Manganese-cobalt bimetallic oxide catalyst as well as preparation method and application thereof
By preparing manganese cobalt dual metal oxide catalysts, the MOF template and water synthesis method are used to solve the long -term activation time and toxicity of cobalt -based catalysts, and the efficient degradation and PMS activation efficiency of Landmine B.
Patent Information
- Application Number
- CN202411534682.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-31
- Publication Date
- 2025-01-21
AI Technical Summary
In the prior art, cobalt-based catalysts have problems with long activation time, low activation efficiency and biotoxicity when activated persulfate (PMS), and their large-scale use may lead to secondary leaching of toxic metal cobalt ions. pollute.
A manganese-cobalt bimetallic oxide catalyst was prepared through a hydrothermal synthesis method. Using MOF as a template and combined with an oxidative calcination step, a catalyst with a hexagonal prism nanorod structure was prepared, which improved the activation efficiency of PMS and reduced the toxicity.
The efficient degradation of Rodin Ming B has improved the activation efficiency of PMS, reducing the toxicity of the catalyst, and showing higher catalytic activity at different PH conditions and different PMS concentrations.
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Figure CN119327479A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of catalysts, and in particular to a manganese-cobalt bimetallic oxide catalyst, a preparation method and application thereof. Background Art
[0002] Rhodamine B is a basic dye widely used in papermaking, textile printing and dyeing, leather manufacturing, colored glass coloring, cell fluorescent dye manufacturing and evolution firecracker manufacturing. These industries produce a large amount of Rhodamine B dye wastewater, which will cause great harm to human health and the ecological environment if not properly treated.
[0003] As an advanced oxidation technology, persulfate-based advanced oxidation processes (PS-AOPs) have attracted much attention in the field of wastewater treatment. This technology uses the generated reactive oxygen species (ROS) to degrade organic pollutants, and has the advantages of mild reaction conditions, high degradation rate, and fast degradation rate. Among them, permonosulfate (PMS) is often used as an oxidant to induce the generation of reactive oxygen species (ROS). PMS not only has a higher oxidation potential, a longer half-life, and a wider pH operating range, but more importantly, it is low in cost and easy to store. However, PMS needs to be activated before it can produce free radicals with high redox potential. How to efficiently activate PMS is currently a key issue in scientific research and industrial applications.
[0004] Among them, cobalt-based catalysts are considered to be the most effective materials for activating PMS, but the large-scale use of cobalt-based catalytic materials is often accompanied by secondary pollution caused by the leaching of toxic metal cobalt ions. Summary of the invention
[0005] Based on this, the object of the present invention is to provide a manganese-cobalt bimetallic oxide catalyst, a preparation method and application thereof.
[0006] In a first aspect, the present invention provides a method for preparing a manganese-cobalt bimetallic oxide catalyst, comprising the following steps: (1) dissolving a cobalt source, a manganese source and 2,5-dihydroxyterephthalic acid in a mixed solution of ethanol and N,N-dimethylamide, and obtaining a precursor of a manganese-cobalt bimetallic oxide catalyst through a hydrothermal synthesis reaction; (2) Oxidatively calcining the precursor of the manganese-cobalt bimetallic oxide catalyst to obtain a manganese-cobalt bimetallic oxide catalyst.
[0007] Compared with the prior art, the present invention uses MOF as a template to prepare cobalt-based bimetallic catalytic materials, which can not only effectively solve the problems of long activation time, low activation efficiency, and biological toxicity of single cobalt catalysts, but also the introduction of low-toxic manganese elements activates rhodamine B and improves the activation efficiency of PMS, thereby achieving high efficiency and low toxicity of rhodamine B degradation catalytic materials.
[0008] In one embodiment, the precursor of the manganese-cobalt bimetallic oxide catalyst is a metal organic framework material.
[0009] In one embodiment, in step (1), the molar ratio of the cobalt source, the manganese source and the 2,5-dihydroxyterephthalic acid is 1:1:1.
[0010] In one embodiment, in step (1), the cobalt source includes any one or both of anhydrous cobalt nitrate and cobalt chloride hexahydrate, and the manganese source includes any one or both of manganese nitrate hexahydrate and manganese chloride tetrahydrate.
[0011] In one embodiment, in step (1), the volumes of ethanol and N, N-dimethylformamide are the same.
[0012] In one embodiment, in step (1), the temperature of the hydrothermal synthesis reaction is 150°C to 250°C, and the insulation time is 24 to 36 hours.
[0013] In one embodiment, in step (2), the oxidation heating rate is 5-10°C min -1 , temperature is 350~600℃, and holding time is 1~3 h.
[0014] In one embodiment, the manganese-cobalt bimetallic oxide catalyst has a hexagonal nanorod structure, and the size of the nanorod is 10-20 μm.
[0015] In a second aspect, the present invention provides a manganese-cobalt bimetallic oxide catalyst, wherein the catalyst is prepared by any of the aforementioned methods for preparing the manganese-cobalt bimetallic oxide catalyst.
[0016] In a third aspect, the present invention provides a use of the manganese-cobalt bimetallic oxide catalyst as described above in the degradation of rhodamine B. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0018] Figure 1 is the XRD pattern of the manganese-cobalt bimetallic oxide catalyst in Example 1 of the present invention; Figure 2 is a SEM image of the manganese-cobalt bimetallic oxide catalyst in Example 1 of the present invention; Figure 3 TEM image of the distribution of Co, Mn and O elements of the manganese-cobalt bimetallic oxide catalyst in Example 1 of the present invention; Figure 4 is a SEM image of the manganese-cobalt bimetallic oxide catalyst in Example 2 of the present invention; Figure 5 is a SEM image of the manganese-cobalt bimetallic oxide catalyst in Example 3 of the present invention; Figure 6 is the XRD diagram of the manganese-based oxide catalyst in Comparative Example 1 of the present invention; Figure 7 is a SEM image of the cobalt-based oxide catalyst in Comparative Example 2 of the present invention; Figure 8 is the XRD pattern of the cobalt-based oxide catalyst in Comparative Example 2 of the present invention; Fig. 9 is a SEM image of the cobalt-based oxide catalyst in Comparative Example 2 of the present invention; Fig.10 XRD diagrams of the precursors of the catalysts prepared in Examples 1-3 and Comparative Examples 1-2 of the present invention; Fig.11 This is a UV absorption spectrum of the degradation of Rhodamine B by the manganese-cobalt bimetallic oxide catalyst in Example 1 of the present invention; Fig.12 This is a UV absorbance spectrum of the degradation of Rhodamine B by the manganese-cobalt bimetallic oxide catalyst in Example 2 of the present invention; Fig.13 This is a UV absorption spectrum of the degradation of Rhodamine B by the manganese-cobalt bimetallic oxide catalyst in Example 3 of the present invention; Fig.14 The ultraviolet absorption spectrum of Rhodamine B degraded by the manganese-based metal oxide catalyst in Comparative Example 1 of the present invention; Fig.15 This is a UV absorbance spectrum of the cobalt-based metal oxide catalyst degrading Rhodamine B in Comparative Example 2 of the present invention. DETAILED DESCRIPTION
[0019] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.
[0020] Metal organic framework (MOF) is a porous material formed by the coordination of transition metal central ions or metal clusters with O or N in organic ligands, and has unique properties such as high specific surface area, porosity, and modifiable structure. The present invention uses MOF as a template to prepare cobalt-based bimetallic catalytic materials, which can not only effectively solve the problems of long activation time, low activation efficiency, and biological toxicity of single cobalt catalysts, but also introduces low-toxic manganese elements to activate rhodamine B and improve the activation efficiency of PMS, thereby achieving high efficiency and low toxicity of rhodamine B degradation catalytic materials.
[0021] Specifically, the present invention provides a method for preparing a manganese-cobalt bimetallic oxide catalyst, comprising the following steps: (1) A cobalt source, a manganese source and 2,5-dihydroxyterephthalic acid are dissolved in a mixed solution of ethanol and N,N-dimethylamide, and a precursor of a manganese-cobalt bimetallic oxide catalyst is obtained through a hydrothermal synthesis reaction.
[0022] (2) The precursor of the manganese-cobalt bimetallic oxide catalyst is oxidatively calcined to obtain the manganese-cobalt bimetallic oxide catalyst.
[0023] In step (1), the cobalt source includes any one or both of anhydrous cobalt nitrate and cobalt chloride hexahydrate, and the manganese source includes any one or both of manganese nitrate hexahydrate and manganese chloride tetrahydrate.
[0024] In step (1), the temperature of the hydrothermal synthesis reaction is 150°C to 250°C, and the insulation time is 24 to 36 h.
[0025] In step (2), the oxidation heating rate is 5-10°C min -1 , temperature is 350~600 ℃, and holding time is 1~3 h.
[0026] In the present invention, unless otherwise specified, the experimental methods used are all conventional methods, and the materials, reagents, etc. used can be purchased from commercial channels.
[0027] Specific embodiments are listed below to illustrate the present invention. Example 1
[0028] In this embodiment, the preparation method of the manganese-cobalt bimetallic oxide catalyst comprises the following steps: (1) Preparation of manganese-cobalt bimetallic oxide catalyst precursor 1 mmol of cobalt chloride hexahydrate, 1 mmol of manganese chloride tetrahydrate and 1 mmol of 2, 5-dihydroxyterephthalic acid were dissolved in 60 ml of a mixed solution of 30 ml of ethanol and 30 ml of N, N-dimethylamide, stirred at room temperature until completely dissolved, then transferred to a sealed high-pressure reactor and hydroheated at 160 ° C for 26 h to obtain a precursor of a manganese-cobalt bimetallic oxide catalyst.
[0029] (2) Preparation of manganese-cobalt bimetallic oxide catalyst 100 mg of the precursor of the manganese-cobalt bimetallic oxide catalyst was placed in a muffle furnace at 6 °C min -1 The heating rate was increased to 360 °C and kept at that temperature for 1 h. After the temperature was naturally cooled, a manganese-cobalt bimetallic oxide catalyst was obtained.
[0030] The manganese-cobalt bimetallic oxide catalyst was subjected to X-ray diffraction analysis, such as Figure 1 As shown, this embodiment synthesized MnCo2O 4.5 . Further reading Figure 2-3 It can be seen that the manganese-cobalt bimetallic oxide catalyst of this embodiment has a hexagonal nanorod structure, the size of the nanorod is about 10-20 μm, and the Mn element, Co element and O element are uniformly dispersed in the hexagonal MnCo2O 4.5 middle. Example 2
[0031] In this embodiment, the preparation method of the manganese-cobalt bimetallic oxide catalyst comprises the following steps: (1) Preparation of manganese-cobalt bimetallic oxide catalyst precursor 1 mmol of cobalt chloride hexahydrate, 1 mmol of manganese chloride tetrahydrate and 1 mmol of 2, 5-dihydroxyterephthalic acid were dissolved in 60 ml of a mixed solution of 30 ml of ethanol and 30 ml of N, N-dimethylamide, stirred at room temperature until completely dissolved, then transferred to a sealed high-pressure reactor and hydroheated at 220 ° C for 30 h to obtain a precursor of a manganese-cobalt bimetallic oxide catalyst.
[0032] (2) Preparation of manganese-cobalt bimetallic oxide catalyst 100 mg of the precursor of the manganese-cobalt bimetallic oxide catalyst was placed in a muffle furnace at 7 °C min -1 The heating rate was increased to 500 °C and kept at this temperature for 2.5 h. After the temperature was naturally cooled, a manganese-cobalt bimetallic oxide catalyst was obtained.
[0033] The SEM scanning analysis of the manganese-cobalt bimetallic oxide catalyst was performed, such as Figure 4 As shown, the manganese-cobalt bimetallic oxide catalyst of this embodiment has a hexagonal nanorod structure, and the size of the nanorod is about 10-20 μm. Example 3
[0034] In this embodiment, the preparation method of the manganese-cobalt bimetallic oxide catalyst comprises the following steps: (1) Preparation of manganese-cobalt bimetallic oxide catalyst precursor 1 mmol of cobalt chloride hexahydrate, 1 mmol of manganese chloride tetrahydrate and 1 mmol of 2, 5-dihydroxyterephthalic acid were dissolved in 60 ml of a mixed solution of 30 ml of ethanol and 30 ml of N, N-dimethylamide, stirred at room temperature until completely dissolved, then transferred to a sealed high-pressure reactor and hydroheated at 245 ° C for 35 h to obtain a precursor of a manganese-cobalt bimetallic oxide catalyst.
[0035] (2) Preparation of manganese-cobalt bimetallic oxide catalyst 100 mg of the precursor of the manganese-cobalt bimetallic oxide catalyst was placed in a muffle furnace at 9 °C min -1 The heating rate was increased to 580 °C and kept at this temperature for 2.9 h. After the temperature was naturally cooled, a manganese-cobalt bimetallic oxide catalyst was obtained.
[0036] The SEM scanning analysis of the manganese-cobalt bimetallic oxide catalyst was performed, such as Figure 5 As shown, the manganese-cobalt bimetallic oxide catalyst of this embodiment has a hexagonal nanorod structure, and the size of the nanorod is about 10-20 μm. Comparative Example 1
[0037] In this comparative example, the preparation method of the manganese-based oxide catalyst comprises the following steps: (1) Preparation of manganese-based oxide catalyst precursor 1 mmol of manganese chloride tetrahydrate and 1 mmol of 2, 5-dihydroxyterephthalic acid were dissolved in 60 ml of a mixed solution of ethanol and N,N-dimethylamide in equal proportions, stirred at room temperature until completely dissolved, and then transferred to a sealed high-pressure reactor and hydroheated at 120 ° C for 24 h to obtain a manganese-based oxide catalyst precursor.
[0038] (2) Preparation of manganese-based oxide catalysts 100 mg of manganese-based oxide catalyst precursor was placed in a muffle furnace at 5 °C min -1 The heating rate was increased to 350°C and kept at that temperature for 1 h, and then the manganese-based oxide catalyst was obtained after natural cooling.
[0039] The manganese-based oxide catalyst was subjected to X-ray diffraction analysis, such as Figure 6 As shown, this comparative example synthesized Mn3O4. Figure 7It can be seen that the manganese-based oxide catalyst of this comparative example has a hexagonal nanorod structure, and the size of the nanorod is about 10-20 μm. Comparative Example 2
[0040] In this comparative example, the preparation method of the cobalt-based oxide catalyst comprises the following steps: (1) Dissolve 1 mmol of cobalt chloride hexahydrate and 1 mmol of 2, 5-dihydroxyterephthalic acid in 60 ml of a mixed solution of ethanol and N, N-dimethylamide in equal proportions, stir at room temperature until completely dissolved, then transfer to a sealed high-pressure reactor and hydroheat at 120 °C for 24 h to obtain a cobalt-based oxide catalyst precursor.
[0041] (2) Preparation of cobalt-based oxide catalysts 100 mg of cobalt-based oxide catalyst precursor was placed in a muffle furnace and heated at 5 °C min -1 The heating rate was increased to 350°C and kept at that temperature for 1 h, and then the cobalt-based oxide catalyst was obtained after natural cooling.
[0042] The cobalt-based oxide catalyst was subjected to X-ray diffraction analysis, such as Figure 8 As shown, this comparative example synthesized Co3O4. Fig. 9 It can be seen that the cobalt-based oxide catalyst of this comparative example has a hexagonal nanorod structure, and the size of the nanorod is about 10-20 μm. Test Example 1
[0043] The catalyst precursors obtained in step (1) of Examples 1-3 and Comparative Examples 1-2 were subjected to X-ray diffraction analysis. Fig.10 It can be seen that the characteristic peaks of Example 1-2 and Comparative Example 1-2 are highly consistent with the standard PDF card of MOF-74, so the catalyst precursors of Example 1-3 and Comparative Example 1-2 are both metal organic framework materials (MOF). Test Example 2
[0044] Add simulated Rhodamine B waste liquid into a beaker, and add the catalysts prepared in Example 1-3 and Comparative Example 1-2 as PMS activators, wherein the concentration of Rhodamine B is 100 mg / L, the amount of catalysts in Example 1-3 and Comparative Example 1-2 is 5 mg, and the concentration of PMS is 0.1 mM.
[0045] As shown in Table 1, the degradation efficiency of Rhodamine B by the manganese-cobalt bimetallic oxide catalyst of Example 1 can reach 94.62% within 2 minutes and 99.61% after 60 minutes. Example 2 can reach a degradation efficiency of 96% at 2 minutes and 99.41% after 60 minutes. Example 3 can reach a degradation efficiency of 95.54% at 2 minutes and 99.84% after 60 minutes. The degradation efficiency of Rhodamine B by the manganese-based oxide catalyst of Comparative Example 1 only reaches 64.01% at 2 minutes and 96.67% after 60 minutes; the cobalt-based oxide catalyst of Comparative Example 2 reaches 74.79% at 2 minutes and 95.65% after 60 minutes. Obviously, the degradation efficiency of Rhodamine B by the manganese-cobalt bimetallic oxide catalyst of the present invention is better than that of the manganese-based oxide catalyst of Comparative Example 1 and the cobalt-based oxide catalyst of Comparative Example 2, and the degradation speed is faster.
[0046] Table 1 Degradation efficiency of catalyst at 2 min and 60 min Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 2min 94.62% 96.01% 95.54% 64.01% 74.79% 60min 99.61% 99.41% 99.84% 96.67% 95.65% In the process of catalyst degradation of rhodamine B, the present invention performs ultraviolet absorption spectrum analysis. Figure 11-15 As shown, blue shift of the ultraviolet peak was found in both Examples 1-3 and Comparative Example 1, but the same phenomenon did not occur in Comparative Example 2. The blue shift of the ultraviolet peak is caused by the generation of N-deethyl intermediates of rhodamine B. It can be seen that in the process of degrading rhodamine B, manganese can activate rhodamine B in a non-radical process. Further, the synergistic effect between cobalt ions and manganese ions accelerates the activation of PMS, thereby promoting the efficient degradation of rhodamine B, so that the degradation efficiency of Examples 1-3 of the present invention is higher than that of Comparative Example 1. Test Example 3
[0047] Add the simulated Rhodamine B waste liquid in a beaker, and add the catalyst prepared in Example 1-3 and Comparative Example 1-2 as an activator of PMS. Wherein, the concentration of Rhodamine B is 100 mg / L, the amount of catalyst used in Example 1-3 and Comparative Example 1-2 is 5 mg, and the concentration of PMS is 0.1 mM. The pH of Rhodamine B was adjusted using 0.1 mM NaOH and 0.1 mM H2SO4, and the degradation test of Rhodamine B was carried out under the conditions of pH 3, 5, 7, 9, and 11, respectively. The concentrations of Rhodamine B in the waste liquid after 2 minutes and 60 minutes are shown in Tables 2 and 3, respectively.
[0048] It can be seen from Tables 2 and 3 that the manganese-cobalt bimetallic oxide catalysts of Examples 1 and 2 of the present invention have high catalytic activity in both acidic and alkaline environments, while the manganese-based oxide catalyst of Comparative Example 1 and the cobalt-based oxide catalyst of Comparative Example 2 have a narrow pH adaptability range.
[0049] Table 2 Rhodamine B concentration in wastewater after 2 min under different pH conditions pH=3 pH=5 pH=7 pH=9 pH=11 Example 1 4.38889 5.8268 3.89869 4.55229 0.25163 Example 2 0.59 0.10784 0.53268 0.51307 0.30392 Example 3 1.545752 5.761438 3.72549 4.388889 0.25163 Comparative Example 1 5.1634 13.04902 12.94801 50.40196 56.23203 Comparative Example 2 41.34967 20.56269 11.38838 41.70915 50.95752 Table 3 Rhodamine B concentration in wastewater after 60 min under different pH conditions pH=3 pH=5 pH=7 pH=9 pH=11 Example 1 0.44771 0.44771 0.97059 0.61111 0 Example 2 0 0 0 0 0 Example 3 0.41503 0.44771 0.11111 0.561117 0.61171 Comparative Example 1 0.55556 2.88562 3.16208 41.97059 40.05556 Comparative Example 2 28.99673 1.05199 0.59939 28.89869 50.5 Test Example 4
[0050] Add simulated Rhodamine B waste liquid in a beaker, and add the catalyst prepared in Example 1-3 and Comparative Example 1-2 as an activator of PMS. Wherein, the concentration of Rhodamine B is 100 mg / L, and the amount of catalyst used in Example 1-2 and Comparative Example 1-2 is 5 mg. The degradation test of Rhodamine B is carried out under the conditions of PMS concentration of 0.1 mM, 0.3 mM, 0.5 mM, 0.7 mM, and 0.9 mM, respectively. The concentration of Rhodamine B in the waste liquid after 2 minutes and 60 minutes is shown in Tables 4 and 5, respectively.
[0051] Table 4 Rhodamine B concentration in wastewater after 2 min under different PMS concentrations 0.1mM 0.3mM 0.5mM 0.7mM 0.9mM Example 1 0.30392 0.51307 0.74183 1.12092 0.23856 Example 2 0.10784 3.17974 5.04248 9.68301 3.17974 Example 3 0.54575 0.93791 0.74183 1.601307 0.336601 Comparative Example 1 58.61765 51.70915 22.85294 20.53268 18.63725 Comparative Example 2 53.70261 44.68301 40.04248 36.87255 32.33007 Table 5 Rhodamine B concentration in wastewater after 60 min under different PMS concentrations 0.1mM 0.3mM 0.5mM 0.7mM 0.9mM Example 1 0 0 0 0.43464 0.20588 Example 2 0 1.03595 0.77451 1.33007 1.06863 Example 3 0 0 0 0.653595 0 Comparative Example 1 35.23856 12.72222 0.34967 0.38235 0.70915 Comparative Example 2 45.27124 30.9902 2.06863 1.74183 0.51307 It can be seen from Table 4 that the degradation efficiency of the manganese-cobalt bimetallic oxide catalysts of Examples 1-3 of the present invention is almost the same within the PMS concentration range of 0.1 mM to 0.9 mM, while the degradation efficiency of Rhodamine B of the manganese-based oxide catalyst of Comparative Example 1 within the PMS concentration range of 0.1 mM to 0.3 mM and the cobalt-based oxide catalyst of Comparative Example 2 within the PMS concentration range of 0.1-0.5 mM are poor.
[0052] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0053] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.
Claims
1. A method for preparing a manganese-cobalt bimetallic oxide catalyst, characterized in that: The following steps are involved: (1) dissolving a cobalt source, a manganese source and 2,5-dihydroxyterephthalic acid in a mixed solution of ethanol and N,N-dimethylamide, and obtaining a precursor of a manganese-cobalt bimetallic oxide catalyst through a hydrothermal synthesis reaction; (2) Oxidatively calcining the precursor of the manganese-cobalt bimetallic oxide catalyst to obtain a manganese-cobalt bimetallic oxide catalyst.
2. The method for preparing the manganese-cobalt bimetallic oxide catalyst according to claim 1, characterized in that: The precursor of the manganese-cobalt bimetallic oxide catalyst is a metal organic framework material.
3. The method for preparing the manganese-cobalt bimetallic oxide catalyst according to claim 1 or 2, characterized in that: In step (1), the molar ratio of the cobalt source, the manganese source and 2,5-dihydroxyterephthalic acid is 1:1:
1.
4. The method for preparing the manganese-cobalt bimetallic oxide catalyst according to claim 1 or 2, characterized in that: In step (1), the cobalt source includes any one or both of anhydrous cobalt nitrate and cobalt chloride hexahydrate, and the manganese source includes any one or both of manganese nitrate hexahydrate and manganese chloride tetrahydrate.
5. The method for preparing the manganese-cobalt bimetallic oxide catalyst according to claim 1 or 2, characterized in that: In step (1), the volumes of ethanol and N, N-dimethylamide are the same.
6. The method for preparing the manganese-cobalt bimetallic oxide catalyst according to claim 1 or 2, characterized in that: In step (1), the temperature of the hydrothermal synthesis reaction is 150°C to 250°C, and the insulation time is 24 to 36 h.
7. The method for preparing the manganese-cobalt bimetallic oxide catalyst according to claim 1 or 2, characterized in that: In step (2), the oxidation heating rate is 5-10°C min -1 , temperature is 350~600 ℃, and holding time is 1~3 h.
8. The method for preparing the manganese-cobalt bimetallic oxide catalyst according to claim 1 or 2, characterized in that: The manganese-cobalt bimetallic oxide catalyst has a hexagonal nanorod structure, and the size of the nanorod is 10-20 μm.
9. A manganese-cobalt bimetallic oxide catalyst, characterized in that: The catalyst is prepared by the method for preparing the manganese-cobalt bimetallic oxide catalyst according to any one of claims 1 to 8.
10. Use of the manganese-cobalt bimetallic oxide catalyst as claimed in claim 9 in the degradation of rhodamine B.