Application of a photocatalytic antibacterial biomass nanomaterial

By preparing copper ferrite/hydroxyapatite photocatalytic antibacterial nanomaterials using oyster shells as a precursor, the problems of environmental friendliness and preparation complexity of existing antibacterial materials have been solved, achieving efficient and safe antibacterial effects and expanding its application fields.

CN116809091BActive Publication Date: 2025-12-02FUJIAN AQUAGEM BIOTECHNOLOGY CO LTD
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Patent Information

Application Number
CN202310383808.1
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2023-04-12
Publication Date
2025-12-02
Estimated Expiration
2043-04-12

AI Technical Summary

Technical Problem

Existing antibacterial materials suffer from high cost, high toxicity, complex preparation processes, and serious environmental pollution, which limits their application and development.

Method used

Using oyster shells as a precursor, nano-flower-like hydroxyapatite was prepared by alkaline thermal treatment, and then copper ferrite was doped into it. Copper ferrite/hydroxyapatite photocatalytic antibacterial nanomaterials were prepared by a one-step hydrothermal method for antibacterial performance research.

Benefits of technology

The prepared material is environmentally friendly and safe, with good photocatalytic antibacterial properties and biocompatibility. It can effectively fight bacteria under simulated sunlight and is recyclable, making it suitable for fields such as nanomedicine and functional coatings.

✦ Generated by Eureka AI based on patent content.

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Abstract

This invention provides a novel method for preparing a biomass-based photocatalytic antibacterial material. The method uses oyster shells, a biological waste, as a precursor. After simple alkaline thermal treatment, nano-flower-like hydroxyapatite with a large specific surface area is obtained. Then, copper ferrite is used to dope and modify the hydroxyapatite, resulting in a copper ferrite / hydroxyapatite photocatalytic antibacterial material with excellent photocatalytic antibacterial effect and high biocompatibility. This invention utilizes a one-step hydrothermal method to obtain the composite antibacterial material. The preparation method is simple and easy to implement, requiring no expensive equipment. Copper ferrite is a magnetic material, and the prepared antibacterial material is recyclable, making it an environmentally friendly material. This novel biomass-based photocatalytic antibacterial material exhibits excellent antibacterial performance and low experimental cost, demonstrating great application potential in fields such as paint production, food, and daily necessities.
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Description

Technical Field

[0001] This invention relates to the technical field of photocatalytic antibacterial materials, and in particular to the application of a photocatalytic antibacterial biomass nanomaterial. Background Technology

[0002] Bacterial infections pose a significant threat to human health, leading to the development and application of numerous antibacterial products. However, many current antibacterial materials suffer from problems such as high material costs, high toxicity, complex preparation processes, or environmental pollution during preparation, severely hindering their development. Therefore, the development of safe, environmentally friendly, and non-toxic novel biomass-based photocatalytic antibacterial materials is urgently needed.

[0003] Oceans cover approximately 71% of the Earth's surface, and marine shellfish shells are a common type of waste, with a high stockpile. Taking oyster shells as an example, their main component is calcium carbonate, accounting for over 95% of their total mass. In addition, they contain trace elements, proteins, polysaccharides, and fatty acids, making them a common mineral and a major component of human bones and teeth. Hydroxyapatite is a renewable biomaterial with good adsorption, strength, and biocompatibility, and can be used as a carrier for composite catalysts, increasing photocatalyst activity through adsorption synergy. Under light irradiation, the phosphate ions on the surface of hydroxyapatite change their electronic structure due to electron transfer, promoting the separation and transfer of photogenerated charge carriers. Copper ferrite, with its narrow band gap, low cost, and carbon cycling, is used as a good photocatalytic material for degrading pollutants; however, under light irradiation, photo-excited electrons and holes easily recombine. The sulfate ions in hydroxyapatite can combine with holes, reducing the electron-hole recombination rate and enhancing the material's photocatalytic effect.

[0004] In view of this, the inventors specifically designed an application of photocatalytic antibacterial biomass nanomaterials, which led to this invention. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a novel biomass-based photocatalytic antibacterial material, its preparation method, and its application. The method uses oyster shells (or other shellfish) as a precursor, obtaining nano-flower-like hydroxyapatite with a large specific surface area through simple alkaline thermal treatment. Then, hydroxyapatite is modified by copper ferrite doping, followed by a one-step hydrothermal method to prepare a copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterial with good photocatalytic antibacterial effect and good biocompatibility. The prepared copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterial was used to study its antibacterial properties against *Escherichia coli* and *Staphylococcus aureus*. Results showed that the composite material exhibited highly efficient antibacterial performance under simulated sunlight irradiation. A literature review revealed no relevant reports to date. The technical solution of this invention is as follows:

[0006] A method for preparing a novel photocatalytic antibacterial biomass material includes the following steps:

[0007] (1) Clean the oyster shells, dry them, grind them into powder using a pulverizer, and then sieve the oyster shell powder to a certain mesh size.

[0008] (2) Weigh a certain amount of the above oyster shell powder, add deionized water and stir magnetically for a certain time, then add diamine hydrogen phosphate, control the calcium / phosphorus atomic ratio, adjust the pH of the slurry to 9 or 10, and react under certain conditions.

[0009] (3) After the reaction is complete, the slurry is washed by centrifugation with deionized water and anhydrous ethanol in sequence, and then the obtained hydroxyapatite is placed in an oven to dry.

[0010] (4) Add a certain amount of ferric chloride hexahydrate, copper chloride dihydrate, sodium acetate and trisodium citrate dihydrate to ethylene glycol in sequence, disperse by ultrasonication and then stir magnetically for a certain time;

[0011] (5) Weigh the hydroxyapatite powder obtained in step (3) and add it to the above solution. After ultrasonic dispersion, stir magnetically for a certain period of time.

[0012] (6) The solution obtained in step (5) is transferred to a polytetrafluoroethylene reactor for hydrothermal reaction. After the reaction is completed, it is cooled to room temperature, washed by centrifugation with deionized water and ethanol in sequence, and then dried in an oven to obtain copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterials.

[0013] Furthermore, the oyster shell powder in step (1) has a mesh size of 200 mesh or 800 mesh.

[0014] Furthermore, in step (2), the oyster shell powder has a mass of 30-50 g, and after adding deionized water, it is magnetically stirred for 30 min. The mass of the diamine hydrogen phosphate is 20-25 g, and the calcium / phosphorus atomic ratio is 1.67. Under certain conditions, the reaction temperature is 80℃-100℃, and the reaction time is 6 h or 8 h.

[0015] Furthermore, the drying temperature in step (3) is 60°C or 100°C, and the time is 8h or 12h.

[0016] Furthermore, in step (4), the masses of ferric chloride hexahydrate, copper chloride dihydrate, sodium acetate, and trisodium citrate dihydrate are 0.6~0.8 g, 0.2~0.3 g, 1~1.5 g, and 0.001~0.01 g, respectively; and after ultrasonic dispersion for 20 min, magnetic stirring is performed for 30 min.

[0017] Furthermore, the mass of the hydroxyapatite powder in step (5) is 5~15g, and it is ultrasonically dispersed for 20 min and then magnetically stirred for 30 min.

[0018] Furthermore, the hydrothermal reaction temperature in step (6) is 100~180 ℃ and the time is 8~12h.

[0019] Furthermore, in steps (3) and (6), the product is washed at least once by centrifugation with deionized water and anhydrous ethanol.

[0020] Furthermore, in step (1), the oyster shell is replaced with other shellfish besides oyster shell powder, and in step (2), it is replaced with powder of other shellfish, such as scallop shells, oyster shells, sea oyster shells, etc.

[0021] A novel photocatalytic antibacterial biomass material is prepared using a novel photocatalytic antibacterial biomass material preparation method.

[0022] Application of a novel photocatalytic antibacterial biomass material: This study investigates the antibacterial properties of a novel photocatalytic antibacterial biomass material.

[0023] The technical effects of this invention are as follows:

[0024] (1) The synthesized copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterials are derived from renewable biomass materials, which are environmentally friendly and safe. The preparation method is simple and easy to implement, and does not require expensive equipment.

[0025] (2) Since copper ferrite has excellent photocatalytic activity, the copper and iron ions in it can also be doped into hydroxyapatite. Compared with pure hydroxyapatite, the antibacterial material prepared by this invention has better photocatalytic antibacterial properties due to the synergistic effect of copper ferrite and hydroxyapatite.

[0026] (3) Since copper ferrite is a magnetic material, the antibacterial nanomaterials prepared can be recycled and are an environmentally friendly material.

[0027] In summary, the preparation method of this invention is simple, the precursor material is readily available, the nanomaterial is recyclable, and biological waste can be recycled. The copper ferrite / hydroxyapatite photocatalytic antibacterial material prepared by this invention can achieve efficient antibacterial activity under simulated sunlight irradiation, providing possibilities for the application of modified hydroxyapatite in fields such as nanomedicine, functional coatings, and degradation of harmful gases. Attached Figure Description

[0028] The accompanying drawings, which are provided to further illustrate the invention and constitute a part of this invention, are illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention.

[0029] in:

[0030] Figure 1 This is the XRD pattern of the copper ferrite / hydroxyapatite photocatalytic antibacterial material prepared in Example 3 of the present invention;

[0031] Figure 2 This is a scanning electron microscope (SEM) image of the copper ferrite / hydroxyapatite photocatalytic antibacterial material prepared in Example 1 of this invention. As shown in the image, spherical copper ferrite is uniformly attached to the nano-flower-like hydroxyapatite.

[0032] Figure 3 This is a diagram showing the antibacterial effect of the copper ferrite / hydroxyapatite photocatalytic antibacterial material prepared in Example 2 of this invention against Staphylococcus aureus.

[0033] Figure 4 This is a diagram showing the antibacterial effect of the copper ferrite / hydroxyapatite photocatalytic antibacterial material prepared in Example 2 of this invention against Escherichia coli.

[0034] Figure 5 This is a specific surface area diagram of the copper ferrite / hydroxyapatite photocatalytic antibacterial material prepared in Example 3 of the present invention; the specific surface area of ​​the material is 52.8 m². 2 / g. Detailed Implementation

[0035] To make the technical problems, solutions, and beneficial effects 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 merely illustrative and not intended to limit the scope of the invention. Example 1

[0036] (1) Oyster shells were cleaned, dried, and ground into powder using a pulverizer. The oyster shell powder was then sieved through a 200-mesh sieve. 30 g of the sieved oyster shell powder was collected, and 500 mL of deionized water was added. The mixture was then magnetically stirred for 30 min to achieve a slurry concentration of 0.06 g / mL. 23.7 g of diammonium hydrogen phosphate was added to the slurry to adjust the calcium / phosphorus atomic ratio to 1.67. Subsequently, sodium hydroxide was added to adjust the pH to 9.0. The mixture was then in an oil bath at 90 °C for 8 h. The resulting product was washed three times by centrifugation with deionized water and anhydrous ethanol to remove ionic solutions and impurities. Finally, the precipitate was dispersed in deionized water and centrifuged at 2000 rpm for 20 min to obtain hydroxyapatite powder. The powder was then dried in a 60 °C oven for 12 h.

[0037] (2) Weigh 720.3 mg ferric chloride hexahydrate, 230 mg copper chloride dihydrate, 1400 mg sodium acetate and 5.2 mg trisodium citrate dihydrate and add them to 60 mL ethylene glycol. Disperse by sonication for 20 min and stir magnetically for 30 min. Weigh 10 g of hydroxyapatite powder obtained in step (1) and add it to the prepared solution. Disperse by sonication for 20 min and stir magnetically for 30 min.

[0038] (3) The solution stirred in step (2) was transferred to a 100 mL polytetrafluoroethylene reactor and hydrothermally reacted at 160 °C for 8 h. After the hydrothermal reaction was completed, it was cooled to room temperature, washed by centrifugation with deionized water and ethanol in sequence, and then placed in a 60 °C oven for 12 h to obtain copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterials. Example 2

[0039] (1) Oyster shells were cleaned, dried, and ground into powder using a pulverizer. The oyster shell powder was then sieved through a 200-mesh sieve. 30 g of the sieved oyster shell powder was collected, and 500 mL of deionized water was added. The mixture was then magnetically stirred for 30 min to achieve a slurry concentration of 0.06 g / mL. 23.7 g of diammonium hydrogen phosphate was added to the slurry to adjust the calcium / phosphorus atomic ratio to 1.67. Subsequently, sodium hydroxide was added to adjust the pH to 9.0. The mixture was then in an oil bath at 90 °C for 8 h. The resulting product was washed three times by centrifugation with deionized water and anhydrous ethanol to remove ionic solutions and impurities. Finally, the precipitate was dispersed in deionized water and centrifuged at 2000 rpm for 20 min to obtain hydroxyapatite powder. The powder was then dried in a 60 °C oven for 12 h.

[0040] (2) 720.3 mg ferric chloride hexahydrate, 230 mg copper chloride dihydrate, 1400 mg sodium acetate and 5.2 mg trisodium citrate dihydrate were added to 60 mL ethylene glycol in sequence, ultrasonically dispersed for 20 min and magnetically stirred for 30 min; 15 g of hydroxyapatite powder obtained in step (1) was weighed and added to the prepared solution, ultrasonically dispersed for 20 min and magnetically stirred for 30 min.

[0041] (3) The solution stirred in step (2) was transferred to a 100 mL polytetrafluoroethylene reactor and hydrothermally reacted at 160 °C for 8 h. After the hydrothermal reaction was completed, it was cooled to room temperature, washed by centrifugation with deionized water and ethanol in sequence, and then placed in a 60 °C oven for 12 h to obtain copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterials. Example 3

[0042] (1) Oyster shells were cleaned, dried, and ground into powder using a pulverizer. The oyster shell powder was then sieved through a 200-mesh sieve. 30 g of the sieved oyster shell powder was collected, and 500 mL of deionized water was added. The mixture was then magnetically stirred for 30 min to achieve a slurry concentration of 0.06 g / mL. 23.7 g of diammonium hydrogen phosphate was added to the slurry to adjust the calcium / phosphorus atomic ratio to 1.67. Subsequently, sodium hydroxide was added to adjust the pH to 9.0. The mixture was then in an oil bath at 90 °C for 8 h. The resulting product was washed three times by centrifugation with deionized water and anhydrous ethanol to remove ionic solutions and impurities. Finally, the precipitate was dispersed in deionized water and centrifuged at 2000 rpm for 20 min to obtain hydroxyapatite powder. The powder was then dried in a 60 °C oven for 12 h.

[0043] (2) 720.3 mg ferric chloride hexahydrate, 230 mg copper chloride dihydrate, 1400 mg sodium acetate and 5.2 mg trisodium citrate dihydrate were added to 60 mL ethylene glycol in sequence, ultrasonically dispersed for 20 min and magnetically stirred for 30 min; 5 g of hydroxyapatite powder obtained in step (1) was weighed and added to the prepared solution, ultrasonically dispersed for 20 min and magnetically stirred for 30 min.

[0044] (3) The solution stirred in step (2) was transferred to a 100 mL polytetrafluoroethylene reactor and hydrothermally reacted at 160 °C for 8 h. After the hydrothermal reaction was completed, it was cooled to room temperature, washed by centrifugation with deionized water and ethanol in sequence, and then placed in a 60 °C oven for 12 h to obtain copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterials. Example 4

[0045] (1) Oyster shells were cleaned, dried, and ground into powder using a pulverizer. The oyster shell powder was then sieved through a 200-mesh sieve. 30 g of the sieved oyster shell powder was collected, and 500 mL of deionized water was added. The mixture was then magnetically stirred for 30 min to achieve a slurry concentration of 0.06 g / mL. 23.7 g of diammonium hydrogen phosphate was added to the slurry to adjust the calcium / phosphorus atomic ratio to 1.67. Subsequently, sodium hydroxide was added to adjust the pH to 9.0. The mixture was then in an oil bath at 90 °C for 8 h. The resulting product was washed three times by centrifugation with deionized water and anhydrous ethanol to remove ionic solutions and impurities. Finally, the precipitate was dispersed in deionized water and centrifuged at 2000 rpm for 20 min to obtain hydroxyapatite powder. The powder was then dried in a 60 °C oven for 12 h.

[0046] (2) 720.3 mg ferric chloride hexahydrate, 230 mg copper chloride dihydrate, 1400 mg sodium acetate and 5.2 mg trisodium citrate dihydrate were added to 60 mL ethylene glycol in sequence, ultrasonically dispersed for 20 min and magnetically stirred for 30 min; 10 g of hydroxyapatite powder obtained in step (1) was weighed and added to the prepared solution, ultrasonically dispersed for 20 min and magnetically stirred for 30 min.

[0047] (3) The solution stirred in step (2) was transferred to a 100 mL polytetrafluoroethylene reactor and hydrothermally reacted at 160 °C for 10 h. After the hydrothermal reaction was completed, it was cooled to room temperature, washed by centrifugation with deionized water and ethanol in sequence, and then placed in a 60 °C oven for 12 h to obtain copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterials. Example 5

[0048] (1) Oyster shells were cleaned, dried, and ground into powder using a pulverizer. The oyster shell powder was then sieved through a 200-mesh sieve. 30 g of the sieved oyster shell powder was collected, and 500 mL of deionized water was added. The mixture was then magnetically stirred for 30 min to achieve a slurry concentration of 0.06 g / mL. 23.7 g of diammonium hydrogen phosphate was added to the slurry to adjust the calcium / phosphorus atomic ratio to 1.67. Subsequently, sodium hydroxide was added to adjust the pH to 9.0. The mixture was then in an oil bath at 90 °C for 8 h. The resulting product was washed three times by centrifugation with deionized water and anhydrous ethanol to remove ionic solutions and impurities. Finally, the precipitate was dispersed in deionized water and centrifuged at 2000 rpm for 20 min to obtain hydroxyapatite powder. The powder was then dried in a 60 °C oven for 12 h.

[0049] (2) 720.3 mg ferric chloride hexahydrate, 230 mg copper chloride dihydrate, 1400 mg sodium acetate and 5.2 mg trisodium citrate dihydrate were added to 60 mL ethylene glycol in sequence, ultrasonically dispersed for 20 min and magnetically stirred for 30 min; 10 g of hydroxyapatite powder obtained in step (1) was weighed and added to the prepared solution, ultrasonically dispersed for 20 min and magnetically stirred for 30 min.

[0050] (3) The solution stirred in step (2) was transferred to a 100 mL polytetrafluoroethylene reactor and hydrothermally reacted at 160 °C for 12 h. After the hydrothermal reaction was completed, it was cooled to room temperature, washed by centrifugation with deionized water and ethanol in sequence, and then placed in a 60 °C oven for 12 h to obtain copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterials. Example 6

[0051] (1) Oyster shells were cleaned, dried, and ground into powder using a pulverizer. The oyster shell powder was then sieved through a 200-mesh sieve. 50 g of the sieved oyster shell powder was collected, and 500 mL of deionized water was added. The mixture was then magnetically stirred for 30 min to achieve a slurry concentration of 0.06 g / mL. 23.7 g of diammonium hydrogen phosphate was added to the slurry to adjust the calcium / phosphorus atomic ratio to 1.67. Subsequently, sodium hydroxide was added to adjust the pH to 9.0. The mixture was then in an oil bath at 90 °C for 8 h. The resulting product was washed three times by centrifugation with deionized water and anhydrous ethanol to remove ionic solutions and impurities. Finally, the precipitate was dispersed in deionized water and centrifuged at 2000 rpm for 20 min to obtain hydroxyapatite powder. The powder was then dried in a 60 °C oven for 12 h.

[0052] (2) 600 mg ferric chloride hexahydrate, 300 mg copper chloride dihydrate, 1400 mg sodium acetate and 5.2 mg trisodium citrate dihydrate were added to 60 mL ethylene glycol in sequence, ultrasonically dispersed for 20 min and magnetically stirred for 30 min; 10 g of hydroxyapatite powder obtained in step (1) was weighed and added to the prepared solution, ultrasonically dispersed for 20 min and magnetically stirred for 30 min.

[0053] (3) The solution stirred in step (2) was transferred to a 100 mL polytetrafluoroethylene reactor and hydrothermally reacted at 160 °C for 12 h. After the hydrothermal reaction was completed, it was cooled to room temperature, washed by centrifugation with deionized water and ethanol in sequence, and then placed in a 60 °C oven for 12 h to obtain copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterials. Example 7

[0054] (1) Oyster shells were cleaned, dried, and ground into powder using a pulverizer. The oyster shell powder was then sieved through a 200-mesh sieve. 40 g of the sieved oyster shell powder was collected, and 500 mL of deionized water was added. The mixture was then magnetically stirred for 30 min to achieve a slurry concentration of 0.06 g / mL. 23.7 g of diammonium hydrogen phosphate was added to the slurry to adjust the calcium / phosphorus atomic ratio to 1.67. Subsequently, sodium hydroxide was added to adjust the pH to 9.0. The mixture was then in an oil bath at 90 °C for 8 h. The resulting product was washed three times by centrifugation with deionized water and anhydrous ethanol to remove ionic solutions and impurities. Finally, the precipitate was dispersed in deionized water and centrifuged at 2000 rpm for 20 min to obtain hydroxyapatite powder. The powder was then dried in a 60 °C oven for 12 h.

[0055] (2) 800 mg ferric chloride hexahydrate, 250 mg copper chloride dihydrate, 1200 mg sodium acetate and 10 mg trisodium citrate dihydrate were added to 60 mL ethylene glycol in sequence, ultrasonically dispersed for 20 min and magnetically stirred for 30 min; 10 g of hydroxyapatite powder obtained in step (1) was weighed and added to the prepared solution, ultrasonically dispersed for 20 min and magnetically stirred for 30 min.

[0056] (3) The solution stirred in step (2) was transferred to a 100 mL polytetrafluoroethylene reactor and hydrothermally reacted at 160 °C for 12 h. After the hydrothermal reaction was completed, it was cooled to room temperature, washed by centrifugation with deionized water and ethanol in sequence, and then placed in a 60 °C oven for 12 h to obtain copper ferrite / hydroxyapatite photocatalytic antibacterial nanomaterials.

[0057] Application Example 1

[0058] The novel biomass-based photocatalytic antibacterial material prepared in this invention is used to study its antibacterial performance under simulated sunlight irradiation.

[0059] 0.2 mg of the photocatalytic antibacterial material was placed in a 96-well plate, and 200 μL of 1×10⁷ CFU Escherichia coli bacterial suspension was added to each well. The plate was then continuously irradiated for 10 min using a 0.25 W cm⁻² xenon lamp with a full-spectrum light source. The Escherichia coli / Staphylococcus aureus bacterial suspension was diluted 100-fold, and 20 μL was spread onto a petri dish containing solid culture medium. The plate was then placed in a 37 ℃ oven and incubated for 24 h before observation and measurement. The specific data from the repeat experiments using the copper ferrite / hydroxyapatite photocatalytic antibacterial material prepared in Example 4 against Escherichia coli and Staphylococcus aureus are shown in Table 1 below.

[0060]

[0061] Table 1

[0062] As shown in the table above, the copper ferrite / hydroxyapatite photocatalytic antibacterial material prepared by this invention can achieve highly efficient antibacterial activity under simulated sunlight irradiation.

[0063] The present invention has been described above by way of example with reference to the accompanying drawings. Obviously, the specific implementation of the present invention is not limited to the above-described manner. Any non-substantial improvements made using the inventive concept and technical solution of the present invention, or the direct application of the inventive concept and technical solution of the present invention to other occasions without modification, are all within the protection scope of the present invention.

Claims

1. An application of a photocatalytic antibacterial biomass nanomaterial, characterized in that, The study of the antibacterial properties of a photocatalytic antibacterial biomass nanomaterial includes the following steps in its preparation method: (1) Clean the oyster shells, dry them, grind them into powder using a pulverizer, and then sieve the oyster shell powder with a mesh size of 200 or 800. (2) Weigh 30-50 g of the above oyster shell powder, add deionized water and stir for a certain time, then add 20-25 g of diammonium hydrogen phosphate, control the calcium / phosphorus atomic ratio, adjust the pH of the slurry to 9 or 10, and react at 80-100 ℃ for 6 or 8 h. (3) After the reaction is complete, the slurry is washed by centrifugation with deionized water and anhydrous ethanol in sequence. Then the obtained hydroxyapatite is placed in an oven to dry at a temperature of 60℃ or 100℃ for 8h or 12h. (4) A certain amount of ferric chloride hexahydrate, copper chloride dihydrate, sodium acetate and trisodium citrate dihydrate are added to ethylene glycol in sequence, ultrasonically dispersed and stirred for a certain period of time. The masses of the ferric chloride hexahydrate, copper chloride dihydrate, sodium acetate and trisodium citrate dihydrate are 0.6-0.8 g, 0.2-0.3 g, 1-1.5 g and 0.001-0.01 g, respectively. (5) Weigh the hydroxyapatite powder obtained in step (3) and add it to the solution obtained in step (4). After ultrasonic dispersion, stir for a certain period of time. The mass of the hydroxyapatite powder weighed is 5-15g. (6) The solution obtained in step (5) is transferred to a polytetrafluoroethylene reactor for hydrothermal reaction. After the reaction is completed, it is cooled to room temperature, washed by centrifugation with deionized water and ethanol in sequence, and then dried in an oven to obtain copper ferrite / hydroxyapatite photocatalytic antibacterial biomass nanomaterials. The hydrothermal reaction temperature is 100-180 ℃ and the time is 8-12 h.

2. The application of the photocatalytic antibacterial biomass nanomaterial according to claim 1, characterized in that, In step (2), after adding deionized water, the mixture is magnetically stirred for 30 minutes, and the calcium / phosphorus atomic ratio is 1.

67.

3. The application of the photocatalytic antibacterial biomass nanomaterial according to claim 1, characterized in that, In step (4), ultrasonic dispersion is performed for 20 min, followed by magnetic stirring for 30 min.

4. The application of the photocatalytic antibacterial biomass nanomaterial according to claim 1, characterized in that, In step (5), ultrasonic dispersion is performed for 20 min, followed by magnetic stirring for 30 min.

5. The application of the photocatalytic antibacterial biomass nanomaterial according to claim 1, characterized in that, In steps (3) and (6), the product is washed at least three times by centrifugation with deionized water and anhydrous ethanol.

Citation Information

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