阅读说明：本技术 一种杀菌薄膜及其制备方法和其在照明装置中的应用 (Sterilization film, preparation method thereof and application thereof in lighting device ) 是由 赵石永 刘玉生 刘浩 于 2020-06-12 设计创作，主要内容包括：本发明提供了一种杀菌薄膜,包括柔性基底和设置在所述柔性基底表面的光催化涂层,所述光催化涂层包括粘结剂及纳米二氧化钛复合颗粒,所述纳米二氧化钛复合颗粒包括纳米二氧化钛颗粒,及复合在所述纳米二氧化钛颗粒表面的金属纳米粒子或其改性粒子与金属单原子。该杀菌薄膜既能利用较宽的光谱进行高效杀菌,又能便捷地在其运用到照明装置中,并具有便捷更换的优点,满足市场对低成本、高效杀菌照明装置的需求。本发明还提供了杀菌薄膜的制备方法及其在照明装置中的应用。(The invention provides a sterilization film which comprises a flexible substrate and a photocatalytic coating arranged on the surface of the flexible substrate, wherein the photocatalytic coating comprises a binder and nano titanium dioxide composite particles, and the nano titanium dioxide composite particles comprise nano titanium dioxide particles, and metal nano particles or modified particles thereof and metal monoatomic atoms which are compounded on the surfaces of the nano titanium dioxide particles. The sterilization film can be used for efficiently sterilizing by utilizing a wider spectrum, can be conveniently applied to the illumination device, has the advantage of convenient replacement, and meets the requirements of the market on the low-cost and efficient sterilization illumination device. The invention also provides a preparation method of the sterilization film and application of the sterilization film in a lighting device.)

1. The bactericidal film is characterized by comprising a flexible substrate and a photocatalytic coating arranged on the surface of the flexible substrate, wherein the photocatalytic coating comprises a binder and nano titanium dioxide composite particles, the nano titanium dioxide composite particles comprise nano titanium dioxide particles, metal nano particles or modified particles thereof compounded on the surfaces of the nano titanium dioxide particles and metal monatomics.

2. The bactericidal film of claim 1, wherein the nano-titania particles have a particle size of 2nm to 100nm, the metal nanoparticles or modified particles thereof have a size of 1nm to 30nm, and the metal monoatomic particles have a size of 0.1nm to 0.5 nm.

3. The bactericidal film of claim 1 or 2, wherein the sum of the mass of the metal nanoparticles or modified particles thereof and the mass of the metal monoatomic atoms is 1% to 50% of the mass of the nano titanium dioxide particles.

4. The bactericidal film of claim 1, wherein the metal nanoparticles or modified particles thereof and the metal element in the metal single atom are independently selected from at least one of gold, silver, palladium, ruthenium, copper, nickel, iron, yttrium, iridium, scandium, molybdenum, and tungsten.

5. The sterilization film as claimed in claim 1, wherein in the photocatalytic coating, the mass ratio of the binder is 1% -10%; the thickness of the photocatalytic coating is 50nm-1 mm.

6. The germicidal film as in claim 1, wherein the flexible substrate has a light transmittance of 70% or more; the material of the flexible substrate comprises one or more of polyimide, polyethylene terephthalate, parylene, polydimethylsiloxane, silane coupling agent, polyethylene, polyvinyl chloride, polystyrene, polypropylene, polycarbonate and perfluoroethylene-propylene copolymer;

the binder is at least one selected from polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, ultraviolet curing glue, cyanoacrylate, epoxy resin, polyurethane acrylate, polyethyleneimine, polyurethane and polyacrylate.

7. A method for preparing a sterilization film is characterized by comprising the following steps:

dispersing nano titanium dioxide particles in a solvent, and adding a soluble metal compound to obtain a mixed solution;

performing at least one of microwave treatment, stirring and heating treatment and xenon lamp irradiation treatment on the mixed solution to obtain a composite solution containing nano titanium dioxide composite particles; the nano titanium dioxide composite particles comprise nano titanium dioxide particles, metal nano particles or modified particles thereof compounded on the surfaces of the nano titanium dioxide particles and metal single atoms;

and adding a binder into the composite solution, preparing the obtained viscous solution on the surface of a flexible substrate, and drying to form a photocatalytic coating on the flexible substrate to obtain the bactericidal film.

8. The preparation method according to claim 7, wherein the microwave power used in the microwave treatment is 500W to 1500W, and the time of the microwave treatment is 1min to 20 min; the heating temperature of the stirring and heating treatment is 50-150 ℃, and the time of the stirring and heating treatment is 30min-10 h; during the irradiation treatment of the xenon lamp, the power of the xenon lamp is within the range of 1000 watts to 10 ten-thousand watts, and the irradiation treatment time of the xenon lamp is 1min-5 h.

9. The method of claim 7, wherein the photocatalytic coating is prepared by printing or coating; wherein the coating comprises one or more of dropping, brushing, spraying, dipping, blade coating and spin coating.

10. A lighting device having a sterilization function, comprising a lighting device body and the sterilization film according to any one of claims 1 to 6 provided on the lighting device body.

Technical Field

The invention relates to the field of sterilization films, in particular to a sterilization film, a preparation method thereof and application thereof in a lighting device.

Background

At present, with the spread of new coronary pneumonia epidemic situation, people have higher and higher pursuit for sterile pollution-free healthy living environment, and how to create a sterile pollution-free living environment with lower cost becomes necessary. Every family all installs lighting apparatus such as lamps and lanterns, if every lamps and lanterns all have the bactericidal action, will bring safe and reliable healthy living environment for every family when saving the bactericidal expense. Therefore, the development of a convenient, practical and sterilizable lighting device is imperative.

At present, the lighting device with the sterilization effect on the market is provided by an internal light-emitting device or an external photocatalytic material (such as nano titanium dioxide), such as CN 200910105473.7. The nanometer titanium dioxide can generate photoproduction electron holes under the excitation of an ultraviolet light source, and decompose and inactivate organic micromolecules (such as formaldehyde, benzene and ethanol) and bacteria in the air, thereby achieving the effects of sterilizing and purifying the air. However, the existing photocatalytic materials all need to work under ultraviolet light, the available spectral range is narrow, the ultraviolet light is harmful to human health, and the sterilization effect is not good; in addition, the photocatalytic material is inconvenient to replace in the lighting device, and some lighting devices even need to replace the whole lighting device, so that the cost is high. Therefore, there is a need to provide a sterilization material with a wide available spectrum and a good sterilization effect, so that the sterilization material can be applied to the lighting device more conveniently and cheaply.

Disclosure of Invention

In view of the above, the present invention provides a sterilization film for a lighting device, and a preparation method and an application thereof, wherein the film comprises a binder and nano titanium dioxide particles compounded with metal nanoparticles or modified particles thereof and metal monoatomic atoms, and the film has good photocatalytic activity, can perform efficient sterilization by using a wide spectrum, can be conveniently applied to the lighting device, has the advantage of convenient replacement, and meets the market demand for low-cost and efficient sterilization lighting devices.

The invention provides a sterilization film, which comprises a flexible substrate and a photocatalytic coating arranged on the surface of the flexible substrate, wherein the photocatalytic coating comprises a binder and nano titanium dioxide composite particles, and the nano titanium dioxide composite particles comprise nano titanium dioxide particles, and metal nano particles or modified particles thereof and metal monoatomic atoms which are compounded on the surfaces of the nano titanium dioxide particles.

The nano titanium dioxide composite particles of the invention are characterized in that metal nano particles and metal monoatomic atoms are introduced into the nano titanium dioxide particles at the same time, compared with pure nano titanium dioxide particles, more photo-generated electron holes are increased, accordingly, the energy of an excitation light source can be obviously reduced, the spectrum between ultraviolet light and visible light can be further utilized, the available spectrum range is widened, the photo-catalytic activity is improved, the living environment of bacteria, viruses and the like can be influenced, the replication of genetic materials of the bacteria, viruses and the like is inhibited, and thus, the higher bacterial and viral inactivation effect is realized.

In addition, the metal nanoparticles or modified particles thereof and the metal monoatomic atoms are synergistic, so that the bacteriostatic and bactericidal capacity of the nano titanium dioxide composite particles is more than 5 times (for example, 5 to 50 times) that of the traditional nano titanium dioxide particles, and compared with the nano titanium dioxide particles only compounded with the metal nanoparticles or modified particles thereof under the same condition, the bacteriostatic and bactericidal capacity of the nano titanium dioxide composite particles can be improved by more than one time.

In the present invention, the metal nanoparticles or modified particles thereof and the metal element in the metal single atom are not titanium, and may be specifically and independently selected from at least one of gold, silver, palladium, ruthenium, copper, nickel, iron, yttrium, iridium, scandium, molybdenum, and tungsten. Preferably, the metal element is at least one of gold, silver, copper, nickel and palladium. Wherein the modified particles of metal nanoparticles comprise partially oxidized metal nanoparticles, metal oxide nanoparticles (i.e., fully oxidized metal nanoparticles). The metal nano-particles are composed of a plurality of metal monoatomic atoms, and the metal monoatomic atoms are dispersed and independently exist.

Optionally, in the present invention, the metal nanoparticles or modified particles thereof and the metal monoatomic atoms are located at defect positions on the surface of the nano titanium dioxide particles. The defect sites are specifically oxygen vacancies.

Optionally, the particle size of the nano titanium dioxide particles is 2nm-100 nm. Optionally, the size of the metal nanoparticles or modified particles thereof is 1nm-30 nm; the size of the metal monoatomic atoms is 0.1nm-0.5nm, so that the metal monoatomic atoms are better compounded into the surface defect positions of the nano titanium dioxide particles. Preferably, the size of the metal nanoparticles or modified particles thereof is 1nm to 10 nm.

Further optionally, the sum of the mass of the metal nanoparticles or modified particles thereof and the mass of the metal monoatomic atoms is 1 to 50 percent of the mass of the nano titanium dioxide particles. The loading capacity of the single atoms, the metal nano particles or the modified particles of the metal nano particles of different metal elements can be realized according to the mass ratio, so that the regulation and control of different bactericidal capacities can be realized.

Optionally, at least one side surface of the flexible substrate is provided with the photocatalytic coating. For example, one side surface of the flexible substrate may be provided with a photocatalytic coating, or both opposite side surfaces of the flexible substrate may be provided with photocatalytic coatings. Preferably, one side surface of the flexible substrate is provided with the photocatalytic coating, and in the subsequent application of the sterilization film, the side surface of the flexible substrate, which is not provided with the photocatalytic coating, can be arranged on the surface of the lighting device body, so that the photocatalytic coating is exposed, and thus, the lighting device body is endowed with good antibacterial property, and meanwhile, unnecessary material waste is avoided.

Optionally, the light transmittance of the flexible substrate is above 70%, i.e., the transparency of the flexible substrate is high. Preferably, the light transmittance of the flexible substrate is 90% or more. Optionally, the material of the flexible substrate includes one or more of polyimide, polyethylene terephthalate, parylene, polydimethylsiloxane, silane coupling agent, polyethylene, polyvinyl chloride, polystyrene, polypropylene, polycarbonate, and perfluoroethylene-propylene copolymer, but is not limited thereto. Optionally, the flexible substrate is film-like.

In the present invention, the binder is also transparent or translucent. Optionally, the adhesive is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, ultraviolet curing glue, cyanoacrylate, epoxy resin, urethane acrylate, polyethyleneimine, polyurethane, and polyacrylate, but is not limited thereto.

Further, the light transmittance of the sterilization film is 70% or more, preferably 80% or more, and more preferably 90% or more.

Optionally, in the photocatalytic coating, the mass ratio of the binder is 1% to 10%. The small amount of the binder can ensure that the contact between the nano titanium dioxide composite particles and the film substrate is good, and can also fully disperse the nano titanium dioxide composite particles to avoid agglomeration under the condition of ensuring that the loading capacity of the nano titanium dioxide composite particles is large.

Optionally, in the photocatalytic coating, the mass ratio of the nano titanium dioxide composite particles is 90% to 99%.

Optionally, the thickness of the photocatalytic coating is 50nm to 1 mm. Preferably between 80nm and 50 μm.

In the invention, the area of the sterilization film can be from 1 square centimeter to hundreds of square meters, thereby being convenient for realizing industrialized production.

The sterilization film provided by the first aspect of the invention contains nano titanium dioxide particles compounded with metal nano particles or modified particles thereof and metal monoatomic atoms, the film can be sterilized by ultraviolet light and visible light, and the sterilization efficiency is far higher than that of a film prepared from unmodified nano titanium dioxide particles under the same condition; the film has good practicability and is environment-friendly. The film can be conveniently applied to the lighting device, the lighting device is endowed with high-efficiency sterilization performance, the film is convenient to replace in the lighting device, and the problems that the existing photocatalytic coating is narrow in available spectral range, low in sterilization efficiency, inconvenient to replace in the lighting device and the like can be solved.

The second aspect of the present invention provides a method for preparing a sterilization film, comprising:

dispersing nano titanium dioxide particles in a solvent, and adding a soluble metal compound to obtain a mixed solution;

performing at least one of microwave treatment, stirring and heating treatment and xenon lamp irradiation treatment on the mixed solution to obtain a composite solution containing nano titanium dioxide composite particles; the nano titanium dioxide composite particles comprise nano titanium dioxide particles, and metal nano particles and metal single atoms which are compounded on the surfaces of the nano titanium dioxide particles;

and adding a binder into the composite solution, preparing the obtained viscous solution on the surface of a flexible substrate, and drying to form a photocatalytic coating on the flexible substrate to obtain the bactericidal film.

The parameters of the prepared sterilization film are the same as those of the first aspect of the present invention, and are not described herein again.

Optionally, the nano-titania particles have a particle size (i.e., diameter) of 2nm to 100 nm. Preferably 20-80 nm. Wherein the nano titanium dioxide particles may exist in anatase type and/or rutile type crystalline phases. In one embodiment of the present invention, the nano titanium dioxide particles coexist in two crystal phases of anatase type and rutile type, wherein anatase type accounts for more than 50%, and in this case, the nano titanium dioxide particles have better catalytic activity.

Alternatively, the soluble metal compound may be a nitrate, chloride, sulfate, or the like of the above-mentioned metal element, and for an inert metal element such as gold, platinum, or the like, it may be corresponding chloroauric acid, chloroplatinic acid, or the like.

Optionally, the microwave power used during the microwave treatment is 500W-1500W, and the microwave treatment time is 1min-20 min. Optionally, the heating temperature of the stirring and heating treatment is 50-150 ℃, and the time of the stirring and heating treatment is 30min-10 h. Optionally, in the xenon lamp irradiation treatment, the power of the used xenon lamp is in the range of 1000 watts to 10 ten-thousand watts, and the time of the xenon lamp irradiation treatment is 1min-5 h. Further, the above-mentioned mixed solution may be stirred during the xenon lamp irradiation treatment, and the xenon lamp irradiation treatment may be carried out while stirring at a heating temperature of, for example, 50 to 100 ℃.

Optionally, the time of the stirring and heating treatment can be 30min-5h, 1-5h or 2-4h, and the like. The temperature is constant during the stirring and heating treatment, and the temperature can be 50-100 ℃.

In the invention, the mixed solution is subjected to at least one of microwave treatment, stirring heating treatment and xenon lamp irradiation treatment, wherein different treatment modes can be used independently and can be used simultaneously or sequentially with other treatment modes. For example, in one embodiment of the present invention, the stirring heat treatment may be directly performed on the mixed solution, or the xenon lamp irradiation treatment may be directly performed. In another embodiment of the present invention, the stirring and heating treatment may be performed after the microwave treatment is performed on the mixed solution. The mixed solution after microwave treatment may have free metal nano particles or modified particles thereof and metal monoatomic atoms, and then stirring and heating treatment are carried out, so that the free metal nano particles or modified particles and the metal monoatomic atoms can be fully adsorbed and compounded on the nano titanium dioxide particles, the compounding effect is improved, and material waste is avoided. In another embodiment of the present invention, the microwave treatment may be performed on the mixed solution, the stirring and heating treatment may be performed on the mixed solution, and the xenon lamp irradiation treatment may be performed on the mixed solution. In still another embodiment of the present invention, the stirring and heating treatment may be performed on the mixed solution after the xenon lamp irradiation treatment is performed, and then the stirring and heating treatment may be performed.

Optionally, the photocatalytic coating is prepared by a printing or coating method; wherein the coating comprises one or more of dropping, brushing, spraying, dipping, blade coating and spin coating. The printing includes at least one of screen printing and ink jet printing.

The preparation method of the sterilization film provided by the second aspect of the invention has the advantages of simple process, easy control and large-scale preparation.

The invention provides a lighting device with sterilization function, which comprises a lighting device body and the sterilization film arranged on the lighting device body.

The sterilizing film can be cut into required size from 1 square centimeter to hundreds of square meters, is suitable for batch production and is matched with the lighting device bodies in different shapes.

When the sterilization film is disposed on the lighting device body, specifically, the surface of the flexible substrate, on which the photocatalytic coating is not disposed, may be disposed on the surface of the lighting device body, so that the photocatalytic coating is exposed.

In an embodiment of the invention, the surface of the flexible substrate, on which the photocatalytic coating is not disposed, may be adsorbed on the surface of the lighting device body after being subjected to electrostatic treatment. Of course, in other embodiments of the present invention, the surface of the flexible substrate, which is not provided with the photocatalytic coating, may be adhered to the surface of the lighting device body by an adhesive tape or the like.

Alternatively, the lighting device body may be a light emitting lamp source such as a fluorescent lamp, an ultraviolet lamp, or a lamp cover.

The lighting device with the sterilization effect provided by the third aspect of the invention has the effects of inhibiting bacteria, killing bacteria and purifying air when lighting, and the sterilization film has certain flexibility and is convenient to replace.

The invention has the following beneficial effects:

1. compared with the pure nano titanium dioxide particles, the nano titanium dioxide composite particles compounded with the metal nano particles or modified particles thereof and the metal monoatomic atoms in the sterilization film have higher photocatalytic activity, and can realize stronger bacteriostatic and bactericidal capacity by utilizing a wider excitation spectrum;

2. the sterilization film has low cost and strong bacteriostatic and bactericidal capability, and can be conveniently applied to the lighting device; wherein, the bacteriostatic and bactericidal capacity of the film containing the nano titanium dioxide composite particles is more than 5 times that of the film prepared from unmodified nano titanium dioxide particles and more than 2 times that of the film prepared from nano titanium dioxide particles only compounded with metal nano particles;

3. the preparation method of the sterilization film is simple and can be used for large-scale preparation;

4. in the lighting device with the sterilization function, the sterilization film can be conveniently replaced on the lighting device body, the replacement cost is low, and the whole lighting device does not need to be replaced.

Drawings

Fig. 1 is a characterization of the morphology of titanium dioxide composite particles co-composited with silver nanoparticles and single atoms thereof and a characterization of the morphology of pure titanium dioxide particles, wherein (a) is a Scanning Electron Microscope (SEM) photograph of pure titanium dioxide particles; (b) SEM photograph of titanium dioxide composite particles in which silver nanoparticles are co-composited with a single atom, (c) low Transmission Electron Microscope (TEM) photograph thereof; (d) - (e) for their high magnification TEM pictures, (f) for their high angle annular dark field scanning projection electron microscope (HAADF-STEM) pictures; (g) scanning transmission electron microscope (ac-STEM) photographs were corrected for their spherical aberration; (h) the film is a film containing titanium dioxide composite particles formed by co-compounding silver nanoparticles and single atoms of the silver nanoparticles, and the surface of the film is coated with the lighting device.

FIG. 2 is a graphical representation and application representation of a titanium dioxide composite particle with gold nanoparticles co-composited with its monoatomic atoms; wherein, (a) is SEM photograph of the composite particle, (b) is low magnification TEM photograph thereof, (c) - (d) are high magnification TEM photograph thereof, (e) is HAADF-STEM photograph thereof, (f) is ac-STEM photograph thereof; (g) is a film containing titanium dioxide composite particles which are formed by co-compounding gold nanoparticles and single atoms thereof; (h) an illumination device having a surface coated with the film of (g).

FIG. 3 is a graphical representation and application representation of a titanium dioxide composite particle with copper nanoparticles co-composited with its single atoms; wherein, (a) is SEM photograph of the composite particle, (b) is low magnification TEM photograph, (c) - (d) are high magnification TEM photograph, (e) is low magnification HAADF-STEM photograph, (f) is ac-STEM photograph; (g) is a film containing titanium dioxide composite particles with copper nanoparticles and single atoms thereof; (h) an illumination device having a surface coated with the film of (g).

FIG. 4 is a graphical representation and application representation of a titanium dioxide composite particle with nickel nanoparticles co-composited with a single atom thereof; wherein, (a) is SEM photograph of the composite particle, (b) is low magnification TEM photograph, (c) - (d) are high magnification TEM photograph, (e) is low magnification HAADF-STEM photograph, (f) is ac-STEM photograph; (g) is a film containing titanium dioxide composite particles which are formed by co-compounding nickel nano particles and single atoms thereof; (h) an illumination device having a surface coated with the film of (g).

Detailed Description

The following are exemplary embodiments of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations are also regarded as the protection scope of the present invention.

Example 1

A preparation method of a sterilization film comprises the following steps:

(1) taking commercial nano TiO with the average diameter of 30nm₂1g of particles (the mass of anatase type accounts for 60%, the mass of rutile type accounts for 40%), adding into 200mL of ethanol, ultrasonically stirring for 20 minutes, adding 100mg of silver nitrate, and ultrasonically stirring for 20 minutes again to uniformly disperse the silver nitrate in the solution; obtaining a mixed solution;

(2) carrying out microwave treatment on the mixed solution for 4 minutes, wherein the microwave power is 900W, continuously stirring the obtained mixed solution for 1 hour at 80 ℃, and then irradiating the stirred solution (80 ℃) for 2 minutes by using a xenon lamp with the power of 1500W to obtain a composite solution, wherein the composite solution contains modified particles of silver nanoparticles and titanium dioxide composite particles of monoatomic compounds of the modified particles;

(3) adding 100g of polytetrafluoroethylene binder into the composite solution, and continuously stirring for 1 hour in a water bath at the temperature of 80 ℃ to obtain a viscous solution; and (3) placing the viscous solution in a spraying system, spraying the viscous solution on one side surface of a polypropylene film substrate, drying the viscous solution by hot air, and forming a photocatalytic coating with the thickness of 10 mu m on the film substrate to obtain the bactericidal film.

The application of the sterilization film comprises the following steps: and (3) performing electrostatic treatment on the surface of the sterilization film, which is not provided with the photocatalytic coating, and adsorbing the sterilization film on the surface of a spherical lighting device (such as a fluorescent lamp) to finally obtain the lighting device with the sterilization function.

FIG. 1 shows the morphology and application of the titanium dioxide composite particle obtained by co-compounding silver nanoparticles with a single atom thereof, and from the comparison between (a) and (b) in FIG. 1, it can be seen that nano TiO₂After the particles are compounded with the silver nanoparticles and the monoatomic atoms, the obtained composite structure is still nanoparticles, the size change before and after compounding is small, the diameter of the composite particles is about 30nm, and the silver is easily oxidized by air, so that the surfaces of the silver nanoparticles are partially oxidized. The low-magnification TEM in (c) of FIG. 1 shows that there is a phenomenon of adhesion between the titanium dioxide nanoparticles after the compounding. High-magnification TEM photographs of (d) to (e) in FIG. 1 show that TiO₂Silver nanoparticles with diameter of 1-5nm are distributed on the surface of the particles; (f) STEM photographs of (g) show that the nano-modified particles of silver and the single silver atom are co-distributed in the nano-TiO₂The location of surface defects of the particles.

Fig. 1 (h) shows a sterilization film formed after the above composite particles are sprayed on a polypropylene film substrate, and the inset shows a lighting device coated with the sterilization film. As a result, it was found that under the same conditions, silver nanoparticles and monoatomic TiO were not compounded with pure silver nanoparticles₂Compared with the film made of particles, the sterilization efficiency of the sterilization film provided by the embodiment 1 is more than 10 times of that of the sterilization film; compared with the same mass of TiO compounded with silver nano particles only₂Compared with the film made of the particles, the sterilization efficiency of the sterilization film provided by the example 1 is improved by 2 times. This shows that the sterilization film provided by the invention has excellent sterilization effect.

In addition, in the bactericidal film provided in example 1, silver is nanoThe sum of the masses of the particles and the monoatomic atoms being TiO₂6.2% of the mass of the particles; in the dried photocatalytic coating, the mass percentage of the binder is 1%.

Example 2

A preparation method of a sterilization film comprises the following steps:

(1) taking commercial nano TiO with average diameter of 25nm₂1.1g of particles (the mass percentage of anatase type is 55%, the mass percentage of rutile type is 45%), adding into 200mL of ethanol, ultrasonically stirring for 20 minutes, adding 100mg of chloroauric acid, and ultrasonically stirring for 20 minutes again to uniformly disperse the chloroauric acid in the solution; obtaining a mixed solution;

(2) stirring and heating the mixed solution for 1 hour in a water bath at 80 ℃, then irradiating the stirred solution (80 ℃) for 5 minutes by using a xenon lamp with the power of 1000W, and then stirring for 30 minutes in the water bath at 80 ℃ to obtain a composite solution, wherein the composite solution contains titanium dioxide composite particles formed by co-compounding gold nanoparticles and single atoms thereof;

(3) adding 100g of polyvinyl alcohol binder into the composite solution, and continuously stirring for 2 hours in a water bath at the temperature of 80 ℃ to obtain a viscous solution; and (3) placing the viscous solution in a spraying system, spraying the viscous solution on one side surface of a polyvinyl chloride film substrate, drying the viscous solution by hot air, and forming a photocatalytic coating with the thickness of 20 mu m on the film substrate to obtain the bactericidal film.

The application of the sterilization film comprises the following steps: and (3) performing electrostatic treatment on the surface of the sterilization film, which is not provided with the photocatalytic coating, and adsorbing the sterilization film on the surface of the square fluorescent lamp to obtain the lighting device with the sterilization function.

FIG. 2 shows the morphology and application of the titanium dioxide composite particle formed by co-compounding gold nanoparticles and their single atoms, and it can be seen from (a) - (b) in FIG. 2 that nano TiO₂After the particles are compounded with gold nanoparticles and monoatomic atoms thereof, the obtained composite structure is still nanoparticles, and the diameter of the composite particles is about 20 nm. The high-power TEM photographs of (c) and (d) in fig. 2 show that the titanium dioxide nanoparticles after the composition are distributed with gold nanoclusters having a diameter of 1-4 nm; (e) STEM photographs of (f) show that gold nanoparticles and individual gold atoms are co-distributed in nano TiO₂The location of surface defects of the particles.

Fig. 2 (g) shows a sterilization film formed after the above composite particles are sprayed on a polyvinyl chloride film substrate, and fig. 2 (h) shows a square lighting device coated with the sterilization film. As a result, it was found that the compound was similar to simple TiO in the same conditions₂Compared with the film made of particles, the sterilization efficiency of the sterilization film provided by the example 2 is 50 times higher. This shows that the sterilization film provided by the invention has excellent sterilization effect.

In addition, in the bactericidal film provided in this embodiment 2, the sum of the mass of the gold nanoparticles and the mass of the monoatomic atoms is TiO₂3.5% of the mass of the particles; in the photocatalytic coating, the mass percentage of the binder is 1%.

Example 3

A preparation method of a sterilization film comprises the following steps:

(1) taking commercial nano TiO with average diameter of 25nm₂1.02g of particles (the mass percentage of anatase type is 65%, the mass percentage of rutile type is 35%), adding into 200mL of ethanol, ultrasonically stirring for 20 minutes, adding 150mg of copper chloride, and ultrasonically stirring for 20 minutes again to uniformly disperse the copper chloride in the solution; obtaining a mixed solution;

(2) stirring and heating the mixed solution for 1 hour in a water bath at the temperature of 80 ℃ to obtain a composite solution, wherein the composite solution contains titanium dioxide composite particles formed by co-compounding copper nanoparticles and monoatomic atoms of the copper nanoparticles;

(3) adding 100g of polyvinyl alcohol binder into the composite solution, and continuously stirring for 2 hours in a water bath at the temperature of 80 ℃ to obtain a viscous solution; and (3) placing the viscous solution in a spraying system, spraying the viscous solution on one side surface of a polyvinyl chloride film substrate, drying the viscous solution by hot air, and forming a photocatalytic coating with the thickness of 20 mu m on the film substrate to obtain the bactericidal film.

The application of the sterilization film comprises the following steps: and (3) performing electrostatic treatment on the surface of the sterilization film, which is not provided with the photocatalytic coating, and adsorbing the sterilization film on the surface of a square ultraviolet lamp to obtain the lighting device with the sterilization function.

FIG. 3 is a graphical representation of a titanium dioxide composite particle with copper nanoparticles co-composited with a single atom thereofAnd the application characterization thereof, as can be seen from (a) - (b) in FIG. 3, the nano TiO₂After the particles are composited with copper nanoparticles and their monoatomic atoms, the resulting composite structure remains a nanoparticle, which has a diameter of about 25 nm. The high-power TEM photographs of (c) and (d) in fig. 3 show that the titanium dioxide nanoparticles after the compounding are distributed with nanoclusters of copper having a diameter of 2 to 5 nm; (e) STEM photographs of (f) show that copper nanoparticles and single gold atoms are co-distributed in nano TiO₂The location of surface defects of the particles.

Fig. 3 (g) shows a sterilization film formed after the above composite particles are sprayed on a pvc film substrate, and fig. 2 (h) shows a square lighting device coated with the sterilization film. As a result, it was found that the compound was similar to simple TiO in the same conditions₂Compared with the film made of particles, the sterilization efficiency of the sterilization film provided by the example 3 is 5 times higher than that of the film made of particles. This shows that the sterilization film provided by the invention has excellent sterilization effect.

In addition, in the bactericidal film provided in this example 3, the sum of the mass of the copper nanoparticles and the mass of the monoatomic atoms is TiO₂6.3% of the mass of the particles; in the dried photocatalytic coating, the mass percentage of the binder is 1%.

Example 4

A preparation method of a sterilization film comprises the following steps:

(1) taking commercial nano TiO with average diameter of 25nm₂1.01g of particles (the mass percentage of anatase type is 60%, the mass percentage of rutile type is 40%), adding into 200mL of ethanol, ultrasonically stirring for 20 minutes, adding 200mg of nickel chloride, and ultrasonically stirring for 20 minutes again to uniformly disperse the nickel chloride in the solution; obtaining a mixed solution;

(2) under the condition of stirring, irradiating the mixed solution for 1 hour by using a xenon lamp with the power of 1 ten-thousand watts to obtain a composite solution, wherein the composite solution contains titanium dioxide composite particles formed by co-compounding nickel nano particles and single atoms of the nickel nano particles;

(3) adding 80g of polytetrafluoroethylene binder into the composite solution, and continuously stirring for 2 hours to obtain a viscous solution; and (3) placing the viscous solution in a spraying system, spraying the viscous solution on one side surface of a polyvinyl chloride film substrate, drying the viscous solution by hot air, and forming a photocatalytic coating with the thickness of 20 mu m on the film substrate to obtain the bactericidal film.

The application of the sterilization film comprises the following steps: and (3) performing electrostatic treatment on the surface of the sterilization film, which is not provided with the photocatalytic coating, and adsorbing the sterilization film on the surface of the square fluorescent lamp to obtain the lighting device with the sterilization function.

FIG. 4 shows the shape and application of the titanium dioxide composite particle co-compounded with nickel nanoparticles and its single atoms, and it can be seen from (a) - (b) in FIG. 4 that nano TiO₂After the particles are compounded with nickel nanoparticles and their monoatomic atoms, the resulting composite structure remains nanoparticles, which have a diameter of about 25 nm. The high-power TEM photographs of (c) and (d) in fig. 3 show that the titanium dioxide nanoparticles after the compounding are distributed with nickel nanoclusters having a diameter of 2 to 5 nm; (e) STEM photographs of (f) show that the nickel nanoparticles and the individual gold atoms are distributed together in the nano TiO₂The location of surface defects of the particles.

Fig. 4 (g) shows a sterilization film formed after the above composite particles are sprayed on a polyvinyl chloride film substrate, and fig. 4 (h) shows a square lighting device coated with the sterilization film. As a result, it was found that the compound was similar to simple TiO in the same conditions₂Compared with the film made of particles, the sterilization efficiency of the sterilization film provided by the example 3 is 2 times higher than that of the film made of particles. This shows that the sterilization film provided by the invention has excellent sterilization effect.

In addition, in the bactericidal film provided in this example 4, the sum of the mass of the nickel nanoparticles and the mass of the monoatomic atoms is TiO₂7.2% of the mass of the particles. In the dried photocatalytic coating, the mass ratio of the binder is 0.8%.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.