阅读说明：本技术 一种磷酸根修饰的二氧化钛光催化抗病毒涂层及其制备方法和应用 (Phosphate radical modified titanium dioxide photocatalytic antiviral coating and preparation method and application thereof ) 是由 史淦升 孙静 谢晓峰 王焱 王晓 陆冠宏 于 2019-10-09 设计创作，主要内容包括：本发明涉及一种磷酸根修饰的二氧化钛光催化抗病毒涂层及其制备方法和应用,所述磷酸根修饰的二氧化钛光催化抗病毒涂层中的二氧化钛的质量百分比为20～100 wt%,磷酸根的质量百分比为0.001～0.1wt%。(The invention relates to a phosphate radical modified titanium dioxide photocatalytic antiviral coating, and a preparation method and application thereof, wherein the mass percent of titanium dioxide in the phosphate radical modified titanium dioxide photocatalytic antiviral coating is 20-100 wt%, and the mass percent of phosphate radicals is 0.001-0.1 wt%.)

1. The phosphate radical modified titanium dioxide photocatalytic antiviral coating is characterized in that the mass percent of titanium dioxide in the phosphate radical modified titanium dioxide photocatalytic antiviral coating is 20-100 wt%, and the mass percent of phosphate radicals is 0.001-0.1 wt%.

2. The phosphate-modified titanium dioxide photocatalytic antiviral coating according to claim 1, wherein the thickness of the phosphate-modified titanium dioxide photocatalytic antiviral coating is 100nm to 2 μm.

3. The preparation method of the titanium dioxide photocatalytic antiviral coating modified by phosphate radical according to claim 1 or 2, characterized in that the titanium dioxide coating is dipped in phosphate solution or the phosphate solution is sprayed on the surface of the titanium dioxide coating, and then the titanium dioxide photocatalytic antiviral coating modified by phosphate radical is obtained after cleaning and drying;

the phosphate solution comprises at least one of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate.

4. The production method according to claim 3, wherein the titanium dioxide coating layer is produced by coating a titanium dioxide powder dispersion or a titanium dioxide sol; preferably, the titanium dioxide sol further comprises a surfactant and a thickener, and the mass ratio of the titanium dioxide sol to the surfactant to the thickener is 100: (0.01-1): (0.01 to 0.1), preferably 100: 0.5: 0.05; preferably, the titanium dioxide coating is prepared by mixing and coating titanium dioxide powder dispersion liquid and a coating, wherein the mass ratio of the titanium dioxide powder dispersion liquid to the coating is 1: (70-99).

5. The method according to claim 3 or 4, characterized in that the phosphate solution has a concentration of 0.05mol/L to 0.5mol/L, preferably a concentration of 1 mol/L.

6. The method according to claim 5, wherein the titanium dioxide particles in the titanium dioxide powder dispersion liquid have a particle diameter of 20 to 1000nm, preferably 20 to 200 nm; the particle size of the titanium dioxide particles in the titanium dioxide sol is 5-50 nm, preferably 10-20 nm.

7. An right as rightThe application of the phosphate radical modified titanium dioxide photocatalytic antiviral coating in virus inactivation and degradation according to claim 1 or 2, which is characterized in that the phosphate radical modified titanium dioxide photocatalytic antiviral coating is placed in a single-wavelength LED light source or natural light at the power of 0.4-1 mW/cm²The illumination time under the illumination intensity is 0.5-1 hour, so that the reduction and inactivation of the target virus infection capacity are realized.

8. The use of claim 7, wherein the target virus is at least one of a single-stranded RNA virus, a double-stranded RNA virus, a single-stranded DNA virus, and a double-stranded DNA virus.

Technical Field

The invention relates to a phosphate radical modified titanium dioxide photocatalytic antiviral coating, a preparation method thereof and application thereof in reducing virus infection capacity and inactivating viruses under a low-light condition, belonging to the field of antivirus.

Background

In recent years, the emergence of highly pathogenic viruses such as influenza virus and enterovirus and some germs with extremely strong drug resistance to common bactericides makes public places such as hospitals, schools and other places with dense people streams become places with extremely high epidemic diseases, and particularly in public health facilities such as hospitals, the emergence possibility of the viruses and the germs is extremely high, and the viruses and the germs have extremely high health hazards to the public. In addition, cross-infection of viruses due to incomplete disinfection is also a potential threat in the use of special medical equipment such as dialysis machines. Therefore, the broad-spectrum antiviral technology which can be suitable for various application scenes has great significance for life safety and social sustainable development of the masses.

The photocatalytic material has been studied and applied more intensively as an indoor air pollution, which is common organic pollutants in indoor air such as formaldehyde and volatile organic compounds. At the same time, as an organic composition, the microorganism can be degraded under the action of photocatalysis. As early as 1985, Tadashi Matsunaga et al found that photocatalytic materials have a significant effect on the removal and degradation of microorganisms. As photocatalytic materials are being studied by more and more people, the removal of viruses gradually comes into the field of people. Among them, titanium dioxide materials are widely noticed due to its excellent photocatalytic performance, its relatively mature production mode, and low cost of raw materials. The conventional titanium dioxide paint additive, i.e., titanium dioxide, has been practically used in the paint field for a long time as a conventional paint additive, and has superior whiteness, tinting strength, hiding power, weather resistance, heat resistance, and chemical stabilityAnd (4) sex. However, since the particle size is too large, the coating layer does not have good photocatalytic performance, and thus the coating layer is not suitable for an additive having antiviral and bactericidal functions. If good photocatalytic properties are required to achieve the antiviral and bactericidal functions, a material capable of forming a coating layer of a nano-particle size is used as an additive. In addition, the application of a large number of photocatalytic materials is focused on antibacterial performance, such as highly pathogenic bacteria such as escherichia coli and staphylococcus aureus, and most researches and products can say that the antibacterial and antiviral performances are classified into one performance, but actually, the mechanisms of photocatalytic antibacterial and antiviral are different. Antioxidant enzyme such as Fe-SOD or Mn-SOD with free radical poisoning resistance in bacteria and fungi can catalyze₂ ^-So that the disproportionation reaction occurs. The reaction process is as follows: SOD + O₂ ^-→SOD^-+O₂；SOD^-+O₂ ^-+2H+→SOD+H₂O₂。

Therefore, the main reason for the inactivation of bacteria or fungi in the application of photocatalytic antibacterial is the destruction of the morphological structure thereof caused by excessive free radical attack, and in the process, high-intensity ultraviolet irradiation is required to cooperate with the catalyst to generate a sufficient amount of active oxygen free radicals, which is time-consuming and easy to generate side effects. However, this defense mechanism is not available to viruses. Analysis of experimental mechanism proves that under the condition of weak light, hydroxyl free radical energy (. OH) generated by the photocatalyst can change the supercoiled structure of RNA and DNA under the condition of not destroying envelope protein or capsid protein of virus, thereby leading to inactivation of virus. Therefore, the titanium oxide-based photocatalytic material can better exert the effects of inhibiting the virus transmission and inactivating the virus through surface modification.

Reference documents:

[1] avian influenza virus and human health (reviewed) [ J ] li le, china journal of food hygiene 1998(05).

[2] Human enterovirus 71 type and hand-foot-and-mouth disease [ J ]. Luyiculu, Jiangqing five, J.disease control 2008(03).

[3] The development of alcohol disinfectants and preparations thereof [ J ]. silver swallow, Zhang \32895.

[4] The application of chlorine-containing disinfectant in medical hygiene [ J ]. Gandong flag, China journal of Disinfection, 1992(01) ].

[5] Research progress of ultraviolet disinfection in sewage treatment [ J ]. zhankokui, wanghong, grandnethiquai, wanlina, proceedings of Shandong university of construction, 2009(04).

[6]Photoelectrochemical sterilization of microbial cells by semiconductorpowders，Tadashi Matsunaga,Ryozo Tomoda,Toshiaki Nakajima and Hitoshi WakeFEMS Microbiology Letters 29(1985)211-21.

[7]Photocatalytic inactivation of viruses using titanium dioxidenanoparticles and low-pressure UV light，DANIEL GERRITY,HODON RYU,JOHNCRITTENDEN and MORTEZA ABBASZADEGAN，Journal of Environmental Science andHealth Part A(2008)43,1261–1270.。

Disclosure of Invention

Aiming at the problems, the invention aims to provide a phosphate radical modified titanium dioxide photocatalytic antiviral coating, a preparation method thereof and application of the phosphate radical modified titanium dioxide photocatalytic antiviral coating in reducing virus infection capacity and inactivating viruses under a low light condition.

In a first aspect, the invention provides a phosphate radical modified titanium dioxide photocatalytic antiviral coating, wherein the mass percent of titanium dioxide in the phosphate radical modified titanium dioxide photocatalytic antiviral coating is 20-100 wt%, and the mass percent of phosphate radicals is 0.001-0.1 wt%.

In the present invention, phosphate radical (PO)₄ ^3-) Can be strongly adsorbed on the surface of titanium dioxide by the internal spherical surface complex, thereby influencing the chemical properties of the surface and the interface of the titanium dioxide. By two-foot chelation, PO₄ ^3-Can be reacted with TiO₂The hydroxyl groups on the surface interact to form stable chemical bonds. Phosphate modified TiO₂The surface is negatively charged, and when the photogenerated electrons are excited from a valence band to a conduction band to generate electron-hole pairs, the photogenerated holes can be better transferred to the surface of the catalyst to promote the separation of the electron-hole pairs due to the negative charge of the surface. At the same time, the phosphate radical can be reacted with the phosphate radical through hydrogen bondsThe interaction of water molecules, the photogenerated holes react with these water molecules to generate hydroxyl radicals, resulting in an increase in overall hydroxyl radical production. The infectious power of the virus can be more effectively reduced and the virus can be inactivated by increasing the OH yield.

Preferably, the thickness of the titanium dioxide photocatalytic antiviral coating modified by phosphate radicals is 100 nm-2 mu m.

On the other hand, the invention provides a preparation method of the phosphate radical modified titanium dioxide photocatalytic antiviral coating, which comprises the steps of dipping the titanium dioxide coating into phosphate solution, or spraying the phosphate solution on the surface of the titanium dioxide coating, cleaning and drying to obtain the phosphate radical modified titanium dioxide photocatalytic antiviral coating;

the phosphate solution comprises at least one of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate.

Preferably, the titanium dioxide coating is prepared by coating titanium dioxide powder dispersion liquid or titanium dioxide sol. The titanium dioxide sol also comprises a surfactant and a thickening agent, wherein the mass ratio of the titanium dioxide sol to the surfactant to the thickening agent is 100: (0.01-1): (0.01 to 0.1), preferably 100: 0.5: 0.05; preferably, the titanium dioxide coating is prepared by mixing and coating titanium dioxide powder dispersion liquid and a coating, wherein the mass ratio of the titanium dioxide powder dispersion liquid to the coating can be 1: (70-99).

Preferably, the concentration of the phosphate solution is 0.05mol/L to 0.5mol/L, and the phosphate solution with the concentration of 1mol/L is preferred.

Preferably, the particle size of the titanium dioxide particles in the titanium dioxide powder dispersion liquid is 20-1000 nm, preferably 20-200 nm; the particle size of the titanium dioxide particles in the titanium dioxide sol is 5-50 nm, preferably 10-20 nm.

In another aspect, the invention provides an application of the phosphate radical modified titanium dioxide photocatalytic antiviral coating in virus inactivation and degradation, wherein the phosphate radical modified titanium dioxide photocatalytic antiviral coating is prepared by adding a certain amount of a solvent to a solution of the phosphate radical modified titanium dioxide photocatalytic antiviral coatingThe photocatalytic antiviral coating is placed in a single-wavelength LED light source (350-²The illumination time under the illumination intensity is 0.5-1 hour, so that the reduction and inactivation of the target virus infection capacity are realized.

In the invention, the titanium dioxide photocatalytic material modified by phosphate radical is used as an antiviral material, and a uniformly dispersed coating is formed on the surface of a base material, so that viruses are inactivated and degraded under the excitation of sunlight and ultraviolet light, thereby preventing the propagation of the viruses. In the photocatalytic reaction, the essential difference between the degradation of volatile organic compounds in mainstream application and the degradation of viruses in the invention is mainly caused by the diffusion mode of target reactants. When dealing with indoor organic volatile pollution, the gas space is very uniform, so large-area coating is needed, and doping modification is needed to graft different polar functional groups on the surface of the material, so as to achieve the purposes of adsorption and degradation. When facing viruses, the surface morphology and photocatalytic activity become important parameters. When the virus contacts the surface of an object through droplets or other pollutants, because the titanium dioxide modified by phosphate radicals can promote the absorption of water molecules, when water in the air is adsorbed on the surface of the titanium dioxide, chemically adsorbed water is formed, and uniformly distributed nano-sized hydrophilic areas are formed on the surface of the titanium dioxide. When a contaminant (typically a droplet) with a virus comes into contact with its surface, it is dispersed into droplets with a small contact angle for the first time, thus increasing the contact area of the contaminant with the phosphate-modified titanium dioxide. At the same time, electrons in the titanium oxide subjected to light irradiation are excited from the valence band to the conduction band to form electron-hole pairs, and water in the liquid phase interacts when these electron-hole pairs migrate to the surface of the titanium oxide particles to generate superoxide radicals (O)₂(-) and a hydroxyl radical (. OH). Experiments prove that the yield of the OH plays a leading role, and the OH can be rapidly improved by modifying the surface phosphate radical, so that the virus can bypass the viral envelope and capsid to directly act on RNA and DNA of a target virus in a shorter time, and the virus loses the infection capacity. By longer treatment, the capsid or envelope of the virus or the like protects the genetic material such as internal nucleic acid or the like from the outsideThe shell is destroyed and broken down, causing the inner material to flow out and continue to be degraded, thereby completely inactivating it.

Preferably, the target virus (virus) is at least one of a single-stranded RNA virus, a double-stranded RNA virus, a single-stranded DNA virus, and a double-stranded DNA virus.

Preferably, the virus is selected from viruses that are readily transmitted in public places, preferably influenza, liver and enteroviruses.

Preferably, the material for preparing the titanium dioxide photocatalytic antiviral coating modified by phosphate radicals is a sterile material, and preferably titanium dioxide powder or sol subjected to sterilization treatment and sterilized phosphate solution are selected.

Preferably, the virus titer test can be performed by a fluorescein staining gel electrophoresis method or a plaque counting method.

Has the advantages that:

in the invention, the titanium dioxide photocatalytic material modified by phosphate radical is applied to the inactivation and degradation of virus and has the following characteristics:

the invention uses a plurality of methods to prepare the titanium dioxide coating modified by phosphate radical, and the titanium dioxide in the coating has uniform grain diameter and is in nanometer scale. Therefore, it has strong photocatalytic activity and excellent broad-spectrum antiviral activity. And because of the preparation methods of various coatings, the coating can be coated on the surfaces of various substrates to meet the requirements of various environments;

the phosphate radical modified photocatalytic titanium dioxide antiviral coating prepared by taking nano titanium dioxide as a main component has many advantages compared with other disinfection methods, such as environmental protection, no toxicity, easy production, simple coating preparation process and suitability for large-area popularization. Through once construction, the effect of inhibiting viruses can be kept for a long time under the condition that a coating layer is not removed by external force, and the effect can be exerted as long as illumination is provided;

the nanometer titanium dioxide photocatalytic coating material modified by phosphate radical and using titanium dioxide sol as a main component has very convenient preparation and coating construction and is suitable for coating construction in a larger space. The preparation process of the titanium dioxide sol is simple, and high-temperature calcination is not needed, so that the preparation method is more environment-friendly compared with the preparation of other titanium dioxide coating materials;

the titanium dioxide photocatalytic material modified by phosphate radical has good chemical stability, and can still keep good virus inhibition activity after virus inactivation and degradation for many times; the phosphate radical modified titanium dioxide photocatalytic material has good biocompatibility, no harm to the environment and no toxicity to human bodies.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.

In the invention, the mass percent of the titanium dioxide in the titanium dioxide photocatalytic antiviral coating modified by the phosphate radical is 20-100 wt% (for example, 60-100 wt%), and the mass percent of the phosphate radical is 0.001-0.1 wt%. In an optional embodiment, the particle size of the titanium dioxide nanoparticles in the coating prepared from the phosphate modified titanium dioxide powder dispersion is 20-1000 nm, and more preferably 20-200 nm. Or the particle size of titanium dioxide nanoparticles in the coating prepared from the phosphate radical modified titanium dioxide sol is 5-50 nm, and more preferably 10-20 nm. In alternative embodiments, the thickness of the coating may be 20nm to 1 μm.

In the invention, the performance of the titanium dioxide photocatalytic antiviral coating modified by phosphate radicals is related to the particle size of the material and the dispersion uniformity degree of the material. The smaller the particle size, the larger the surface activity, the more hydroxyl radicals and superoxide radicals are generated per unit area, and accordingly, the better the degradation capability of the particles for virus inactivation is; the uniformity of dispersion is also important for antiviral ability, such as where the nano-titania material is uncovered or less covered in certain small areas of a substrate where the virus is still inactivated and still infectious. Therefore, the titanium dioxide material is selected from titanium dioxide powder or sol with the particle size of 5-200 nm. Similarly, for uniform dispersion, surfactant can be used or the dispersion can be made uniform by physical dispersion means, such as ultrasonic treatment, ball milling and stirring of the dispersion containing titanium dioxide before coating, preferably, if a powdery titanium dioxide material is selected to prepare an antiviral coating, the dispersion is subjected to ultrasonic treatment and then ball milling, and is shaken or stirred before coating to make the dispersion uniform.

In the invention, the phosphate radical modified titanium dioxide photocatalytic antiviral coating can be prepared in various ways as long as the nano-scale phosphate radical modified titanium dioxide is obtained. The following is an exemplary description of the preparation method of the above-described phosphate-modified titanium dioxide photocatalytic antiviral coating.

The method comprises the following steps: dispersing the nano titanium dioxide powder in a solvent to obtain a dispersion liquid. And uniformly coating the obtained dispersion liquid on a base material after ultrasonic dispersion or ball milling, and drying to obtain the nano-scale antiviral titanium dioxide coating. After the uniform titania coating is formed, it is immersed in a phosphate solution or a phosphate solution is uniformly applied on the titania sol coating. And taking out the film, drying, and washing with deionized water to remove the redundant phosphate on the surface to prepare the phosphate radical modified titanium dioxide coating. The obtained coating can be used for reducing the virus infection capacity of the surface of the coating under the illumination condition and inactivating the surface of the coating. The nano titanium dioxide powder is prepared by a hydrothermal method, a sol-gel method or flame combustion of titanium tetrachloride hydrogen, preferably the nano titanium dioxide powder prepared by flame combustion of titanium tetrachloride hydrogen. The solvent is one of deionized water, ethanol, methanol, isopropanol and ethylene glycol, preferably ethanol. The base material is a glass substrate, a wooden substrate, a ceramic substrate, a metal substrate or a high polymer material substrate. The coating means may be one of drop coating, spray coating, knife coating, spin coating or brush coating. The mass ratio of the nano titanium dioxide powder to the solvent is 1: (5-50). The phosphate solution is a solution prepared from one or a combination of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate, and the concentration of the phosphate solution is 0.05 mol/L-0.5 mol/L, preferably 1 mol/L.

The second method comprises the following steps: adding a surfactant into the nano titanium dioxide sol, and thickening the nano titanium dioxide sol to prepare a mixed solution. And dispersing the mixed solution in an alkaline aqueous solution to prepare a dispersion solution of the nano titanium dioxide sol. And uniformly coating the dispersion liquid on a base material, and drying to obtain the nano-scale titanium dioxide coating. After the uniform titania sol coating layer is formed, it is immersed in a phosphate solution or a phosphate solution is uniformly applied on the titania sol coating layer. And taking out the film, drying, and washing with deionized water to remove the redundant phosphate on the surface to prepare the phosphate radical modified titanium dioxide coating. The coating is used for reducing the virus infection capacity of the surface of the coating and inactivating the surface of the coating under the illumination condition. In an optional embodiment, the nano titania sol is a nano titania sol in which the mass percent of titania is 0.1% to 10%, and preferably the mass percent of titania is 5%. The surfactant is 0.1-10% of anionic surfactant or nonionic surfactant. The thickening method is to add 0.1 to 1 mass percent of polyethylene glycol into the nano titanium dioxide sol, wherein the molecular weight of the polyethylene glycol is 200-2000-. The solvent is one of deionized water, ethanol, methanol, isopropanol and ethylene glycol, preferably ethanol. The base material is a glass substrate, a wooden substrate, a ceramic substrate, a metal substrate or a high polymer material substrate. The coating means may be one of drop coating, spray coating, knife coating, spin coating or brush coating. The phosphate solution is a solution prepared from one or a combination of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate, and the concentration of the phosphate solution is 0.05 mol/L-0.5 mol/L, preferably 1 mol/L.

The third method comprises the following steps: and (3) adding the nano titanium dioxide sol dispersion liquid obtained in the second method into the coating to prepare a mixed solution. And uniformly coating the mixed solution on a base material, and drying to obtain a coating containing the nano-scale titanium dioxide material. After a uniform titanium dioxide sol coating is formed, phosphate is uniformly coated on the surface of the titanium dioxide sol coating. And washing with deionized water after drying to remove the excessive phosphate on the surface to prepare the phosphate modified titanium dioxide coating. The coating is used for reducing the virus infection capacity of the surface of the coating and inactivating the surface of the coating under the illumination condition. The coating is used for reducing the virus infection capacity of the surface of the coating and inactivating the surface of the coating under the illumination condition. In alternative embodiments, the coating is a household coating, such as wall coating, furniture coating, metal product coating, and the like. The base material comprises wood base material, metal base material, high polymer material base material and wall surface. The mass ratio of the titanium dioxide powder dispersion liquid to the coating can be 1: (70-99). The phosphate solution may be applied by one of drop coating, spray coating, knife coating, spin coating, or brush coating. The phosphate solution is a solution prepared from one or a combination of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate, and the concentration of the phosphate solution is 0.05 mol/L-0.5 mol/L, preferably 1 mol/L.

The method four comprises the following steps: adding a surfactant into the nano titanium dioxide sol, and thickening the nano titanium dioxide sol to prepare a mixed solution. And dispersing the mixed solution in an alkaline aqueous solution to prepare a dispersion solution of nano titanium dioxide sol, immersing the substrate in the dispersion solution and slowly lifting upwards, and firing the substrate with the nano titanium dioxide sol on the surface to obtain the nano titanium dioxide photocatalytic coating on the surface of the substrate. After the uniform titania coating is formed, it is immersed in a phosphate solution or a phosphate solution is uniformly applied on the titania sol coating. And taking out the film, drying, and washing with deionized water to remove the redundant phosphate on the surface to prepare the phosphate radical modified titanium dioxide coating. The coating is used for reducing the virus infection capacity of the surface of the coating and inactivating the surface of the coating under the illumination condition. In an optional embodiment, the nano titania sol is a nano titania sol in which the mass percent of titania is 0.1% to 10%, and preferably the mass percent of titania is 5%. The surfactant is 0.1-10% of anionic surfactant or nonionic surfactant. The thickening method is to add 0.1 to 1 mass percent of polyethylene glycol into the nano titanium dioxide sol, wherein the molecular weight of the polyethylene glycol is 200-2000-. The solvent is one of deionized water, ethanol, methanol, isopropanol and ethylene glycol, preferably ethanol. The substrate is a glass substrate, a ceramic substrate, or a metal substrate. The firing temperature may be from 180 ℃ to 500 ℃, preferably 480 ℃. The phosphate solution may be applied by one of drop coating, spray coating, knife coating, spin coating, or brush coating. The phosphate solution is a solution prepared from one or a combination of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate, and the concentration of the phosphate solution is 0.05 mol/L-0.5 mol/L, preferably 1 mol/L.

In general, the preparation of the coating of the phosphate-modified titanium dioxide photocatalytic material of the present invention is composed of titanium dioxide and a solvent/dispersant and a phosphate solution. When the titanium dioxide photocatalytic antiviral coating modified by phosphate radical is prepared by powder, the mass ratio of titanium dioxide powder to solvent is 1: (5 to 80), preferably 1: 50. when the titanium dioxide photocatalytic antiviral coating modified by phosphate radicals is prepared by the nano titanium dioxide sol, the content of titanium dioxide in the nano titanium dioxide sol is 0.1-10% by mass, and the nano titanium dioxide sol with the titanium dioxide mass percent of 5% is preferred. The mass ratio of the nano titanium dioxide sol, the surfactant and the thickening agent is 100: (0.01-1): (0.01-0.1), preferably 100: 0.5:0.05. The mass percentage content of the phosphate radical is 0.001-0.1 wt%, preferably 0.05 wt%. The phosphate solution may be applied by one of drop coating, spray coating, knife coating, spin coating, or brush coating. The phosphate solution is a solution prepared from one or a combination of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate, and the concentration of the phosphate solution is 0.05 mol/L-0.5 mol/L, preferably 1 mol/L.

The invention discovers that the molecular weight is 0.4-1 mW/cm through systematic research²Under the irradiation of a single-wavelength LED light source (350-. Meanwhile, the prepared phosphate radical modified nano titanium dioxide film is simple in coating process, and a miniaturized LED lamp bank is adopted as a light source, so that the phosphate radical modified nano titanium dioxide film can be simply coated by the LED lamp bankThe improved medical equipment is integrated on the existing medical equipment for disinfection assistance, and medical accidents caused by cleaning negligence are avoided. The invention takes the nano titanium dioxide powder and the nano titanium dioxide sol as main materials to prepare the phosphate radical modified titanium dioxide photocatalytic antiviral coating with antiviral property, the preparation method is simple, energy-saving and environment-friendly, and has the advantages of strong persistence, no harm to human bodies and the like, the antiviral activity is high, and the coating has very high inactivation and degradation properties on influenza viruses, liver viruses and enteroviruses when being applied to virus inactivation and degradation experiments.

In the embodiment of the invention, the titanium dioxide photocatalytic antiviral coating modified by phosphate radicals prepared by different methods is applied to various viruses, and the titanium dioxide photocatalytic coating material modified by the phosphate radicals is 0.4-1 mW/cm²The single wavelength LED light source (350-.

In one embodiment of the invention, a sterilized cell culture well plate is used as a vector for the virus. The sterilized cell culture well plate is coated with a phosphate modified titanium dioxide antiviral coating or a thin sheet substrate containing the phosphate modified titanium dioxide antiviral coating. The substrate can be a glass substrate, a wooden substrate, a ceramic substrate, a metal substrate or a polymer material substrate.

According to the invention, the titanium dioxide antiviral coatings modified by phosphate radicals are prepared on the polystyrene cell culture pore plate and the glass culture dish, and inactivation and degradation experiments are respectively carried out on influenza virus (PR8) for 30 minutes, wherein the inactivation rate is 69-99.5%. Among them, the virus in example 1(P25, 100 wt.%) was inactivated at the highest rate, and the influenza virus was inactivated at 99.5%. The virus inactivation efficiencies of example 2(Sol-gel, wt.% 100), example 3(Sol-gel/wall paint, wt.% 50), example 4(Sol-gel, wt.% 100) were all higher than those of comparative example 1 (blank well plate with light) and comparative example 2 (blank well plate without light).

The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.