Visible light response graphdiyne modified ternary heterojunction medical antibacterial material
By constructing graphyne modified ternary heterojunction material with visible light response, the antibacterial and biocompatibility problems of the hemostatic material are solved, and efficient wound treatment effects are achieved, avoiding infection and healing delays.
Patent Information
- Application Number
- CN202510727404.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-03
- Publication Date
- 2025-08-29
AI Technical Summary
Existing hemostatic materials lack antibacterial functions and are difficult to integrate well with wound tissue, which can easily lead to infection and delayed healing. Traditional antibiotics face drug resistance problems, making it difficult to effectively prevent and control wound infection.
TiO2 micron flower was prepared by acidic hydrothermal method, and layered g-C3N4 was loaded and a three-dimensional flower-like TiO2/g-C3N4 composite material was constructed. GDY was then combined on its surface to form a graphiteyne-modified ternary heterojunction with visible light response, enhancing photogenerated carrier separation and material absorption capacity, and producing efficient reactive oxygen groups.
A 99% antibacterial rate is achieved under visible light, avoiding inflammation and swelling caused by bacterial infection around the wound, and has good biocompatibility and broad-spectrum antibacterial ability.
Smart Images
Figure CN120550171A_ABST
Abstract
Description
[0001] Visible light-responsive graphyne-modified ternary heterojunction medical antibacterial materials Technical Field
[0002] The present invention belongs to the technical field of biomedical materials, and specifically relates to a method for preparing a visible light-responsive graphyne-modified ternary heterojunction medical antibacterial material. In particular, the constructed graphyne-modified ternary heterojunction composite material can impart excellent broad-spectrum antibacterial ability to hemostatic products. Background Art
[0003] In the treatment of wounds and wounds on human surfaces, conventional hemostatic products (such as gauze, hemostatic powders, and gels) can quickly achieve physical hemostasis, but they still have significant limitations in clinical application. First, these materials generally lack antimicrobial properties and cannot proactively address the risk of wound infection, making infection one of the most common complications in wound care. Second, the biological inertness of conventional hemostatic materials makes it difficult to integrate well with wound tissue, potentially delaying the healing process and even causing secondary trauma during wound healing. The development of infection is a core challenge in wound care. Once bacteria adhere to the wound surface or hemostatic materials, they rapidly form a biofilm, which is difficult to remove. The complex three-dimensional structure and protective extracellular matrix of the biofilm provide a physical barrier for bacteria, allowing them to evade antibiotic attack and exhibit strong drug resistance. This drug resistance not only increases the difficulty of treating infections but can also lead to delayed healing, tissue necrosis, and even systemic inflammatory responses. Furthermore, the complexity of infections necessitates prolonged treatment or additional medical interventions, including secondary hospitalizations, surgical debridement, and even implant removal. This not only significantly increases medical costs, but may also cause both physical and psychological burdens on patients.
[0004] Although antibiotics are the cornerstone of treating infectious diseases, the irrational use of antibiotics has led to an increasing level of drug resistance in pathogens. The spread of multidrug-resistant bacteria has gradually rendered traditional antimicrobial drugs ineffective, posing a huge challenge to infection prevention and control in routine medical procedures such as surgery and transplantation. In this context, how to balance hemostatic efficiency, biocompatibility and antimicrobial properties in hemostatic materials has become a key issue that needs to be urgently addressed in the field of wound treatment. Current research directions are gradually shifting from single-functional materials to multifunctional composite materials, such as enhancing antimicrobial properties by introducing antimicrobial agents, antimicrobial peptides or antimicrobial nanoparticles, while optimizing the biocompatibility and tissue integration capabilities of the materials. This multi-dimensional synergistic strategy is expected to break the limitations of traditional hemostatic materials and provide more efficient and safer solutions for wound treatment.
[0005] Photodynamic therapy (PDT) is a non-invasive medical technology used to treat various cancers as well as bacterial, fungal or viral infections, and has received widespread attention in the past few decades. It uses photosensitizers (PSs) and light to convert molecular oxygen into highly reactive and destructive reactive oxygen species (ROS). ROS are a group of oxygen-containing reactive molecules, including hydroxyl radicals (·OH), superoxide radicals (·O2 - ) and singlet oxygen ( 1 O2). Materials that rely on photosensitizers or generate ROS under appropriate light. In recent years, PDT strategies based on photosensitizers or photoresponsive materials have emerged. These strategies utilize the reactive oxygen species (ROS) produced by photosensitizers under light irradiation to effectively kill bacteria without requiring specific targeted interactions with bacteria. Consequently, they offer the advantages of broad antimicrobial spectrum and reduced drug resistance. They have been proven to be effective against multidrug-resistant strains, providing innovative solutions for modern antimicrobial therapy and attracting significant attention in the field.
[0006] TiO2 is a green, harmless semiconductor photocatalytic material with high physical and chemical stability. When irradiated with light of a specific wavelength, it can be excited to produce reactive oxygen species (ROS). ROS can damage bacterial cell membranes, DNA, and proteins, ultimately killing the bacteria. However, its large bandgap means it can only absorb light in the near-ultraviolet region and is difficult to be excited in the visible light region, while ultraviolet light accounts for less than 5% of natural light. At the same time, the high recombination rate of photogenerated carriers makes it difficult to separate the photogenerated carriers generated under light excitation, resulting in low efficiency of TiO2's utilization of natural light, greatly reducing its photocatalytic performance and limiting its practical application.
[0007] Graphitic carbon nitride (g-C3N4) is a non-toxic and environmentally friendly polymer semiconductor material with a relatively narrow band gap (2.7 eV), stable physical and chemical properties, and abundant raw materials. Its unique two-dimensional layered structure is composed of two basic units: triazine rings and 3-s-triazine rings. The layers are bonded by van der Waals forces. This structure gives it excellent thermal and chemical stability, allowing it to maintain stable performance in high temperatures and strong acid and alkaline environments. In terms of applications, g-C3N4 shows great potential in the field of photocatalysis due to its visible light responsiveness and can be used in the photocatalytic degradation of organic pollutants and other fields.
[0008] Graphdiyne (GDY) is a new type of two-dimensional carbon allotrope with a unique sp-sp 2The carbon atom arrangement, linear acetylenic bonds, uniform pore structure, and highly conjugated properties of graphyne show great potential in the field of photocatalysis. Its narrow bandgap and excellent photogenerated carrier mobility enable it to efficiently absorb visible light and reduce the electron-hole recombination rate. At the same time, the surface is rich in active sites, providing excellent conditions for photocatalytic reactions. At the same time, the carbon defects in graphyne can capture photogenerated electrons, forming local charge-rich regions, thereby enhancing the catalytic ability of the reaction active sites. In addition, the two-dimensional structure and highly conjugated properties of graphyne enable photogenerated electrons to quickly migrate to the active sites, further improving the photocatalytic efficiency.
[0009] In order to enhance the photocatalytic performance of TiO2, it needs to be modified. Common modification methods include constructing heterojunctions, element doping, depositing precious metals, and photosensitization. Constructing a heterojunction on a graphyne (GDY) matrix can effectively promote the separation of photogenerated electrons and holes, reduce the recombination rate between the two, and thus improve the photocatalytic efficiency. At the same time, the construction of the heterojunction also enhances the material's ability to absorb light and broadens the light response range. In addition, by optimizing the energy band structure of TiO2 through its unique photogenerated charge transport properties, it is possible to reduce the band gap of TiO2 and enhance its absorption of visible light, thereby promoting the migration and separation of photogenerated carriers and ultimately improving the photocatalytic performance of the material.
[0010] The present invention combines an acidic hydrothermal method and a calcination method to prepare a TiO2 / g-C3N4 composite material, and simultaneously composites graphene (GDY) on the surface of the TiO2 / g-C3N4 composite material to prepare a visible light responsive graphene modified ternary heterojunction medical antibacterial material. The synergistic effect of the two enhances the material's absorption capacity for visible light, while reducing the recombination efficiency of photogenerated carriers, increasing the specific surface area of the material to provide more active sites for generating reactive oxygen species (ROS). The generated ROS destroys bacterial cell membranes, DNA, and proteins, killing bacteria, and endowing the visible light responsive graphene modified ternary heterojunction medical antibacterial material with excellent broad-spectrum antibacterial ability. Its antibacterial rate can be increased to 99% under visible light irradiation, which can avoid the adverse symptoms such as inflammation and swelling caused by bacterial infection around the wound, greatly improving its application potential in the medical field of wound treatment, etc., which is rarely reported in the field of biomaterial-related technology. Based on this, the present invention provides a visible light responsive graphene modified ternary heterojunction medical antibacterial material. Summary of the Invention
[0011] The purpose of this invention is to address the urgent need for biomedical wound dressings and propose a visible light-responsive graphyne-modified ternary heterojunction medical antibacterial material. This material can effectively resist bacteria and avoid adverse symptoms such as inflammation and swelling caused by bacterial infection around the wound, while also having good biosafety.
[0012] The material is prepared primarily through the acidic hydrothermal method, where TiO2 microflowers are hydrothermally synthesized under acidic conditions. Lamellar g-C3N4 is then loaded onto the surface of the microflowers via a physical mixing method. A three-dimensional flower-like TiO2 / g-C3N4 composite is then constructed via calcination. Finally, GDY is added to the surface of the TiO2 / g-C3N4 composite using a non-deprotection method, resulting in a visible-light-responsive graphyne-modified ternary heterojunction medical antibacterial material. Under visible light irradiation, the graphyne-modified ternary heterojunction medical antibacterial material exhibits excellent antibacterial activity and biocompatibility, and all materials used are non-toxic. Overall, the use of this material can effectively reduce the risk of bacterial infection in wound treatment.
[0013] The present invention is specifically achieved through the following technical solutions:
[0014] 1. A visible light-responsive graphyne-modified ternary heterojunction medical antibacterial material, characterized in that a TiO2 micron flower matrix material is prepared by an acidic hydrothermal method, lamellar g-C3N4 is then loaded on the surface of the micron flower by a physical mixing method, and a heterojunction is constructed by a calcination method to form a three-dimensional flower-shaped TiO2 / g-C3N4 composite material. Finally, GDY is composited on the surface of the TiO2 / g-C3N4 composite material by a non-deprotection method to construct a g-C3N4 / GDY heterojunction, ultimately obtaining a visible light-responsive graphyne-modified ternary heterojunction medical antibacterial material. The material effectively reduces the band gap, enhances the material's absorption range and ability for visible light, improves the separation efficiency of photogenerated carriers, increases the specific surface area to provide more active sites, and enables the material to generate more ROS. The antibacterial rate can be increased to 99% under visible light irradiation, which can avoid adverse symptoms such as inflammation and swelling caused by bacterial infection around wounds, greatly improving its application potential in wound treatment and other aspects in the medical field. The method for preparing the visible light responsive graphyne modified ternary heterojunction medical antibacterial material comprises the following steps:
[0015] (1) providing urea, cuprous chloride and 1,2,3,4,5,6-hexa[2-(trimethylsilyl)ethynyl]benzene as raw materials;
[0016] (2) providing an acidic solution of tetrabutyl titanate and acetic acid;
[0017] (3) providing a neutral ethanol solution;
[0018] (4) providing a neutral solution of N,N-dimethylformamide;
[0019] (5) Pre-treating urea, placing it in a ceramic boat with a lid and wrapping it with tin foil, and annealing it at high temperature in a muffle furnace to form lamellar g-C3N4;
[0020] (6) After the tetrabutyl titanate and the acetic acid solution are ultrasonically mixed and uniformly mixed, a hydrothermal reaction is carried out in a high-pressure hydrothermal reactor to grow a TiO2 micron flower matrix. After the hydrothermal reaction is completed, the TiO2 micron flower matrix is taken out, rinsed, and dried;
[0021] (7) placing the g-C3N4 in step (5) and the TiO2 micron flower matrix dried in step (6) into the neutral ethanol solution in step (3), stirring at room temperature to load the TiO2 micron flower matrix with lamellar g-C3N4, and taking out and drying after stirring;
[0022] (8) placing the TiO2 micron flower obtained in step (7) in a muffle furnace for high-temperature annealing to form a three-dimensional flower-shaped TiO2 / g-C3N4 composite material;
[0023] (9) The TiO2 / g-C3N4 composite material powder obtained in step (8) was dispersed in a glass bottle containing N,N-dimethylformamide, and then cuprous chloride and 1,2,3,4,5,6-hexa[2-(trimethylsilyl)ethynyl]benzoate were added in sequence and ultrasonicated. The glass bottle was then sealed and placed in an oven for insulation. The TiO2 / g-C3N4-GDY was washed with N,N-dimethylformamide, anhydrous ethanol, and deionized water in sequence and dried to obtain a visible light responsive graphyne-modified ternary heterojunction medical antibacterial material TiO2 / g-C3N4-GDY. The obtained product was named TCN / GDY.
[0024] Furthermore, the preparation method of the visible light responsive graphyne modified ternary heterojunction medical antibacterial material is characterized in that the concentration of tetrabutyl titanate in the tetrabutyl titanate and acetic acid acidic solution in step (2) is 0.05-0.1 mmol / mL, and the concentration of acetic acid is 10-17 mmol / mL.
[0025] Furthermore, the temperature of the high-temperature annealing in the muffle furnace in step (5) is 400-600° C., the heating rate is 5° C. / min, and the annealing time is 2-4 hours.
[0026] Furthermore, the ultrasonic time of step (6) is 30-60 minutes, and the temperature parameter of the hydrothermal reaction is 100-180° C. for 8-24 hours.
[0027] Furthermore, the stirring time in step (7) is 1 to 2 hours.
[0028] Furthermore, the temperature of the high-temperature annealing in the muffle furnace in step (8) is 400-600° C., the heating rate is 5° C. / min, and the annealing time is 2-4 hours.
[0029] Furthermore, in the step (9), the mass of the TiO2 / g-C3N4 composite material powder is 20 to 150 mg, the mass of cuprous chloride is 0.2 to 0.8 mg, the mass fraction of 1,2,3,4,5,6-hexa[2-(trimethylsilyl)ethynyl]benzene is 0.5 to 2%, the volume of N,N-dimethylformamide is 5 to 30 mL, the ultrasonic time is 20 to 40 minutes, the oven insulation parameters are 40 to 80°C for 12 to 24 hours, and the drying temperature after washing is 40 to 80°C for 12 to 24 hours.
[0030] Beneficial effects
[0031] The beneficial effects of the present invention are:
[0032] (1) The powder has good antibacterial effects against Staphylococcus aureus and Escherichia coli, which can give biomedical materials antibacterial properties and reduce the risk of wound infection;
[0033] (2) The powder has a simple structure, is easy to prepare, and has good antibacterial and biocompatibility;
[0034] (3) The powder does not require a complicated preparation process, is inexpensive, easy to prepare, and has universal applicability. BRIEF DESCRIPTION OF THE DRAWINGS
[0035] Figure 1 : is a schematic diagram of a flow chart in an embodiment of the present invention.
[0036] Figure 2 : This is a low-magnification scanning electron microscope (SEM) image of the surface morphology of the TiO2 micron flower loaded with GDY and g-C3N4 in Example 1.
[0037] Figure 3 : This is a high-magnification scanning electron microscope (SEM) image of the surface morphology of the TiO2 micron flower of GDY-loaded g-C3N4 in Example 2.
[0038] Figure 4 : is the X-ray diffraction pattern (XRD) in Example 1.
[0039] Figure 5 : is the X-ray photoelectron spectroscopy (XPS) in Example 2.
[0040] Figure 6 : The antibacterial test results of TiO2 microflowers loaded with GDY in Example 1 against Staphylococcus aureus under 420nm light.
[0041] Figure 7 : The antibacterial test results of TiO2 micron flowers loaded with GDY in Example 2 against Escherichia coli under xenon lamp light.
[0042] Figure 8 : The biocompatibility test results of TiO2 microflowers loaded with GDY in Example 2. DETAILED DESCRIPTION
[0043] Example 1
[0044] (1) Urea was selected as the raw material. 5 g of urea was annealed in a muffle furnace for 2 hours at a temperature of 550°C, a heating rate of 5°C / min, and an annealing time of 120 min. Lamellar g-C3N4 was obtained and the powder was collected for later use.
[0045] (2) Select a tetrabutyl titanate and acetic acid solution. Slowly add 1 ml of tetrabutyl titanate to 30 ml of acetic acid solution and ultrasonicate for 40 minutes to form a uniform milky white suspension.
[0046] (3) The suspension in step (2) was placed in a high-pressure hydrothermal reactor lining for hydrothermal heating at a temperature of 160° C. for 10 h. After the hydrothermal heating was completed, the TiO2 powder was collected by centrifugation at a speed of 8000 r / min, and finally washed three times with deionized water and anhydrous ethanol, and dried for later use.
[0047] (4) Select an ethanol neutral solution. Mix the g-C3N4 powder in step (1) and the TiO2 powder in step (3) in a mass ratio of 1:1 in 30 ml of ethanol solution, stir for 1 hour, and then dry in an oven for 12 hours to collect the TiO2 / g-C3N4 composite material powder. The temperature is 80°C, the heating rate is 5°C / min, and the drying time is 12 hours.
[0048] (5) The TiO2 / g-C3N4 composite material powder in step (4) was annealed in a muffle furnace at a high temperature for 2 hours, with an annealing temperature of 550°C, a heating rate of 5°C / min, and an annealing time of 120 min.
[0049] (6) 30 mg of the TiO2 / g-C3N4 composite material powder after annealing in (5) was dispersed in a glass bottle containing 10 mL of N,N-dimethylformamide solution, and 0.5 mg of cuprous chloride and 1% by mass of 1,2,3,4,5,6-hexa[2-(trimethylsilyl)ethynyl]benzoate were added in sequence. The mixture was ultrasonicated for 30 min, and then the glass bottle was sealed and placed in an oven at 65°C for 18 h. After the reaction was completed, the photocatalyst was washed several times with N,N-dimethylformamide solution, anhydrous ethanol, and deionized water. Finally, the brown powder photocatalyst was dried at 60°C for 24 h. The resulting product was named TCN / GDY.
[0050] Figure 2: This is a low-magnification scanning electron microscope (SEM) image of the surface morphology of the TiO2 micron flower loaded with GDY and g-C3N4 in Example 1.
[0051] Figure 4 : X-ray diffraction pattern (XRD) in Example 1.
[0052] Figure 6 : The antibacterial experimental results of the g-C3N4 TiO2 micron flower loaded with GDY in Example 1 against Staphylococcus aureus under 420nm light showed that the antibacterial rate of TCN / GDY under 420nm light was 99%.
[0053] Example 2
[0054] (1) Urea was selected as the raw material. 5 g of urea was annealed in a muffle furnace for 2 hours at a temperature of 550°C, a heating rate of 5°C / min, and an annealing time of 120 min. Lamellar g-C3N4 was obtained and the powder was collected for later use.
[0055] (2) Select a tetrabutyl titanate and acetic acid solution. Slowly add 1 ml of tetrabutyl titanate to 30 ml of acetic acid solution and ultrasonicate for 30 minutes to form a uniform milky white suspension.
[0056] (3) The suspension in step (2) was placed in a high-pressure hydrothermal reactor lining for hydrothermal heating at a temperature of 140° C. for 12 h. After the hydrothermal process, the TiO2 powder was collected by centrifugation at a speed of 8000 r / min, and finally washed three times with deionized water and anhydrous ethanol, and dried for later use.
[0057] (4) Select an ethanol neutral solution. Mix the g-C3N4 powder in step (1) and the TiO2 powder in step (3) in a mass ratio of 1:1 in 30 ml of ethanol solution, stir for 1 hour, and then dry in an oven for 12 hours to collect the TiO2 / g-C3N4 composite material powder. The temperature is 80°C, the heating rate is 5°C / min, and the drying time is 12 hours.
[0058] (5) The TiO2 / g-C3N4 composite material powder in step (4) was annealed in a muffle furnace at a high temperature for 2 hours, with an annealing temperature of 550°C, a heating rate of 5°C / min, and an annealing time of 120 min.
[0059] (6) 100 mg of the TiO2 / g-C3N4 composite material powder after annealing in (5) was dispersed in a glass bottle containing 20 mL of N,N-dimethylformamide solution, and 0.5 mg of cuprous chloride and 1% by mass of 1,2,3,4,5,6-hexa[2-(trimethylsilyl)ethynyl]benzoate were added in sequence and ultrasonicated for 30 min. The glass bottle was then sealed and placed in an oven at 65°C for 24 h. After the reaction was completed, the photocatalyst was washed several times with N,N-dimethylformamide solution, anhydrous ethanol, and deionized water. Finally, the brown powder photocatalyst was dried at 60°C for 12 h. The resulting product was named TCN / GDY.
[0060] Figure 3 : This is a high-magnification scanning electron microscope (SEM) image of the surface morphology of the TiO2 micron flower of GDY-loaded g-C3N4 in Example 2.
[0061] Figure 5 : is the X-ray photoelectron spectroscopy (XPS) in Example 2.
[0062] Figure 7 : The antibacterial test results of the GDY-loaded g-C3N4 TiO2 micron flower against Escherichia coli under xenon lamp light in Example 2. The antibacterial rate of TCN / GDY under the action of xenon lamp is 99%.
[0063] Figure 8 : The biocompatibility test results of TiO2 microflowers loaded with GDY in Example 2.
[0064] Obviously, the above embodiments are merely examples for the purpose of clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications may be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. However, such obvious variations or modifications arising from the spirit of the present invention remain within the scope of protection of the present invention.
Claims
1. A visible light-responsive graphyne-modified ternary heterojunction medical antibacterial material, characterized in that: The graphyne-modified ternary heterojunction medical antibacterial material is composed of a TiO2 micron flower matrix material prepared by an acidic hydrothermal method and lamellar g-C3N4 and graphyne (GDY) loaded thereon; the TiO2 micron flower matrix material is prepared by uniformly mixing tetrabutyl titanate and an acetic acid solution, followed by hydrothermal growth in a high-pressure hydrothermal reactor; the visible light responsive function is achieved by the excellent visible light responsiveness of the three-dimensional flower-like structure of the graphyne-modified ternary heterojunction medical antibacterial material; the visible light responsive graphyne-modified ternary heterojunction medical antibacterial material has a small bandgap, excellent visible light responsiveness and good biocompatibility; the preparation method of the visible light responsive graphyne-modified ternary heterojunction medical antibacterial material comprises the following steps: (1) providing urea, cuprous chloride and 1,2,3,4,5,6-hexa[2-(trimethylsilyl)ethynyl]benzene as raw materials; (2) providing an acidic solution of tetrabutyl titanate and acetic acid; (3) providing a neutral ethanol solution; (4) providing a neutral solution of N,N-dimethylformamide; (5) Pre-treating the urea, placing it in a ceramic boat with a lid and wrapping it with tin foil, and annealing it at high temperature in a muffle furnace for 2 to 4 hours to form lamellar g-C3N4; (6) After the tetrabutyl titanate and the acetic acid solution are ultrasonically mixed and uniformly mixed, a hydrothermal reaction is carried out in a high-pressure hydrothermal reactor to grow a TiO2 micron flower matrix. After the hydrothermal reaction is completed, the TiO2 micron flower matrix is taken out, rinsed, and dried; (7) placing the g-C3N4 in step (5) and the TiO2 micron flower matrix dried in step (6) into the neutral ethanol solution in step (3), stirring at room temperature to load the TiO2 micron flower matrix with lamellar g-C3N4, and taking out and drying after stirring; (8) placing the TiO2 micron flower obtained in step (7) in a muffle furnace for high-temperature annealing to form a three-dimensional flower-shaped TiO2 / g-C3N4 composite material; (9) The TiO2 / g-C3N4 composite material powder obtained in step (8) was dispersed in a glass bottle containing N,N-dimethylformamide, and then cuprous chloride and 1,2,3,4,5,6-hexa[2-(trimethylsilyl)ethynyl]benzo[ ...
2. The method for preparing the visible light responsive graphyne modified ternary heterojunction medical antibacterial material according to claim 1, characterized in that: In the tetrabutyl titanate and acetic acid solution in step (2), the concentration of tetrabutyl titanate is 0.05-0.1 mmol / mL, and the concentration of acetic acid is 10-17 mmol / mL.
3. The method for preparing the visible light responsive graphyne modified ternary heterojunction medical antibacterial material according to claim 1, characterized in that: The temperature of the high-temperature annealing in the muffle furnace in step (5) is 400-600° C., the heating rate is 5° C. / min, and the annealing time is 2-4 hours.
4. The method for preparing the visible light responsive graphyne modified ternary heterojunction medical antibacterial material according to claim 1, characterized in that: The ultrasonic time of step (6) is 30-60 minutes, and the temperature parameter of the hydrothermal reaction is 100-180° C. for 8-24 hours.
5. The method for preparing the visible light responsive graphyne modified ternary heterojunction medical antibacterial material according to claim 1, characterized in that: The stirring time in step (7) is 1 to 2 hours.
6. The method for preparing the visible light responsive graphyne modified ternary heterojunction medical antibacterial material according to claim 1, characterized in that: The temperature of the high-temperature annealing in the muffle furnace in step (8) is 400-600° C., the heating rate is 5° C. / min, and the annealing time is 2-4 hours.
7. The method for preparing the visible light responsive graphyne modified ternary heterojunction medical antibacterial material according to claim 1, characterized in that: In the step (9), the mass of TiO2 / g-C3N4 powder is 20-150 mg, the mass of cuprous chloride is 0.2-0.8 mg, the mass fraction of 1,2,3,4,5,6-hexa[2-(trimethylsilyl)ethynyl]benzene is 0.5-2%, the volume of N,N-dimethylformamide is 5-30 mL, the ultrasonic time is 20-40 minutes, the oven insulation temperature and time parameters are 40-80°C and 12-24 hours respectively, and the drying temperature and time after washing are 40-80°C and 12-24 hours respectively.