Preparation method and application of high-entropy amorphous catalytic material

Abstract

The invention provides a preparation method and application of a high-entropy amorphous catalytic material, and belongs to the technical field of materials. The preparation method comprises the following steps: by taking waste biomass calcium shells as a raw material, washing, drying, calcining and grinding to obtain biomass calcium oxide as a precursor, taking nitrogen as a protective gas, enabling the precursor to fully react with a methanol solution to obtain a reaction intermediate calcium methoxide, then adding a methanol solution containing transition metal salt, performing ion exchange, stirring, centrifuging and washing to obtain a calcium methoxide precursor; and freezing and drying to obtain the high-entropy amorphous catalytic material. The prepared high-entropy amorphous catalytic material can activate PMS, 10 ppm of an enrofloxacin solution can be rapidly degraded within 5 min, and the high-entropy amorphous catalytic material has high degradation activity on various antibiotics and dyes. The preparation method has the characteristics of high economic benefit, simple preparation process and capability of realizing large-scale industrial production, and has good economic benefit and environmental benefit.

Description

Technical Field

[0001] The present invention belongs to the technical field of materials, and particularly relates to a preparation method and application of a high-entropy amorphous catalytic material. Background Art

[0002] In recent years, amorphous catalytic materials have become promising catalysts due to their unique structures and chemical properties. The disordered atomic structure of amorphous materials can promote efficient charge transfer, reactant diffusion, and adsorption-desorption during the reaction process, thereby improving catalytic activity. Due to the absence of grain boundaries and lattice defects, amorphous materials have a high specific surface area, structural defects, and abundant unsaturated coordination sites. Moreover, amorphous materials exhibit macroscopic uniformity, with an isotropic atomic environment and adjustable components. Due to these characteristics, amorphous materials show potential for practical applications in fields such as catalysis and degradation and have received extensive attention as promising advanced catalytic materials. Using biomass calcium oxide as a precursor, high-entropy amorphous catalytic materials were prepared using the obtained nano-sized calcium methoxide as a template, providing a new strategy for the preparation of amorphous catalytic materials and the reuse of biomass calcium shells.

[0003] With the development of society, the market demand for marine shellfish in China has been continuously expanding, and the breeding scale and processing scale of shellfish represented by oysters have increased significantly. However, a large amount of shellfish waste has not been effectively recycled and properly treated in the production and consumption links, and most of the waste shells are directly discarded without any treatment. This has caused serious environmental pollution, resource waste, and various safety hazards. In the past, some researchers have conducted simple research and utilization of these shells, but it has not been possible to achieve efficient comprehensive utilization. The unique structure of amorphous catalysts makes them excellent catalysts, but there is currently a lack of a simple and general method for large-scale production of amorphous nano-catalytic materials. To solve this bottleneck problem, it is of great significance to design a simple hydrothermal synthesis method to realize the preparation of high-entropy amorphous catalytic materials based on biomass calcium oxide by a template method.

[0004] Using waste biomass as a raw material to prepare catalytic materials is an environmentally friendly and economical method, but most current research focuses on the simple conversion of biomass or the preparation of single-metal catalytic materials. Therefore, this patent provides a preparation method and application of a high-entropy amorphous catalytic material, which can regulate the stable formation of an amorphous material with five metal centers and has higher catalytic performance than single-metal center materials. Summary of the Invention

[0005] The object of the present invention is to provide a preparation method of a high-entropy amorphous catalytic material for efficiently and rapidly degrading enrofloxacin in view of the deficiencies of the prior art. The present invention uses biomass calcium oxide (CaO) as a precursor, nitrogen as a protective gas, and converts biomass calcium oxide into calcium methoxide in a methanol solution, and then reacts with transition metal salt ions to obtain a high-entropy amorphous catalytic material. First, the washed biomass calcium shell is calcined into biomass calcium oxide, and then under a nitrogen atmosphere, methanol and calcium oxide react completely to form calcium methoxide, and then a transition metal salt solution is added to cause ion exchange between calcium methoxide and transition metal salt ions, and finally a high-entropy amorphous catalytic material is formed. The present invention provides a green synthesis method of a high-entropy amorphous catalytic material with simple process, strong versatility and applicability. Moreover, the prepared high-entropy amorphous catalytic material has extremely high catalytic activity for the degradation of enrofloxacin, the method is simple, the cost is low, and it has good economic and environmental benefits, and can also be applied to large-scale production.

[0006] To achieve the above object, the present invention adopts the following technical solutions: A preparation method of a high-entropy amorphous catalytic material, comprising the following steps: (1) Wash and dry the biomass calcium shell, and then obtain the reaction precursor biomass calcium oxide through calcination and grinding. The biomass calcium shell is one of oyster shell, egg shell, and clam shell; (2) Add calcium oxide into methanol, and stir well under a nitrogen atmosphere to make solution A; (3) Add transition metal salts manganese chloride, cobalt chloride hexahydrate, ferrous chloride tetrahydrate, nickel chloride hexahydrate, and copper chloride dihydrate into methanol, ultrasonically dissolve them to make solution B. The frequency of ultrasonic wave is 38000 Hz - 42000 Hz, the temperature of ultrasonic wave is 26 - 28 °C, and the ultrasonic time is 5 min; (4) Add solution B into solution A, magnetically stir and react for 24 h, and then obtain the high-entropy amorphous catalytic material through centrifugation, washing, and freeze-drying.

[0007] Further, the calcination step in step (1) is: calcine at 1000 - 1250 °C for 60 - 180 min with a heating rate of 5 - 20 °C / min.

[0008] Further, the dosage of methanol in step (2) is 150 - 450 mL for every 0.56 - 1.68 g of calcium oxide.

[0009] Further, the specific stirring in step (2) is: magnetically stir at a speed of 500 - 1000 rpm for 12 - 36 h.

[0010] Further, in step (3), the mass ratio of manganese chloride, cobalt chloride hexahydrate, ferrous chloride tetrahydrate, nickel chloride hexahydrate and copper chloride dihydrate is (0.3775 - 1.132):(0.7138 - 2.1414):(0.1988 - 0.5964):(0.2377 - 0.7131):(0.3410 - 1.0230), and the dosage of methanol is 100 - 300 mL.

[0011] Further, the ultrasonic treatment in step (3) is specifically as follows: ultrasonic frequency: 38000 Hz - 42000 Hz; ultrasonic temperature: 26 - 28 °C; ultrasonic time: 5 min.

[0012] Further, the stirring speed in step (4) is 500 - 1000 rpm; the stirring time is 12 - 36 h.

[0013] Further, the centrifugation speed in step (4) is 8000 rpm, and the time is 2 min.

[0014] Further, the freeze-drying in step (4) is vacuum freeze-drying at -53 °C for 6 - 12 h.

[0015] The present invention provides a high-entropy amorphous catalytic material prepared by the above method and its application in the degradation of enrofloxacin.

[0016] The beneficial effects of the present invention are as follows: (1) The present invention adopts the template method to realize the preparation of a high-entropy amorphous catalytic material based on waste biomass calcium carbonate, provides a new synthesis method for high-entropy amorphous catalytic materials, and provides new ideas for the preparation of amorphous nano-catalytic materials and the efficient utilization of waste biomass calcium carbonate.

[0017] (2) The surface of the high-entropy amorphous catalytic material prepared by the present invention is in a flaky structure, the single particle size is about 800 nm, and the surface has a large number of stacked nanosheets.

[0018] (3) The raw materials and equipment required by 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 mass-produced industrially; by changing the types of metal ions added, amorphous materials with similar appearances can be obtained, which have high degradation ability, are an environmentally friendly new material, and have good promotion and application value and usage prospects. Description of the Drawings

[0019] Figure 1 The high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2), the X-ray diffraction (XRD) patterns of the high-entropy amorphous catalytic materials (Mn 3.5 Co 3 FeNiCu 1.5 ), prepared in Comparative Example 1, the high-entropy amorphous catalytic materials (Mn 2.5 Co 3 FeNiCu 2.5 ), prepared in Comparative Example 2, and the high-entropy amorphous catalytic materials (Mn 2 Co 3 FeNiCu 3 ), prepared in Comparative Example 3.

[0020] Figure 2 The scanning electron microscope (SEM) image of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ), prepared in Example 1.

[0021] Figure 3 The transmission electron microscope image (200 nm) of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ), prepared in Example 1.

[0022] Figure 4 The transmission electron microscope image (50 nm) of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ), prepared in Example 1.

[0023] Figure 5 The SEM image of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ), prepared in Example 2.

[0024] Figure 6 The SEM image of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ), prepared in Example 3.

[0025] Figure 7 The SEM image of the high-entropy amorphous catalytic material (Mn 3.5 Co 3 FeNiCu 1.5 ), prepared in Comparative Example 1.

[0026] Figure 8 The SEM image of the high-entropy amorphous catalytic material (Mn 2.5 Co3 FeNiCu 2.5 SEM image of

[0027] Figure 9 The high-entropy amorphous catalytic material (Mn 2 Co 3 FeNiCu 3 ) prepared in Comparative Example 3

[0028] Figure 10 The high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1, the high-entropy amorphous catalytic material (Mn 3.5 Co 3 FeNiCu 1.5 ) prepared in Comparative Example 1, the high-entropy amorphous catalytic material (Mn 2.5 Co 3 FeNiCu 2.5 ) prepared in Comparative Example 2, and the high-entropy amorphous catalytic material (Mn 2 Co 3 FeNiCu 3 ) prepared in Comparative Example 3 for the degradation rate diagram of enrofloxacin.

[0029] Figure 11 The high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1 for the performance diagram of the cyclic experiment.

[0030] Figure 12 The high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1 for the degradation performance diagram of different antibiotics.

[0031] Figure 13 The high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1 for the degradation performance diagram of different dyes. Detailed implementation methods

[0032] In order to make the objectives, technical solutions and advantages of the present invention more clear and understandable, the present 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 only used to explain the present invention and are not used to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined as long as they do not conflict with each other.

[0033] Example 1 Preparation of high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 , abbreviated as Mn3): (1) Wash the oyster shells, dry them at 80 °C for 6 h, and increase the temperature from room temperature to 1250 °C at a rate of 5 °C / min, and calcine at 1250 °C for 2 h; (2) Grind the calcined oyster shells with a mortar and pestle, weigh 0.56 g and add it to a three-necked flask. Then add 150 mL of methanol to obtain a mixed solution. Under the condition of nitrogen as a protective gas, stir the mixed solution at 500 rpm with magnetic stirring for 24 h to obtain solution A; (3) Weigh 0.3775 g of manganese chloride (MnCl 2 ), 0.7138 g of cobalt chloride hexahydrate (CoCl 2 ·6H 2 O), 0.1988 g of ferrous chloride tetrahydrate (FeCl 2 ·4H 2 O), 0.2377 g of nickel chloride hexahydrate (NiCl 2 ·6H 2 O), 0.3410 g of copper chloride dihydrate (CuCl 2 ·2H 2 O), add 100 mL of methanol, and ultrasonically mix to form solution B; ultrasonic frequency: 40000 Hz; ultrasonic temperature: 26 °C; ultrasonic time: 5 min.

[0034] (4) Add solution B to solution A, stir at 500 rpm with magnetic stirring for 24 h, centrifuge at 8000 rpm for 2 min to separate the precipitate, wash it 3 times with ethanol and 3 times with deionized water, and freeze-dry at -53 °C under vacuum for 12 h to obtain the high-entropy amorphous catalytic material (Mn3).

[0035] Example 2 Preparation of high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 , abbreviated as Mn3): (1)Wash the eggshells, dry them at 80 °C for 6 h, and increase the temperature from room temperature to 1250 °C at a heating rate of 5 °C / min, then calcine at 1250 °C for 2 h; (2)Grind the calcined eggshells in a mortar, weigh 0.56 g and add it to a three-necked flask, then add 150 mL of methanol to obtain a mixed solution; under the condition of nitrogen as the protective gas, stir the mixed solution with magnetic stirring at 500 rpm for 24 h to obtain solution A; (3)Weigh 0.3775 g of manganese chloride (MnCl 2 ), 0.7138 g of cobalt chloride hexahydrate (CoCl 2 ·6H 2 O), 0.1988 g of ferrous chloride tetrahydrate (FeCl 2 ·4H 2 O), 0.2377 g of nickel chloride hexahydrate (NiCl 2 ·6H 2 O), 0.3410 g of copper chloride dihydrate (CuCl 2 ·2H 2 O) respectively with an electronic balance, add 100 mL of methanol, and ultrasonically mix to form solution B; ultrasonic frequency: 40000 Hz; ultrasonic temperature: 26 °C; ultrasonic time: 5 min.

[0036] (4)Add solution B to solution A, stir with magnetic stirring at 500 rpm for 24 h, centrifuge at 8000 rpm for 2 min to separate the precipitate, wash it 3 times with ethanol and 3 times with deionized water, and freeze-dry at -53 °C under vacuum for 12 h to obtain the high-entropy amorphous catalytic material (Mn3).

[0037] Example 3 Preparation of high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 , Mn3): (1)Wash the clam shells, dry them at 80 °C for 6 h, and increase the temperature from room temperature to 1250 °C at a heating rate of 5 °C / min, then calcine at 1250 °C for 2 h; (2)Grind the calcined clam shells in a mortar, weigh 0.56 g and add it to a three-necked flask, then add 150 mL of methanol to obtain a mixed solution; then under the condition of nitrogen as the protective gas, stir the mixed solution with magnetic stirring at 500 rpm for 24 h to obtain solution A; (3)Weigh 0.3775 g of manganese chloride (MnCl 2 ), 0.7138 g of cobalt chloride hexahydrate (CoCl 2 ·6H2 O), 0.1988 g of ferrous chloride tetrahydrate (FeCl 2 ·4H 2 O), 0.2377 g of nickel chloride hexahydrate (NiCl 2 ·6H 2 O), 0.3410 g of copper chloride dihydrate (CuCl 2 ·2H 2 O), add 100 mL of methanol, and ultrasonically mix to form solution B; ultrasonic frequency: 40000 Hz; ultrasonic temperature: 26 °C; ultrasonic time: 5 min.

[0038] (5) Add solution B to solution A, stir magnetically at 500 rpm for 24 h, centrifuge at 8000 rpm for 2 min to separate the precipitate, wash it 3 times with ethanol and 3 times with deionized water, and freeze-dry at -53 °C under vacuum for 12 h to obtain the high-entropy amorphous catalytic material (Mn3).

[0039] Comparative Example 1 Preparation of high-entropy amorphous catalytic material (Mn 3.5 Co 3 FeNiCu 1.5 , abbreviated as Mn3.5): (1) Wash the oyster shells, dry them at 80 °C for 6 h, increase the temperature from room temperature to 1250 °C at a rate of 5 °C / min, and calcine at 1250 °C for 2 h; (2) Grind the calcined oyster shells in a mortar and weigh 0.56 g and add it to a three-necked flask, then add 150 mL of methanol to obtain a mixed solution; then, under the condition of nitrogen as the protective gas, stir the mixed solution magnetically at 500 rpm for 24 h to obtain solution A; (3) Weigh 0.4404 g of manganese chloride (MnCl 2 ), 0.7138 g of cobalt chloride hexahydrate (CoCl 2 ·6H 2 O), 0.1988 g of ferrous chloride tetrahydrate (FeCl 2 ·4H 2 O), 0.2377 g of nickel chloride hexahydrate (NiCl 2 ·6H 2 O), 0.2557 g of copper chloride dihydrate (CuCl 2 ·2H 2 O), add 100 mL of methanol, and ultrasonically mix to form solution B; ultrasonic frequency: 40000 Hz; ultrasonic temperature: 26 °C; ultrasonic time: 5 min.

[0040] (4) Add solution B to solution A, stir magnetically at 500 rpm for 24 h, centrifuge at 8000 rpm for 2 min to obtain a precipitate, wash it 3 times with ethanol and 3 times with deionized water, and freeze-dry it under vacuum at -53 °C for 12 h to obtain a high-entropy amorphous catalytic material (Mn3.5).

[0041] Comparative Example 2 High-entropy amorphous catalytic material (Mn 2.5 Co 3 FeNiCu 2.5 , abbreviated as Mn2.5) preparation: (1) Wash the oyster shells, dry them at 80 °C for 6 h, and increase the temperature from room temperature to 1250 °C at a rate of 5 °C / min, and calcine at 1250 °C for 2 h; (2) Grind the calcined oyster shells in a mortar, weigh 0.56 g and add it to a three-necked flask, then add 150 mL of methanol to obtain a mixed solution; then, under the condition of nitrogen as a protective gas, stir the mixed solution magnetically at 500 rpm for 24 h to obtain solution A; (3) Weigh 0.3146 g of manganese chloride (MnCl 2 ), 0.7138 g of cobalt chloride hexahydrate (CoCl 2 ·6H 2 O), 0.1988 g of ferrous chloride tetrahydrate (FeCl 2 ·4H 2 O), 0.2377 g of nickel chloride hexahydrate (NiCl 2 ·6H 2 O), 0.4262 g of copper chloride dihydrate (CuCl 2 ·2H 2 O) with an electronic balance, add 100 mL of methanol, and ultrasonically mix to form solution B; ultrasonic frequency: 40000 Hz; ultrasonic temperature: 26 °C; ultrasonic time: 5 min.

[0042] (4) Add solution B to solution A, stir magnetically at 500 rpm for 24 h, centrifuge at 8000 rpm for 2 min to obtain a precipitate, wash it 3 times with ethanol and 3 times with deionized water, and freeze-dry it under vacuum at -53 °C for 12 h to obtain a high-entropy amorphous catalytic material (Mn2.5).

[0043] Comparative Example 3 High-entropy amorphous catalytic material (Mn 2 Co 3 FeNiCu 3 , abbreviated as Mn2) preparation: (1) Wash the oyster shells, dry them at 80 °C for 6 h, and increase the temperature from room temperature to 1250 °C at a heating rate of 5 °C / min, and calcine at 1250 °C for 2 h; (2) Grind the calcined oyster shells with a mortar and weigh 0.56 g with an electronic balance and add it to a three-necked flask, then add 150 mL of methanol to obtain a mixed solution; then, under the condition of nitrogen as a protective gas, stir the mixed solution at 500 rpm with magnetic stirring for 24 h to obtain solution A; (3) Weigh 0.2517 g of manganese chloride (MnCl 2 ), 0.7138 g of cobalt chloride hexahydrate (CoCl 2 ·6H 2 O), 0.1988 g of ferrous chloride tetrahydrate (FeCl 2 ·4H 2 O), 0.2377 g of nickel chloride hexahydrate (NiCl 2 ·6H 2 O), 0.5114 g of copper chloride dihydrate (CuCl 2 ·2H 2 O) with an electronic balance, add 100 mL of methanol, and ultrasonically mix to form solution B; ultrasonic frequency: 40000 Hz; ultrasonic temperature: 26 °C; ultrasonic time: 5 min.

[0044] (4) Add solution B to solution A, stir magnetically at 500 rpm for 24 h, centrifuge at 8000 rpm for 2 min to obtain a precipitate, wash it 3 times with ethanol and 3 times with deionized water, and freeze-dry at -53 °C under vacuum for 12 h to obtain a high-entropy amorphous catalytic material (Mn2).

[0045] Application Example 1 Use the high-entropy amorphous catalytic material (Mn3) obtained in Example 1 to degrade enrofloxacin, and the specific steps are as follows: (1) Prepare a 10 ppm aqueous solution of enrofloxacin and a 1 M aqueous solution of potassium peroxymonosulfate (PMS); (2) Take 40 mL of a 10 ppm enrofloxacin solution, add 4 mg of the high-entropy amorphous catalytic material (Mn3), and ultrasonicate for 5 min; (3) Then add 80 μL of a 1 M PMS solution to the solution obtained in step (2); (4) After different time periods, use a UV-visible spectrophotometer to measure the UV absorption value of enrofloxacin in water and calculate the removal rate of enrofloxacin.

[0046] Control samples with each single element removed in Example 1 were prepared and their degradation performance for enrofloxacin was tested. The results are asFigure 10 As shown, it was found that the Co element had the greatest impact on the performance, while the Fe and Ni elements had relatively the least impact on the performance.

[0047] Next, the effect of the high-entropy amorphous catalytic material (Mn3) on the degradation of other dyes and antibiotics was investigated. The other steps were the same as those in Application Example 1.

[0048] Application Example 2 The high-entropy amorphous catalytic material (Mn3.5) obtained in Comparative Example 1 was used to degrade enrofloxacin. The specific steps were as follows: (1) Prepare a 10 ppm enrofloxacin solution and a 1 M PMS solution; (2) Take 40 mL of the enrofloxacin solution, add 4 mg of the high-entropy amorphous catalytic material (Mn3.5), and ultrasonicate for 5 min; (3) Add 80 μL of the 1 M PMS solution to the above solution; (4) After different time periods, use a UV-visible spectrophotometer to measure the UV absorption value of enrofloxacin in the water and calculate the removal rate of enrofloxacin.

[0049] Application Example 3 The high-entropy amorphous catalytic material (Mn2.5) obtained in Comparative Example 2 was used to degrade enrofloxacin. The specific steps were as follows: (1) Prepare a 10 ppm enrofloxacin solution and a 1 M PMS solution; (2) Take 40 mL of the enrofloxacin solution, add 4 mg of the high-entropy amorphous catalytic material (Mn2.5), and ultrasonicate for 5 min; (3) Add 80 μL of the 1 M PMS solution to the above solution; (4) After different time periods, use a UV-visible spectrophotometer to measure the UV absorption value of enrofloxacin in the water and calculate the removal rate of enrofloxacin.

[0050] Application Example 4 The high-entropy amorphous catalytic material (Mn2) obtained in Comparative Example 3 was used to degrade enrofloxacin. The specific steps were as follows: (1) Prepare a 10 ppm enrofloxacin solution and a 1 M PMS solution; (2) Take 40 mL of the enrofloxacin solution, add 4 mg of the high-entropy amorphous catalytic material (Mn2), and ultrasonicate for 5 min; (3) Add 80 μL of the 1 M PMS solution to the above solution; (4) After different time periods, use a UV-visible spectrophotometer to measure the UV absorption value of enrofloxacin in the water and calculate the removal rate of enrofloxacin.

[0051] Figure 1 is the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ), the high-entropy amorphous catalytic material (Mn 3.5 Co 3 FeNiCu 1.5 ), the high-entropy amorphous catalytic material (Mn 2.5 Co 3 FeNiCu 2.5 ), and the high-entropy amorphous catalytic material (Mn 2 Co 3 FeNiCu 3 ) prepared in Comparative Example 3. The X-ray diffraction (XRD) patterns show that all samples exhibit an amorphous structure.

[0052] Figure 2 is the SEM image of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1. Figure 3 、 4 are its transmission electron microscope (TEM) images. It can be seen from the figures that the surface of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) shows a flaky structure, with a single particle size of about 800 nm and a large number of stacked nanosheets on the surface. In addition, it can be seen from Figure 5 and Figure 6 that the preparation method proposed in the present invention has great calcium source universality.

[0053] Figure 7 、 Figure 8 and Figure 9 are the high-entropy amorphous catalytic materials (Mn 3.5 Co 3 FeNiCu 1.5 ), the high-entropy amorphous catalytic material (Mn 2.5 Co 3 FeNiCu 2.5 ), and the high-entropy amorphous catalytic material (Mn 2 Co 3 FeNiCu 3SEM images of (), from which it can be seen that as the proportion of Mn element increases and the proportion of Cu element decreases, the morphology of the material gradually changes from irregular particle aggregates to regular concave disc-shaped materials, and the small particles on the surface gradually transform into flakes, and the performance gradually improves. When the proportion of Mn element reaches 30% and the proportion of Cu element reaches 20%, it has the best morphology and performance (i.e., Example 1). Continuing to increase the proportion of Mn element and decrease the proportion of Cu element, it is found that the morphology of the material has a tendency to change from close stacking to dispersed collapse, and the performance decreases accordingly. The high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1 of the present invention has the best morphology and the corresponding best performance.

[0054] Figure 10 is the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1 of the present invention, the high-entropy amorphous catalytic material (Mn 3.5 Co 3 FeNiCu 1.5 ) prepared in Comparative Example 1, the high-entropy amorphous catalytic material (Mn 2.5 Co 3 FeNiCu 2.5 ) prepared in Comparative Example 2, and the high-entropy amorphous catalytic material (Mn 2 Co 3 FeNiCu 3 ) prepared in Comparative Example 3, the rate diagram of enrofloxacin degradation. It can be seen that the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1 has the best degradation activity, and its degradation rate is much greater than that of other prepared materials. Enrofloxacin can be degraded to 90% in 1 min, and the degradation of enrofloxacin can reach 95.45% in 5 min. Figure 11 is the schematic diagram of the degradation performance of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1 of the present invention during the cyclic reaction. After 4 cycles, the performance of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) basically does not decrease significantly.

[0055] Figure 12 is the high-entropy amorphous catalytic material (Mn 3 Co3 FeNiCu 2 ) Degradation performance diagrams for different antibiotics. The results show that Mn 3 Co 3 FeNiCu 2 has good degradation effects on ciprofloxacin, tetracycline, and bisphenol A.

[0056] Figure 13 is the degradation performance diagram of the high-entropy amorphous catalytic material (Mn 3 Co 3 FeNiCu 2 ) prepared in Example 1 for different dyes.

[0057] It is easy for those skilled in the art to understand that the above are only preferred examples of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a high entropy amorphous catalytic material, characterized in that: The following steps are involved: (1) washing and drying the biomass calcium shell, calcining and grinding it to obtain a reaction precursor biomass calcium oxide, wherein the biomass calcium shell is one of oyster shell, egg shell and clam shell; (2) Add calcium oxide to methanol and stir thoroughly under a nitrogen atmosphere to prepare solution A; (3) adding transition metal salts of manganese chloride, cobalt chloride hexahydrate, ferrous chloride tetrahydrate, nickel chloride hexahydrate and cupric chloride dihydrate into methanol for ultrasonic dissolution to prepare solution B; the ultrasonic frequency is 38000 Hz-42000 Hz, the ultrasonic temperature is 26-28 °C, and the ultrasonic time is 5 min; (4) Solution B was added to solution A and reacted under magnetic stirring for 24 h. After centrifugation, washing, and freeze-drying, a high-entropy amorphous catalytic material was obtained.

2. The method for preparing a high entropy amorphous catalytic material according to claim 1, characterized in that: The calcination step in step (1) is: calcining at 1000-1250°C for 60-180 min at a heating rate of 5-20°C / min.

3. The method for preparing a high entropy amorphous catalytic material according to claim 1, characterized in that: The amount of methanol used in step (2) is 150-450 mL for every 0.56-1.68 g of calcium oxide.

4. The method for preparing a high entropy amorphous catalytic material according to claim 1, characterized in that: The sufficient stirring in step (2) specifically includes: magnetic stirring at a speed of 500-1000 rpm for 12-36 hours.

5. The method for preparing a high entropy amorphous catalytic material according to claim 1, characterized in that: In step (3), the mass ratios of manganese chloride, cobalt chloride hexahydrate, ferrous chloride tetrahydrate, nickel chloride hexahydrate and cupric chloride dihydrate are (0.3775-1.132):(0.7138-2.1414):(0.1988-0.5964):(0.2377 -0.7131):(0.3410-1.0230), and the amount of methanol used is 100-300 mL.

6. The method for preparing a high entropy amorphous catalytic material according to claim 1, characterized in that: The stirring speed in step (4) is 500-1000 rpm; the stirring time is 12-36 h.

7. The method for preparing a high entropy amorphous catalytic material according to claim 1, characterized in that: The centrifugation speed in step (4) is 8000 rpm and the time is 2 min.

8. The method for preparing a high entropy amorphous catalytic material according to claim 1, characterized in that: The freeze drying in step (4) is vacuum freeze drying at -53°C for 6-12 hours.

9. A high entropy amorphous catalytic material prepared by the method according to any one of claims 1 to 8.

10. Use of the high entropy amorphous catalytic material as claimed in claim 9 in degrading enrofloxacin.

Images