ZnO-CaO2 composite nanomaterials with antibacterial activity, their preparation methods and applications

Abstract

This invention discloses a ZnO-CaO2 composite nanomaterial with antibacterial activity, its preparation method, and its application, belonging to the field of nano-antibacterial materials. The preparation method of the ZnO-CaO2 composite nanomaterial is as follows: (1) Mixing and homogenizing a brown algae polyphenol solution with a zinc acetate solution, and allowing it to stand in a dark environment to obtain a precipitate; (2) calcining the above precipitate, naturally cooling it to room temperature, and grinding it to obtain a powdered calcined product; (3) dispersing the powdered calcined product in anhydrous ethanol, and sequentially adding calcium chloride, triethylamine, and hydrogen peroxide, allowing it to react fully to obtain the final product. The ZnO-CaO2 composite nanomaterial is used in the preparation or as an antibacterial material. The composite material of this invention organically integrates the strong bactericidal ability of calcium peroxide with the long-lasting antibacterial properties and good biocompatibility of zinc oxide, possessing both excellent antibacterial activity and low cytotoxicity, and has good prospects for large-scale application.

Description

Technical Field

[0001] This invention relates to a ZnO-CaO2 composite nanomaterial with antibacterial activity, its preparation method and application, belonging to the field of nano-antibacterial materials. Background Technology

[0002] In the wave of modern technological development, nanomaterials for antibacterial purposes have gained prominence due to their low toxicity and low tendency to induce antibiotic resistance in bacteria, leading to their widespread application in fields such as medical health and food safety. Among these, nano-zinc oxide, a classic semiconductor metal nanomaterial for antibacterial purposes, has attracted considerable attention due to its low synthesis cost, mature synthesis process, and excellent material safety. The antibacterial properties and safety of zinc oxide primarily stem from its unique dual-action mechanism: on the one hand, zinc oxide can slowly release zinc ions into the surrounding environment. Compared to human cells, bacteria have a lower tolerance for zinc, and zinc ions can disrupt the normal metabolic processes of bacteria, thereby inhibiting their growth and reproduction. On the other hand, under specific external stimuli such as light and ultrasound, zinc oxide generates reactive oxygen species that interfere with the normal physiological functions of bacteria, ultimately leading to bacterial death. However, in practical applications, it is often difficult to continuously provide the corresponding stimulation to zinc oxide, failing to achieve the ideal antibacterial effect and severely limiting its application.

[0003] Calcium peroxide, a mature and widely used disinfectant, decomposes gradually in solution to produce hydrogen peroxide and calcium hydroxide. Hydrogen peroxide rapidly reacts with intracellular biomolecules, leading to bacterial death. Simultaneously, the highly alkaline environment created by calcium hydroxide is also unfavorable for bacterial survival, further enhancing its bactericidal effect. However, the application of calcium peroxide is significantly limited. On the one hand, it exhibits strong cytotoxicity; numerous studies have confirmed that even at low concentrations, calcium peroxide can still damage biological tissues. This characteristic severely restricts its application in scenarios with high biosafety requirements. On the other hand, calcium peroxide has poor long-lasting antibacterial ability; the hydrogen peroxide produced by its hydrolysis is easily decomposed in the environment, making it difficult to maintain an effective antibacterial concentration for a prolonged period, thus failing to meet the needs of some applications requiring long-term antibacterial activity. Currently, there are no reports of calcium peroxide loaded onto zinc oxide. Summary of the Invention

[0004] In view of the above-mentioned prior art, the present invention provides a ZnO-CaO2 composite nanomaterial with antibacterial activity, its preparation method and application.

[0005] This invention is achieved through the following technical solution: A method for preparing a ZnO-CaO2 composite nanomaterial with antibacterial activity includes the following steps: (1) Mix the brown algae polyphenol solution with the zinc acetate solution, let it stand at 0-4℃ in the dark to obtain the precipitate, wash and dry it; (2) The above precipitate was calcined, cooled naturally to room temperature, and ground to obtain a powdered calcined product; (3) Disperse the powdered calcined product in anhydrous ethanol, add calcium chloride, triethylamine and hydrogen peroxide in sequence, and react fully to obtain ZnO-CaO2 composite nanomaterials. Separate, wash and dry.

[0006] Further, in step (1), the ratio of brown algae polyphenols to zinc acetate is: 35-45 g of brown algae polyphenols are added for every 1 mol of zinc acetate, preferably 40 g of brown algae polyphenols are added for every 1 mol of zinc acetate.

[0007] Further, in step (1), the concentration of the brown algae polyphenol solution is 8-12 g / L, preferably 10 g / L; the concentration of the zinc acetate solution is 0.05-0.15 mol / L, preferably 0.1 mol / L.

[0008] Furthermore, in step (1), the settling time is 20 to 28 hours, preferably 24 hours.

[0009] Furthermore, in step (1), the specific method of mixing is to stir for 1 hour.

[0010] Furthermore, in step (1), the specific method of washing is to wash three times with ultrapure water.

[0011] Furthermore, in step (1), the drying method is to dry at 60°C for 24 hours.

[0012] Furthermore, in step (2), the specific method of calcination treatment is: calcination at 550-650°C for 3.5-4.5 hours, preferably calcination at 600°C for 4 hours.

[0013] Furthermore, in step (3), the mass ratio of the calcined product to calcium chloride is 1:(2-8), preferably 1:2, 1:4, or 1:6.

[0014] Furthermore, in step (3), the concentration of the calcined product in anhydrous ethanol is 0.5–2 mg / mL, preferably 1 mg / mL.

[0015] Further, in step (3), the volume ratio of anhydrous ethanol, triethylamine and hydrogen peroxide is 100:(1.5-2.5):(3.5-4.5), preferably 100:1.9:3.8.

[0016] Furthermore, in step (3), the interval between adding calcium chloride, triethylamine and hydrogen peroxide in sequence is 5 minutes, and the reaction continues for 30 minutes after adding hydrogen peroxide.

[0017] Furthermore, in step (3), the specific method of dispersion is ultrasonic dispersion.

[0018] Furthermore, in step (3), the specific method of separation is centrifugation, the specific method of washing is washing three times with anhydrous ethanol, and the specific method of drying is natural drying for 24 hours.

[0019] The ZnO-CaO2 composite nanomaterial with antibacterial activity prepared by the above method has a Zn / Ca molar ratio of 1:(0.9–2.6), preferably 1:0.9, 1:1.7, or 1:2.6. This ZnO-CaO2 composite nanomaterial exhibits excellent antibacterial effect, sustained antibacterial ability, and low cytotoxicity, and can be used as an antibacterial material.

[0020] Application of the ZnO-CaO2 composite nanomaterial with antibacterial activity in preparation or as an antibacterial material.

[0021] Furthermore, the antibacterial material inhibits Gram-negative bacteria and / or Gram-positive bacteria; even further, the Gram-negative bacteria are selected from *Escherichia coli* (…). E. coli The Gram-positive bacteria are selected from Staphylococcus aureus (Staphylococcus aureus). S.aureus ).

[0022] This invention uses brown algal polyphenols as a complexing agent to synthesize ZnO via calcination, followed by surface modification (using CaO2) through co-precipitation. Leveraging the hydrogen peroxide release characteristic of calcium peroxide hydrolysis, a continuous and stable source of reactive oxygen species is provided for ZnO, effectively overcoming the dependence of ZnO's antibacterial properties on external stimuli while significantly reducing the biotoxicity of CaO2. The composite material of this invention exhibits both excellent antibacterial activity and low cytotoxicity, and its preparation process is simple and controllable, showing promising prospects for large-scale application.

[0023] This invention relates to a ZnO-CaO2 composite nanomaterial with antibacterial activity. By surface-modifying nano-zinc oxide with calcium peroxide, the two materials achieve functional complementarity and synergistic effects. Zinc oxide acts as a carrier, providing uniform and relatively closed attachment sites for calcium peroxide, reducing direct contact between calcium peroxide and the aquatic environment. Through interfacial interactions, it alters the chemical bond energy state of calcium peroxide, increasing its decomposition activation energy and significantly slowing its hydrolysis rate. This slow-release effect transforms the explosive decomposition of calcium peroxide into a sustained and controllable decomposition mode, enabling the stable release of hydrogen peroxide over a longer period. This provides a persistent and stable source of reactive oxygen species for the composite material, compensating for the insufficient reactive oxygen species generation of zinc oxide under no external stimulation. Simultaneously, it inhibits the direct interaction between calcium peroxide and biological tissues, reducing the potential cytotoxicity risk of the material. Through this surface modification strategy, the potent bactericidal ability of calcium peroxide is organically integrated with the long-lasting antibacterial properties and good biocompatibility of zinc oxide. The composite material of the present invention achieves efficient and long-lasting antibacterial properties while significantly reducing the limitations of each individual component, providing a feasible technical path for developing novel nano-antibacterial materials with both high activity and high safety.

[0024] The various terms and phrases used in this invention have their general meanings known to those skilled in the art. Attached Figure Description

[0025] Figure 1 Homemade ZnO, ZnO@CaO 2（1∶2） The images show SEM images of ZnO, with the left image being a self-made ZnO image and the right image being a ZnO@CaO image. 2（1∶2） SEM image.

[0026] Figure 2 ZnO@CaO 2（1∶2） The TEM images and elemental distribution maps are shown. The top left image is the elemental distribution map; the top middle image is the TEM image; and the top right, bottom left, bottom middle, and bottom right images are the distribution maps of C, O, Zn, and Ca elements, respectively.

[0027] Figure 3 Commercially available ZnO, homemade ZnO, and ZnO@CaO 2（1∶2） FTIR plot.

[0028] Figure 4 ZnO@CaO 2（1∶2） The image shows the inhibition zone, with Escherichia coli on the left and Staphylococcus aureus on the right.

[0029] Figure 5 ZnO@CaO 2（1∶2） The antibacterial rate statistics chart.

[0030] Figure 6 ZnO@CaO 2（1∶2） The image shows the antibacterial effect.

[0031] Figure 7 : A diagram showing the hemolysis test results for each material.

[0032] Figure 8 ZnO@CaO 2（1∶2） Comparison of hemolysis rate results with CaO2. Detailed Implementation

[0033] The present invention will be further described below with reference to embodiments. However, the scope of the present invention is not limited to the following embodiments. Those skilled in the art will understand that various changes and modifications can be made to the present invention without departing from the spirit and scope thereof.

[0034] Unless otherwise specified, the instruments, reagents, and materials used in the following embodiments are all conventional instruments, reagents, and materials already available in the prior art and can be obtained through legitimate commercial channels. Unless otherwise specified, the experimental methods and detection methods used in the following embodiments are all conventional experimental methods and detection methods already available in the prior art.

[0035] The brown algae polyphenols of this invention (97% purity, unbleached) were purchased from Shaanxi Baichuan Kangze Co., Ltd.

[0036] The commercially available ZnO (food grade) of this invention was purchased from Guangdong Guangtai Food Technology Co., Ltd.

[0037] All data results in this invention are expressed as mean ± standard deviation.

[0038] Example 1: Preparation of ZnO@CaO2 composite nanomaterials The steps are as follows: (1) Mix 1000 mL of 0.1 M / L zinc acetate solution with 400 mL of 10 g / L brown algae polyphenol solution, stir at room temperature for 1 h, and then transfer to a 4℃ refrigerator for 24 h in the dark. The phenolic hydroxyl groups in the polyphenol structure chelate zinc ions to form a brown algae polyphenol-zinc(II) complex precipitate. Centrifuge (10 min, 4000 rpm / min, 4℃), discard the supernatant, wash the precipitate three times with ultrapure water, and then dry it in a 60℃ forced-air oven for 24 h to obtain the dried product.

[0039] (2) The dried product was transferred to a muffle furnace for calcination at a temperature of 600℃ for 4 hours and a heating rate of 5℃ / min. After natural cooling, the calcined product (mainly ZnO) was obtained, which is referred to as self-made ZnO.

[0040] (3) Disperse 0.1 g of self-made ZnO in 100 mL of anhydrous ethanol and sonicate for 1 h to ensure complete dispersion. Take 0.05, 0.1, 0.2, 0.4, 0.6, and 0.8 g of anhydrous calcium chloride respectively and add them to 100 mL of the dispersion. After stirring for 5 min, add 1.9 mL of triethylamine and continue stirring for 5 min. Then add 3.8 mL of hydrogen peroxide and continue stirring for 30 min to ensure complete reaction. After the reaction is complete, centrifuge and discard the supernatant. Wash the precipitate three times with anhydrous ethanol and place it in a fume hood to air dry for 24 h to obtain ZnO@CaO2 composite nanomaterials with different calcium chloride dosages. Record them as ZnO@CaO2 according to the mass ratio of zinc oxide to calcium chloride. 2（1:0.5） ZnO@CaO 2（1:1） ZnO@CaO 2（1:2） ZnO@CaO 2（1:4） ZnO@CaO 2（1:6） and ZnO@CaO 2（1:8） Meanwhile, CaO2 without ZnO was prepared as a control.

[0041] The prepared ZnO and ZnO@CaO2 were both white, fine powders, while pure CaO2 was a translucent, slightly yellow granule. Among them, ZnO@CaO... 2（1∶8） After drying, obvious yellow particles appeared on the upper layer of the sample, indicating that CaO2 had reached its maximum loading. At this point, the Zn / Ca molar ratio was 1:3.5, and only the lower white precipitate was taken as the final product.

[0042] After conversion, ZnO@CaO 2（1:2） ZnO@CaO 2（1:4） ZnO@CaO 2（1:6） The Zn / Ca molar ratios were 1:0.9, 1:1.7, and 1:2.6, respectively.

[0043] Example 2 Characterization of ZnO@CaO2 composite nanomaterials The self-made ZnO and ZnO@CaO2 composite materials prepared in Example 1 were examined using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). The ZnO@CaO2 composite material was used as the basis for further analysis. 2（1∶2） As the representative.

[0044] Homemade ZnO, ZnO@CaO 2（1∶2） SEM image as follows Figure 1 As shown, it can be seen that homemade ZnO and ZnO@CaO 2（1∶2） All particles are irregularly shaped and nearly spherical. The average particle size of the self-made ZnO is 103.97 ± 20.06 nm. ZnO@CaO 2（1∶2）The average particle size is 62.27 ± 10.75 nm.

[0045] ZnO@CaO 2（1∶2） TEM images and elemental distribution maps, such as Figure 2 As shown, the main elements of the material include carbon, zinc, oxygen, and calcium. Furthermore, the atomic content and mass percentage of the four elements can be obtained from the EDS analysis results, as shown in Table 1.

[0046] Table 1

[0047] Commercially available ZnO, homemade ZnO and ZnO@CaO 2（1∶2） FTIR plot as shown Figure 3 As shown in the figure. It can be seen that all three samples are at approximately 427 cm. -1 and 547 cm -1 The presence of absorption peaks at the spectral density, attributed to the characteristic stretching vibrations of the Zn-O bond, confirms the successful synthesis of ZnO prepared using brown algae polyphenols as a complexing agent and the ZnO component in ZnO@CaO2. Compared to commercially available ZnO, the Zn-O characteristic peaks of the self-prepared ZnO exhibit a significant blue shift. This can be attributed to the effective inhibition of ZnO grain growth by brown algae polyphenols during calcination, resulting in the synthesized ZnO possessing smaller nanoscale sizes and more abundant surface defects. Compared to the spectrum of ZnO, ZnO@CaO... 2（1∶2） At 856cm -1 A new absorption peak appeared at approximately 3400 cm⁻¹, corresponding to the stretching vibration of the O-Ca-O bond, confirming the successful loading of CaO₂. Furthermore, all samples showed an absorption peak at approximately 3400 cm⁻¹. -1 and 1358 cm -1 All ZnO samples showed stretching vibration peaks of the OH bond, with the intensity showing the order of commercially available ZnO < homemade ZnO < ZnO@CaO. 2（1∶2） The increasing trend: The enhancement of hydroxyl groups in the self-made ZnO mainly stems from the residual hydroxyl groups after the carbonization of the brown algae polyphenol complexing agent, while ZnO@CaO 2（1∶2） The further increase in the strength of the hydroxyl group is attributed to the hygroscopic properties of the supported CaO2 component.

[0048] Example 3: Detection of the antibacterial ability of ZnO@CaO2 composite nanomaterials Using Escherichia coli ( E. coli (Representative of Gram-negative bacteria) and Staphylococcus aureus ( S.aureusThe antibacterial ability of the ZnO@CaO2 composite nanomaterials prepared in Example 1 was tested (representing Gram-positive bacteria). The material samples examined included: commercially available ZnO, antibacterial CaO nanoparticles with a ZnO coating (hereinafter referred to as ZnO-CaO), self-made ZnO, CaO2 (prepared in Example 1), and ZnO@CaO. 2（1:0.5） ZnO@CaO 2（1:1） ZnO@CaO 2（1:2） ZnO@CaO 2（1:4） ZnO@CaO 2（1:6） Unless otherwise specified, all biological materials used, including LB medium, MH medium, and physiological saline, have undergone high-temperature sterilization.

[0049] The ZnO-CaO was prepared according to the method described in Example 1 of CN 106924052 A, with a Zn / Ca molar ratio of 8:1. CN 106924052 A discloses a ZnO-coated CaO nanoparticle antibacterial material and its preparation method. The method involves preparing the ZnO-coated CaO nanoparticle antibacterial material through simple liquid precipitation and calcination. This technical solution uses CaO nanoparticles as a carrier to load the ZnO coating.

[0050] (1) Detection of minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) Commercially available ZnO, ZnO-CaO, self-made ZnO, CaO2, and ZnO@CaO2 were placed in a clean bench and sterilized with ultraviolet light for 30 minutes. They were then diluted with physiological saline to a suitable initial concentration. Subsequently, they were continuously diluted with physiological saline to obtain diluents of different concentrations.

[0051] The bacterial strain preserved in glycerol tubes at -80℃ was streaked into LB medium and purified by a second streak. Single colonies obtained from purification were picked and inoculated into LB liquid medium. After incubation at 220 rpm / min and 37℃ for 20 h on a shaker, the bacterial pellet was collected by centrifugation (10 min, 4000 rpm / min, 4℃). The concentration was adjusted to approximately 1×10⁻⁶ saline. 8 CFU / mL, then diluted to 5×10⁻⁶ CFU / mL with MH liquid medium at a 2-fold concentration (standard medium is 40 g / L, here 80 g / L is used because the final well plate contains material diluent, bacterial culture, and a small amount of negligible staining solution; concentrated medium is used to prepare the bacterial culture to ensure the final well medium concentration reaches the normal level). 6 CFU / mL, to obtain bacterial suspension.

[0052] Cultures were performed using 96-well plates. 100 μL of bacterial suspension, 100 μL of different concentrations of dilutions of the tested materials, and 20 μL of 1% tetrazolium red (TTC) stain were added sequentially to each well. Positive controls (bacterial suspension) and negative controls (culture medium) were also included. Color changes were observed after 1 and 7 days of incubation at 37°C. The lowest concentration at which no color change was recorded as the MIC. Subsequently, 50 μL of each well from the uncolored plate was spread onto LB medium and incubated at 37°C for 24 h. The lowest concentration at which no colony growth was observed was recorded as the MBC. All experiments were performed in at least three biological replicates.

[0053] The MIC and MBC test results of each tested material are shown in Table 2.

[0054] Table 2

[0055] The results showed that the self-made ZnO prepared using brown algae polyphenols as a complexing agent exhibited significant antibacterial activity, and its antibacterial performance was significantly better than that of commercially available ZnO. The ZnO@CaO2 composite material constructed based on this exhibited significantly improved antibacterial ability compared to the self-made ZnO, and was significantly superior to the similar material ZnO-CaO. With increasing calcium source content, the antibacterial performance of the composite material gradually increased; when the mass ratio of zinc oxide to calcium chloride was 1:2, the MIC and MBC of the composite material surpassed those of CaO2, indicating that the components in the composite material synergistically enhanced, ultimately exhibiting excellent antibacterial effects. (2) Determination of inhibition zone The inhibition zone was determined using the perforation method with ZnO@CaO. 2（1∶2） For example, 10 μL of the solution diluted with physiological saline was obtained according to the method described in (1) above. 8 A bacterial suspension of CFU / mL was thoroughly applied to MH agar plates using a sterile cotton swab, with 3-4 applications per plate to ensure uniform bacterial adhesion. Subsequently, wells were punched using a sterile pipette tip, and 50 μL of ZnO@CaO at different concentrations was added to each well. 2（1∶2） Diluted with physiological saline, incubated at 37°C for 24 h, and the size of the inhibition zone was observed and measured. All experiments were performed in biological replicates at least three times.

[0056] ZnO@CaO 2（1∶2） The antibacterial zone display diagram is as follows Figure 4 As shown, ZnO@CaO 2（1∶2） The statistical results of the inhibition zone diameter are shown in Table 3.

[0057] Table 3

[0058] The results showed that low concentrations of ZnO@CaO2（1∶2） Even at 1 / 2 MIC, a clear inhibition zone was still observed, further confirming the material's excellent antibacterial ability. The material's effect on... S.aureus Its antibacterial effect is better than E. coli This is related to the different properties of bacteria. Gram-negative bacteria have a dense outer membrane in their cell walls, which hinders the invasion of reactive oxygen species and zinc and calcium ions, making them more resistant to materials.

[0059] (3) In vitro antibacterial test ZnO@CaO 2（1∶2） To represent the in vitro antibacterial activity of the composite material, 10 μL of the composite material was diluted with 2x MH liquid culture medium according to the method described in (1) above. 6 CFU / mL bacterial suspension, 500 μL of ZnO@CaO at different concentrations 2（1∶2） After vortexing the physiological saline dilution with an equal volume of bacterial suspension, the culture was incubated at 37°C for 16 h on a shaker. Subsequently, serial dilutions were performed using physiological saline, with 10 μL of each dilution added dropwise to LB medium. After incubation at 37°C for 24 h, bacterial counts were performed. The inhibition rate (n) was: In the formula: n represents the inhibition rate (%); A0 represents the number of colonies (CFU) in the blank control; A1 represents the number of colonies (CFU) in the treatment group. All experiments were performed in biological replicates at least three times.

[0060] ZnO@CaO 2（1∶2） The antibacterial rate statistics are shown in the figure below. Figure 5 As shown, ZnO@CaO 2（1∶2） The antibacterial effect is shown in the following figure. Figure 6 As shown, the results once again confirm that the material has good and sustained antibacterial ability.

[0061] Example 4 Hemolysis Rate Experiment The CaO2 and ZnO@CaO2 prepared in Example 1 were dissolved in PBS solution to prepare suspensions of different concentrations, and the suspensions were incubated at 37°C for 20 min. Then, 1 mL of fresh citrate-anticoagulated rabbit blood was mixed with 9 mL of PBS solution and centrifuged (2000 rpm / min, 10 min) to collect red blood cells. Subsequently, 50 μL of red blood cells were mixed with 500 μL of sample suspension, incubated at 37°C for 1 h, and then centrifuged (2000 rpm / min, 10 min). The absorbance of the supernatant at 542 nm was measured using a microplate reader. A positive control (0.1% Triton X-100) and a negative control (PBS) were also included. The hemolysis rate was: In the formula: A S A P and A TThe absorbance values ​​represent the sample, PBS, and Triton X-100 mixed with red blood cells, respectively.

[0062] The results of the hemolysis test for each material are shown in the figure below. Figure 7 As shown, ZnO@CaO 2（1∶2） Comparison of hemolysis rate results with CaO2, for example Figure 8 As shown, the composite material exhibits lower cytotoxicity and significantly improved safety compared to CaO2.

[0063] The above embodiments are provided to those skilled in the art to fully disclose and describe how the claimed implementations can be carried out and used, and are not intended to limit the scope of the disclosure herein. Modifications that will be obvious to those skilled in the art will be within the scope of the appended claims.

Claims

1. A method for preparing a ZnO-CaO2 composite nanomaterial with antibacterial activity, characterized in that, Includes the following steps: (1) Mix the brown algae polyphenol solution with the zinc acetate solution, and let it stand at 0-4℃ in the dark to obtain the precipitate; (2) The precipitate was calcined, cooled to room temperature, and ground to obtain a powdered calcined product; (3) Disperse the powdered calcined product in anhydrous ethanol, and add calcium chloride, triethylamine and hydrogen peroxide in sequence. After the reaction is complete, ZnO-CaO2 composite nanomaterials are obtained.

2. The method for preparing the ZnO-CaO2 composite nanomaterial with antibacterial activity according to claim 1, characterized in that, In step (1), the ratio of brown algae polyphenols to zinc acetate is: 35-45 g of brown algae polyphenols are added for every 1 mol of zinc acetate.

3. The method for preparing the ZnO-CaO2 composite nanomaterial with antibacterial activity according to claim 1, characterized in that: In step (1), the concentration of the brown algae polyphenol solution is 8–12 g / L; the concentration of the zinc acetate solution is 0.05–0.15 mol / L.

4. The method for preparing the ZnO-CaO2 composite nanomaterial with antibacterial activity according to claim 1, characterized in that: In step (2), the specific method of calcination is to calcine at 550-650℃ for 3.5-4.5 hours.

5. The method for preparing the ZnO-CaO2 composite nanomaterial with antibacterial activity according to claim 1, characterized in that: In step (3), the mass ratio of the calcined product to calcium chloride is 1:(2-8).

6. The method for preparing the ZnO-CaO2 composite nanomaterial with antibacterial activity according to claim 1, characterized in that: In step (3), the volume ratio of anhydrous ethanol, triethylamine and hydrogen peroxide is 100:(1.5-2.5):(3.5-4.5); the interval between adding calcium chloride, triethylamine and hydrogen peroxide is 5 minutes, and the reaction continues for 30 minutes after adding hydrogen peroxide.

7. The ZnO-CaO2 composite nanomaterial with antibacterial activity prepared by the preparation method according to any one of claims 1 to 7, characterized in that: The Zn / Ca molar ratio in the ZnO-CaO2 composite nanomaterial is 1:(0.9~2.6).

8. The ZnO-CaO2 composite nanomaterial with antibacterial activity according to claim 7, characterized in that: The Zn / Ca molar ratio in the ZnO-CaO2 composite nanomaterial is 1:0.9, 1:1.7, or 1:2.

6.

9. The application of the ZnO-CaO2 composite nanomaterial with antibacterial activity as described in claim 7 or 8 in the preparation or as an antibacterial material.

10. The application according to claim 9, characterized in that: The antibacterial material inhibits Gram-negative bacteria and / or Gram-positive bacteria; the Gram-negative bacteria are selected from Escherichia coli; the Gram-positive bacteria are selected from Staphylococcus aureus.

Images