Preparation method of Ag / Pt bimetal cluster modified nitrogen / boron co-doped carbon porous microspheres as well as product and application of Ag / Pt bimetal cluster modified nitrogen / boron co-doped carbon porous microspheres

Abstract

The invention belongs to the field of antibacterial material synthesis, and relates to a preparation method of Ag / Pt bimetal cluster modified nitrogen / boron co-doped carbon porous microspheres and a product and application thereof.The preparation method comprises the steps that urea, boric acid, polyethylene glycol and zinc nitrate hexahydrate are evenly mixed and subjected to heat treatment in the atmosphere of air and nitrogen, and the nitrogen / boron co-doped carbon porous microspheres are obtained; placing the microspheres in a nitric acid aqueous solution, removing Zn ions in the system, reserving vacancies for subsequent Ag and Pt modification, placing the obtained sample in a mixed solution of silver nitrate and hexachloroplatinic acid, freeze-drying to ensure that the silver nitrate and hexachloroplatinic acid are uniformly attached to the interiors and surfaces of the pores of the porous microspheres, and then performing heat treatment in a hydrogen-argon mixed gas atmosphere to obtain the silver / Pt / Ag composite microspheres. And reducing silver nitrate and hexachloroplatinic acid to obtain the Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres. The prepared antibacterial material is good in high-temperature stability and excellent in performance, can meet the requirements of various fields for efficient, long-acting and safe antibacterial agents, is particularly used for preparing plastic with an antibacterial function through a direct addition method or an antibacterial master batch method, can also be used for forming fibers with antibacterial and peculiar smell removal functions through a melt spinning or solution spinning process, and is suitable for industrial production. The antibacterial agent can also be dispersed in a solution to carry out post-treatment on textiles and the like so as to realize antibacterial and odor-removing functions.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of nanomaterial synthesis, and particularly relates to a composite material modified carbon porous microsphere, and particularly relates to a preparation method of Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere, a product thereof and application of the product. BACKGROUND

[0002] With the increase of environmental pollution and population density, the infection of various bacteria, viruses and other microorganisms shows a trend of increasing year by year, and the public demand for fast-paced and healthy life is higher and higher. This trend has given rise to huge demand for antibacterial material market. Whether in the medical industry, food packaging, automobile accessories, various toys and other industries, the antibacterial function of plastic products provides safety protection for people's health, and the addition of antibacterial and odor-removing materials to close-to-body clothes, towels and other products has important guarantee for preventing various skin problems and maintaining health. In short, the development of the market for high-efficiency, long-acting and safe antibacterial materials has great market value for creating a healthy and safe living environment and reducing the rate of bacterial infection.

[0003] To create a healthy and safe living environment for people and greatly reduce the risk of bacterial infection At present, various nanomaterials have wide application in the field of antibacterial materials. However, nanomaterials based on inorganic semiconductors are limited in practical application due to problems such as excessive metal ions. In recent years, the vigorous development of carbon-based materials has promoted their application in various fields. However, the antibacterial performance of pure carbon-based materials is limited. The present application can improve the catalytic performance of nitrogen and boron co-doped carbon materials, fully utilize their photocatalytic effect to realize the sterilization function, and introduce different antibacterial principles by modifying them with bimetallic materials. The combination of photocatalytic antibacterial and ion sterilization mechanisms can meet more extensive application scenarios. SUMMARY

[0004] The purpose of the present application is to provide a preparation method of Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere, which can realize the functionalization and improvement of traditional materials.

[0005] Another purpose of the present application is to provide an Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere product prepared by the above method.

[0006] Another purpose of the present application is to provide the application of the above product.

[0007] The application is achieved by the following scheme: a method for preparing Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres, urea, boric acid, polyethylene glycol and zinc nitrate hexahydrate are uniformly mixed, and heat treatment is carried out in air and nitrogen atmosphere to obtain nitrogen / boron co-doped carbon porous microspheres, the microspheres are placed in an aqueous nitric acid solution to remove Zn ions in the system, leaving vacancies for subsequent Ag and Pt modification, the obtained sample is placed in a mixed solution of silver nitrate and hexachloroplatinic acid, freeze-dried at-80 DEG C, to ensure that the silver nitrate and hexachloroplatinic acid are uniformly attached to the pores and surface of the porous microspheres, and then heat treatment is carried out in a hydrogen-argon mixed gas atmosphere to reduce the silver nitrate and hexachloroplatinic acid, thereby obtaining Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres. The method comprises the following steps: Step one: a certain amount of urea, boric acid, polyethylene glycol and zinc nitrate hexahydrate are taken as powder materials, and are ball milled in a ball mill for 20 min; after the ball milling is completed, the materials are collected and dried in a blast drying oven, and are ground; The mass ratio of the urea, boric acid, polyethylene glycol and zinc nitrate hexahydrate is 1.9-4.5:0.08-0.15:0.2-0.4:0.02-0.05; the polyethylene glycol is at least one of PEG-2000, PEG-3000, PEG-4000 and PEG-6000; The ball milling is wet ball milling, and the mass ratio of zirconium beads, powder materials and deionized water is 100-150:30-60:30-80; Step two: the sample obtained in step one is heat treated in an atmosphere furnace, and after being cooled to room temperature, nitrogen / boron co-doped carbon porous microspheres are obtained; The gas atmosphere in the atmosphere furnace is air and nitrogen, and the ratio of air to nitrogen is 10:80-90; the heat treatment temperature is 850-950 DEG C, the heating rate is 3-8 DEG C / min, and the holding time is 2-4 h; Step three: the sample obtained in step two is placed in an aqueous nitric acid solution with a concentration of 0.1-0.5 M, and is hydrothermally reacted at 160-180 DEG C for 18-24 h; after being cooled to room temperature, the precipitate is centrifuged, washed repeatedly with deionized water and ethanol, and dried and ground; Step four: the sample obtained in step three is placed in an aqueous solution of silver nitrate and hexachloroplatinic acid, ultrasonically treated for 30 min, freeze-dried at-80 DEG C, and then heat treated in a hydrogen-argon mixed gas, and after being cooled to room temperature, Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres are obtained; The total molar concentration of silver nitrate and hexachloroplatinic acid in the aqueous solution is 0.0008-0.0015 M; The volume concentration of hydrogen in the hydrogen-argon mixed gas is 5-8%, the heat treatment temperature is 550-650 DEG C, the heating rate is 1-3 DEG C / min, and the holding time is 1-2 h.

[0008] The application provides an Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere, which is prepared according to any of the above methods.

[0009] The application provides an application of the Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere as an antibacterial agent in preparation of a plastic master batch.

[0010] The Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere provided by the application has a very large specific surface area, so that the material has more contact area and the antibacterial effect can be improved; the Ag and Pt clusters are distributed in pores and surfaces, and the antibacterial performance can be further strengthened. The composite material not only has excellent antibacterial performance, but also has very good biocompatibility, can meet the safety requirements of use in various fields, and can effectively replace most products on the market in terms of performance improvement requirements.

[0011] The antibacterial material prepared by the application has good high-temperature stability and excellent performance, can meet the requirements of high efficiency, long-acting and safe antibacterial agents in various fields, and is especially used for preparing plastics with antibacterial function by a direct addition method or an antibacterial master batch method, can form fibers with antibacterial and odor-removing functions through melt spinning or solution spinning processes, and can be dispersed in a solution to realize the functions of antibacterial and odor-removing by post-processing of textiles. DETAILED DESCRIPTION

[0012] Example 1 An Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere is prepared according to the following steps: Step one: according to the mass ratio of 2:0.08:0.3:0.04, urea, boric acid, PEG-2000 and zinc nitrate hexahydrate powder materials are taken and placed in a ball mill, wet ball milling is adopted, the mass ratio of zirconium beads: powder material: deionized water is 100:35:50, and ball milling is performed for 20 min; after ball milling, the material is collected, dried in a blast drying oven and ground; Step two: the sample obtained in step one is placed in an atmosphere furnace, the gas atmosphere is air and nitrogen in a ratio of 10:90, heat treatment is performed at 850 DEG C for 3 h, the temperature rising speed is 3 DEG C / min, after being reduced to room temperature, a nitrogen / boron co-doped carbon porous microsphere is obtained; Step three: the nitrogen / boron co-doped carbon porous microsphere obtained in step two is placed in a 0.1M nitric acid aqueous solution, hydrothermal reaction is performed at 180 DEG C for 24 h, after being reduced to room temperature, the precipitate is centrifuged, washed repeatedly with deionized water and ethanol, dried and ground, and a sample in which Zn ions in the system are removed is obtained; Step four: the sample obtained in step three was placed in an aqueous solution of silver nitrate and hexachloroplatinic acid, the molar concentration of silver nitrate was 0.0004, and the molar concentration of hexachloroplatinic acid was 0.0004, after ultrasonic treatment for 30 min, freeze-drying at-80 ℃, and then heat treatment in hydrogen-argon mixed gas at 650 ℃ for 2 h, the volume concentration of hydrogen in the hydrogen-argon mixed gas was 5 %, the heating rate was 2 ℃ / min, and after cooling to room temperature, Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres were obtained.

[0013] The Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres obtained in this example were used as antibacterial agents to prepare plastic master batches, and then PP plastic plates were prepared, the content of the Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres in the PP plastic was 0.3 %, and the antibacterial activity was determined by the ISO22196:2011(E) method, the antibacterial activity value of this example on Staphylococcus aureus ATCC6538P was greater than 5.7, and the antibacterial activity value on Escherichia coli ATCC8739 was greater than 4.3.

[0014] Example 2: An Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere was prepared by the following steps: Step one: take urea, boric acid, PEG-2000 and zinc nitrate hexahydrate as powder materials according to the mass ratio of 1.9:0.15:0.2:0.04, place them in a ball mill, and use wet ball milling, the mass ratio of zirconium beads: powder materials: deionized water is 150:60:80, and ball mill for 20 min; after ball milling, collect the material, dry it in a drum dryer, and grind it; Step two: place the sample obtained in step one in a gas furnace, the gas atmosphere is air and nitrogen in a ratio of 10:85, the heat treatment temperature is 900 ℃, the heating rate is 7 ℃ / min, and the holding time is 3 h, and after cooling to room temperature, nitrogen / boron co-doped carbon porous microspheres are obtained; Step three: place the nitrogen / boron co-doped carbon porous microspheres obtained in step two in a 0.5M nitric acid aqueous solution, hydrothermal reaction at 160 ℃ for 18 h, after cooling to room temperature, centrifuge the precipitate, wash it repeatedly with deionized water and ethanol, dry it, and grind it to obtain a sample in which the Zn ions in the system are removed; Step four: place the sample obtained in step three in an aqueous solution of silver nitrate and hexachloroplatinic acid, the molar concentration of silver nitrate is 0.0005, and the molar concentration of hexachloroplatinic acid is 0.001, after ultrasonic treatment for 30 min, freeze-drying at-80 ℃, and then heat treatment in hydrogen-argon mixed gas, the volume concentration of hydrogen in the hydrogen-argon mixed gas is 8 %, the heat treatment temperature is 550 ℃, the heating rate is 3 ℃ / min, the holding time is 1 h, and after cooling to room temperature, Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres are obtained.

[0015] The sample obtained in this example was dissolved in deionized water, and after ultrasonic treatment for 30 min, a solution with antibacterial function was obtained. The wet wipes were post-processed to obtain wet wipes with antibacterial function. The antibacterial activity value of this example against Staphylococcus aureus ATCC6538P was greater than 6.1, and the antibacterial activity value against Escherichia coli ATCC8739 was greater than 5.9.

[0016] Example 3: An Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere was prepared according to the following steps: Step one: take urea, boric acid, PEG-2000 and zinc nitrate hexahydrate as powder materials in a mass ratio of 4.5:0.15:0.3:0.02, and place them in a ball mill. Wet ball milling is adopted, and the mass ratio of zirconium beads: powder materials: deionized water is 130:50:60. Ball milling is performed for 20 min. After ball milling, the material is collected, dried in a blast drying oven, and ground. Step two: place the sample obtained in step one in an atmosphere furnace, and heat treat it at a temperature of 950 ℃ with an air / nitrogen ratio of 10:80 and a heating rate of 5 ℃ / min. The holding time is 3 h. After cooling to room temperature, a nitrogen / boron co-doped carbon porous microsphere is obtained. Step three: place the nitrogen / boron co-doped carbon porous microsphere obtained in step two in a 0.3M nitric acid aqueous solution, and hydrothermally react it at 170 ℃ for 20 h. After cooling to room temperature, the precipitate is centrifuged, washed repeatedly with deionized water and ethanol, dried, and ground to remove Zn ions in the system. Step four: place the sample obtained in step three in an aqueous solution of silver nitrate and hexachloroplatinic acid, with a molar concentration of silver nitrate of 0.0005 and a molar concentration of hexachloroplatinic acid of 0.0007. After ultrasonic treatment for 30 min, freeze-drying is performed at -80 ℃. Then, heat treatment is performed in a hydrogen-argon mixed gas with a hydrogen volume concentration of 8% at a temperature of 650 ℃ with a heating rate of 3 ℃ / min and a holding time of 1 h. After cooling to room temperature, an Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere is obtained.

[0017] The sample obtained in this example is used as an antibacterial agent to prepare plastic master batches, and then PP plastic plates. The content of the Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microsphere in the PP plastic is 0.2%. The antibacterial activity value of this example against Staphylococcus aureus ATCC6538P is greater than 4.3, and the antibacterial activity value against Escherichia coli ATCC8739 is greater than 3.6.

Claims

1. A method for preparing Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres, characterized in that, urea, boric acid, polyethylene glycol and zinc nitrate hexahydrate are mixed in a mass ratio of 1.9-4.5:0.08-0.15:0.2-0.4:0.02-0.05, and then heat-treated in an air and nitrogen atmosphere to obtain nitrogen / boron co-doped carbon porous microspheres; the microspheres are placed in an aqueous nitric acid solution to remove Zn ions in the system, and the obtained sample is pre-reserved with vacancies for subsequent Ag and Pt modification; the obtained sample is placed in a mixed solution of silver nitrate and hexachloroplatinic acid, freeze-dried to ensure that the silver nitrate and hexachloroplatinic acid are uniformly attached to the pores and surface of the porous microspheres, and then heat-treated in a hydrogen and argon mixed atmosphere to reduce the silver nitrate and hexachloroplatinic acid, thereby obtaining Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres. The method comprises the following steps: 2.The method according to claim 1, wherein the method is characterized by: Step one: urea, boric acid, polyethylene glycol and zinc nitrate hexahydrate powder materials are placed in a ball mill and ball-milled for 20 min; after the ball-milling is completed, the materials are collected, dried in a blast drying oven and ground; Step two: the sample obtained in step one is placed in a heat treatment atmosphere furnace and heat-treated in an air and nitrogen atmosphere; after being cooled to room temperature, nitrogen / boron co-doped carbon porous microspheres are obtained; Step three: the nitrogen / boron co-doped carbon porous microspheres obtained in step two are placed in an aqueous nitric acid solution with a concentration of 0.1-0.5 M, and subjected to hydrothermal reaction at 160-180 ℃ for 18-24 h; after being cooled to room temperature, the precipitate is centrifuged, repeatedly washed with deionized water and ethanol, dried and ground to obtain a sample with Zn ions removed; Step four: the sample obtained in step three is placed in an aqueous solution of silver nitrate and hexachloroplatinic acid, the total molar concentration of silver nitrate and hexachloroplatinic acid is 0.0008-0.0015 M, ultrasonic treatment is performed for 30 min, then freeze-drying is performed at-80 ℃, and heat treatment is performed in a hydrogen and argon mixed atmosphere; after being cooled to room temperature, Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres are obtained. In step one, the polyethylene glycol is at least one of PEG-2000, PEG-3000, PEG-4000 and PEG-6000. 3.The method of claim 1 or 2, wherein the method comprises the following steps: (1) preparing a porous microsphere of nitrogen / boron co-doped carbon; (2) preparing a Ag / Pt bimetallic cluster; (3) modifying the porous microsphere of nitrogen / boron co-doped carbon with the Ag / Pt bimetallic cluster. In step two, the gas atmosphere in the atmosphere furnace is air and nitrogen, the ratio of air to nitrogen is (10-20):(80-90), heat treatment is performed at 850-950 ℃ for 2-4 h, and the heating rate is 3-8 ℃ / min.

4. The preparation method of the Ag / Pt bimetallic cluster modified N / B co-doped carbon porous microspheres according to claim 2, characterized in that: In step four, the hydrogen volume concentration in the hydrogen and argon mixed gas in step four is 5-8%, heat treatment is performed at 550-650 ℃ for 1-2 h, and the heating rate is 1-3 ℃ / min.

5. The preparation method of Ag / Pt bimetallic cluster modified N / B co-doped carbon porous microspheres according to claim 2, characterized in that: The method is prepared according to the following steps:

6. The preparation method of the Ag / Pt bimetallic cluster modified N / B co-doped carbon porous microspheres according to claim 1 or 2, characterized in that, Step one: urea, boric acid, PEG-2000 and zinc nitrate hexahydrate powder materials are taken in a mass ratio of 2:0.08:0.3:0.04, placed in a ball mill, wet ball-milled with a zirconium bead:powder material:deionized water mass ratio of 100:35:50, and ball-milled for 20 min; after the ball-milling is completed, the materials are collected, dried in a blast drying oven and ground; ​ Step two: the sample obtained in step one was placed in an atmosphere furnace, the gas atmosphere was air and nitrogen in a ratio of 10:90, and heat treatment was carried out at 850 DEG C for 3 h, the temperature rising speed was 3 DEG C / min, after being reduced to room temperature, nitrogen / boron co-doped carbon porous microspheres were obtained; Step three: the nitrogen / boron co-doped carbon porous microspheres obtained in step two were placed in a 0.1M nitric acid aqueous solution, and hydrothermal reaction was carried out at 180 DEG C for 24 h, after being reduced to room temperature, the precipitate was centrifuged, washed repeatedly with deionized water and ethanol, dried, ground, and a sample in which Zn ions were removed was obtained; Step four: the sample obtained in step three was placed in a silver nitrate and hexachloroplatinic acid aqueous solution, the molar concentration of silver nitrate was 0.0004, the molar concentration of hexachloroplatinic acid was 0.0004, after being ultrasonically treated for 30 min, freeze-drying was carried out at-80 DEG C, then heat treatment was carried out in a hydrogen and argon mixed gas, the hydrogen gas volume concentration in the hydrogen and argon mixed gas was 5%, the temperature rising speed was 2 DEG C / min, heat treatment was carried out at 650 DEG C for 2 h, after being reduced to room temperature, Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres were obtained.

7. The preparation method of the Ag / Pt bimetallic cluster modified N / B co-doped carbon porous microspheres according to claim 1 or 2, characterized in that, Preparation was carried out according to the following steps: Step one: according to the mass ratio of 1.9:0.15:0.2:0.04, urea, boric acid, PEG-2000 and zinc nitrate hexahydrate were taken as powder materials, placed in a ball mill, wet ball milling was adopted, the mass ratio of zirconium beads: powder materials: deionized water was 150:60:80, and ball milling was carried out for 20 min; after ball milling, the materials were collected, placed in a blast drying oven for drying, and ground; Step two: the sample obtained in step one was placed in an atmosphere furnace, the gas atmosphere was air and nitrogen in a ratio of 10:85, heat treatment was carried out at 900 DEG C, the temperature rising speed was 7 DEG C / min, the holding time was 3 h, after being reduced to room temperature, nitrogen / boron co-doped carbon porous microspheres were obtained; Step three: the nitrogen / boron co-doped carbon porous microspheres obtained in step two were placed in a 0.5M nitric acid aqueous solution, and hydrothermal reaction was carried out at 160 DEG C for 18 h, after being reduced to room temperature, the precipitate was centrifuged, washed repeatedly with deionized water and ethanol, dried, and ground, to obtain a sample in which Zn ions were removed; Step four: the sample obtained in step three was placed in a silver nitrate and hexachloroplatinic acid aqueous solution, the molar concentration of silver nitrate was 0.0005, the molar concentration of hexachloroplatinic acid was 0.001, after being ultrasonically treated for 30 min, freeze-drying was carried out at-80 DEG C, then heat treatment was carried out in a hydrogen and argon mixed gas, the hydrogen gas volume concentration in the hydrogen and argon mixed gas was 8%, heat treatment was carried out at 550 DEG C, the temperature rising speed was 3 DEG C / min, the holding time was 1 h, after being reduced to room temperature, Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres were obtained. 8.The method of claim 1 or 2, wherein the Ag / Pt bimetallic cluster modified N / B co-doped carbon porous microspheres are prepared by the following steps: (1) preparing a porous carbon microsphere; (2) modifying the porous carbon microsphere with a nitrogen and boron co-doped carbon layer; (3) modifying the porous carbon microsphere with a Ag / Pt bimetallic cluster layer. Preparation was carried out according to the following steps: Step one: according to the mass ratio of 1.9:0.15:0.2:0.04, urea, boric acid, PEG-2000 and zinc nitrate hexahydrate were taken as powder materials, placed in a ball mill, wet ball milling was adopted, the mass ratio of zirconium beads: powder materials: deionized water was 150:60:80, and ball milling was carried out for 20 min; after ball milling, the materials were collected, placed in a blast drying oven for drying, and ground; Step two: the sample obtained in step one was placed in an atmosphere furnace, the gas atmosphere was air and nitrogen in a ratio of 10:80, the heat treatment temperature was 950℃, the heating rate was 5℃ / min, the holding time was 3h, after cooling to room temperature, nitrogen / boron co-doped carbon porous microspheres were obtained; Step three: the nitrogen / boron co-doped carbon porous microspheres obtained in step two were placed in a 0.3M nitric acid aqueous solution, hydrothermal reaction was carried out at 170℃ for 20h, after cooling to room temperature, the precipitate was centrifuged, washed repeatedly with deionized water and ethanol, dried, ground, and a sample with Zn ions removed from the system was obtained; Step four: the sample obtained in step three was placed in an aqueous solution of silver nitrate and hexachloroplatinic acid, the molar concentration of silver nitrate was 0.0005, the molar concentration of hexachloroplatinic acid was 0.0007, after ultrasonic treatment for 30min, freeze-drying was carried out at-80℃, then heat treatment was carried out in a hydrogen-argon mixed gas, the hydrogen volume concentration in the hydrogen-argon mixed gas was 8%, the heat treatment temperature was 650℃, the heating rate was 3℃ / min, the holding time was 1h, after cooling to room temperature, Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres were obtained. The sample obtained in this example was used as an antibacterial agent to prepare plastic master batches, then PP plastic plates were prepared, the content of Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres in the PP plastic was 0.2%, antibacterial determination was carried out by ISO22196:2011(E) method, the antibacterial activity value of this example against Staphylococcus aureus ATCC6538P was greater than 4.3, and the antibacterial activity value against Escherichia coli ATCC8739 was greater than 3.

6.

9. Ag / Pt bimetallic cluster decorated nitrogen / boron co-doped carbon porous microspheres, characterized in that Prepared according to any one of claims 1-8.

10. The use of Ag / Pt bimetallic cluster modified nitrogen / boron co-doped carbon porous microspheres according to claim 9 as an antibacterial agent in the preparation of plastic master batches.