CN113462243A

CN113462243A - Coating for adsorbing inactivated viruses and application

Info

Publication number: CN113462243A
Application number: CN202010238160.5A
Authority: CN
Inventors: 马磊; 吴春田; 侯宝林; 朴海龙; 李林; 王稳; 冯璐; 张万生; 黄延强; 王晓东; 张涛
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2020-03-30
Filing date: 2020-03-30
Publication date: 2021-10-01
Anticipated expiration: 2040-03-30
Also published as: CN113462243B

Abstract

The invention provides a coating for adsorbing and inactivating viruses, which comprises porous material powder, polyacrylate, hydroxypropyl methyl cellulose, polyethylene glycol and water, wherein the shell of the porous material particle is made of an oxygen storage material SiO₂‑CeO₂The core is a hierarchical pore molecular sieve. The coating can be used for adsorbing and inactivating viruses, and further, the coating is coated on indoor wall surfaces and is used for air purification of large public places in closed spaces such as hospitals, civil aviation, high-speed rails, subways, buses and office buildings.

Description

Coating for adsorbing inactivated viruses and application

Technical Field

The invention relates to indoor air purification and protection technology of epidemic virus diseases, in particular to a coating for adsorbing and inactivating viruses and application thereof.

Background

The spread of the new coronavirus (COVID-19) seriously threatens the safety of people's life. The development of drugs and vaccines is currently under progress, but according to the law of drug and vaccine development, related products are unlikely to rapidly enter the clinical practical stage in a short time. In order to prevent the spread of viruses, there is an urgent need for long-term, efficient virus scavengers and inactivators for use in hospital, large public, home and personal care.

According to reports, the novel coronavirus transmission path comprises the transmission of droplets, aerosol and dust in the air, so that the air purification of large public places in enclosed spaces such as hospitals, civil aviation, high-speed rails, subways, buses and office buildings is very important, and the indoor inner wall coating has the functions of sterilizing and killing viruses, and plays a positive role in inhibiting the transmission of infectious diseases and viruses and preventing and treating epidemic situations.

The materials with the sterilization and disinfection effects currently used in the air purification field are mainly photocatalyst and silver-loaded activated carbon.

The photocatalyst is a photo-semiconductor material having a photocatalytic function represented by nano-sized titanium dioxide. Under the irradiation of light (especially ultraviolet light), the photocatalytic reaction similar to photosynthesis is produced to produce free hydroxyl radical and active oxygen with powerful oxidation capacity, so that the photocatalyst has powerful photooxidation and reduction function, and can oxidize and decompose various organic compounds and partial inorganic matters to destroy the cell membrane of bacteria and solidify the protein of virus. However, the photocatalyst needs a matched ultraviolet light source device, and in practical application, the photocatalyst faces the disadvantages of low catalytic efficiency, unstable long-term purification effect, and the like, so that the application is limited to a certain extent.

The silver-loaded activated carbon is mainly compounded with silver particles with a sterilization effect through an activated carbon material with excellent adsorption performance, and plays a role in adsorbing and inactivating viruses and bacteria. However, the silver loaded by the silver-loaded activated carbon is mainly combined with the activated carbon through physical adsorption, so that the active components are easy to lose, and the service life is short; the uneven distribution and particle size of silver lead to unstable sterilization and disinfection performance, and most of the silver can only play a role in bacteriostasis.

Although the traditional inorganic antibacterial agent has good antibacterial effect, the antiviral effect is unclear. This is because the inorganic antibacterial agent is mainly composed of a metal compound, and the effective components of the metal compound, such as silver and copper, are considered to exhibit antibacterial properties by inhibiting bacterial metabolism. It is known that these antibacterial metals have an effect of inactivating viruses. There is no necessary connection between the antibacterial and antiviral effects of the metal-based compounds. Bacteria are organisms consisting of cell walls, cell membranes, cytoplasm, nuclei, and are capable of metabolism; the virus is a non-cell type organism which is small and simple in structure, only contains a nucleic acid (DNA or RNA), is required to be parasitic in living cells and proliferated in a replication mode, consists of a long nucleic acid chain and a protein shell, and has no own metabolic mechanism and enzyme system, which departs from the definition of the organism. If the mechanism of action of the antimicrobial metal is to inhibit the metabolism of bacteria, the inactivation effect is not ideal for non-metabolized viruses.

In conclusion, the development of an inorganic antiviral material with good inactivation performance on high-infectious disease viruses such as novel coronavirus (COVID-19) is a key technology for effectively inactivating viruses in the air.

Adding the antibacterial and virus-inactivating material into the interior wall coating, and spraying or brushing the antibacterial and virus-inactivating material on the interior wall to form an antibacterial and virus-inactivating material coating layer on the interior wall; after bacteria and viruses are adsorbed on the coating layer of the wall surface, the bacteria and the viruses are inactivated by the antibacterial and virus-killing materials, and then indoor germs and viruses are reduced and eliminated through the continuous adsorption and inactivation process. The functional antibacterial and virus-killing coating is an effective mode for inhibiting transmission of germs and viruses. The traditional antibacterial coating is formed by adding a photocatalyst or a silver-loaded oxide antibacterial agent into an aqueous coating. CN107189585A discloses a silica-loaded nano-silver water-based antibacterial coating and a preparation method thereof. The water-based antibacterial coating is prepared from water, acrylic resin, polyurethane resin, silver-loaded porous silicon dioxide and the like. CN108342136A discloses an antibacterial coating, which is composed of a nano zinc compound, acrylic resin, polyethylene glycol, dimethyl silicone oil, water and the like. CN1445312A discloses a water-based functional coating with self-cleaning, anti-mildew, sterilization and air purification functions, which is composed of nano anatase titanium oxide, water-soluble resin or polymer emulsion or silica sol and a compound thereof.

At present, inorganic antiviral materials and antiviral material coatings with better inactivation effect on high infectious disease viruses such as novel coronavirus (COVID-19) and related patents are not reported and disclosed.

Disclosure of Invention

The invention aims to provide a coating for adsorbing and inactivating viruses and application thereof, which have the function of adsorbing and inactivating the viruses and can be applied in the fields of indoor air purification and the like, so that the propagation of the viruses is effectively inhibited or reduced, and the occurrence of public health events is prevented.

The technical scheme of the invention comprises the following steps: the coating for adsorbing and inactivating viruses is provided, and comprises porous material powder, polyacrylate, hydroxypropyl methyl cellulose, polyethylene glycol and water; wherein the mass of the porous material powder accounts for 20-50% of the coating, the mass of the polyacrylate accounts for 10-30%, the mass of the hydroxypropyl methyl cellulose accounts for 0.1-1%, the mass of the polyethylene glycol accounts for 0.01-1%, and the balance of water; the granularity is 0.1-10um, preferably 0.5-5 um; the coating adhesion measured according to GB/T9286-1998 is less than grade 2, the pencil hardness of the coating measured according to GB/T6739-2006 is less than 4H, the flexibility of the coating measured according to GB/T1731-1993 is less than 4mm, the impact resistance of the coating measured according to GB/T1732-1993 is more than 40cm, the tack-free time of the coating measured according to GB/T1728-1979(1989) method B is less than 30min, and the solid-dry time of the coating measured according to GB/T1728-1979(1989) method A is less than 4H.

The porous material particle is composed of a shell layer with macropores and mesopores and a mesoporous molecular sieve core;

wherein the shell is made of porous oxygen storage material SiO₂-CeO₂The composition or composition material comprises a porous oxygen storage material SiO₂-CeO₂，SiO₂With CeO₂In a mass ratio of 1:1 to 100:1, preferably 2:1 to 10:1, more preferably 3: 1; wherein the pores in the shell comprise macropores and mesopores, the pore size distribution of the macropores in the shell is between 50 and 500nm, the average pore size of the macropores is between 60 and 300nm, the pore volume of the macropores is between 0.3 and 1.0ml/g, preferably between 0.35 and 0.7ml/g, the pore size distribution of the mesopores is between 2 and less than 50nm, the average pore size of the mesopores is between 5 and 40nm, the pore volume of the mesopores is between 0.05 and 0.3ml/g, preferably between 0.1 and 0.25ml/g, and the thickness of the shell is between 60 and 500 nm;

the core is a hierarchical pore molecular sieve, the pore size distribution comprises mesopores and micropores, wherein the pore size distribution range of the micropores is 0.3nm to less than 2nm, the average pore size of the micropores is 0.5 to 1.9nm, the pore size distribution range of the mesopores is 2nm to less than 50nm, the average pore size of the mesopores is 5 to 40nm, the pore volumes of the mesopores and the micropores are respectively 0.05 to 0.25ml/g and 0.25 to 0.4ml/g, preferably 0.1 to 0.2ml/g and 0.3 to 0.35ml/g, and the particle size is 100nm to 10 mu m, preferably 300nm to 1 mu m.

The oxygen storage material of the porous material particle shell also contains p-SiO₂-CeO₂A modified modifier is ZrO₂、La₂O₃、Pr₂O₃、Nd₂O₃、Y₂O₃The addition amount of the modifier is 0.01-2% of the shell mass, preferably 0.05-1%.

The molecular sieve is one or more than two of ZSM-5, A type, X type and Y type.

The coating allows the structure and surface modification of the molecular sieve, the modification element is one or more of Pt, Ir, Au, Ag, Ba, Mg, Ca, Cs, Cu, Co, Ni, Ti, Ga, Fe, Zn, La, Pr, Nd and Y, and the mass of the modification element accounts for 0.01-20%, preferably 0.05-10% of the mass of the porous material core.

The coating is used for adsorbing and/or inactivating viruses.

The coating is used for air purification and is used as an adsorbing material and/or a virus inactivating material.

The paint is sprayed or brushed on indoor wall surfaces, so that a virus adsorption and inactivation material paint layer is formed on the inner wall, and the paint is further used for air purification of large public places in closed spaces such as hospitals, civil aviation, high-speed railways, subways, buses and office buildings.

The application environment or condition of the coating is normal pressure, temperature of-10-50 ℃ and relative humidity of 0-100% air.

The preparation method of the paint for adsorbing and inactivating viruses comprises the following steps:

1. preparation of powdery core-shell structure hierarchical pore material

(1) A, mixing a molecular sieve with 0.1-0.5mol/L NaOH solution according to the volume ratio of 1:5-1:30, heating and stirring at 50-80 ℃, filtering the mixed solution, washing the solid to be neutral by deionized water, drying at 150 ℃ and roasting at 550 ℃ in sequence to obtain the hierarchical pore molecular sieve, namely the core of the catalytic material. Or B, mixing the hierarchical pore molecular sieve with the aqueous solution containing the modified element ions, stirring overnight at room temperature, filtering, washing, drying, and roasting at 400-550 ℃ to obtain the core of the catalytic material containing the modified element.

(2) A: mixing the nano CeO₂Hydroxypropyl methylcellulose, triblock copolymer P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide, EO)₂₀PO₇₀EO₂₀) And (2) adding the core-shell structure into silica sol, homogenizing, soaking the core material obtained in the step (1) with the liquid, and performing centrifugal separation, drying and roasting to obtain the core-shell structure hierarchical pore catalytic material. Or B, with a nitrate solution of a modifier (e.g. Zr (NO)₃)₄·5H₂Aqueous solution of O) impregnated with CeO₂After drying, the product obtained after roasting at 400-550 ℃ replaces the nano CeO in the step 2A₂And (4) preparing a shell layer to finally obtain the shell layer modified catalytic material.

2. Coating synthesis

Uniformly mixing 20-50 wt.% of the porous material particles prepared in the step 1 with 10-30 wt.% of polyacrylate, 0.1-1 wt.% of hydroxypropyl methyl cellulose, 0.01-1 wt.% of polyethylene glycol and the balance of deionized water, and performing ball milling for 0.1-24 hours at the rotating speed of 50-1000 r/min to obtain a water-based coating, wherein the average particle size of the obtained coating is 0.1-10 mu m; the coating adhesion measured according to GB/T9286-1998 is less than grade 2, the pencil hardness of the coating measured according to GB/T6739-2006 is less than 4H, the flexibility of the coating measured according to GB/T1731-1993 is less than 4mm, the impact resistance of the coating measured according to GB/T1732-1993 is more than 40cm, the tack-free time of the coating measured according to GB/T1728-1979(1989) method B is less than 30min, and the solid-dry time of the coating measured according to GB/T1728-1979(1989) method A is less than 4H.

The principle of the invention is as follows: the coating for adsorbing and inactivating viruses contains a hierarchical pore material with a core-shell structure, wherein a shell with a macroporous structure can effectively adsorb microbe aerosol (0.1-20 mu m) related to diseases in air at room temperature, furthermore, coronavirus particles (0.08-0.2 mu m) in the aerosol are adsorbed into mesoporous channels of a hierarchical pore molecular sieve core, oxygen in the air is activated and migrated into the core by a shell layer oxygen storage material, meanwhile, a modification element loaded on the core dissociates oxygen in the air to form oxygen anions with strong oxidation capability, and the hydrolysis and oxidation of organisms (protein shells and nucleic acids of the viruses) are catalyzed under the synergistic action of the shell layer activated oxygen, the oxygen anions in the core and the adsorption active sites of the molecular sieve in the core, so that the viruses are inactivated. In addition, the shell has the functions of adsorbing and activating oxygen, and can also prevent the loss of the modification component loaded on the core, stabilize the inactivation performance of the catalytic material and prolong the service life of the catalytic material. The binder adopted in the preparation of the core-shell structure hierarchical pore coating for adsorbing and inactivating viruses can remarkably promote the firm combination between the core-shell structure hierarchical pore material particles and a wall body, and can keep the super-strong virus inactivating performance of the material. Can be used for air purification in hospitals, office buildings, schools, houses and other cities.

Compared with the prior art, the invention has the following beneficial effects:

1. the shell of the core-shell structure hierarchical porous material particles in the coating for adsorbing and inactivating viruses has multiple functions, can adsorb aerosol and spray carrying viruses, can store and activate more oxygen, and prevents loss of modification components loaded on the core. This activated oxygen can oxidize viral proteins or nucleic acids (DNA or RNA), destroying their structure, resulting in their inactivation. Therefore, the shell structure simultaneously solves the technical problems of low adsorption efficiency and short service life of oxygen activation and functional coating;

2. the core of the core-shell structure hierarchical pore material particles in the coating for adsorbing and inactivating viruses has a hierarchical pore structure, is suitable for virus particles to pass through, is favorable for the virus particles to fully contact with adsorption active sites on the core, and can provide more bulk phase adsorption active sites and negative oxygen ions. The increased adsorption activity site makes the-SH group in the surface protein of virus, DNA polymerase (DNA virus), RNA polymerase or reverse transcriptase (RNA virus) and the cation of the molecular sieve skeleton easier to combine, so that the structure of the protein and enzyme is changed and the bioactivity is lost. On the other hand, the molecular sieve can activate oxygen in water and air under the promotion of the modifying element to generate more active oxygen anions (O)₂ ^-) And hydroxyl radical (. OH), active oxygen ions have a strong oxidizing ability, and can oxidize and destroy proteins or nucleic acids (DNA or RNA) in a short time to inactivate viruses.

3. The unique core-shell hierarchical pore structure of the hierarchical pore material particles with the core-shell structure in the coating for adsorbing and inactivating the viruses is different from the traditional silver-loaded metal ion sterilization material in that the action mechanism of the traditional silver-loaded bactericide is a single Ag ion sterilization and inactivation mechanism, the material promotes the virus inactivation effect through the synergistic effect of active oxygen formed by a shell layer, rich adsorption active sites of mesoporous and microporous cores and negative oxygen ions, the virus inactivation efficiency of the material is higher, and particularly the adsorption and inactivation rate of the novel coronavirus (COVID-19) can reach 100%. The virus-inactivating material with the special structure not only solves the technical problems of poor sterilization and virus-inactivating effect, unstable performance and short service life of the existing material, but also can reduce the content of metal elements in the material and reduce the material cost. Compared with silver-loaded materials with simple structures such as silver-loaded activated carbon, silver-loaded titanium oxide and the like, the material has the advantages that the pore size distribution of the unique hierarchical pore structure is wider, more macropores and mesopores in a shell layer are provided, and rich mesopores and micropores are provided in a core, so that viruses are easier to diffuse and adsorb in the material, and more virus-killing active sites and oxygen-activating sites are adsorbed, so that the virus-inactivating performance of the material can be greatly improved, and the material has more excellent performance compared with the traditional silver-loaded sterilization material.

4. Compared with photocatalyst, the coating of the invention does not depend on other light sources and other equipment for adsorbing and inactivating viruses, and has wider application range.

5. The coating has the advantages of easily available raw materials, low cost, mature synthetic route and easy industrialization.

Detailed Description

The invention is further illustrated by the following examples.

The preparation of the catalytic material of the invention comprises the following steps:

1. preparation of powdery core-shell structure hierarchical pore material

(1) Preparing a core: reacting NH₄ZSM-5 molecular Sieve (SiO)₂/Al₂O₃25, specific surface area 550m²Per g, particle size of 2.3 μm, average pore size of 0.54nm) and 0.35mol/L NaOH solution in a volume ratio of 1:30, heating and stirring the mixture in water bath at 75 ℃ for 2 hours, filtering the mixed solution, washing the solid to be neutral, drying the solid at 120 ℃ for 6 hours and roasting the solid at 500 ℃ for 2 hours to obtain the hierarchical pore molecular sieve, namely the core of the catalytic material. The average mesoporous diameter of 24.3nm, the pore distribution of 2.0-49.9nm, the average micropore diameter of 0.55nm, the pore distribution of 0.3-1.99nm, the mesoporous volume of 0.18ml/g and the micropore volume of 0.32ml/g are measured by a full-automatic physical adsorption instrument (American Micromeritics, ASAP 2460) capable of measuring the distribution and the pore volume of the mesopores and the micropores. The average particle size was 2.1 μm as determined by a nanometer laser particle sizer (Zetasizer Nano ZS, Malvern, UK) and the particle size distribution was 0.07-10.0. mu.m.

By type A (SiO)₂/Al₂O₃2, specific surface area 750m²A particle size of 3.6 μm, an average pore diameter of 0.48nm, and X-type (SiO)₂/Al₂O₃2.8, specific surface area 650m²G, particle diameter of 6.2 μm, average pore diameter of 1.04nm), Y-type (SiO)₂/Al₂O₃Specific surface area 886m ═ 5²A particle size of 8.5 μm and an average pore diameter of 1.25nm) moleculesScreen replacing NH₄And (3) repeating the operation of the step (1) by using the ZSM-5 molecular sieve to obtain the corresponding hierarchical molecular sieve core.

The average mesoporous aperture of the A-type hierarchical pore molecular sieve core is 33.2nm, the pore distribution is 2.9-42.3nm, the average micropore aperture is 0.48nm, the pore distribution is 0.47-0.50nm, the mesoporous pore volume is 0.16ml/g, the micropore pore volume is 0.30ml/g, the average particle diameter is 3.4 mu m, and the particle size distribution is 0.05-10.0 mu m.

The X-type hierarchical pore molecular sieve core material is measured to have an average mesoporous pore diameter of 27.1nm, a pore distribution of 4.2-40.2nm, an average microporous pore diameter of 1.04nm, a pore distribution of 1.02-1.06nm, a mesoporous pore volume of 0.13ml/g, a microporous pore volume of 0.33ml/g, an average particle diameter of 6.1 mu m and a particle size distribution of 0.07-10.0 mu m.

The Y-type hierarchical pore molecular sieve core material is measured to have an average mesoporous pore diameter of 38.1nm, pore distribution of 4.5-42.3nm, an average microporous pore diameter of 1.22nm, pore distribution of 1.20-1.26nm, mesoporous pore volume of 0.23ml/g and microporous pore volume of 0.39 ml/g. The average grain diameter is 8.4 μm, and the grain size distribution is 0.0,6-10.0 μm.

Alternatively, further, 7.8g of Zn (NO) may be added₃)₂·6H₂Dissolving O in 300ml of deionized water, weighing 100g of the hierarchical pore molecular sieve obtained in the step 1, stirring overnight at room temperature, filtering, washing, drying and roasting at 500 ℃ for 2 hours to obtain the core material containing the modification element Zn. The method for preparing core material containing Ag and other modifying elements is similar to the process, except that Zn (NO) is added₃)₂·6H₂O is replaced by nitrate of other modifying elements such as Ag.

(2) Preparing a shell: nano CeO₂Preparing a shell layer: 1.3g of nano CeO₂(specific surface area 234 m)²(g, average particle diameter 23.5 nm)), 0.057g of hydroxypropyl methylcellulose, 0.067g of triblock copolymer P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide, EO₂₀PO₇₀EO₂₀) Adding into 88.7g of 2.6 wt.% silica sol (average particle diameter of 10.1nm), homogenizing at high speed, soaking 30.7g of Zn-ZSM-5 hierarchical pore molecular sieve core material obtained in step 1 with the liquid, centrifuging, drying, and calcining at 550 deg.C for 2 hr to obtain the final product with SiO 2₂-CeO₂Zn-ZSM-5 hierarchical pore catalyst coated with shell layerChemical material Zn-ZSM-5@ SiO₂-CeO₂。

Measuring average macropore diameter of the shell layer to be 87nm, macropore volume to be 0.52ml/g and macropore pore size distribution to be 50-201nm by using a full-automatic mercury porosimeter (Micromerics, AutoPore V, USA) capable of measuring macropore diameter and macropore volume; measuring the average mesoporous diameter of 27nm, the mesoporous volume of 0.19ml/g and the mesoporous diameter distribution of 4-40nm by using a full-automatic physical adsorption instrument (American Micromeritics, ASAP 2460) capable of measuring the mesoporous diameter and the mesoporous volume; the shell thickness distribution was 85 to 204nm and the average shell thickness was 156nm as determined by transmission electron microscopy (JMS-800D, Japan Electron Ltd.) after resin embedding and cutting.

Alternatively, with a nitrate solution of the modifier (e.g. Zr (NO)₃)₄·5H₂Aqueous solution of O and/or nitrate of other modifier for the shell layer, the modifier being ZrO₂、La₂O₃、Pr₂O₃、Nd₂O₃、Y₂O₃One or two or more of) impregnated CeO₂Drying and roasting at 500 deg.c for 2 hr to obtain modified nanometer CeO₂Material, using the modified material to replace the nano CeO in the step 2₂And (4) preparing a shell layer to finally obtain the shell layer modified catalytic material.

2. Coating synthesis

And (2) uniformly mixing 40 wt.% of the powdery core-shell structure porous material prepared in the step (1), 10 wt.% of polyacrylate, 1 wt.% of hydroxypropyl methyl cellulose, 1 wt.% of polyethylene glycol and the balance of deionized water, and performing ball milling at the rotating speed of 50 rpm for 24 hours to obtain the water-based paint.

The average particle size of the slurry was measured to be 1.8um using a nanometer laser particle sizer (Zetasizer Nano ZS, malvern, uk). The adhesion of the coating, measured according to GB/T9286-1998, is grade 1, the pencil hardness of the coating, measured according to GB/T6739-2006, is 3H, the flexibility of the coating, measured according to GB/T1731-1993, is 3mm, the impact resistance of the coating, measured according to GB/T1732-1993, is 50cm, the tack-free time of the coating, measured according to GB/T1728-1979(1989) method B, is 20min and the actual dry time of the coating, measured according to GB/T1728-1979(1989) method A, is 3H.

The compositions and corresponding parameters of the specific core-shell structure porous material and coating obtained by the preparation method are shown in tables 1 and 2. (the numerical values in parentheses in the following tables are each SiO₂With CeO₂The mass ratio of (1) is that the mass of the modifying element accounts for the mass of the catalytic material core, the addition amount of the modifier accounts for the mass of the shell layer, the macroporous distribution of the shell layer material is 50-500nm, the mesoporous distribution of the shell layer is 2-less than 50nm, the mesoporous distribution of the core is 2-less than 50nm, the micropore distribution of the core is 0.3-less than 2nm, the particle size distribution of the core is 100nm-10 microns, and the particle size distribution of the coating is 0.1-10um)

Examples 1 to 4

TABLE 1

TABLE 2

Examples 5 to 20

Second, testing the adsorption inactivation of the virus

1. Virus preparation:

separately preparing TCIDs₅₀The COVID-19 virus liquid (4.37 is multiplied by 10)⁸copies/ml) and TCID₅₀The tool Lenti (pLenti) virus solution (7X 10)⁹copies/ml) for powder materialTesting the adsorption and inactivation of the material and the coating on the novel coronavirus and the lentivirus;

2. preparing 9 multi-level porous material coatings (powder ground after drying at room temperature) with the serial numbers of TL-1 to TL-9, weighing 267mg of each material and 267mg of the coating without the porous material component (coating slurry on a polytetrafluoroethylene plate, drying at room temperature, scraping and weighing), respectively putting the coating slurry into a sterile 1.5mL EP tube, and dropwise adding 0.8mL of TCID₅₀The lentivirus (pLenti) virus solution is acted for 30 minutes at room temperature, and the mixture of the test substance and the virus solution is stirred and mixed once every 5 minutes, so that the sufficient action of the material and the virus is ensured. A blank control (containing only 0.8mL of TCID) was also prepared₅₀3 parts of lentivirus (pLenti) virus solution) were placed in sterile 1.5ml EP tubes and stirred at room temperature for 30 minutes at 5 minute intervals. The results are given in examples 23 to 31;

two sets of 3 powdered materials, numbered AX-1 to AX-3, were prepared, and 200mg of each material, as well as 200mg of control glass microspheres (particle size 10 μm), one set using COVID-19 virus solution and one set using tool lentivirus (pLenti) virus solution, were weighed and the above procedure was repeated, and the results were found in examples 21 to 23;

3. after 30 minutes of action, centrifuge at 3000rpm for 5 minutes, pipette 250ul of supernatant into new sterile EP tubes (ensuring equal supernatant aspiration per tube)

4. RNA was extracted from 250ul of supernatant based on nucleic acid isolation procedure. The specific method comprises the following steps: 750ul TRIzol was added to 250ul of the treated sample, and the blow with a gun was repeated to lyse the virus. After standing at room temperature for 5 minutes, 200. mu.l of chloroform was added to the above EP tube, and the tube was covered with an EP tube lid and left at room temperature for 2 to 3 minutes, followed by centrifugation at 12000rpm (2 to 8 ℃) for 15 minutes. Placing the upper aqueous phase in a new EP tube, adding 500ul isopropanol, placing at room temperature (15-30 ℃) for 10 minutes, and centrifuging at 12000rpm (2-8 ℃) for 10 minutes; carefully discarding the supernatant, adding 1ml of 75% ethanol along the tube wall for washing, carrying out short vortex mixing, centrifuging at 7500rpm (2-8 ℃) for 5 minutes, and discarding the supernatant; allowing the precipitated RNA to dry naturally at room temperature; and dissolving the RNA precipitate by using RNase-free water.

5. Quantitative PCR (qRT-PCR) experiments were performed using the extracted RNA and Invitrogen-Taqman kit (AM1728) (according to the AM1728 kit protocol). The RNA extracted from each tube was repeated 3 times, and the number of viruses in the supernatant was obtained by averaging.

6. Investigation of different materials to reduce viral load in the supernatant

Assuming that the virus content in the supernatant of the untreated group is 100%, if the virus content in the supernatant of the treated group is 0, the virus content of the treated group is determined to be reduced by 100% relative to that of the untreated group, which corresponds to 100% of the adsorption inactivation rate.

As a result, as shown in Table 3, the powder materials AX-1 to AX-3 have the adsorption inactivation effect on both the novel coronavirus (COVID-19) and the lentivirus (pLenti), the coatings TL-1 to TL-9 have the direct adsorption inactivation effect on the lentivirus (pLenti), and the adsorption inactivation effect on the novel coronavirus (COVID-19) and/or the lentivirus (pLenti) by the coating control, the glass microsphere control and the blank control which do not contain the core-shell structure hierarchical pore material component is not detected.

The viral adsorption inactivation ratio (%) {1- (number of viruses in supernatant of blank control sample-number of viruses in supernatant of test material)/number of viruses in supernatant of blank control sample } × 100%

Examples 21 to 32

TABLE 3

Comparative example 1

Silver-loaded activated carbon (Ag content 2.67 wt.%, specific surface area 1235 m)²/g, mean particle size 57.2 μm, mean pore diameter 1.3nm, pore volume 0.88ml/g) coating materials prepared in place of the multi-stage porous material of example 1 were tested for the adsorption and inactivation of lentiviruses by the same procedure as in examples 21-32, and the results showed a 50% reduction in the virus content of the remaining supernatant compared to the untreated group.

Comparative example 2

Silver-loaded mordenite (Ag content 3.25 wt.%, specific surface area 325 m)²G, average particle diameter of 5.3 μm, average pore diameter of 0.66nm, pore volume of 0.27ml/g) instead of the hierarchical porous material of example 1The same procedure as in comparative example 1 was followed for the slow virus adsorption and inactivation tests, and the results showed a 65% reduction in virus content in the remaining supernatant compared to the untreated group.

Comparative example 3

Will commercialize SiO₂(specific surface area 436 m)²Perg, pore diameter of 6.9nm, particle diameter of 430nm), CeO₂(specific surface area 57.2 m)²G, average pore diameter of 23.4nm and particle size of 1.7 μm) were used instead of the multi-stage porous material of example 1, respectively, to perform adsorption and inactivation tests on lentiviruses, the procedure was the same as in comparative example 1, and the results showed that the virus content in the remaining supernatant was reduced by 9% and 13%, respectively, compared to the untreated group.

Comparative example 4

Commercializing mordenite (with a specific surface area of 325 m)²G, average particle size 6.2 μm, average pore size 0.67nm, pore volume 0.27ml/g) instead of the multi-stage porous material of example 1, a slow virus adsorption and inactivation test was performed, the procedure of which was the same as that of comparative example 1, and the results showed that the virus content in the remaining supernatant was reduced by 23% relative to that in the non-treated group.

Comparative example 5

The Pt-loaded 5A molecular sieve (Pt content 1.93 wt.%, specific surface area 536 m)²/g, mean pore diameter 0.5nm, mean particle diameter 2.7 μm, pore volume 0.38ml/g) coating materials prepared in place of the multi-stage porous material of example 1 were tested for adsorption and inactivation of lentivirus by the same procedure as in comparative example 1, and the results showed a reduction of the virus content in the remaining supernatant of 59% relative to the untreated group.

Comparative example 6

The prepared hierarchical pore ZSM-5 molecular sieve core (average mesopore diameter of 24.3nm, pore distribution of 3.2-48.7nm, average micropore diameter of 0.55nm, pore distribution of 0.51-0.58nm, mesopore volume of 0.18ml/g and micropore volume of 0.32ml/g) is used for preparing the coating instead of the hierarchical pore material in the example 1, and the slow virus adsorption and inactivation test is carried out, the method steps are the same as the comparative example 1, and the result shows that the virus content in the residual supernatant is reduced by 70 percent relative to the non-treated group.

Comparative example 7

The prepared shell material CeO₂-SiO₂(average macropore diameter 87nm, macropores)The pore volume is 0.52ml/g, and the pore size distribution of macropores is 50-201 nm; average mesoporous pore diameter of 27nm, mesoporous pore volume of 0.19ml/g, mesoporous pore size distribution of 4-40nm) was substituted for the multi-stage porous material of example 1 to prepare a coating, and the slow virus adsorption and inactivation test was performed, the same procedure as in comparative example 2, and the results showed that the virus content in the remaining supernatant was reduced by 45% compared to the untreated group.

Comparative example 8

Adopting the shell material CeO prepared in the second step₂-SiO₂(the average macropore diameter is 87nm, the macropore volume is 0.52ml/g, the macropore diameter distribution is 50-201 nm; the average mesopore diameter is 27nm, the mesopore volume is 0.19ml/g, the mesopore diameter distribution is 4-40nm) coating mordenite (the specific surface area is 325 m)²/g, mean particle size 6.2 μm, mean pore diameter 0.67nm, pore volume 0.27ml/g) of the porous particles were tested for the adsorption and inactivation of lentiviruses by the same procedure as in comparative example 2, and the results showed a reduction of the virus content in the remaining supernatant of 63% relative to the untreated group.

Comparative example 9

Adopting the shell material CeO prepared in the second step₂-SiO₂(the average macropore diameter is 87nm, the macropore volume is 0.52ml/g, the macropore aperture distribution is 50-201 nm; the average mesopore diameter is 27nm, the mesopore volume is 0.19ml/g, the mesopore aperture distribution is 4-40nm) is coated with silver-loaded mordenite (the Ag content is 3.25 wt%, the specific surface area is 325 m)²Per g, mean particle size 5.3 μm, mean pore diameter 0.66nm, pore volume 0.27ml/g) particles were tested for lentivirus adsorption and inactivation by the same procedure as in comparative example 2, showing a 44% reduction in virus content in the remaining supernatant compared to the untreated group.

Comparative example 10

Using commercial SiO₂(specific surface area 436 m)²Perg, pore diameter of 6.9nm, particle diameter of 430nm), CeO₂(specific surface area 57.2 m)²G, average pore diameter of 23.4nm and particle diameter of 1.7 mu m) coated on the silver-loaded hierarchical pore ZSM-5 molecular sieve core (Ag content of 1.52 wt.%, average mesoporous pore diameter of 24.3nm, pore distribution of 3.2-48.7nm, average microporous pore diameter of 0.55nm, pore distribution of 0.51-0.58nm, mesoporous pore volume of 0.18ml/g and microporous pore volume of 0.32ml/g) prepared in the first stepThe coating was tested for lentivirus adsorption and inactivation using the same procedure as in comparative example 2, and the results showed a 47% reduction in virus content in the remaining supernatant compared to the untreated group.

Claims

1. The coating for adsorbing and inactivating viruses is characterized in that: the coating comprises porous material powder, polyacrylate, hydroxypropyl methyl cellulose, polyethylene glycol and water; wherein the mass of the porous material powder accounts for 20-50% of the coating, preferably 30-40%, the mass of the polyacrylate accounts for 10-30%, preferably 15-25%, the mass of the hydroxypropyl methylcellulose accounts for 0.1-1%, preferably 0.3-0.8%, the mass of the polyethylene glycol accounts for 0.01-1%, preferably 0.1-0.8%, and the balance of water.

2. The coating of claim 1, wherein:

the particle size distribution of the porous material powder is 0.1-10um, preferably 0.5-5um, and the average particle size is 0.5-5um, preferably 0.7-3 um.

3. The coating of claim 1, wherein: the porous material particles are composed of a mesoporous molecular sieve core and a shell layer which is coated on the outer surface of the mesoporous molecular sieve core and has macropores and mesopores;

wherein the shell is made of porous oxygen storage material SiO₂-CeO₂The composition or composition material comprises a porous oxygen storage material SiO₂-CeO₂，SiO₂With CeO₂In a mass ratio of 1:1 to 100:1, preferably 2:1 to 10:1, more preferably 3: 1; wherein the pores in the shell comprise macropores and mesopores, wherein the pore size distribution of the macropores in the shell is in the range of 50-500nm, the average pore size of the macropores is in the range of 60-300nm, preferably 70-200nm, the pore volume of the macropores is 0.3-1.0ml/g, preferably 0.35-0.7ml/g, the pore size distribution of the mesopores is in the range of 2-less than 50nm, the average pore size of the mesopores is in the range of 5-40nm, preferably 10-30nm, the pore volume of the mesopores is 0.05-0.3ml/g, preferably 0.1-0.25ml/g, and the thickness of the shell is 60-500nm, preferably 80-300 nm;

the core is a hierarchical pore molecular sieve, the pore size distribution comprises mesopores and micropores, wherein the pore size distribution range of the micropores is 0.3nm to less than 2nm, the average pore size of the micropores is 0.5 to 1.9nm, preferably 0.6 to 1.6nm, the pore size distribution range of the mesopores is 2nm to less than 50nm, the average pore size of the mesopores is 5 to 40nm, preferably 7 to 30nm, the pore volumes of the mesopores and the micropores are respectively 0.05 to 0.25ml/g and 0.25 to 0.4ml/g, preferably 0.1 to 0.2ml/g and 0.3 to 0.35ml/g, and the particle size is 100nm to 10 mu m, preferably 300nm to 1 mu m.

4. The coating of claim 3, wherein: the oxygen storage material of the porous material particle shell also contains p-SiO₂-CeO₂A modified modifier is ZrO₂、La₂O₃、Pr₂O₃、Nd₂O₃、Y₂O₃The addition amount of the modifier is 0.01-2% of the shell mass, preferably 0.05-1%.

5. The coating of claim 3, wherein: the molecular sieve is one or more than two of ZSM-5, A type, X type and Y type.

6. The coating of claim 3 or 5, wherein: allowing the molecular sieve to be subjected to structure and surface modification, wherein the modification elements are one or more of Pt, Ir, Au, Ag, Ba, Mg, Ca, Cs, Cu, Co, Ni, Ti, Ga, Fe, Zn, La, Pr, Nd and Y, and the mass of the modification elements accounts for 0.01-20%, preferably 0.05-10% of the mass of the porous material core.

7. Use of a coating according to any of claims 1 to 6, wherein: the coating is used for the adsorption and/or inactivation of viruses.

8. Use of a coating according to any of claims 1 to 6 for air purification as an adsorbent material and/or as a virus inactivating material.

9. The application of the paint according to claim 7 or 8, wherein the paint is sprayed or brushed on indoor wall surfaces, so that a paint layer of virus adsorbing and inactivating materials is formed on the inner wall surfaces, and the paint layer is further used for air purification of large public places in closed spaces such as hospitals, civil aviation, high-speed rails, subways, buses or office buildings.

10. Use of a coating according to claim 6 or 7 or 8, wherein the environment or conditions of application of the coating are atmospheric pressure, -a temperature of-10-50 ℃, and a relative humidity of 0-100% air.