A manganese-cerium bimetallic oxide carbon composite catalyst and a preparation method and application thereof

Abstract

The application provides a manganese-cerium bimetallic oxide carbon composite catalyst and a preparation method and application thereof, and belongs to the field of catalyst materials. N , N The manganese salt and the cerium salt are added into dimethylformamide to obtain a manganese-cerium mixed solution by stirring; then, the manganese-cerium mixed solution is added with trimesic acid, and after uniform stirring, the mixture is transferred into a reaction kettle for reaction; after the reaction is completed, the MnCe-BTC precursor is obtained through treatment; and the MnCe-BTC precursor is calcined under the protection of an inert atmosphere to obtain the manganese-cerium bimetallic oxide carbon composite catalyst. The method can effectively avoid the problem of metal particle agglomeration, prevent the dissolution of metal ions, and reduce the risk of secondary pollution. The prepared catalyst has high catalytic activity, high stability and excellent cycle performance.

Description

Technical Field

[0001] This invention belongs to the fields of catalyst materials and fine chemical synthesis, specifically relating to a manganese-cerium bimetallic oxide carbon composite catalyst, its preparation method, and its application. Background Technology

[0002] Phenolic compounds are aromatic compounds with one or more hydroxyl groups attached to their aromatic rings. They mainly originate from various industrial wastewaters from petroleum refining and chemical synthesis, and can also be produced naturally in aquatic environments through algal secretions and lignin conversion. Humans can come into contact with phenolic substances through food, industrial products, and daily necessities. Phenolic substances are corrosive, and long-term or repeated exposure can harm the respiratory tract, eyes, and skin. In vitro experiments have demonstrated that phenolic pollutants can induce diseases in various human organs. Therefore, the ecological risks of phenolic pollutants are receiving increasing attention, highlighting the urgent need to develop effective removal technologies.

[0003] Advanced oxidation technologies (AORs) are environmentally friendly processes, and heterogeneous AORs, in particular, have been widely studied due to their recyclable and highly stable catalysts. In recent years, potassium persulfate (PMS)-Fenton-like systems have become a research hotspot due to their convenient and safe transportation and storage, high oxidation potential, and fast oxidation rate. In these systems, the development of efficient and stable heterogeneous catalysts is crucial. Numerous studies have shown that manganese-based catalysts and their composites with carbon materials exhibit good activation efficiency for PMS. However, to promote the application of manganese-based catalysts and their carbon composites in practical water treatment, further improvements in PMS activation efficiency and the resolution of secondary pollution caused by ion leaching from manganese-based catalysts in water are needed. Summary of the Invention

[0004] The purpose of this invention is to provide a manganese-cerium bimetallic oxide carbon composite catalyst, its preparation method and application, which effectively overcomes the problems of poor catalyst activation efficiency and secondary pollution caused by ion dissolution in the prior art.

[0005] To achieve the above or other objectives, the present invention is implemented through the following technical solutions.

[0006] A method for preparing a manganese-cerium bimetallic oxide carbon composite catalyst includes the following steps: (1) Add manganese salt and cerium salt to N , N A manganese-cerium mixed solution was obtained by stirring dimethylformamide. (2) Add pyromellitic acid to the manganese-cerium mixed solution, stir evenly, transfer to the reaction vessel for reaction, and after the reaction is completed, process to obtain the MnCe-BTC precursor; (3) The MnCe-BTC precursor was calcined under an inert atmosphere to obtain a manganese cerium bimetallic oxide carbon composite catalyst, which is denoted as MnO-CeO2 / C composite catalyst.

[0007] Further, the manganese salt is selected from one or more of manganese chloride, manganese nitrate, manganese sulfate, and manganese acetate. Preferably, the manganese salt is manganese nitrate.

[0008] Further, the cerium salt is selected from one or more of cerium chloride, cerium nitrate, cerium acetate, and cerium sulfate. Preferably, the cerium salt is cerium nitrate.

[0009] Furthermore, the ratio of manganese salt to cerium salt satisfies the following: the molar ratio of Mn to Ce is 4:1 to 3:2.

[0010] Preferably, the ratio of manganese salt to cerium salt satisfies the following condition: the molar ratio of Mn to Ce is 3:2.

[0011] Furthermore, in step (1), the concentration of manganese salt in the manganese-cerium mixed solution is 0.10~0.20 mol·L⁻¹. −1 .

[0012] Furthermore, the ratio of manganese salt to pyromellitic acid (H3BTC) satisfies the following: the molar ratio of Mn to H3BTC is 3:5 to 1:1.

[0013] Furthermore, in step (2), the reaction temperature is 140~160℃ and the reaction time is 5~10 h.

[0014] Furthermore, after the reaction in step (2) is completed, the treatment methods include, but are not limited to, centrifugation, washing, and vacuum drying.

[0015] Furthermore, during calcination in step (3), the inert atmosphere selected is nitrogen or argon. Preferably, the inert atmosphere is argon.

[0016] Furthermore, in step (3), the heating rate during calcination is 3~5℃ / min, the calcination temperature is 600~850℃, and the holding time is 2~4 hours.

[0017] This invention also protects the manganese-cerium bimetallic oxide-carbon composite catalyst prepared by the above method. The obtained manganese-cerium bimetallic oxide-carbon composite catalyst has a flower-like structure with a size of 4~10 μm.

[0018] In another aspect, this invention also protects the application of the above-mentioned manganese-cerium bimetallic oxide carbon composite catalyst as a catalyst in the activation of PMS for the degradation of phenolic organic pollutants.

[0019] A method for activating PMS to degrade phenolic organic pollutants, using the above-mentioned manganese-cerium bimetallic oxide carbon composite catalyst as a catalyst, wherein the phenolic organic pollutants are selected from one or more of p-chlorophenol, bisphenol A, phenol, and aminophenol.

[0020] Further, the method includes the following steps: dispersing the manganese-cerium bimetallic oxide carbon composite catalyst in an aqueous solution, dissolving phenolic organic pollutants in the solution, adding PMS oxidant to carry out the degradation reaction, monitoring the concentration of phenolic organic pollutants using high performance liquid chromatography during the reaction, and treating and recovering the catalyst until the reaction is completed.

[0021] Furthermore, the mass ratio of the manganese-cerium bimetallic oxide carbon composite catalyst, phenolic organic pollutants, and PMS oxidant is (25~35):3:(25~100).

[0022] Furthermore, the degradation reaction temperature is 25~28℃.

[0023] Furthermore, after the reaction is complete, the processing methods include, but are not limited to, centrifugation and drying.

[0024] The method for preparing the manganese-cerium bimetallic oxide-carbon composite catalyst provided by this invention employs a hydrothermal and high-temperature calcination synthesis method. The hydrothermal process primarily synthesizes the MnCe-BTC precursor, while the high-temperature calcination process synthesizes a flower-like structure with uniform elemental distribution, forming the MnO-CeO2 / C composite catalyst. By introducing Ce into MnO, the variable valence state of Ce is achieved (Ce... 3 + / Ce 4+ (mutual conversion) and Mn element (Mn 2+ / Mn 3+ / Mn 4+ This creates a synergistic effect. Simultaneously, uniformly loading manganese-cerium bimetallic oxide onto a high-specific-surface-area C support not only effectively inhibits the aggregation of metal oxide particles and improves catalyst dispersibility, but also leverages the excellent adsorption and conductivity of the C support. On one hand, it enhances the catalyst's physical and chemical adsorption capabilities for organic pollutant molecules in water, achieving pollutant molecule enrichment on the catalyst surface. On the other hand, it accelerates the electron transfer rate between PMS molecules and the catalyst's active sites, lowering the energy barrier for PMS activation. Ultimately, this significantly improves the catalyst's activation efficiency for PMS, as well as its degradation efficiency, degradation rate, and mineralization rate of organic pollutant molecules in water, demonstrating promising prospects for practical application.

[0025] In summary, the method for preparing manganese-cerium bimetallic oxide carbon composite catalysts provided by this invention can effectively avoid the problem of metal particle agglomeration, prevent metal ion dissolution, and reduce the risk of secondary pollution. It fully utilizes the core advantages of manganese-based MOFs (high electron transfer performance) and cerium-based MOFs (good redox activity and high specific surface area) to prepare high-performance PMS activators with high catalytic activity, strong stability, and excellent cycle performance, providing an efficient and feasible technical path for the rapid degradation and deep removal of phenolic pollutants. Attached Figure Description

[0026] Figure 1 This is a scanning electron microscope image of the manganese-cerium bimetallic oxide-carbon composite catalyst prepared in Example 1.

[0027] Figure 2 The powder X-ray diffraction pattern is shown for the manganese-cerium bimetallic oxide carbon composite catalyst prepared in Example 1.

[0028] Figure 3 The image shows the elemental surface distribution energy spectrum of the manganese-cerium bimetallic oxide-carbon composite catalyst prepared in Example 1.

[0029] Figure 4 The graph shows the degradation effect of phenol under different catalyst conditions.

[0030] Figure 5 This is a comparison chart of the phenol degradation effect at different PMS concentrations.

[0031] Figure 6 Comparison of PMS degradation of phenol under different pH conditions using manganese-cerium bimetallic oxide-carbon composite catalyst.

[0032] Figure 7 The image shows a comparison of the morphology of the manganese-cerium bimetallic oxide-carbon composite catalyst prepared in Example 1 before and after the reaction using scanning electron microscopy. Detailed Implementation

[0033] The following specific embodiments illustrate 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 also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, unless otherwise specified, the following embodiments and features described therein can be combined with each other.

[0034] It should be noted that the illustrations provided in this embodiment are only schematic representations of the basic concept of the present invention. Therefore, the drawings only show the components related to the present invention and are not drawn according to the actual number, shape and size of the components in the actual implementation. In the actual implementation, the form, quantity and proportion of each component can be arbitrarily changed, and the layout of the components may also be more complex.

[0035] It should be noted that the terms such as "upper", "lower", "left", "right", "middle" and "one" used in this specification are only for clarity of description and are not intended to limit the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered as part of the scope of the invention.

[0036] The technical solution of the present invention will be described in detail below through several specific embodiments. Unless otherwise stated, the raw materials and reagents used in the following embodiments are commercially available products, or can be prepared by conventional methods in the art. Unless otherwise specified, the detection methods used in the embodiments of the present invention are conventional detection methods in the industry.

[0037] Example 1

[0038] The preparation method of the manganese-cerium bimetallic oxide carbon composite catalyst is as follows: (1) 0.0039 mol of Mn(NO3)2·4H2O and 0.0026 mol of Ce(NO3)3·6H2O were added to 30 mL of DMF and dissolved. The concentration of manganese nitrate in the resulting solution was 0.13 mol·L. −1 Then, 0.0065 mol of trimesic acid was added, the solution was transferred to a reaction vessel, and the reaction vessel was placed in an oven at 160°C for 5 hours.

[0039] (2) After the reaction was completed, the solid in the reactor was centrifuged and washed, and dried under vacuum at 60°C to obtain the MnCe-BTC precursor. It was then transferred to a quartz glass boat, and the heating program of the tube furnace was set to 3°C / min, the holding time was 3 hours, the protective atmosphere was argon, the argon flow rate was 5 mL / min, and the calcination temperature was 800°C. After the program was completed, the flower-like MnO-CeO2 / C catalyst was obtained.

[0040] The obtained MnO-CeO2 / C catalyst was subjected to scanning electron microscopy, and the resulting spectra are shown below. Figure 1 As shown, the MnO-CeO2 / C catalyst exhibits a flower-like structure with a size of 5 μm.

[0041] The obtained MnO-CeO2 / C catalyst was subjected to powder X-ray diffraction analysis, and the results are as follows: Figure 2As shown, by comparing with the standard PDF card, it can be proven that the crystal structure of the material obtained after high-temperature calcination of the MnCe-BTC precursor is a mixture of MnO, CeO2 and C.

[0042] The obtained MnO-CeO2 / C catalyst was subjected to elemental surface area scanning analysis using transmission electron microscopy, and the results are as follows: Figure 3 As shown in the figure, C, Mn, Ce, and O elements are uniformly distributed and form a stable composite structure. By introducing Ce into the MnO lattice system, the variable valence state property of Ce is utilized. 3+ / Ce 4+ (mutual conversion) and Mn element (Mn 2 + / Mn 3+ / Mn 4+ The synergistic effect is formed, and the oxide is loaded on the C support, which can effectively improve the adsorption of organic pollutant molecules by the catalyst and the electron transfer rate between PMS molecules and active sites, ultimately improving the activation efficiency of the catalyst for PMS and the degradation efficiency of pollutant molecules.

[0043] Example 2

[0044] The preparation method of the manganese-cerium bimetallic oxide carbon composite catalyst is as follows: (1) Manganese sulfate and cerium chloride with a molar ratio of Mn:Ce of 4:1 were added to DMF and dissolved, and the concentration of manganese sulfate in the resulting solution was 0.1 mol·L⁻¹. −1 Then, pyromellitic acid (Mn and H3BTC in a molar ratio of 4:5) was added, the solution was transferred to a reaction vessel, and the reaction vessel was placed in an oven at 150°C for 5 hours.

[0045] (2) After the reaction was completed, the solid in the reactor was centrifuged and washed, and dried under vacuum at 60°C to obtain the MnCe-BTC precursor. It was then transferred to a quartz glass boat, and the heating program of the tube furnace was set to 3°C / min, the holding time was 3 hours, the protective atmosphere was argon, the argon flow rate was 5 mL / min, and the calcination temperature was 850°C. After the program was completed, the flower-like MnO-CeO2 / C catalyst was obtained.

[0046] Example 3

[0047] The preparation method of the manganese-cerium bimetallic oxide carbon composite catalyst is as follows: (1) Manganese chloride and cerium acetate with a molar ratio of Mn:Ce of 2:1 were added to DMF and dissolved, and the concentration of manganese sulfate in the resulting solution was 0.2 mol·L⁻¹. −1Then, pyromellitic acid (Mn and H3BTC in a molar ratio of 1:1) was added, the solution was transferred to a reaction vessel, and the reaction vessel was placed in an oven at 140°C for 6 hours.

[0048] (2) After the reaction was completed, the solid in the reactor was centrifuged and washed, and dried under vacuum at 60°C to obtain the MnCe-BTC precursor. It was then transferred to a quartz glass boat, and the heating program of the tube furnace was set to 4°C / min, the holding time was 2 hours, the protective atmosphere was argon, the argon flow rate was 5 mL / min, and the calcination temperature was 600°C. After the program was completed, the flower-like MnO-CeO2 / C catalyst was obtained.

[0049] Example 4

[0050] The preparation method of the manganese-cerium bimetallic oxide carbon composite catalyst is as follows: (1) Manganese acetate and cerium sulfate with a molar ratio of Mn:Ce of 3:2 were added to DMF and dissolved, and the concentration of manganese sulfate in the resulting solution was 0.2 mol·L⁻¹. −1 Then, pyromellitic acid (Mn and H3BTC in a molar ratio of 1:1) was added, the solution was transferred to a reaction vessel, and the reaction vessel was placed in an oven at 150°C for 8 hours.

[0051] (2) After the reaction was completed, the solid in the reactor was centrifuged and washed, and dried under vacuum at 60°C to obtain the MnCe-BTC precursor. It was then transferred to a quartz glass boat, and the heating program of the tube furnace was set to 5°C / min, the holding time was 2 hours, the protective atmosphere was argon, the argon flow rate was 5 mL / min, and the calcination temperature was 800°C. After the program was completed, the flower-like MnO-CeO2 / C catalyst was obtained.

[0052] Comparative Example 1 Preparation of MnO / C catalyst: (1) Prepare a clear solution using Mn(NO3)2·4H2O and DMF (30 mL) to achieve a manganese nitrate concentration of 0.22 mol·L⁻¹. −1 Then, 0.0065 mol of trimesic acid was added to the above clear solution, the solution was transferred to a reaction vessel, and the reaction vessel was placed in an oven at 150°C for 5 hours.

[0053] (2) After the reaction was completed, the solid in the reactor was centrifuged and washed, and dried under vacuum at 60°C to obtain the Mn-BTC precursor. It was then transferred to a quartz glass boat, and the heating program of the tube furnace was set to 3°C / min, the holding time was 3 hours, the protective atmosphere was argon, the argon flow rate was 5 mL / min, and the calcination temperature was 800°C. After the program was completed, the rod-shaped MnO / C catalyst was obtained.

[0054] Comparative Example 2 Preparation of CeO2 / C catalyst: (1) Prepare a clear solution using Ce(NO3)3·6H2O and DMF (30 mL) to make the concentration of cerium nitrate in the solution 0.22 mol·L. −1 Then, 0.0065 mol of trimesic acid was added to the above clear solution, the solution was transferred to a reaction vessel, and the reaction vessel was placed in an oven at 160°C for 5 hours.

[0055] (2) The solid in the reactor was centrifuged and washed, and then dried under vacuum at 60°C to obtain the MnCe-BTC precursor. It was then transferred to a quartz glass boat. The heating program of the tube furnace was set to 3°C / min, the holding time was 3 hours, the protective atmosphere was argon, the argon flow rate was 5 mL / min, and the calcination temperature was 800°C. After the program was completed, the rod-shaped CeO2 / C catalyst was obtained.

[0056] Application Example 1 Take 20 mg·L −1 30 mL of phenol solution was used as the target pollutant. 5 mg of the flower-shaped MnO-CeO2 / C catalyst prepared in Example 1 was weighed and added to the phenol solution. After sonication for 5 min, the solution was placed in a water bath at 25°C and stirred for 30 min to allow the phenol molecules in the solution to reach adsorption-desorption equilibrium on the catalyst surface. 10 mg of PMS was added to initiate the reaction. During the reaction, a certain volume of the reaction mixture was taken every 2 min and added to a liquid chromatography vial containing 2 mg of Na2S2O3. The phenol content in the solution was determined by high performance liquid chromatography.

[0057] Application Example 2 This application example is the same as application example 1, except that 5 mg of PMS is added in application example 2.

[0058] Application Example 3 This application example is the same as application example 1, except that 15 mg of PMS is added in application example 2.

[0059] Application Example 4 This application example is the same as application example 1, except that 20 mg of PMS is added in application example 2.

[0060] Application Example 5 The method is the same as in Application Example 1, except that 30 mL of 20 mg·L⁻¹ is used. −1 Add 0.3 mL of pH=1 H2SO4 solution to the phenol solution to adjust the pH of the phenol solution to 3.

[0061] Application Example 6 The method is the same as in Application Example 1, except that 30 mL of 20 mg·L⁻¹ is used. −1 Add 0.03 mL of NaOH solution with pH=12 to the phenol solution to adjust the pH of the phenol solution to 9.

[0062] Application Example 7 The method is the same as in Application Example 1, except that 26.4 mL of deionized water is taken and 600 μL of 1000 mg·L⁻¹ is added. −1 Phenol solution: Add 3 mL of NaOH solution with pH=12 to the phenol solution to adjust the pH of the phenol solution to 11.

[0063] Application Example 8 The method is the same as in Application Example 1. The difference is that the pollutant used in this application example is p-chlorophenol. The degradation of p-chlorophenol is determined by high performance liquid chromatography. The degradation rate reaches more than 95% after 10 minutes.

[0064] Application Example 9 The method is the same as in Application Example 1. The difference is that the pollutant used in this application example is aminophenol. The degradation of aminophenol is determined by high performance liquid chromatography. The degradation rate reaches more than 95% after 10 minutes.

[0065] Application performance testing 1. Performance Testing of Different Catalysts on Phenol Degradation: To verify the effect of different catalysts on the degradation of phenol by PMS, a control experiment was conducted. MnO / C catalysts (comparative example 1) and CeO2 / C catalysts (comparative example 2) prepared in Comparative Example 1 and Comparative Example 2, respectively, were added to a phenol solution for degradation reaction, using the same method as in Application Example 1. High-performance liquid chromatography (HPLC) was performed every 2 minutes during the reaction. Control group 1 (PMS only) and control group 2 (MnO-CeO2 / C catalyst only) were also set up. Control group 1 did not add any catalyst, only 30 mL of 20 mg·L⁻¹ PMS was used. −1 Adding 10 mg PMS to the phenol solution initiated the degradation reaction; the treatment method for control group 2 differed from that in application example 1: 30 mL of 20 mg·L⁻¹ PMS was added. −1 A phenol solution was added with 5 mg of MnO-CeO2 / C catalyst and placed in a water bath at 25°C for stirring. No PMS was added. The phenol content in the solution was measured by high performance liquid chromatography every 2 minutes during the reaction.

[0066] The results measured in Application Example 1 (corresponding to MnO-CeO2 / C catalyst), Comparative Example 1 (MnO / C catalyst), Comparative Example 2 (CeO2 / C catalyst), Control Group 1 (PMS only), and Control Group 2 (MnO-CeO2 / C catalyst only) were compared. Figure 4 As shown in the figure, when only PMS or only MnO-CeO2 / C catalyst is used, the degradation rate of phenol at 10 min is almost 0. The degradation rate of phenol in the catalytic system composed of MnO / C catalyst, CeO2 / C catalyst and PMS containing only one oxide is only 38% and 35% at 10 min, respectively. However, when MnO-CeO2 / C catalyst and PMS are added, the degradation rate of phenol in the catalytic system reaches 99% at 10 min. This indicates that the MnO-CeO2 / C catalyst achieves efficient activation of PMS and efficient degradation of pollutants through the combination of two oxides.

[0067] 2. Effect of PMS concentration on degradation rate To further verify the effect of PMS concentration on degradation efficiency, the test results of phenol solutions degraded with different amounts of PMS in Application Examples 1, 2, 3, and 4 were compared. Figure 5 As shown, Figure 5 The graph shows the degradation effect of the manganese-cerium bimetallic oxide carbon composite catalyst at different PMS concentrations. It can be seen that as the PMS concentration increases from 167 mg·L⁻¹, the degradation effect decreases. −1 (Corresponding to 5 mg PMS) increased to 500 mg·L −1 (Corresponding to 15 mg PMS), the degradation rate of the catalytic system gradually increased, while when the PMS concentration increased from 500 mg / L... −1 (Corresponding to 15 mg PMS) Increased by 667 mg L −1 When the reaction rate was 20 mg PMS, the reaction rate actually decreased. This is because the excessive free radicals generated in the reaction system would have a quenching effect, which would reduce the concentration of active species in the system and thus reduce the reaction rate.

[0068] 3. Stability testing of manganese-cerium bimetallic oxide carbon composite catalyst To investigate the effect of manganese-cerium bimetallic oxide-carbon composite catalyst on the degradation of phenol solutions by PMS at different pH values, the liquid phase results measured during the degradation processes of Application Example 1, Application Example 5 (pH=3), Application Example 6 (pH=9), and Application Example 7 (pH=11) were compared. Figure 6 As shown in the figure, when the pH range of the external environment is between 3 and 11, the degradation rate of phenol by PMS can still reach 80% after 10 min in the presence of the manganese-cerium bimetallic oxide carbon composite catalyst, indicating that the manganese-cerium bimetallic oxide carbon composite catalyst has high stability over a wide pH range.

[0069] The manganese-cerium bimetallic oxide-carbon composite catalyst recovered after the degradation reaction in Application Example 1 was subjected to scanning electron microscopy (SEM) analysis, and its morphology was compared with that of the manganese-cerium bimetallic oxide-carbon composite catalyst before the degradation reaction. Figure 7 As shown in the figure, the manganese-cerium bimetallic oxide carbon composite catalyst recovered after the phenol degradation reaction can still maintain its flower-like structure, indicating that the catalyst has high stability.

[0070] In summary, the manganese-cerium bimetallic oxide carbon composite catalyst prepared by this invention has high activation efficiency for PMS, high degradation efficiency for phenol, good stability, and the structure of the manganese-cerium bimetallic oxide carbon composite catalyst recovered after participating in the degradation reaction remains unchanged, indicating high potential for practical application.

[0071] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A method for preparing a manganese-cerium bimetallic oxide carbon composite catalyst, characterized in that, Includes the following steps: (1) Add manganese salt and cerium salt to N , N A manganese-cerium mixed solution was obtained by stirring dimethylformamide. (2) Add pyromellitic acid to the manganese-cerium mixed solution, stir evenly, transfer to the reaction vessel for reaction, and after the reaction is completed, process to obtain the MnCe-BTC precursor; (3) The MnCe-BTC precursor was calcined under an inert atmosphere to obtain a manganese cerium bimetallic oxide carbon composite catalyst, which is denoted as MnO-CeO2 / C composite catalyst.

2. The method as described in claim 1, characterized in that, The manganese salt is selected from one or more of manganese chloride, manganese nitrate, manganese sulfate, and manganese acetate; the cerium salt is selected from one or more of cerium chloride, cerium nitrate, cerium acetate, and cerium sulfate.

3. The method as described in claim 1, characterized in that, The ratio of manganese salt to cerium salt satisfies the following: the molar ratio of Mn to Ce is 4:1 to 3:

2.

4. The method as described in claim 1, characterized in that, The ratio of manganese salt to pyromellitic acid satisfies the following: based on the molar ratio of Mn to H3BTC, the molar ratio of Mn to H3BTC is 3:5 to 1:

1.

5. The method as described in claim 1, characterized in that, In step (2), the reaction temperature is 140~160℃ and the reaction time is 5~10 h.

6. The method as described in claim 1, characterized in that, In step (3), the heating rate is 3~5℃ / min, the calcination temperature is 600~850℃, and the holding time is 2~4 hours.

7. The manganese-cerium bimetallic oxide carbon composite catalyst prepared by the method according to any one of claims 1 to 6.

8. The application of the manganese-cerium bimetallic oxide carbon composite catalyst of claim 7 as a catalyst in the activation of PMS for the degradation of phenolic organic pollutants.

9. A method for activating PMS to degrade phenolic organic pollutants using a manganese-cerium bimetallic oxide carbon composite catalyst as a catalyst, wherein the manganese-cerium bimetallic oxide carbon composite catalyst described in claim 7 is used.

10. The method of claim 9, wherein the mass ratio of manganese-cerium bimetallic oxide carbon composite catalyst, phenolic organic pollutants, and PMS oxidant is (25~35):3:(25~100).

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