtain manganese oxalate precursor; S3. Calcining the manganese oxalate precursor yields porous manganese trioxide (Mn2O3). S4. Immerse porous manganese trioxide (Mn2O3) in an ammonium salt solution, stir at room temperature, and let stand to obtain manganese trioxide (Mn2O3) impregnated with ammonium salt. S5. Calcining manganese trioxide (Mn2O3) impregnated with ammonium salt yields a manganese-based composite material.

[0012] Based on the above-mentioned technical means, manganese oxalate precursor is generated by oxalate precipitation. During its thermal decomposition, it releases CO2 gas and constructs a porous Mn2O3 framework in situ, significantly increasing the specific surface area and exposing active sites. The porous structure facilitates the capillary penetration and uniform dispersion of ammonium salt solution, and room temperature impregnation ensures that acid radical ions fully enter the pores. Secondary calcination promotes the decomposition of ammonium salt and its uniform chemical bonding with the surface of manganese oxide, so that acid radical ions are stably anchored to the pore walls, forming a heterogeneous structure with both high porosity and surface functionalization. As a result, when the prepared manganese-based composite material is used as a catalyst, it can significantly improve the accessibility of catalytic active centers, enhance the mass transfer efficiency of reactants, and strengthen structural stability.

[0013] Preferably, the manganese oxalate precursor is calcined at a temperature of 400~550℃ for 2~4 hours.

[0014] Preferably, the manganese oxalate precursor is calcined at 400°C for 2 hours.

[0015] Preferably, the manganese trioxide (Mn2O3) impregnated with ammonium salt is calcined at a temperature of 400~700℃ for 2~4 hours; Preferably, the calcination of the manganese trioxide (Mn2O3) impregnated with ammonium salt is performed by programmed heating at a rate of 2°C / min.

[0016] Preferably, the soluble inorganic manganese salt is selected from at least one of manganese chloride, manganese nitrate, manganese sulfate, and manganese acetate.

[0017] Preferably, the soluble oxalate is selected from at least one of sodium oxalate, potassium oxalate, and ammonium oxalate.

[0018] Preferably, the ammonium salt solution is selected from one or both of ammonium sulfate solution and ammonium phosphate solution.

[0019] SO42 can be produced by using porous Mn2O3 obtained by oxalate precipitation as a matrix and ammonium sulfate or ammonium phosphate as a modifying agent, followed by a simple impregnation-calcination process. 2- Or PO4 3- Uniform bonding on the Mn2O3 surface allows for a simple and convenient preparation process with low equipment requirements, facilitating the large-scale industrial production of catalyst products.

[0020] Preferably, the inorganic solvent is selected from water.

[0021] Preferably, the concentration of the soluble inorganic manganese salt in solution A is 0.1~0.25 mol / L.

[0022] Preferably, the concentration of soluble oxalate in solution B is 0.1~0.25 mol / L.

[0023] Preferably, the ammonium salt solution is an aqueous solution of ammonium salt, and the concentration of ammonium salt in the aqueous solution is 0.25~1 mol / L.

[0024] Preferably, the molar ratio of manganese ions in solution A to oxalate ions in solution B is 1:1 to 1.1.

[0025] Preferably, the ratio of manganese trioxide (Mn2O3) to the ammonium salt solution is 1g:50~60mL.

[0026] Preferably, S2 includes: Solution A is added to solution B, the mixture is stirred and reacted, and solid-liquid separation is performed to obtain the precursor precipitate. The precursor precipitate was washed with water and anhydrous ethanol, and then dried at a temperature of 60~90℃ to obtain the manganese oxalate precursor.

[0027] Preferably, S4 includes: Porous manganese trioxide (Mn2O3) was immersed in an ammonium salt solution and stirred at room temperature for 2-4 hours, then allowed to stand for 12-24 hours and filtered to obtain a precipitate impregnated with ammonium salt. The precipitate impregnated with ammonium salt was dried at a temperature of 60~90℃ to obtain manganese trioxide (Mn2O3) impregnated with ammonium salt.

[0028] The preparation method of the manganese-based composite material of the present invention is simple, low-cost, highly active, stable, and easy to recycle. It can be used as a catalyst for periodate activation and has potential and broad application prospects in the field of organic waste liquid treatment.

[0029] This invention also provides an application of the manganese-based composite material prepared by the method of this invention as a catalyst.

[0030] Preferably, the manganese-based composite material is used as a catalyst to activate periodate to degrade organic matter in organic waste liquid.

[0031] The manganese-based composite material of this invention, when used as a catalyst to activate periodate, can effectively break the stable tetrahedral structure of periodate, causing the iodine-oxygen bond to break and generate a variety of highly active intermediate products (such as free radicals such as •OH, •O2-, and •IO3). 1 O2 (non-free radicals, etc.) are used to achieve the goal of efficient oxidation and degradation of organic pollutants.

[0032] Preferably, the manganese-based composite material is used as a catalyst to activate at least one of the cationic dye Rhodamine B, the cationic dye Methylene Blue, and the anionic dye Acid Orange 7 in the periodate degradation organic waste liquid.

[0033] Preferably, the periodate is selected from sodium periodate.

[0034] When the manganese-based composite material prepared by the method of this invention is used as a catalyst, the performance of the Mn2O3-based catalyst inevitably gradually declines with increasing usage. The regeneration method involves re-impregnating the recovered Mn2O3-based catalyst in ammonium sulfate or ammonium phosphate solution and then calcining it to restore its activity. This not only ensures the efficiency of catalyst recycling but also has the advantage of a simple regeneration process, effectively realizing the resource recycling of manganese-based composite materials and reducing environmental pollution.

[0035] The beneficial effects of this invention are: The manganese-based composite material of the present invention effectively alters the micro-electronic environment of Mn ions by chemically bonding acid radical ions to the surface of a manganese trioxide (Mn2O3) matrix material. This results in a significantly enhanced catalyst performance for the reaction of IO4+ in the reaction solution. - The adsorption and polarization of metal ions facilitate the subsequent adsorption and polarization of IO4-. - The electronic transfer facilitated the development of IO4 - The breaking of bonds facilitates the generation of more reactive oxygen species, significantly improving the efficiency of Mn2O3 / periodate in degrading organic waste liquid. This is due to SO4... 2- Or PO4 3- The modified Mn2O3 exhibits increased activity, significantly reducing its dosage in advanced oxidation reaction systems and effectively lowering operating costs.

[0036] The method for preparing the manganese-based composite material of the present invention involves generating a manganese oxalate precursor through oxalate precipitation, which releases CO2 gas upon thermal decomposition, thereby constructing a porous Mn2O3 framework in situ, significantly increasing the specific surface area and exposing active sites. The porous structure facilitates capillary penetration and uniform dispersion of the ammonium salt solution, while room-temperature impregnation ensures sufficient entry of acid radical ions into the pores. Secondary calcination promotes the decomposition of the ammonium salt and its uniform chemical bonding with the manganese oxide surface, stably anchoring the acid radical ions to the pore walls, forming a heterogeneous structure with both high porosity and surface functionalization. This results in a manganese-based composite material that, when used as a catalyst, significantly improves the accessibility of catalytic active centers, enhances reactant mass transfer efficiency, and strengthens structural stability. Furthermore, the preparation process is simple, requires minimal equipment, and is easily scalable for large-scale and stable industrial production of catalyst products.

[0037] The manganese-based composite material of the present invention has good adaptability to various organic waste liquids as a catalyst. It can be used as a universal catalyst for the activation of periodate and for the treatment of organic waste liquids. It has promotion and application value in the field of water pollution control technology. Attached Figure Description

[0038] Figure 1 Here is a SEM image of the manganese-based composite material prepared in Example 1; Figure 2 The image shows the EDS spectrum of the manganese-based composite material prepared in Example 1. Figure 3 The full-area XPS spectra of the manganese-based composite material prepared in Example 1 and the porous manganese trioxide prepared in Comparative Example 1 are shown. Figure 4 The P 2p high-resolution XPS spectrum of the manganese-based composite material prepared in Example 1; Figure 5 Fourier transform infrared spectra of the manganese-based composite material prepared in Example 1 and the porous manganese trioxide prepared in Comparative Example 1. Figure 6 The images show the XRD patterns of the manganese-based composite material prepared in Example 1 and the porous manganese trioxide prepared in Comparative Example 1. Figure 7 The graph shows the degradation rate of RhB by the manganese-based composite material prepared in Example 1 and the porous manganese trioxide activated periodate prepared in Comparative Example 1. Figure 8 This is a comparison of the kinetic reaction rates of the manganese-based composite material prepared in Example 1 and the porous manganese trioxide activated periodate degrading RhB prepared in Comparative Example 1. Figure 9 The graph shows the degradation rate of RhB by periodate activated by porous manganese trioxide (Mn2O3) prepared in Comparative Example 1, manganese dioxide (MnO2) prepared in Comparative Example 2, and manganese tetroxide (Mn3O4) prepared in Comparative Example 3. Detailed Implementation

[0039] The following description, with reference to preferred embodiments, illustrates the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be understood that the preferred embodiments are merely illustrative of the present invention and not intended to limit the scope of protection of the present invention.

[0040] Example 1 A method for preparing a manganese-based composite material includes the following steps: S1. Dissolve soluble manganese sulfate in water to obtain solution A, where the concentration of manganese sulfate in solution A is 0.1 mol / L; Soluble ammonium oxalate was dissolved in water to obtain solution B, in which the concentration of ammonium oxalate was 0.1 mol / L. S2. Under vigorous stirring, solution A from S1 is rapidly added to solution B. Stirring continues until the reaction is complete, resulting in solid-liquid separation and the precipitation of the precursor. The manganese ions (Mn) in solution A are then removed. 2+ ) and oxalate ions (C2O4) in solution B 2- The molar ratio of ) is 1:1; The precursor precipitate was washed sequentially with deionized water and anhydrous ethanol, and then dried at 60°C to obtain the manganese oxalate precursor. S3. The manganese oxalate precursor obtained in S2 was placed in a muffle furnace and calcined at 400℃ for 2 hours to obtain porous manganese trioxide (Mn2O3). S4. Immerse 1.0 g of porous manganese trioxide (Mn2O3) obtained in S3 into 50 mL of a 1.0 mol / L ammonium phosphate aqueous solution, stir at room temperature for 2 h, then let stand for 24 h, filter, and obtain a precipitate impregnated with ammonium phosphate: The precipitate impregnated with ammonium phosphate was dried at a temperature of 60°C to obtain manganese trioxide (Mn2O3) impregnated with ammonium phosphate. S5. Manganese trioxide (Mn2O3) impregnated with ammonium phosphate was placed in a muffle furnace and heated to 400℃ at a rate of 2℃ / min. Then it was calcined at a constant temperature of 400℃ for 2 hours to obtain a manganese-based composite material.

[0041] The obtained manganese-based composite material includes a manganese trioxide (Mn2O3) matrix material and PO4 chemically bonded to the surface of the manganese trioxide (Mn2O3) matrix material. 3- .

[0042] Example 2 A method for preparing a manganese-based composite material includes the following steps: S1. Dissolve soluble manganese sulfate in water to obtain solution A, where the concentration of manganese sulfate in solution A is 0.1 mol / L; Soluble ammonium oxalate was dissolved in water to obtain solution B, in which the concentration of ammonium oxalate was 0.1 mol / L. S2. Under vigorous stirring, solution A from S1 is rapidly added to solution B. Stirring continues until the reaction is complete, resulting in solid-liquid separation and the precipitation of the precursor. The manganese ions (Mn) in solution A are then removed. 2+) and oxalate ions (C2O4) in solution B 2- The molar ratio of ) is 1:1; The precursor precipitate was washed sequentially with deionized water and anhydrous ethanol, and then dried at 60°C to obtain the manganese oxalate precursor. S3. The manganese oxalate precursor obtained in S2 was placed in a muffle furnace and calcined at 400℃ for 2 hours to obtain porous manganese trioxide (Mn2O3). S4. Immerse 1.0 g of porous manganese trioxide (Mn2O3) obtained in S3 into 50 mL of 0.75 mol / L ammonium sulfate aqueous solution, stir at room temperature for 2 h, then let stand for 24 h, filter, and obtain a precipitate impregnated with ammonium sulfate: The precipitate impregnated with ammonium sulfate was dried at a temperature of 60°C to obtain manganese trioxide (Mn2O3) impregnated with ammonium sulfate. S5. Manganese trioxide (Mn2O3) impregnated with ammonium sulfate was placed in a muffle furnace and heated to 400℃ at a rate of 2℃ / min. Then it was calcined at a constant temperature of 400℃ for 2 hours to obtain a manganese-based composite material.

[0043] The obtained manganese-based composite material includes a manganese trioxide (Mn2O3) matrix material and SO4 atoms chemically bonded to the surface of the manganese trioxide (Mn2O3) matrix material. 2- .

[0044] Example 3 A method for preparing a manganese-based composite material includes the following steps: S1. Dissolve soluble manganese sulfate in water to obtain solution A, where the concentration of manganese sulfate in solution A is 0.1 mol / L; Soluble ammonium oxalate was dissolved in water to obtain solution B, in which the concentration of ammonium oxalate was 0.1 mol / L. S2. Under vigorous stirring, solution A from S1 is rapidly added to solution B. Stirring continues until the reaction is complete, resulting in solid-liquid separation and the precipitation of the precursor. The manganese ions (Mn) in solution A are then removed. 2+ ) and oxalate ions (C2O4) in solution B 2- The molar ratio of ) is 1:1.1; The precursor precipitate was washed sequentially with deionized water and anhydrous ethanol, and then dried at 90°C to obtain the manganese oxalate precursor. S3. The manganese oxalate precursor obtained in S2 was placed in a muffle furnace and calcined at 400℃ for 2 hours to obtain porous manganese trioxide (Mn2O3). S4. 1.0 g of porous manganese trioxide (Mn2O3) obtained in S3 was immersed in 50 mL of 0.25 mol / L ammonium phosphate aqueous solution, stirred at room temperature for 4 h, then allowed to stand for 12 h, and filtered to obtain a precipitate impregnated with ammonium phosphate. The precipitate impregnated with ammonium phosphate was dried at 90°C to obtain manganese trioxide (Mn2O3) impregnated with ammonium phosphate. S5. Manganese trioxide (Mn2O3) impregnated with ammonium phosphate was placed in a muffle furnace and heated to 400℃ at a rate of 2℃ / min. Then it was calcined at a constant temperature of 400℃ for 2 hours to obtain a manganese-based composite material.

[0045] The obtained manganese-based composite material includes a manganese trioxide (Mn2O3) matrix material and PO4 chemically bonded to the surface of the manganese trioxide (Mn2O3) matrix material. 3- .

[0046] Example 4 A method for preparing a manganese-based composite material includes the following steps: S1. Dissolve soluble manganese sulfate in water to obtain solution A, where the concentration of manganese sulfate in solution A is 0.1 mol / L; Soluble ammonium oxalate was dissolved in water to obtain solution B, in which the concentration of ammonium oxalate was 0.1 mol / L. S2. Under vigorous stirring, solution A from S1 is rapidly added to solution B. Stirring continues until the reaction is complete, resulting in solid-liquid separation and the precipitation of the precursor. The manganese ions (Mn) in solution A are then removed. 2+ ) and oxalate ions (C2O4) in solution B 2- The molar ratio of ) is 1:1.1; The precursor precipitate was washed sequentially with deionized water and anhydrous ethanol, and then dried at 90°C to obtain the manganese oxalate precursor. S3. The manganese oxalate precursor obtained in S2 was placed in a muffle furnace and calcined at 550℃ for 4 hours to obtain porous manganese trioxide (Mn2O3). S4. 1.0 g of porous manganese trioxide (Mn2O3) obtained in S3 was immersed in 50 mL of 0.75 mol / L ammonium phosphate aqueous solution, stirred at room temperature for 4 h, then allowed to stand for 12 h, and filtered to obtain a precipitate impregnated with ammonium phosphate. The precipitate impregnated with ammonium phosphate was dried at 90°C to obtain manganese trioxide (Mn2O3) impregnated with ammonium phosphate. S5. Manganese trioxide (Mn2O3) impregnated with ammonium phosphate was placed in a muffle furnace and heated to 700℃ at a rate of 2℃ / min. Then it was calcined at a constant temperature of 700℃ for 2 hours to obtain a manganese-based composite material.

[0047] The obtained manganese-based composite material includes a manganese trioxide (Mn2O3) matrix material and PO4 chemically bonded to the surface of the manganese trioxide (Mn2O3) matrix material. 3- .

[0048] Example 5 A method for preparing a manganese-based composite material includes the following steps: S1. Dissolve soluble manganese sulfate in water to obtain solution A, where the concentration of manganese sulfate in solution A is 0.1 mol / L; Soluble ammonium oxalate was dissolved in water to obtain solution B, in which the concentration of ammonium oxalate was 0.1 mol / L. S2. Under vigorous stirring, solution A from S1 is rapidly added to solution B. Stirring continues until the reaction is complete, resulting in solid-liquid separation and the precipitation of the precursor. The manganese ions (Mn) in solution A are then removed. 2+ ) and oxalate ions (C2O4) in solution B 2- The molar ratio of ) is 1:1.1; The precursor precipitate was washed sequentially with deionized water and anhydrous ethanol, and then dried at 70°C to obtain the manganese oxalate precursor. S3. The manganese oxalate precursor obtained in S2 was placed in a muffle furnace and calcined at 400℃ for 2 hours to obtain porous manganese trioxide (Mn2O3). S4. 1.0 g of porous manganese trioxide (Mn2O3) obtained in S3 was immersed in 50 mL of 0.50 mol / L ammonium phosphate aqueous solution, stirred at room temperature for 3 h, then allowed to stand for 16 h, and filtered to obtain a precipitate impregnated with ammonium phosphate. The precipitate impregnated with ammonium phosphate was dried at 80°C to obtain manganese trioxide (Mn2O3) impregnated with ammonium phosphate. S5. Manganese trioxide (Mn2O3) impregnated with ammonium phosphate was placed in a muffle furnace and heated to 500℃ at a rate of 2℃ / min. Then it was calcined at a constant temperature of 500℃ for 2 hours to obtain a manganese-based composite material.

[0049] The obtained manganese-based composite material includes a manganese trioxide (Mn2O3) matrix material and PO4 chemically bonded to the surface of the manganese trioxide (Mn2O3) matrix material. 3- .

[0050] Example 6 A method for preparing a manganese-based composite material includes the following steps: S1. Dissolve soluble manganese acetate in water to obtain solution A, where the concentration of manganese acetate is 0.25 mol / L; Soluble potassium oxalate was dissolved in water to obtain solution B, in which the concentration of potassium oxalate was 0.25 mol / L. S2. Under vigorous stirring, solution A from S1 is rapidly added to solution B. Stirring continues until the reaction is complete, resulting in solid-liquid separation and the precipitation of the precursor. The manganese ions (Mn) in solution A are then removed. 2+ ) and oxalate ions (C2O4) in solution B 2- The molar ratio of () is 1:1.05; The precursor precipitate was washed sequentially with deionized water and anhydrous ethanol, and then dried at 70°C to obtain the manganese oxalate precursor. S3. The manganese oxalate precursor obtained in S2 was placed in a muffle furnace and calcined at 450℃ for 3 hours to obtain porous manganese trioxide (Mn2O3). S4. Immerse 1.0 g of porous manganese trioxide (Mn2O3) obtained in S3 into 60 mL of 0.50 mol / L ammonium sulfate aqueous solution, stir at room temperature for 3 h, then let stand for 14 h, filter, and obtain a precipitate impregnated with ammonium sulfate: The precipitate impregnated with ammonium sulfate was dried at a temperature of 80°C to obtain manganese trioxide (Mn2O3) impregnated with ammonium sulfate. S5. Manganese trioxide (Mn2O3) impregnated with ammonium sulfate was placed in a muffle furnace and heated to 600℃ at a rate of 2℃ / min. Then it was calcined at a constant temperature of 600℃ for 2 hours to obtain a manganese-based composite material.

[0051] The obtained manganese-based composite material includes a manganese trioxide (Mn2O3) matrix material and SO4 atoms chemically bonded to the surface of the manganese trioxide (Mn2O3) matrix material. 2- .

[0052] Example 7 A method for preparing a manganese-based composite material includes the following steps: S1. Dissolve soluble manganese nitrate in water to obtain solution A, where the concentration of manganese nitrate in solution A is 0.20 mol / L; Soluble sodium oxalate was dissolved in water to obtain solution B, in which the concentration of sodium oxalate was 0.20 mol / L. S2. Under vigorous stirring, solution A from S1 is rapidly added to solution B. Stirring continues until the reaction is complete, resulting in solid-liquid separation and the precipitation of the precursor. The manganese ions (Mn) in solution A are then removed. 2+ ) and oxalate ions (C2O4) in solution B 2- The molar ratio of () is 1:1.05; The precursor precipitate was washed sequentially with deionized water and anhydrous ethanol, and then dried at 60°C to obtain the manganese oxalate precursor. S3. The manganese oxalate precursor obtained in S2 was placed in a muffle furnace and calcined at 400℃ for 2 hours to obtain porous manganese trioxide (Mn2O3). S4. Immerse 1.0 g of porous manganese trioxide (Mn2O3) obtained in S3 into 55 mL of 0.40 mol / L ammonium sulfate aqueous solution, stir at room temperature for 2 h, then let stand for 16 h, filter, and obtain a precipitate impregnated with ammonium sulfate: The precipitate impregnated with ammonium sulfate was dried at a temperature of 75°C to obtain manganese trioxide (Mn2O3) impregnated with ammonium sulfate. S5. Manganese trioxide (Mn2O3) impregnated with ammonium sulfate was placed in a muffle furnace and heated to 450℃ at a rate of 2℃ / min. Then it was calcined at a constant temperature of 450℃ for 2 hours to obtain a manganese-based composite material.

[0053] The obtained manganese-based composite material includes a manganese trioxide (Mn2O3) matrix material and SO4 atoms chemically bonded to the surface of the manganese trioxide (Mn2O3) matrix material. 2- .

[0054] Example 8 A method for preparing a manganese-based composite material includes the following steps: S1. Dissolve soluble manganese chloride in water to obtain solution A, where the concentration of manganese chloride is 0.20 mol / L; Soluble sodium oxalate was dissolved in water to obtain solution B, in which the concentration of sodium oxalate was 0.20 mol / L. S2. Under vigorous stirring, solution A from S1 is rapidly added to solution B. Stirring continues until the reaction is complete, resulting in solid-liquid separation and the precipitation of the precursor. The manganese ions (Mn) in solution A are then removed. 2+ ) and oxalate ions (C2O4) in solution B 2- The molar ratio of () is 1:1.05; The precursor precipitate was washed sequentially with deionized water and anhydrous ethanol, and then dried at 60°C to obtain the manganese oxalate precursor. S3. The manganese oxalate precursor obtained in S2 was placed in a muffle furnace and calcined at 400℃ for 2 hours to obtain porous manganese trioxide (Mn2O3). S4. Immerse 1.0 g of porous manganese trioxide (Mn2O3) obtained in S3 into 50 mL of 0.75 mol / L ammonium sulfate aqueous solution, stir at room temperature for 2 h, then let stand for 20 h, filter, and obtain a precipitate impregnated with ammonium sulfate: The precipitate impregnated with ammonium sulfate was dried at a temperature of 85°C to obtain manganese trioxide (Mn2O3) impregnated with ammonium sulfate. S5. Manganese trioxide (Mn2O3) impregnated with ammonium sulfate was placed in a muffle furnace and heated to 500℃ at a rate of 2℃ / min. Then it was calcined at a constant temperature of 500℃ for 2 hours to obtain a manganese-based composite material.

[0055] The obtained manganese-based composite material includes a manganese trioxide (Mn2O3) matrix material and SO4 atoms chemically bonded to the surface of the manganese trioxide (Mn2O3) matrix material. 2- .

[0056] Comparative Example 1 A method for preparing porous manganese trioxide includes the following steps: S1. Dissolve soluble manganese sulfate in water to obtain solution A, where the concentration of manganese sulfate in solution A is 0.1 mol / L; Soluble ammonium oxalate was dissolved in water to obtain solution B, in which the concentration of ammonium oxalate was 0.1 mol / L. S2. Under vigorous stirring, solution A from S1 is rapidly added to solution B. Stirring continues until the reaction is complete, resulting in solid-liquid separation and the precipitation of the precursor. The manganese ions (Mn) in solution A are then removed. 2+ ) and oxalate ions (C2O4) in solution B 2- The molar ratio of ) is 1:1; The precursor precipitate was washed sequentially with deionized water and anhydrous ethanol, and then dried at 60°C to obtain the manganese oxalate precursor. S3. The manganese oxalate precursor obtained in S2 was placed in a muffle furnace and calcined at 400℃ for 2 hours to obtain porous manganese trioxide (Mn2O3).

[0057] Comparative Example 2 A method for preparing a manganese dioxide (MnO2) catalyst material includes the following steps: Under magnetic stirring, 0.01 mol of KMnO4 was dissolved in 250 mL of water, followed by the addition of 100 mL of a 1 mol / L hydrochloric acid aqueous solution, and stirring continued for 30 min to ensure homogeneity. The mixture was then transferred to a 500 mL stainless steel hydrothermal reactor lined with polytetrafluoroethylene (PTFE), sealed, and reacted at 150 °C for 6 h. After the reactor cooled naturally to room temperature, the precipitate was collected and washed sequentially with deionized water and anhydrous ethanol, then dried at 50 °C to obtain the MnO2 catalyst material.

[0058] Comparative Example 3 A method for preparing a manganese tetroxide (Mn3O4) catalyst material includes the following steps: Prepare 200 mL of a 0.1 mol / L manganese sulfate solution and 200 mL of a 0.5 mol / L ammonia solution. In a water bath at 50°C, under vigorous stirring, slowly add the ammonia solution dropwise to the manganese sulfate solution. After the addition is complete, continue the reaction for 1 hour. Vacuum filter the solution, collect the precipitate, and wash it 4-5 times with deionized water and ethanol. Dry the precipitate at 50°C. Then, place the dried powder in a muffle furnace and heat it to 1000°C at a programmed rate of 2°C / min, holding it at that temperature for 2 hours. After natural cooling in the furnace, the resulting product is the Mn3O4 catalyst material.

[0059] Detection and Analysis 1) Scanning electron microscopy analysis The manganese-based composite material prepared in Example 1 was tested and analyzed using a scanning electron microscope equipped with an EDS detector (SEM-EDS), and the results are as follows: Figure 1 and Figure 2 As shown.

[0060] from Figure 1 Observation reveals that the manganese-based composite material prepared in Example 1 exhibits a blocky morphology with good dispersibility and uniformity, a particle size of approximately several µm, and a slit-like porous structure on the catalyst surface. Figure 2 Further EDS analysis confirmed that P was successfully introduced into the manganese-based composite material through an impregnation-calcination step.

[0061] 2) XPS Analysis X-ray photoelectron spectroscopy was used to analyze the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1 and the manganese-based composite material (PMO) prepared in Example 1. The results are as follows: Figure 3 and Figure 4 As shown.

[0062] from Figure 3 and Figure 4Analysis revealed that the main chemical composition of the manganese-based composite material prepared in Example 1 was Mn, O, and P, with the C signal originating from carbon contamination within the instrument itself. High-resolution P2p spectroscopy (peak value 133.57 eV) confirmed that the P element on the surface of the manganese-based composite material prepared in Example 1 was in the form of +5, i.e., PO4. 3- It exists in the form of.

[0063] 3) Fourier transform infrared spectroscopy analysis The porous manganese trioxide (Mn2O3) prepared in Comparative Example 1 and the manganese-based composite material (PMO) prepared in Example 1 were analyzed using Fourier transform infrared spectroscopy (FTIR spectroscopy). The results are as follows: Figure 5 As shown.

[0064] from Figure 5 Comparative analysis shows that, compared with the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1, the manganese-based composite material (PMO) prepared in Example 1 has a higher infrared spectrum at wavenumber 1030 cm⁻¹. -1 The location belongs to PO4. 3- The characteristic absorption peaks of PO4 confirmed that PO4 3- Successfully bonded to the surface of Mn2O3, forming Mn2O3 / PO4 3- structure.

[0065] 4) XRD analysis The porous manganese trioxide (Mn2O3) prepared in Comparative Example 1 and the manganese-based composite material (PMO) prepared in Example 1 were analyzed using X-ray diffraction. The results are as follows: Figure 6 As shown.

[0066] from Figure 6 Comparative analysis shows that the phase composition of the manganese-based composite material (PMO) prepared in Example 1 and the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1 is Mn2O3.

[0067] 5) Catalyst activity evaluation Degradation test of cationic dye Rhodamine B (RhB) The specific operating steps are as follows: Accurately weigh 0.0100 g of the manganese-based composite material (PMO) prepared in Examples 1-8, and 0.0100 g of the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1, respectively, as catalysts for activating periodate. Then, add them to an aqueous solution of the cationic dye Rhodamine B (RhB). Mechanical stirring is turned on, and the mixture is thoroughly mixed for 20 min to reach adsorption saturation. Samples are taken and the concentration of RhB in the RhB solution at adsorption saturation is measured and recorded as C0. Subsequently, a certain amount of sodium periodate is added to bring the concentration to 0.20 mM, stirring continues, and samples are taken at given time points (t-1 min) to determine the RhB concentration in the RhB solution at different reaction times, recorded as C. t-1 . The initial concentration of RhB in the RhB solution was 60 mg·L⁻¹. -1 The volume was 500 mL; to avoid the influence of reaction temperature on the activity of periodate, all degradation experiments were carried out in a constant temperature water bath at 25℃.

[0068] The concentration of RhB in the RhB solution was determined by spectrophotometry. Each sample was 3.5 mL. The sample was first filtered through a 0.22 μm polyethersulfone filter membrane, and then 0.15 mL of anhydrous methanol was added immediately to quench the reaction. Finally, the maximum absorbance value at wavelengths of 400-600 nm was measured (the maximum absorption wavelength was 554 nm).

[0069] The degradation rate D0 of RhB is calculated using the following formula (Ⅰ): In equation (I), C0 represents the RhB concentration (mg·L⁻¹) in the RhB solution when adsorption saturation is achieved. -1 ); C t-1 This indicates the concentration of RhB in the RhB solution (mg·L) at t-1 min of the reaction. -1 D0 represents the degradation rate (%) of RhB.

[0070] The results are as follows: In Example 1, the manganese-based composite material (PMO) used as a catalyst for activating periodate showed a RhB degradation rate of 94.21% after 20 min (t⁻¹ min). In Example 3, the manganese-based composite material (PMO) used as a catalyst for activating periodate showed a RhB degradation rate of 80.02% after 20 min (t⁻¹ min). In Example 4, the manganese-based composite material (PMO) used as a catalyst for activating periodate showed a RhB degradation rate of 73.21% after 20 min (t⁻¹ min). In Example 5, the manganese-based composite material (PMO) used as a catalyst for activating periodate showed a RhB degradation rate of 86.34% after 20 min (t⁻¹ min). In Comparative Example 1, the porous manganese trioxide (Mn2O3) used as a catalyst for activating periodate showed a calculated RhB degradation rate of only 60.54% after 20 min (t-1 min) of reaction. This demonstrates that the RhB degradation rate obtained by the present invention, after being activated by PO4, is significantly lower than that obtained by the catalyst. 3- Modified Mn2O3, as a catalyst, exhibits excellent performance in activating the degradation of RhB by periodate.

[0071] In Example 2, 0.0100 g of the manganese-based composite material (SMO) was used as a catalyst for activating periodate. After 20 min (t-1 min) of reaction, the calculated degradation rate of RhB was 81.74%. In Example 6, the manganese-based composite material (SMO) was used as a catalyst for activating periodate. After 20 min (t-1 min) of reaction, the calculated degradation rate of RhB was 83.75%. In Example 7, 0.0100 g of the manganese-based composite material (SMO) was used as a catalyst for activating periodate. After 20 min (t-1 min) of reaction, the calculated degradation rate of RhB was 86.48%. In Example 8, the manganese-based composite material (SMO) was used as a catalyst for activating periodate. After 20 min (t-1 min) of reaction, the calculated degradation rate of RhB was 87.35%. This demonstrates that the RhB degradation rate prepared by this invention after SO42-... 2- Modified Mn2O3, as a catalyst, exhibits excellent performance in activating the degradation of RhB by periodate.

[0072] In addition, 0.0300 g of porous manganese trioxide (Mn2O3) prepared in Comparative Example 1, manganese dioxide (MnO2) prepared in Comparative Example 2, and manganese tetroxide (Mn3O4) prepared in Comparative Example 3 were accurately weighed as catalysts for activating periodate. These were then added to aqueous solutions of the cationic dye Rhodamine B (RhB), and mechanical stirring was initiated to allow for thorough mixing for 20 min to reach adsorption saturation. Samples were taken and the RhB concentration in the RhB solution at adsorption saturation was measured and denoted as C0. Subsequently, a certain amount of sodium periodate was added to bring the concentration to 0.60 mM, stirring continued, and samples were taken at given time points (t-1 min) to determine the RhB concentration in the RhB solution at different reaction times, denoted as C. t-1 . The initial concentration of RhB in the RhB solution was 40 mg·L⁻¹. -1 The volume was 500 mL; to avoid the influence of reaction temperature on the activity of periodate, all degradation experiments were carried out in a constant temperature water bath at 25℃.

[0073] The concentration of RhB in the RhB solution was determined spectrophotometrically. Each sample was 3.5 mL in size. The sample was first filtered through a 0.22 μm polyethersulfone membrane, then immediately quenched with 0.15 mL of anhydrous methanol. Finally, the maximum absorbance value at wavelengths of 400–600 nm was measured (maximum absorption wavelength at 554 nm). The degradation rate D0 of RhB was calculated using equation (I).

[0074] The results are as follows: In Comparative Example 1, the porous manganese trioxide (Mn₂O₃) used as a catalyst for activating periodate showed a calculated RhB degradation rate of 85.11% after 20 min (t⁻¹ min). In Comparative Example 2, the manganese dioxide (MnO₂) used as a catalyst for activating periodate showed a RhB degradation rate of 78.70% after 20 min (t⁻¹ min). In Comparative Example 3, the manganese tetroxide (Mn₃O₄) used as a catalyst for activating periodate showed a RhB degradation rate of 59.73% after 20 min (t⁻¹ min). Therefore, among the three manganese oxides, Mn₂O₃ exhibits the best performance in activating periodate.

[0075] The degradation curves of RhB were based on the manganese-based composite material (PMO) prepared in Example 1 and the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1 as catalysts to activate periodate. A first control group (PI) was established with only periodate added and no catalyst added, while a second control group (PMO) was established with only the manganese-based composite material (PMO) prepared in Example 1 added and no periodate added. The degradation test procedures were the same as those for the degradation test of the cationic dye Rhodamine B (RhB) described above. The results are as follows: Figure 7 As shown. The corresponding reaction rate for the degradation of RhB solution by activated periodate was calculated based on the first-order kinetic fitting curve, as shown below. Figure 8 As shown.

[0076] Figure 7 and Figure 8 In the figures, PI represents the first control group with only periodate added and no catalyst added; PMO represents the second control group with only manganese-based composite material (PMO) prepared in Example 1 added and no periodate added; PI+Mn2O3 represents the experimental group with both porous manganese trioxide (Mn2O3) prepared in Comparative Example 1 and periodate added; and PI+PMO represents the experimental group with both manganese-based composite material (PMO) prepared in Example 1 and periodate added.

[0077] from Figure 7 and Figure 8 Analysis showed that the manganese-based composite material (PMO) prepared in Example 1 and the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1, as catalysts for activating periodate, had reaction rates of 0.1396 min for the degradation of RhB solution. -1 and 0.0351min -1 That is, the rate at which the manganese-based composite material (PMO) prepared in Example 1 activates the degradation of RhB solution by periodate as a catalyst is 3.98 times that of the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1 under the same conditions.

[0078] The degradation curves of RhB based on porous manganese trioxide (Mn2O3) prepared in Comparative Example 1, manganese dioxide (MnO2) prepared in Comparative Example 2, and manganese trioxide (Mn3O4) prepared in Comparative Example 3 as catalysts for activating periodate are shown in the figure. Figure 9 As shown.

[0079] from Figure 9 In the study, the calculated reaction rates of the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1, the manganese dioxide (MnO2) prepared in Comparative Example 2, and the manganese trioxide (Mn3O4) prepared in Comparative Example 3 for activating periodate to degrade RhB solution were 0.0801 min. -1 0.0685 min -1 and 0.0363min -1 In other words, the Mn2O3 catalyst has the best performance in activating the degradation of RhB by periodate.

[0080] Degradation test of the anionic dye Acid Orange 7 (AO7) The specific operating steps are as follows: Accurately weigh 0.0100 g of the manganese-based composite material (PMO) prepared in Example 1 and 0.0100 g of the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1 as catalysts for activating periodate. Then, add them separately to an aqueous solution of the anionic dye Acid Orange 7 (AO7). Mechanical stirring is turned on, and the mixture is thoroughly mixed for 20 min to reach adsorption saturation. Samples are taken and the concentration of AO7 in the AO7 solution at adsorption saturation is measured and denoted as C1. Subsequently, a certain amount of sodium periodate is added to bring the concentration to 0.20 mM, stirring continues, and samples are taken at given time points (t-2 min) to determine the AO7 concentration in the solution at different reaction times, denoted as C. t-2 .

[0081] The initial concentration of AO7 in the AO7 solution was 40 mg·L⁻¹. -1 The volume was 500 mL; to avoid the influence of reaction temperature on the activity of periodate, all degradation experiments were carried out in a constant temperature water bath at 25℃.

[0082] The concentration of AO7 in the AO7 solution was determined spectrophotometrically. Each sample was 3.5 mL in size. The sample was first filtered through a 0.22 μm polyethersulfone membrane, then immediately quenched with 0.15 mL of anhydrous methanol. Finally, the maximum absorbance value at wavelengths of 200–550 nm was measured. The degradation rate D1 of AO7 was calculated using the following formula (II): In formula (II), C1 represents the concentration of AO7 in the AO7 solution (mg·L⁻¹) when adsorption saturation is reached. -1 ); C t-2 This indicates the concentration of AO7 in the AO7 solution (mg·L) when the reaction proceeds to t-2 min. -1 D1 represents the degradation rate (%) of AO7.

[0083] The results were as follows: The manganese-based composite material (PMO) prepared in Example 1, used as a catalyst for activating periodate, showed a calculated degradation rate of 93.57% for AO7 after 20 min (t-2 min). In contrast, the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1, used as a catalyst for activating periodate, showed a calculated degradation rate of 30.52% for AO7 after 20 min (t-2 min). This demonstrates that the degradation of AO7 by PO4 prepared in this invention… 3- Modified Mn2O3, as a catalyst, exhibits excellent performance in activating the degradation of AO7 by periodate.

[0084] Degradation test of the cationic dye methylene blue (MB) The specific operating steps are as follows: Accurately weigh 0.0100 g of the manganese-based composite material (PMO) prepared in Example 1 and 0.0100 g of the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1 as catalysts for activating periodate. Then, add them separately to an aqueous solution of the cationic dye methylene blue (MB). Mechanical stirring is initiated, and the mixture is allowed to mix thoroughly for 20 min to reach adsorption saturation. Samples are taken and the MB concentration in the MB solution at adsorption saturation is measured, denoted as C2. Subsequently, a certain amount of sodium periodate is added to bring the concentration to 0.20 mM. Stirring continues, and samples are taken at given time points (t-3 min) to determine the MB concentration in the MB solution at different reaction times, denoted as C. t-3 .

[0085] The initial concentration of MB in the MB solution was 10 mg·L⁻¹. -1 The volume was 500 mL; to avoid the influence of reaction temperature on the activity of periodate, all degradation experiments were carried out in a constant temperature water bath at 25℃.

[0086] The concentration of MB in the MB solution was determined spectrophotometrically. Each sample was 3.5 mL. The sample was first filtered through a 0.22 μm polyethersulfone membrane, then immediately quenched with 0.15 mL of anhydrous methanol. Finally, the maximum absorbance at wavelengths of 500–700 nm was measured. The degradation rate D2 of MB was calculated using the following formula (Ⅲ): In formula (Ⅲ), C2 represents the MB concentration (mg·L⁻¹) in the MB solution when adsorption saturation is achieved. -1 ); C t-3 This indicates the concentration of MB in the MB solution (mg·L) at t-3 min of the reaction. -1 D2 represents the degradation rate (%) of MB.

[0087] The results were as follows: The manganese-based composite material (PMO) prepared in Example 1, used as a catalyst for activating periodate, showed a calculated MB degradation rate of 87.90% after 20 min (t-3 min). In contrast, the porous manganese trioxide (Mn2O3) prepared in Comparative Example 1, used as a catalyst for activating periodate, showed a MB degradation rate of 61.48% after 20 min (t-3 min). This demonstrates that the degradation of MB prepared in this invention, after being processed with PO4... 3- Modified Mn2O3, as a catalyst, exhibits excellent performance in activating the degradation of MB by periodate.

[0088] In summary, the manganese-based composite material of the present invention comprises a Mn2O3 matrix material and SO4 chemically bonded to the surface of the matrix material. 2- Or PO4 3- SO42- Or PO4 3- The bonding on the Mn2O3 surface alters the micro-electronic environment of Mn ions, enhancing their dependence on IO4 in the reaction solution. - The adsorption and polarization of metal ions facilitate the subsequent adsorption and polarization of IO4-. - The electronic transfer facilitated the development of IO4 - The breaking of bonds facilitates the generation of more reactive oxygen species, significantly improving the efficiency of Mn2O3 / periodate in degrading organic waste liquid. This is due to SO4... 2- Or PO4 3- The modified Mn2O3 exhibits increased activity, significantly reducing its dosage in advanced oxidation reaction systems and lowering operating costs.

[0089] The method for preparing the manganese-based composite material of the present invention uses porous Mn2O3 obtained by oxalate precipitation as the matrix and inexpensive inorganic ammonium sulfate or ammonium phosphate as the modifying agent. SO42- can be achieved through a simple impregnation-calcination step. 2- Or PO4 3- Uniform bonding on the Mn2O3 surface, simple preparation process, low equipment requirements, and easy to achieve large-scale and stable industrial preparation of catalyst products.

[0090] The performance of the manganese-based composite material of the present invention inevitably declines with increasing use of the Mn2O3-based catalyst. However, by re-impregnating the recovered manganese-based composite material in ammonium sulfate or ammonium phosphate solution and then calcining it, its activity can be restored. This not only ensures the efficiency of catalyst recycling but also offers the advantage of a simple regeneration process.

[0091] The manganese-based composite material of this invention, as a catalyst for activating periodate, exhibits good adaptability to various organic waste liquids and can be used as a universal catalyst for the activation of periodate and the treatment of organic waste liquids. It has significant potential for widespread application in the field of water pollution control technology.

[0092] The above embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention.

Claims

1. A manganese-based composite material, characterized in that, The manganese oxide (Mn2O3) matrix material and acid radical ions bonded to the surface of the manganese oxide (Mn2O3) matrix material.

2. The manganese-based composite material according to claim 1, characterized in that, the acid radical is selected from one or both of SO4 2- and PO4 3- , the acid radical being chemically bonded to the surface of the manganese sesquioxide (Mn2O3) base material.

3. A method of producing the manganese-based composite material as claimed in claim 1 or claim 2, characterized by, The method comprises the following steps: S1, dissolving a soluble inorganic manganese salt in an inorganic solvent to obtain solution A; dissolving a soluble oxalate in an inorganic solvent to obtain solution B; S2, adding the solution A to the solution B, stirring and reacting, solid-liquid separation, to obtain a manganese oxalate precursor; S3, calcining the manganese oxalate precursor to obtain porous manganese oxide (Mn2O3); S4, immersing the porous manganese oxide (Mn2O3) in an ammonium salt solution, stirring at room temperature, and standing to obtain manganese oxide (Mn2O3) impregnated with ammonium salt; S5, calcining the manganese oxide (Mn2O3) impregnated with ammonium salt to obtain a manganese-based composite material.

4. The method of producing a manganese-based composite material according to claim 3, characterized by, The temperature for calcining the manganese oxalate precursor is 400-550℃, and the time is 2-4h; And / or, the temperature for calcining the manganese oxide (Mn2O3) impregnated with ammonium salt is 400-700℃, and the time is 2-4h; And / or, the temperature for calcining the manganese oxide (Mn2O3) impregnated with ammonium salt is 400-700℃, and the time is 2-4h; 5. The method of producing a manganese-based composite material according to claim 3, characterized by, The soluble inorganic manganese salt is selected from at least one of manganese chloride, manganese nitrate, manganese sulfate and manganese acetate; And / or, the soluble oxalate is selected from at least one of sodium oxalate, potassium oxalate and ammonium oxalate; And / or, the ammonium salt solution is selected from one or both of ammonium sulfate solution and ammonium phosphate solution; And / or, the inorganic solvent is water.

6. The method of producing a manganese-based composite material according to claim 3, characterized by, The concentration of the soluble inorganic manganese salt in the solution A is 0.1-0.25mol / L; And / or, the concentration of the soluble oxalate in the solution B is 0.1-0.25mol / L; And / or, the ammonium salt solution is an ammonium salt aqueous solution, and the concentration of the ammonium salt in the ammonium salt aqueous solution is 0.25-1mol / L; And / or, the molar ratio of manganese ions in the solution A to oxalate ions in the solution B is 1:1-1.1; And / or, the ratio of the manganese oxide (Mn2O3) to the ammonium salt solution is 1g:50-60mL.

7. The method of producing a manganese-based composite material according to claim 3, characterized by, The S2 comprises: adding the solution A to the solution B, stirring and reacting, solid-liquid separation, to obtain a precursor precipitate; washing the precursor precipitate with water and anhydrous ethanol, and then drying at a temperature of 60-90℃ to obtain the manganese oxalate precursor; And / or, the S4 comprises: immersing the porous manganese oxide (Mn2O3) in an ammonium salt solution, stirring at room temperature for 2-4h, and then standing for 12-24h, to obtain a precipitate impregnated with ammonium salt: drying the precipitate impregnated with ammonium salt at a temperature of 60-90℃ to obtain the manganese oxide (Mn2O3) impregnated with ammonium salt.

8. Use of the manganese-based composite material prepared by the preparation method of any one of claims 3-7 as a catalyst.

9. Use according to claim 8, characterized in that, The manganese-based composite material is used as a catalyst for activating a perperiodate to degrade organic matter in an organic waste liquid.

10. Use according to claim 9, characterized in that, The manganese-based composite material is used as a catalyst for activating a persulfate to degrade at least one of a cationic dye rhodamine B, a cationic dye methylene blue and an anionic dye acid orange 7 in an organic waste liquid; And / or, the persulfate is selected from sodium persulfate.

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