Titanium-zinc-based heterojunction bifunctional antibacterial material constructed by one step based on high-energy ball milling method and preparation method of titanium-zinc-based heterojunction bifunctional antibacterial material

Abstract

The preparation method is characterized in that TiO2 and a zinc source are placed in a ball-milling tank, water is used as a dispersing agent, the rotating speed is controlled to be 200-1000 r / min, the ball-milling time is 0.5-24 h, the ball-milling reaches certain impact energy, and then the titanium-zinc-based heterojunction bifunctional antibacterial material is prepared. The titanium-zinc-based heterojunction bifunctional antibacterial material is formed by the material. The high-energy ball milling technology is adopted to synchronously realize increase of interface energy caused by material grain refinement and extra energy caused by surface stress, so that in-situ construction of a nano-structured and heterojunction interface is realized, and finally, the material with degradation and antibacterial dual functions is obtained. The method breaks through a traditional step-by-step preparation process, time can be saved, cost can be reduced, single-step integration of photocatalytic active sites and antibacterial functional units can be achieved, and an innovative solution is provided for large-scale production of environment purification materials.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial materials, and particularly relates to a titanium-zinc-based heterojunction bifunctional antibacterial material constructed by one step based on high-energy ball milling method and a preparation method thereof. Background Art

[0002] In recent years, due to the influence of factors such as global warming and air pollution, the incidence of respiratory diseases and heart diseases has been increasing continuously. Developing new antibacterial and purification materials to create a clean and safe living environment for humans is of great significance for improving the human living environment and ensuring people's physical health. "Antibacterial" materials, as a new type of functional material, have developed rapidly in the 1990s, which is the general term for sterilization, disinfection, decontamination, antibacterial, bacteriostasis, sterilization, antisepsis, mildew prevention and antibacterial. Photocatalytic antibacterial materials have the functions of effectively inhibiting bacteria and photocatalytically degrading organic pollutants, and the ability to inhibit and kill microorganisms. Semiconductor photocatalytic technology uses clean and easily available solar energy as the energy source, and is considered to be a bactericidal method with great application prospects, and has the characteristics of being fast, effective, and not easily generating bacterial drug resistance.

[0003] Nano-TiO 2 is the most common photocatalytic antibacterial agent, and its energy band structure is composed of a low-energy valence band filled with electrons and an empty high-energy conduction band. Under sunlight, especially under the irradiation of ultraviolet light, electrons in the valence band obtain the energy of photons, generate the photoelectric effect and jump to the conduction band to form photogenerated electrons (e-), and correspondingly form photogenerated holes (h + ), thus generating e- / h + pairs. Oxygen adsorbed on the surface of TiO 2 captures electrons to form superoxide anions, while holes oxidize OH 2 and H - adsorbed on the surface of TiO 2 O into HO·. The generated superoxide anions and hydroxyl radicals have strong oxidizing properties. When these radicals come into contact with microorganisms, they can quickly and effectively decompose the organic components of microorganisms, cause bacterial protein mutation, and thus kill microorganisms in a short time.

[0004] However, nano-TiO 2 has a relatively wide band gap and can only utilize ultraviolet light with a wavelength less than 387 nm, which accounts for about 3-5% of sunlight, resulting in a low utilization rate of solar energy. In addition, the recombination probability of photogenerated electrons and holes is relatively high, leading to extremely low quantum efficiency. Therefore, the actual bactericidal effect of pure-phase nano-TiO 2 is not ideal.

[0005] Nano-ZnO has stable chemical properties and low cost. On the one hand, as a metal oxide antibacterial material, it can utilize the activity of zinc ions to kill microorganisms. On the other hand, it is also an excellent photocatalyst with photocatalytic bactericidal activity. Research shows that nano-ZnO has a good killing effect on Gram-positive bacteria. However, due to the easy photocorrosion of ZnO itself and its easy dissolution in strong acid and alkaline solutions, its practical application is also restricted to a certain extent.

[0006] Currently, the preparation method of the composite material of nano-TiO 2 and ZnO mainly adopts coprecipitation, and then obtains the product through operations such as calcination, which is a step-by-step preparation method. For example:

[0007] Chinese Patent Application No. 201210456102.5 discloses a preparation method of zinc oxide / titanium dioxide nano-composite material, which adopts the coprecipitation-supercritical fluid drying method to prepare ZnO / TiO 2 nano-composite material. Although this method has a high output ratio, the reaction conditions are harsh and the reaction needs to be carried out in a supercritical reactor under high temperature and high pressure, which restricts the application of this method to a certain extent.

[0008] CN 118020790 A dissolves zinc acetate dihydrate and nano-titanium dioxide in deionized water, stirs to obtain a mixed solution, dries the mixed solution to constant weight, and collects the sample; calcines the collected sample, and then naturally cools it to room temperature to obtain a calcined powder sample, and mixes and ball-mills the calcined powder sample with stearic acid, carboxymethyl cellulose and cyclohexane to obtain a nano-titanium dioxide-zinc oxide composite antibacterial agent.

[0009] The above methods have problems such as complex operation methods and high production costs. Summary of the Invention

[0010] Aiming at the above technical problems, the first object of the present invention is to provide a preparation method for one-step constructing a titanium-zinc-based heterojunction bifunctional antibacterial material based on high-energy ball milling method, and the second object is to one-step construct a titanium-zinc-based heterojunction bifunctional antibacterial material based on high-energy ball milling method. By introducing a heterojunction structure to enhance its performance, high defect density can be generated in-situ in the material, which can improve its activity and accelerate the process of chemical reaction. This method is suitable for industrial mass production, shortens the preparation process and time, and provides a new method for the mass production of antibacterial materials.

[0011] To achieve the above first object, the present invention provides a preparation method for one-step constructing a titanium-zinc-based heterojunction bifunctional antibacterial material, which is characterized in that: placing the mixed material of TiO 2 and zinc source in a ball milling tank, using water as a dispersant, controlling the rotation speed at 200 - 1000 r / min, adding ball milling media, and the ball milling time is 0.5 - 24 h to obtain TiO2 A type-II heterojunction structure is formed at the interface with the zinc source compound, and finally an antibacterial material with both photocatalytic degradation and zinc ion slow-release dual functions is obtained.

[0012] The heterojunction is TiO 2 Forms a type-II staggered energy band structure with the zinc source through mechanical alloying, realizing the effective separation of electron-hole pairs.

[0013] A heterojunction is a composite structure formed by the interfacial coupling of two different semiconductor materials. Its core advantage lies in the spatial separation of photo-generated carriers through energy band matching. The heterojunction structure can integrate the advantages of TiO 2 and another substance, adjust the energy band structure, promote charge separation, and greatly improve the photocatalytic activity of the heterojunction system. The common types of heterostructures are type-I, type-II, and Z-type. The type-II heterojunction has staggered energy band positions. The electrons and holes generated by photoexcitation will be transferred to the relatively more positive conduction band (CB) and the relatively more negative valence band (VB) respectively. Since these two are not on the same semiconductor, this is conducive to the effective spatial separation of electrons and holes.

[0014] In the TiO 2 / ZnO type-II heterojunction constructed in the present invention, the conduction band position of ZnO (-0.69 eV) is higher than that of TiO 2 (-0.13 eV), while the valence band positions (ZnO 2.52 eV, TiO 2 2.70 eV) form a stepped arrangement. Under illumination, electrons migrate from the ZnO conduction band to the TiO 2 conduction band, and the holes migrate in the opposite direction to the ZnO valence band, increasing the carrier separation efficiency by 3-5 times (compared with single-phase materials). This synergistic effect not only enhances the photocatalytic degradation ability of organic pollutants (such as the degradation rate in Example 1 is 96.7%), but also the slow-release effect of Zn 2+ and the generation of photocatalytic reactive oxygen species (ROS) produce a synergistic antibacterial effect. The killing rate of Escherichia coli (E.c) in the dark state can reach 74% (Example 1), which is nearly 5 times higher than that of traditional physically mixed materials (only 15% in Example 4).

[0015] In the above scheme: The mixed materials and the grinding medium are put in a ratio of 1:5 - 1:20. Preferably 15:1.

[0016] In the above scheme: The grinding medium uses multi-graded zirconia beads, and the particle size gradient configuration is in a volume ratio combination of large beads Φ5 - 10 mm, medium beads Φ3 - 5 mm, small beads Φ1 - 3 mm, 1 - 3:2 - 5:3 - 8.

[0017] In the above scheme: The TiO 2is at least one of anatase type, rutile type, and brookite type, and the zinc source is ZnO, ZnCl 2 , Zn(OH) 2 , ZnCO 3 , basic zinc carbonate, zinc sulfate, Zn(NO 3 ), 2 or one of them.

[0018] In the above solution: the ball milling time of the antibacterial agent is 4 - 8 h, and the ball milling speed is 300 - 450 r / min. With a higher speed, the ball milling time can be relatively shortened.

[0019] In the above solution: according to the mass ratio, the proportion of the zinc source is 5 - 90%.

[0020] In the above solution: the mass ratio of TiO 2 to the zinc source is 5:4 - 5:1.

[0021] In the above solution: the particle size of the titanium-zinc-based heterojunction bifunctional antibacterial material is 20 nanometers - 10 micrometers.

[0022] The second object of the present invention is achieved as follows: a titanium-zinc-based heterojunction bifunctional antibacterial material prepared by the preparation method of the high-energy ball milling method for one-step construction of a titanium-zinc-based heterojunction bifunctional antibacterial material.

[0023] The ball milling method (Ball Milling Method) continuously grinds particles for a long time. The particles are crushed under strong collisions, and the shape and size of the particles change. The mechanochemical ball milling method can endow the catalyst with a series of unique properties. Mechanical collisions generate a high defect density in situ in the material, which can improve its activity and accelerate the process of chemical reactions. Two powders are put into a ball mill equipped with a ball milling tank for ball milling. During this process, the powder particles go through processes such as rolling, pressing, crushing, and re-pressing in a cyclic manner, and finally a material with uniform tissue and composition distribution and having a heterojunction is obtained. At the same time, the high-energy ball milling method has also been widely concerned due to its advantages such as low price, environmental friendliness, high controllability, and high efficiency, and this method is also suitable for large-scale industrial production.

[0024] This method (1) avoids the use of solvents, which conforms to the concept of green chemistry; (2) the metal components are atomically dispersed through mechanical alloying; (3) the process parameters (rotation speed, time, ball-to-powder ratio, etc.) can precisely control the microstructure of the material.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) Single-step process synergy realization: Through the mechanochemical effect of high-energy ball milling, raw material nanosizing, heterojunction formation, and defect engineering modification are synchronously completed. The process is simple and the cost is low.

[0027] (2) Interface engineering innovation: Establish a regulation mechanism of "stress-induced lattice distortion - interface charge redistribution" to achieve the controllable construction of type-II heterojunctions.

[0028] (3) Bifunctional synergistic effect: ZnO can fill the problem of excessive oxygen vacancies after ball milling and produce a synergistic effect with the photocatalytic performance of TiO 2 through defect mediation, significantly improving the antibacterial rate in the dark state. 2 Description of the Drawings

[0029] Figure 1 SEM image of Example 1.

[0030] Figure 2 SEM image of Example 2.

[0031] Figure 3 SEM image of Example 3.

[0032] Figure 4 XPS spectrum of ZnO -80 -TiO 2 in Example 4.

[0033] Figure 5 SEM image of Example 5.

[0034] Figure 6 SEM image of Example 6 with a ball milling time of 20 min and a ball milling speed of 200 r / min.

[0035] Figure 7 SEM image of Example 7.

[0036] Figure 8 SEM image of Example 8.

[0037] Figure 9 Photodegradation device diagram. Detailed Implementation Modes

[0038] The present invention will be further described below through examples in combination with the drawings:

[0039] Example 1

[0040] Anatase TiO 2TiO₂ and ZnO were mixed in a ball milling jar of a three-dimensional planetary ball mill at a mass ratio of 5:4. Water was used as the dispersant. Zirconia beads were added at a ball-to-material ratio of 15:1. According to the volume ratio of large beads: medium beads: small beads (the particle sizes of large, medium, and small are: large beads Φ5 - 10mm, medium beads Φ3 - 5mm, small beads Φ1 - 3mm) = 1:3:6, the ball milling speed was 300 r / min, and the ball milling time was 8 h. Then, the titanium-zinc-based antibacterial agent powder was obtained through suction filtration and drying. The antibacterial experiments on S.a and E.c were carried out using the oscillation method. After two hours of dark reaction oscillation, the antibacterial rate of S.a was 60%, and the antibacterial rate of E.c was 74%; the size of the inhibition zone was 4 mm for both. Under the irradiation of a 300W mercury lamp, the photocatalytic degradation rate was 96.7%, and the photocatalytic degradation time was 90 min.

[0041] The morphological structure of the synthesized material was revealed by applying a scanning electron microscope (SEM). Figure 1 (a) TiO₂ nanoparticles were seen to form a close contact interface with ZnO nanorods in some regions. 2 The TiO₂ nanoparticles formed a close contact interface with ZnO nanorods. Figure 1 (b) The TiO₂ component existed in the form of irregular spherical nanoparticles (particle size distribution: 80 - 150 nm), and ZnO was an irregular column. Their combination mode conformed to the typical morphological characteristics of the heterojunction structure. 2 The TiO₂ component existed in the form of irregular spherical nanoparticles (particle size distribution: 80 - 150 nm), and ZnO was an irregular column. Their combination mode conformed to the typical morphological characteristics of the heterojunction structure.

[0042] In the photocatalytic degradation experiment, methyl orange was used to simulate organic water pollutants (the following examples were carried out in the same way). The specific operation was as follows:

[0043] (1) 0.1 g of the prepared titanium-zinc-based antibacterial agent powder was added to a 10 mg / L methyl orange solution (100 mL).

[0044] (2) The beaker was placed in an environment without light (ignoring the influence of natural light) and stirred for 30 min, and then a sample was taken.

[0045] (3) The photocatalytic device was turned on, and samples were taken every 0.5 h during stirring until the photocatalytic reaction ended. The experimental device was self-made, as shown in Figure 9 .

[0046] In the concentration range of 0 to 20 mg / L, the concentration at this absorbance could be calculated using the standard curve equation y = 0.086x - 0.0385, and then the degradation rate was calculated using the following degradation rate formula:

[0047]

[0048] In the formula: η represents the degradation rate of the methyl orange solution (%); C 0 represents the initial concentration of methyl orange (mg / L); C t represents the concentration of the methyl orange solution at time t calculated according to the standard curve (mg / L).

[0049] Example 2

[0050] Rutile TiO 2 and ZnO were mixed in a ball milling tank of a three-dimensional planetary ball mill at a mass ratio of 5:4. Water was used as a dispersant. Zirconia beads were added at a ball-to-material ratio of 15:1. According to the volume ratio of large beads: medium beads: small beads = 1:3:6, the ball milling speed was 360 r / min, and the ball milling time was 8 h. Then, a titanium-zinc-based antibacterial agent powder was obtained through suction filtration and drying. The antibacterial experiments were carried out on S.a and E.c respectively using the oscillation method. After two hours of dark reaction oscillation, the antibacterial rate of S.a was 59%, and the antibacterial rate of E.c was 84%; the size of the inhibition zone was 4 mm for both. Under the irradiation of a 300 W mercury lamp, the photocatalytic degradation rate was 96.7%, and the photocatalytic degradation time was 90 min.

[0051] Figure 2 (a) is a partial enlarged view, where the TiO 2 component exists in the form of irregular spherical nanoparticles (particle size distribution: 20 - 80 nm). Under high-speed rotation, ZnO presents smaller irregular cylinders. Figure 2 (b) is the overall view. It can be seen that there are no large particles as a whole, and TiO 2 nanoparticles and ZnO nanorods form a tight contact interface in some areas, and their combination mode conforms to the typical morphological characteristics of the heterojunction structure.

[0052] Example 3

[0053] Brookite TiO 2 and ZnO were mixed in a ball milling tank of a three-dimensional planetary ball mill at a mass ratio of 5:1. Water was used as a dispersant. Zirconia beads were added at a ball-to-material ratio of 15:1. According to the volume ratio of large beads: medium beads: small beads = 1:3:6, the ball milling speed was 450 r / min, and the ball milling time was 4 h. Then, a titanium-zinc-based antibacterial agent powder was obtained through suction filtration and drying. The antibacterial experiments were carried out on S.a and E.c respectively using the oscillation method. After two hours of dark reaction oscillation, the antibacterial rate of S.a was 51%, and the antibacterial rate of E.c was 63%; the size of the inhibition zone of S.a was 1 mm, and the size of the inhibition zone of E.c was 3.5 mm. Under the irradiation of a 300 W mercury lamp, the photocatalytic degradation rate was 92.85%, and the photocatalytic degradation time was 60 min.

[0054] The morphological structure of the synthesized material was revealed by applying a scanning electron microscope (SEM). The ZnO / TiO 2 nanocomposite was an irregular sphere ( Figure 3 a). As can be seen from Figure 3 b, the TiO 2 was small particles with a diameter range of 20 - 50 nm. Figure 3The morphology of ZnO in (c) is similar to columnar particles with irregular shapes, with a length of about 100 - 300 nm and a diameter of about 150 nm. It can be clearly observed from Figure 3 (c), Ti and Zn that there are TiO 2 small particles tightly coated on the surface of ZnO. It is speculated that a stable heterojunction is formed between TiO 2 and ZnO.

[0055] Figure 4 Figure 2 is the XPS spectrum of ZnO-80-TiO Figure 4 a shows that strong C1s, Zn2p3, Zn2p1, Ti2p and O1s peaks appear in ZnO -80 -TiO2, confirming the presence of zinc, titanium, oxygen and carbon elements. Figure 4 b is the high-resolution spectrum of Zn2p. Characteristic peaks of Zn2p3 / 2 and Zn2p1 / 2 appear at 1021.2 eV and 1044.3 eV, and the double-peak spacing of Zn2p is 22 eV, indicating that Zn exists in the +2 valence state. Figure 4 c is the high-resolution spectrum of Ti2p. Ti2p3 / 2 and Ti2p1 / 2 appear at 458.2 eV and 463.8 eV, and the difference between them is the spin energy gap, calculated to be 5.6 eV, corresponding to Ti4+. Figure 3 In b and c, the binding energies of Zn2p3 / 2 and Zn2p1 / 2 shift to the high field in ZnO -80- TiO 2 (the theoretical values of Zn2p 3 / 2 and Zn2p 1 / 2 are 1020.4 eV and 1043.4 eV respectively). There is electron loss, which reduces the electron cloud density around the Zn nucleus, resulting in an increase in the binding energy, so the characteristic peaks shift towards higher energy; the binding energies of Ti2p3 / 2 and Ti2p1 / 2 shift to the low field in ZnO -80- TiO 2 (the theoretical values of Ti2p3 / 2 and Ti2p1 / 2 are 458.4 eV and 464.1 eV respectively), indicating electron enrichment. The gain of electrons causes a shift in the binding energy due to the increase in the electron cloud density around the Ti nucleus, resulting in a decrease in the binding energy, manifested as a shift of the characteristic peaks towards lower energy. This is not only due to the strong interaction between TiO 2 and ZnO, but also because there is electron transfer between TiO 2 and ZnO, and electrons transfer from the ZnO nucleus to the TiO 2 layer.

[0056] Example 4

[0057] Anatase TiO 2Mix TiO and ZnO in a beaker according to a mass ratio of 5:4, ultrasonically mix them, then let them stand for 4 h, and dry for later use. The antibacterial experiments on S.a and E.c were carried out by the oscillation method. After two hours of dark reaction oscillation, the antibacterial rate of S.a was 21%, and the antibacterial rate of E.c was 15%. The size of the antibacterial zone of S.a was 2 mm, and the size of the antibacterial zone of E.c was 0 mm. Under the irradiation of a 300 W mercury lamp, the photodegradation rate was 94.24%, and the photodegradation time was 90 min. In Figure 5 (a), we can clearly observe that TiO 2 is not coated on the surface of ZnO, and TiO 2 appears as large particles of 0.1 - 20 μm. Through Figure 5 (b), we can clearly observe that small ZnO particles do not exist on the surface of TiO 2 . Later, through Figure 4 (c)- Figure 5 (d), it can be seen that Zn and Ti are not evenly dispersed, and Ti does not exist on the surface of Zn. Therefore, no heterojunction is formed.

[0058] Example 5

[0059] Mix anatase TiO 2 and ZnO in a ball milling tank of a three-dimensional planetary ball mill according to a mass ratio of 5:4. Use water as a dispersant, put zirconia beads according to a ball-to-material ratio of 15:1, and according to a volume ratio of large beads:medium beads:small beads (the particle sizes of large, medium, and small are: large beads Φ5 - 10 mm, medium beads Φ3 - 5 mm, small beads Φ1 - 3 mm) = 1:3:6. The ball milling speed is 200 r / min, and the ball milling time is 20 min. Then, obtain the titanium-zinc-based antibacterial agent powder through suction filtration and drying. In Figure 6 (a), we can clearly observe that TiO 2 and ZnO form smaller particles. However, through Figure 6 (b), it can be seen that TiO 2 is not coated on the surface of ZnO, and small ZnO particles exist on the surface of TiO 2 . Through Figure 6 (c)- Figure 6 (d), it can also be seen that Ti does not exist on the surface of Zn. Therefore, no heterojunction is formed. The antibacterial experiments on S.a and E.c were carried out by the oscillation method. After two hours of dark reaction oscillation, the antibacterial rate of S.a was 35%, and the antibacterial rate of E.c was 25%.

[0060] Example 6

[0061] Mix anatase TiO 2 and Zn(NO 3 ) 2Mix in a ball milling jar of a three-dimensional planetary ball mill at a mass ratio of 5:4. Use water as a dispersant. Put zirconia beads according to a ball-to-material ratio of 15:1. According to a volume ratio of large beads: medium beads: small beads (the particle sizes of large, medium, and small are: large beads Φ5 - 10 mm, medium beads Φ3 - 5 mm, small beads Φ1 - 3 mm) = 1:3:6. The ball milling speed is 800 r / min, and the ball milling time is 2 h. Then obtain the titanium-zinc-based antibacterial agent powder through suction filtration and drying. Through Figure 7 (a)- Figure 7 (d), it can be seen that TiO 2 and Zn(NO 3 ) 2 form a stable heterojunction. Use the oscillation method to conduct antibacterial experiments on S.a and E.c respectively. After two hours of dark reaction oscillation, the antibacterial rate of S.a is 62%, and the antibacterial rate of E.c is 75%; the size of the inhibition zone is 3.6 mm for both. Under the irradiation of a 300 W mercury lamp, the photocatalytic degradation rate is 96.2%, and the photocatalytic degradation time is 90 min.

[0062] Example 7

[0063] Mix anatase TiO 2 and ZnCl 2 in a ball milling jar of a three-dimensional planetary ball mill at a mass ratio of 5:4. Put zirconia beads according to a ball-to-material ratio of 15:1. According to a volume ratio of large beads: medium beads: small beads (the particle sizes of large, medium, and small are: large beads Φ5 - 10 mm, medium beads Φ3 - 5 mm, small beads Φ1 - 3 mm) = 1:3:6. The ball milling speed is 1000 r / min, and the ball milling time is 0.5 h to obtain the titanium-zinc-based antibacterial agent powder. Through Figure 8 (a)- Figure 8 (d), it can be seen that a stable heterojunction is formed between TiO 2 and ZnCl 2 . Use the oscillation method to conduct antibacterial experiments on S.a and E.c respectively. After two hours of dark reaction oscillation, the antibacterial rate of S.a is 61%, and the antibacterial rate of E.c is 74%; the size of the inhibition zone is 3.2 mm for both. Under the irradiation of a 300 W mercury lamp, the photocatalytic degradation rate is 95.9%, and the photocatalytic degradation time is 90 min.

[0064] The present invention is not limited to the above embodiments. When ball milling, the mixed material and the grinding medium can be put in any ratio of 1:5 - 1:20. The zinc source is ZnO, ZnCl 2 , Zn(OH) 2 , ZnCO 3 , basic zinc carbonate, zinc sulfate, Zn(NO 3 ) 2One of them. Those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the claims and their equivalents.

Claims

1. A method for preparing a titanium-zinc-based heterojunction dual-functional antibacterial material by one step based on high-energy ball milling, characterized in that: The TiO2 and zinc source mixture is placed in a ball mill, water is used as a dispersant, the rotation speed is controlled at 200-1000r / min, ball milling media is added, and the ball milling time is 0.5-24h to obtain an antibacterial material with both photocatalytic degradation and zinc ion sustained release, which forms a type II heterojunction structure at the interface of TiO2 and the zinc source compound.

2. According to claim 1, the method for preparing a titanium-zinc-based heterojunction dual-functional antibacterial material by one step based on high-energy ball milling is characterized by: The mixed material and the grinding medium are added in a ratio of 1:5-1:

20.

3. The method for preparing a titanium-zinc-based heterojunction dual-functional antibacterial material based on high-energy ball milling in one step according to claim 1, characterized in that: The grinding medium adopts multi-graded zirconium oxide beads, and the gradient ratio from large to small particle size is 1:3:

6.

4. The method for preparing a titanium-zinc-based heterojunction dual-functional antibacterial material by one step based on high-energy ball milling according to claim 1, characterized in that: The TiO2 is at least one of anatase, rutile, and brookite types, and the zinc source is one of ZnO, ZnCl2, Zn(OH)2, ZnCO3, basic zinc carbonate, zinc sulfate, and Zn(NO3)2.

5. The method for preparing a titanium-zinc-based heterojunction dual-functional antibacterial material based on high-energy ball milling in one step according to any one of claims 1 to 4, characterized in that: The ball milling time is 4-8h.

6. The method for preparing a titanium-zinc-based heterojunction dual-functional antibacterial material by one step based on high-energy ball milling according to claim 5, characterized in that: The ball mill speed is 300-450r / min.

7. The method for preparing a titanium-zinc-based heterojunction dual-functional antibacterial material by one step based on high-energy ball milling according to claim 6, characterized in that: According to the mass ratio, the zinc source accounts for 5-90%.

8. The method for preparing a titanium-zinc-based heterojunction dual-functional antibacterial material by one step based on high-energy ball milling according to claim 7, characterized in that: The mass ratio of TiO2 and zinc source is 5:4-5:

1.

9. The method for preparing a titanium-zinc-based heterojunction dual-functional antibacterial material by one step based on high-energy ball milling according to claim 1, characterized in that: The particle size of the titanium-zinc-based heterojunction bifunctional antibacterial material is 20 nanometers to 10 microns.

10. A titanium-zinc-based heterojunction bifunctional antibacterial material prepared by the method for preparing a titanium-zinc-based heterojunction bifunctional antibacterial material by one step high-energy ball milling as claimed in any one of claims 1 to 9.

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