Preparation method and application of Mn-doped Co catalyst material with large specific surface area and porous flower-shaped structure

Abstract

The invention relates to a preparation method and application of a Mn-doped Co catalyst material with a large specific surface area and a porous flower-shaped structure, wherein the Mn-doped Co catalyst material is constructed by adopting a one-step hydrothermal method. The prepared Mn-doped Co catalyst material with the large specific surface area and the porous flower-shaped structure can rapidly activate PMS to generate a large amount of < 1 > O2, so that 100% of an enrofloxacin solution can be degraded within 30 min, and after four times of circulation, the performance of the catalyst is still kept stable. The Mn-doped Co catalyst material with a large specific surface area and a porous flower-shaped structure is prepared by adopting a one-step hydrothermal method. The method has the characteristics of simple preparation method and preparation conditions, high economic benefit and capability of large-scale industrial production, and has good economic benefit and environmental benefit.

Description

Technical Field

[0001] This invention belongs to the field of materials technology, specifically relating to a method for preparing Mn-doped Co catalyst materials with large specific surface area and porous flower-like structure, and their application. Background Technology

[0002] In recent years, advanced oxidation technologies using PMS as the main oxidant have become one of the most effective methods for wastewater treatment due to their high stability, strong oxidizing power, and relatively low cost, and have been widely studied. Furthermore, transition metal ions can coordinate with PMS, promoting its decomposition and generating ROS, such as SO42-. − •OH and 1 O2 and other substances can oxidize and degrade organic pollutants in wastewater. A one-step hydrothermal method was used to prepare Mn-doped Co catalyst materials with a large specific surface area and porous flower-like structure, providing a new approach and method for the preparation and application of metal-doped manganese-based materials.

[0003] Currently, precise material design remains a significant challenge in wastewater treatment. The relationship between ROS regulation and precise material design primarily lies in the preparation of catalytic materials with specific characteristics, such as large specific surface area, pore structure, high electron transport efficiency, and abundant catalytic active sites, to achieve efficient degradation of organic pollutants in wastewater. To address this bottleneck, designing a simple synthetic method to prepare Mn-doped Co catalyst materials with large specific surface area and porous flower-like structure is of great importance. Summary of the Invention

[0004] The purpose of this invention is to address the shortcomings of existing technologies by providing a method for preparing a highly efficient and rapid enrofloxacin-degrading Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure. This invention uses manganese carbonate, formic acid, and deionized water as raw materials. After heating, stirring, rotary evaporation, and drying, manganese formate dihydrate powder is obtained. This powder is then mixed with CoCl₂·6H₂O and methanol, subjected to ultrasonication and stirring, and subjected to a hydrothermal reaction. Following centrifugation, washing, and freeze-drying, a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure is obtained.

[0005] This invention provides a green synthesis method for Mn-doped Co catalyst materials with large specific surface area and porous flower-like structure, which is simple, versatile, and highly applicable. Furthermore, the obtained Mn-doped Co catalyst material with large specific surface area and porous flower-like structure exhibits extremely high catalytic activity for the degradation of enrofloxacin. The method is simple, low-cost, and offers good economic and environmental benefits, and can be used for large-scale production.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure, and its application, comprising the following raw materials: manganese carbonate (MnCO3), formic acid (HCOOH), cobalt chloride hexahydrate (CoCl2·6H2O), and methanol (CH3OH).

[0007] A method for preparing a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure, and its application: Solution A is obtained by heating and stirring manganese carbonate, formic acid, and deionized water. Solution A is then subjected to rotary evaporation and drying to obtain manganese formate dihydrate powder. C₂H₆MnO₆ and CoCl₂·6H₂O are then mixed with methanol and subjected to ultrasonic treatment and stirring to obtain solution B. Solution B is subjected to a hydrothermal reaction under certain conditions, followed by centrifugation, washing, and freeze-drying to obtain a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure.

[0008] The Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure specifically includes the following steps: (1) A certain amount of manganese carbonate, deionized water and formic acid are added to a single-necked flask and heated and stirred to obtain solution A; (2) Solution A was subjected to rotary evaporation. After the liquid in the flask evaporated, a certain amount of deionized water was added, and the rotary evaporation was performed again. Finally, the rotary evaporation was stopped when a certain amount of solution remained in the flask, and the solution was dried to obtain manganese formate dihydrate powder. (3) Weigh a certain amount of manganese formate dihydrate C2H6MnO6, CoCl2·6H2O and methanol and add them to a beaker. After sonication, stir thoroughly until the solution is completely mixed to obtain solution B; (4) Solution B is subjected to a hydrothermal reaction under certain conditions, and then centrifuged, washed and dried until the water is completely evaporated to obtain a catalyst material of Mn-doped Co with a large specific surface area and a porous flower-like structure.

[0009] Further, the solution A described in step (1) consists of 1.15 g of manganese carbonate, 75 mL of deionized water, and 20 mL of formic acid.

[0010] Further, the heating and stirring in step (1) specifically includes: heating temperature of 80 ºC; magnetic stirring; stirring speed of 500 rpm; and stirring time of 2 h.

[0011] Further, the rotary evaporation process described in step (2) specifically involves: a temperature of 60 ºC; magnetic stirring; and a stirring speed of 80 rpm.

[0012] Furthermore, the specific amount of deionized water in step (2) is 50 mL.

[0013] Furthermore, the specific amount of solution in step (2) is 10 mL.

[0014] Furthermore, the drying process described in step (2) is specifically: vacuum freeze drying at -53 ℃ for 12 h.

[0015] Further, the composition of solution B in step (3) is as follows: C2H6MnO6 is 0.1810 g; CoCl2·6H2O is 0.072 g; and methanol is 60 mL.

[0016] Furthermore, the ultrasound in step (3) specifically refers to the following: ultrasound frequency of 38000 Hz - 42000 Hz; ultrasound temperature of 26 - 28 ℃; and ultrasound time of 5 min.

[0017] Further, the stirring described in step (3) specifically refers to: magnetic stirring; stirring speed of 500-1000 rpm; stirring time of 30-60 min.

[0018] Furthermore, the specific conditions mentioned in step (4) are: the hydrothermal temperature is 180 ℃; the reaction time is 18h.

[0019] Further, the centrifugation in step (4) specifically involves centrifuging at a speed of 8000 rpm for 3 minutes.

[0020] Further, the washing in step (4) specifically involves washing with ethanol 3 times and washing with deionized water 3 times.

[0021] Furthermore, the drying in step (4) specifically involves: vacuum freeze drying at -53 ℃ for 12 h.

[0022] The beneficial effects of this invention are as follows: (1) The present invention uses a one-step hydrothermal method to realize the preparation of Mn-doped Co catalyst material with large specific surface area and porous flower structure, and provides a new method for synthesizing metal-doped manganese-based materials, providing a new idea for the preparation of catalysts for efficient and rapid degradation of enrofloxacin.

[0023] (2) The Mn-doped Co catalyst material with a large specific surface area and porous flower-like structure prepared by the present invention is a cobalt-doped Mn3O4 material, wherein Mn exists in a mixture of +2, +3, and +4 valences, and Co exists in a mixture of +2 and +3 valences. The material is formed by the self-assembly of many two-dimensional nanosheets supporting each other into a nanoflower structure with a diameter of about 10 μm and uniform particle size.

[0024] (3) The raw materials and equipment required for the preparation method of the present invention are simple and easy to obtain, the process is simple, easy to operate and safe, the cost is relatively low, and it can be industrialized on a large scale. Different products with similar morphologies can be obtained by changing the type of transition metal ions added. Compared with the products prepared by other traditional methods, it has high degradation ability and is an environmentally friendly new material with good promotion and application value and application prospects. Attached Figure Description

[0025] Figure 1 These are X-ray diffraction (XRD) patterns of the Mn-doped Co catalyst material with large specific surface area and porous flower-like structure prepared in Example 1 of the present invention (MnCo / 0.3), the Mn-doped Co catalyst material with large specific surface area and porous flower-like structure prepared in Comparative Example 1 (MnCo / 0), the Mn-doped Co catalyst material with large specific surface area and porous flower-like structure prepared in Comparative Example 2 (MnCo / 0.1), and the Mn-doped Co catalyst material with large specific surface area and porous flower-like structure prepared in Comparative Example 3 (MnCo / 0.2). Figure 2 This is a graph showing the rate of enrofloxacin degradation of the following catalyst materials prepared in this invention: Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0.3) prepared in Example 1, Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0) prepared in Comparative Example 1, Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0.1) prepared in Comparative Example 2, and Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0.2) prepared in Comparative Example 3. Figure 3 This is a performance graph of the Mn-doped Co catalyst material (MnCo / 0.3) with a large specific surface area and porous flower-like structure prepared in Example 1 of the present invention, after undergoing a cycle experiment. Figure 4 This is a scanning electron microscope (SEM) image of the Mn-doped Co catalyst material (MnCo / 0.3) with a large specific surface area and porous flower-like structure prepared in Example 1 of the present invention. Figure 5This is a transmission electron microscope (TEM) image of the Mn-doped Co catalyst material (MnCo / 0.3) with a large specific surface area and a porous flower-like structure prepared in Example 1 of the present invention. Figure 6 This is a SEM image of the Mn-doped Ni catalyst material (MnNi / 0.3) with a large specific surface area and a porous flower-like structure prepared in Example 2 of the present invention. Figure 7 This is a SEM image of the Mn-doped Cu catalyst material (MnCu / 0.3) with a large specific surface area and a porous flower-like structure prepared in Example 3 of the present invention. Figure 8 This is a SEM image of the Mn-doped Co catalyst material (MnCo / O) with a large specific surface area and a porous flower-like structure prepared in Comparative Example 1 of this invention. Figure 9 This is a SEM image of the Mn-doped Co catalyst material (MnCo / 0.1) with a large specific surface area and a porous flower-like structure prepared in Comparative Example 2 of this invention. Figure 10 This is a SEM image of the Mn-doped Co catalyst material (MnCo / 0.2) with a large specific surface area and a porous flower-like structure prepared in Comparative Example 3 of this invention. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined as long as they do not conflict with each other.

[0027] Example 1 Preparation of Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0.3, where 0.3 is the molar ratio of Co to Mn): (1) Weigh 1.15 g of manganese carbonate using a balance and put it into a single-necked flask. Then, use a graduated cylinder to take out 75 mL of deionized water and 20 mL of formic acid and add them into the flask one by one. (2) The flask was placed in an oil bath at 80 ºC and 500 rpm and heated and stirred for 2 h until the solution became colorless and transparent. Then, the obtained solution was subjected to rotary evaporation at 60 ºC and 80 rpm. After the liquid in the flask evaporated, 50 mL of deionized water was added and rotary evaporation was performed again. Finally, when 10 mL of solution remained in the flask, the rotary evaporation was stopped, and the flask was removed and freeze-dried for 12 h to obtain manganese formate dihydrate powder (C2H6MnO6). (3) Weigh 0.1810 g of C2H6MnO6 and 0.072 g of CoCl2·6H2O using a balance and add them to a beaker equipped with a stir bar. Then, measure 60 mL of methanol using a graduated cylinder and add it to the beaker. Sonicate the beaker for 5 min, and then stir it on a stirring table for 30 min. (4) The solution was placed at 180 °C for 18 h of hydrothermal reaction, followed by centrifugation and washing. Finally, the precipitate obtained by centrifugation was freeze-dried for 12 h to obtain a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure.

[0028] Example 2 Preparation of Mn-doped Ni catalyst material with large specific surface area and porous flower-like structure (MnNi / 0.3, where 0.3 is the molar ratio of Ni to Mn): (1) Weigh 1.15 g of manganese carbonate using a balance and put it into a single-necked flask. Then, use a graduated cylinder to take out 75 mL of deionized water and 20 mL of formic acid and add them into the flask one by one. (2) The flask was placed in an oil bath at 80 ºC and 500 rpm and heated and stirred for 2 h until the solution became colorless and transparent. Then, the obtained solution was subjected to rotary evaporation at 60 ºC and 80 rpm. After the liquid in the flask evaporated, 50 mL of deionized water was added and rotary evaporation was performed again. Finally, when 10 mL of solution remained in the flask, the rotary evaporation was stopped, and the flask was removed and freeze-dried for 12 h to obtain manganese formate dihydrate powder (C2H6MnO6). (3) Weigh 0.1810 g of C2H6MnO6 and 0.0713 g of NiCl2·6H2O using a balance and add them to a beaker equipped with a stir bar. Next, measure 60 mL of methanol using a graduated cylinder and add it to the beaker. Sonicate the beaker for 5 min, and then stir it on a stirring table for 30 min. (4) The solution was placed at 180 °C for 18 h of hydrothermal reaction, followed by centrifugation and washing. Finally, the precipitate obtained by centrifugation was freeze-dried for 12 h to obtain a Mn-doped Ni catalyst material with a large specific surface area and a porous flower-like structure.

[0029] Example 3 Preparation of Mn-doped Cu catalyst material with large specific surface area and porous flower-like structure (MnCu / 0.3, where 0.3 is the molar ratio of Cu to Mn): (1) Weigh 1.15 g of manganese carbonate using a balance and put it into a single-necked flask. Then, use a graduated cylinder to take out 75 mL of deionized water and 20 mL of formic acid and add them into the flask one by one. (2) The flask was placed in an oil bath at 80 ºC and 500 rpm and heated and stirred for 2 h until the solution became colorless and transparent. Then, the obtained solution was subjected to rotary evaporation at 60 ºC and 80 rpm. After the liquid in the flask evaporated, 50 mL of deionized water was added and rotary evaporation was performed again. Finally, when 10 mL of solution remained in the flask, the rotary evaporation was stopped, and the flask was removed and freeze-dried for 12 h to obtain manganese formate dihydrate powder (C2H6MnO6). (3) Weigh 0.1810 g of C2H6MnO6 and 0.051 g of CuCl2·2H2O using a balance and add them to a beaker equipped with a stir bar. Then, measure 60 mL of methanol using a graduated cylinder and add it to the beaker. Sonicate the beaker for 5 min, and then stir it on a stirring table for 30 min. (4) The solution was placed at 180 °C for 18 h of hydrothermal reaction, followed by centrifugation and washing. Finally, the precipitate obtained by centrifugation was freeze-dried for 12 h to obtain a Mn-doped Cu catalyst material with a large specific surface area and a porous flower-like structure.

[0030] Comparative Example 1 Preparation of Mn-doped Co catalyst material (MnCo / O) with large specific surface area and porous flower-like structure: (1) Weigh 1.15 g of manganese carbonate using a balance and put it into a single-necked flask. Then, use a graduated cylinder to take out 75 mL of deionized water and 20 mL of formic acid and add them into the flask one by one. (2) The flask was placed in an oil bath at 80 ºC and 500 rpm and heated and stirred for 2 h until the solution became colorless and transparent. Then the obtained solution was subjected to rotary evaporation at 60 ºC and 80 rpm. After the liquid in the flask evaporated, 50 mL of deionized water was added and rotary evaporation was performed again. Finally, when 10 mL of solution remained in the flask, the rotary evaporation was stopped, the flask was removed and freeze-dried for 12 h to obtain manganese formate dihydrate powder (C2H6MnO6). (3) Weigh 0.1810 g of C2H6MnO6 using a balance and add it to a beaker equipped with a stir bar. Then, measure 60 mL of methanol using a graduated cylinder and add it to the beaker. Sonicate the beaker for 5 min, and then stir it on a stirring table for 30 min. (4) The solution was placed at 180 °C for 18 h of hydrothermal reaction, followed by centrifugation and washing. Finally, the precipitate obtained by centrifugation was freeze-dried for 12 h to obtain a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure.

[0031] Comparative Example 2 Preparation of Mn-doped Co catalyst material (MnCo / 0.1) with large specific surface area and porous flower-like structure: (1) Weigh 1.15 g of manganese carbonate using a balance and put it into a single-necked flask. Then, use a graduated cylinder to take out 75 mL of deionized water and 20 mL of formic acid and add them into the flask one by one. (2) The flask was placed in an oil bath at 80 ºC and 500 rpm and heated and stirred for 2 h until the solution became colorless and transparent. Then, the obtained solution was subjected to rotary evaporation at 60 ºC and 80 rpm. After the liquid in the flask evaporated, 50 mL of deionized water was added and rotary evaporation was performed again. Finally, when 10 mL of solution remained in the flask, the rotary evaporation was stopped, and the flask was removed and freeze-dried for 12 h to obtain manganese formate dihydrate powder (C2H6MnO6). (3) Weigh 0.1810 g of C2H6MnO6 and 0.024 g of CoCl2·6H2O using a balance and add them to a beaker equipped with a stir bar. Then, measure 60 mL of methanol using a graduated cylinder and add it to the beaker. Sonicate the beaker for 5 min, and then stir it on a stirring table for 30 min. (4) The solution was placed at 180 °C for 18 h of hydrothermal reaction, followed by centrifugation and washing. Finally, the precipitate obtained by centrifugation was freeze-dried for 12 h to obtain a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure.

[0032] Comparative Example 3 Preparation of Mn-doped Co catalyst material (MnCo / 0.2) with large specific surface area and porous flower-like structure: (1) Weigh 1.15 g of manganese carbonate using a balance and put it into a single-necked flask. Then, use a graduated cylinder to take out 75 mL of deionized water and 20 mL of formic acid and add them into the flask one by one. (2) The flask was placed in an oil bath at 80 ºC and 500 rpm and heated and stirred for 2 h until the solution became colorless and transparent. Then, the obtained solution was subjected to rotary evaporation at 60 ºC and 80 rpm. After the liquid in the flask evaporated, 50 mL of deionized water was added and rotary evaporation was performed again. Finally, when 10 mL of solution remained in the flask, the rotary evaporation was stopped, and the flask was removed and freeze-dried for 12 h to obtain manganese formate dihydrate powder (C2H6MnO6). (3) Weigh 0.1810 g of C2H6MnO6 and 0.048 g of CoCl2·6H2O using a balance and add them to a beaker equipped with a stir bar. Then, measure 60 mL of methanol using a graduated cylinder and add it to the beaker. Sonicate the beaker for 5 min, and then stir it on a stirring table for 30 min. (4) The solution was placed at 180 °C for 18 h of hydrothermal reaction, followed by centrifugation and washing. Finally, the precipitate obtained by centrifugation was freeze-dried for 12 h to obtain a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure.

[0033] Organic matter degradation experiment Application Example 1 The Mn-doped Co catalyst material (MnCo / 0.3) with a large specific surface area and porous flower-like structure obtained in Example 1 was used to degrade organic matter. The specific steps are as follows: (1) Prepare a 10 ppm enrofloxacin solution and a 1 M PMS solution; (2) Weigh 40 ml of enrofloxacin solution using a graduated cylinder; (3) Take 2 mg of Mn-doped Co catalyst material with large specific surface area and porous flower-like structure, add it into the above solution, and sonicate for 5 min; (4) Take 80 μl of 1 M PMS solution and add it to the above solution; (5) After different time periods, the ultraviolet absorbance of enrofloxacin in water was measured using an ultraviolet-visible spectrophotometer, and the removal rate of enrofloxacin was calculated.

[0034] Application Comparative Example 1 The Mn-doped Co catalyst material (MnCo / 0) with a large specific surface area and porous flower-like structure obtained in Comparative Example 1 was used to degrade organic matter. The specific steps are as follows: (1) Prepare a 10 ppm enrofloxacin solution and a 1 M PMS solution; (2) Weigh 40 ml of enrofloxacin solution using a graduated cylinder; (3) Take 2 mg of Mn-doped Co catalyst material with large specific surface area and porous flower-like structure, add it into the above solution, and sonicate for 5 min; (4) Take 80 μl of 1 M PMS solution and add it to the above solution; (5) After different time periods, the ultraviolet absorbance of enrofloxacin in water was measured using an ultraviolet-visible spectrophotometer, and the removal rate of enrofloxacin was calculated.

[0035] Application Comparative Example 2 The Mn-doped Co catalyst material (MnCo / 0.1) with a large specific surface area and porous flower-like structure obtained in Comparative Example 2 was used to degrade organic matter. The specific steps are as follows: (1) Prepare a 10 ppm enrofloxacin solution and a 1 M PMS solution; (2) Weigh 40 ml of enrofloxacin solution using a graduated cylinder; (3) Take 2 mg of Mn-doped Co catalyst material with large specific surface area and porous flower-like structure, add it into the above solution, and sonicate for 5 min; (4) Take 80 μl of 1 M PMS solution and add it to the above solution; (5) After different time periods, the ultraviolet absorbance of enrofloxacin in water was measured using an ultraviolet-visible spectrophotometer, and the removal rate of enrofloxacin was calculated.

[0036] Application Comparative Example 3 The Mn-doped Co catalyst material (MnCo / 0.2) with a large specific surface area and porous flower-like structure obtained in Comparative Example 3 was used to degrade organic matter. The specific steps are as follows: (1) Prepare a 10 ppm enrofloxacin solution and a 1 M PMS solution; (2) Weigh 40 ml of enrofloxacin solution using a graduated cylinder; (3) Take 2 mg of Mn-doped Co catalyst material with large specific surface area and porous flower-like structure, add it into the above solution, and sonicate for 5 min; (4) Take 80 μl of 1 M PMS solution and add it to the above solution; (5) After different time periods, the ultraviolet absorbance of enrofloxacin in water was measured using an ultraviolet-visible spectrophotometer, and the removal rate of enrofloxacin was calculated.

[0037] Figure 2 This diagram illustrates the degradation of enrofloxacin by the following catalysts prepared in this invention: Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0.3) prepared in Example 1, Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0) prepared in Comparative Example 1, Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0.1) prepared in Comparative Example 2, and Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0.2) prepared in Comparative Example 3. It can be seen that the Mn-doped Co catalyst material with large specific surface area and porous flower-like structure (MnCo / 0.3) prepared in Example 1 exhibits the best degradation activity, with a degradation rate far exceeding that of the other prepared materials, degrading the substrate completely within 30 minutes. Figure 3 This is a schematic diagram of the degradation performance of the Mn-doped Co catalyst material (MnCo / 0.3) with a large specific surface area and porous flower-like structure prepared in Example 1 of the present invention during cyclic reaction. After 4 cycles, the performance of the Mn-doped Co catalyst material (MnCo / 0.3) with a large specific surface area and porous flower-like structure prepared in Example 1 is basically not significantly reduced. Figure 4 , Figure 5 The images show SEM and TEM images of the Mn-doped Co catalyst material (MnCo / 0.3) with a large specific surface area and porous flower-like structure prepared in Example 1. As can be seen from the images, the Mn-doped Co catalyst material (MnCo / 0.3) with a large specific surface area and porous flower-like structure prepared in Example 1 exhibits a nano-flower-like structure formed by the self-assembly of many two-dimensional nanosheets supporting each other, with the flower-like structure having a diameter of approximately 10 μm. Furthermore, from... Figure 6 and Figure 7 It can be seen that the preparation method proposed in this invention has strong universality for most transition metals.

[0038] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a Mn-doped Co catalyst material with large specific surface area, porous flower-like structure, characterized in that: Comprising the following steps: (1) A certain amount of manganese carbonate, deionized water and formic acid are added to a single-necked flask, and a solution A is obtained by heating and stirring; (2) The solution A is subjected to rotary evaporation treatment, after the liquid in the flask is evaporated, a certain amount of deionized water is added, and rotary evaporation treatment is carried out again; finally, when a certain amount of solution is left in the flask, rotary evaporation is stopped, and drying is carried out to obtain a manganese formate dihydrate powder; (3) A certain amount of manganese formate dihydrate C2H6MnO6, CoCl2·6H2O and methanol are weighed and added to a beaker, and after ultrasonic treatment, the solution is fully stirred to obtain a solution B; (4) The solution B is subjected to hydrothermal reaction under certain conditions; (5) The solution after hydrothermal reaction is subjected to centrifugation, washing and drying until the moisture is completely volatilized to obtain the Mn-doped Co catalyst material with large specific surface area and porous flower-like structure.

2. The method for preparing a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure according to claim 1, characterized in that: In step (1), the solution A is composed of 1.15 g of manganese carbonate, 75 mL of deionized water and 20 mL of formic acid.

3. The method for preparing a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure according to claim 1, characterized in that: In step (1), the heating and stirring are specifically as follows: the heating temperature is 80 °C; magnetic stirring; the stirring speed is 500 rpm; and the stirring time is 2 h.

4. The method for preparing a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure according to claim 1, characterized in that: In step (2), the rotary evaporation treatment is specifically as follows: the temperature is 60 °C; magnetic stirring; the stirring speed is 80 rpm; and the drying in steps (2) and (5) is specifically as follows: the drying method is vacuum-53 ℃ freeze-drying, and the drying time is 12 h.

5. The method of claim 1, wherein the method is characterized by: In step (2), the certain amount of deionized water is 50 mL; and the certain amount of solution is 10 mL.

6. The method for preparing a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure according to claim 1, characterized in that: In step (3), the solution B is composed of 0.1810 g of C2H6MnO6, 0.072 g of CoCl2·6H2O and 60 mL of methanol.

7. The method for preparing a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure according to claim 1, characterized in that: In step (3), the ultrasonic treatment is specifically as follows: the ultrasonic frequency is 38000 Hz-42000 Hz; the ultrasonic temperature is 26-28 ℃; the ultrasonic time is 5 min; and the stirring is specifically as follows: magnetic stirring; the stirring speed is 500-1000 rpm; and the stirring time is 30-60 min.

8. The method for preparing a Mn-doped Co catalyst material with a large specific surface area and a porous flower-like structure according to claim 1, characterized in that: In step (4), the certain conditions are specifically as follows: the hydrothermal temperature is 180 ℃; and the reaction time is 18 h.

9. A Mn-doped Co catalyst material with large specific surface area and porous flower-like structure prepared by the method of any one of claims 1-8.

10. Use of the Mn-doped Co catalyst material with large specific surface area and porous flower-like structure of claim 9 in efficient degradation of enrofloxacin.

Images