CN113461440B - Honeycomb ceramic for adsorbing inactivated virus and application - Google Patents
Honeycomb ceramic for adsorbing inactivated virus and application Download PDFInfo
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Abstract
The invention provides a honeycomb ceramic for adsorbing and inactivating viruses, which consists of a honeycomb ceramic substrate and a coating, wherein the coating consists of porous particles for adsorbing and inactivating viruses and a binder roasting product, the porous particles consist of a shell and a core, and the shell is made of an oxygen storage material SiO 2 ‑CeO 2 Forming; the core is a hierarchical pore molecular sieve. The honeycomb ceramic can be used for adsorbing and inactivating viruses, and further can be used as a filtering component for the manufacturing field of air purification equipment with large flow rate, such as an air purifier, an air conditioner, a fresh air system and the like.
Description
Technical Field
The invention relates to indoor air purification and protection technology of epidemic virus diseases, in particular to honeycomb ceramic 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 being pursued, but according to the laws of drug and vaccine development, it is feared that the relevant products rapidly enter the clinical practice stage in a short time. In order to prevent the spread of viruses, there is an urgent need for long-term, highly effective virus-inactivating materials for use in hospitals, large public places, homes, and personal protections.
According to reports, the novel coronavirus transmission path comprises the transmission of droplets, aerosol, dust and the like in the air, so that the air purification equipment and the fresh air system in large public places in closed spaces such as hospitals, civil aviation, high-speed rails, subways, buses and office buildings play a positive role in preventing and treating epidemic situations if the air purification equipment and the fresh air system have the purification functions of adsorbing and inactivating viruses.
The inorganic antibacterial material with sterilization and disinfection effects currently used in the air purification field is 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. On the other hand, the silver-loaded activated carbon has the main defects of easy crushing, large bed flow resistance and pressure drop and difficulty in firm loading on a supporting material to form a filtering material with a three-dimensional space structure. Therefore, it is difficult to apply to air cleaning apparatuses of large flow rate such as air cleaners, air conditioners, and fresh air systems.
Although the traditional inorganic antibacterial agent has better antibacterial effect, the antiviral effect is limited. 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 metal-based compounds. Bacteria are organisms consisting of cell walls, cell membranes, cytoplasm, and cell nucleus, and are capable of metabolizing; the virus is a non-cellular organism which is small and simple in structure, only contains a nucleic acid (DNA or RNA), is parasitic in living cells and proliferates in a replication mode, consists of a long nucleic acid chain and a protein shell, and has no own metabolic mechanism and enzyme system, so that the definition of the organism is deviated. If the mechanism of action of the antimicrobial metal is to inhibit the metabolism of bacteria, its inactivation effect is not ideal for non-metabolized viruses. Therefore, 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.
On the other hand, the biggest defects of the particle materials in the using process are that the flow resistance and the pressure drop are large, and the particle materials are difficult to apply in the air purification process with high flow rate. The honeycomb ceramic has small flow resistance and pressure drop, can eliminate the defects of high flow resistance, high pressure drop and the like of a granular material bed layer, greatly reduces the using amount and the cost of a catalytic material due to the thin coating material, and is easy to implement on devices such as an air purifier and the like.
CN104844274A discloses a preparation method of an antibacterial honeycomb ceramic, which is characterized in that after the honeycomb ceramic is treated by a mixed solution of sulfuric acid, hydrofluoric acid and water, impregnation liquid containing antibacterial metal ions, mainly solutions of silver nitrate, copper sulfate, zinc sulfate, titanium sulfate and the like, are used for soaking the fired honeycomb ceramic, and the antibacterial honeycomb ceramic is obtained after roasting, and has a sterilization effect. The obvious disadvantages are that because the specific surface area of the honeycomb ceramic is very small, active components such as silver loaded on the surface of the ceramic cannot be firmly combined with a matrix and exist in the form of particles with larger micron-sized particles, the activity is low, the sterilization effect is poor, the active components are easy to fall off, and the long-term sterilization stability is poor.
At present, the honeycomb ceramic type inorganic antiviral material which has better inactivation effect on high-infectious disease viruses such as novel coronavirus (COVID-19) and the like, and the preparation and the application thereof are not reported and disclosed in related patents.
Disclosure of Invention
The invention aims to provide a honeycomb ceramic for adsorbing and inactivating viruses, which has the function of adsorbing and inactivating the viruses and can be applied to the fields of protective materials, equipment, indoor air purification and the like, so that the propagation of the viruses is effectively inhibited or reduced, and the occurrence of public health incidents is prevented.
The technical scheme of the invention comprises the following steps: provides a honeycomb ceramic for adsorbing and inactivating viruses, which consists of a honeycomb ceramic matrix and coatings coated on the inner walls of pore channels of the honeycomb ceramic matrix.
The coating is composed of porous particles for adsorbing inactivated viruses and an inorganic binder roasting product, and the porous particles account for 50-95% of the mass of the coating, preferably 60-90%; the coating accounts for 1-50%, preferably 5-20% of the mass of the honeycomb ceramic for adsorbing and inactivating viruses; the thickness range of the coating is 0.5-60um, preferably 5-20um, and the average thickness is 0.7-55um, preferably 5-20um; the firmness of the coating is that the weight loss rate of the coating after the water phase ultrasonic oscillation for 60 minutes is less than 5 percent of the mass of the coating before the ultrasonic oscillation under the conditions of 250W and 53 kHz.
The honeycomb ceramic substrate is made of one of cordierite, mullite, cordierite-mullite and aluminum titanate, the pore density is 200-1075 pores per square inch, the wall thickness is 0.1-0.2mm, and the pore channel is one of square, hexagon, circle and triangle.
The porous particles are composed of a shell layer with macropores and mesopores and a hierarchical pore molecular sieve core; wherein the shell is made of porous oxygen storage material SiO 2 -CeO 2 The composition or composition material comprising a porous oxygen storage material SiO 2 -CeO 2 ，SiO 2 With CeO 2 1 to 100, preferably 2: 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 500nm; 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 particle shell also contains p-SiO 2 -CeO 2 A modified modifier is ZrO 2 、La 2 O 3 、Pr 2 O 3 、Nd 2 O 3 、Y 2 O 3 One or more than two of the above; the addition amount of the modifier is 0.01-2% of the shell mass, and preferably 0.05-1%.
The molecular sieve is one or more than two of ZSM-5, A type, X type and Y type;
allowing the molecular sieve to be subjected to structure and surface modification, wherein the modification elements are one or more than two of Pt, ir, au, ag, ba, mg, ca, cs, cu, co, ni, ti, ga, fe, zn, la, pr, nd and Y; the mass of the modifying element accounts for 0.01-20% of the mass of the catalytic material core, and preferably 0.05-10%.
The inorganic binder is a composition of aluminum dihydrogen phosphate and one or more than two of silica sol, aluminum sol, titanium sol and zirconium sol, wherein the aluminum dihydrogen phosphate accounts for 0.1-50% of the solid content of the binder.
The honeycomb ceramic is used for adsorbing and/or inactivating viruses.
The honeycomb ceramic is used for air purification and/or water purification and is used as a material for adsorbing and inactivating viruses.
The honeycomb ceramic is used as a component and applied to air purification equipment with large flow rate, such as an air purifier, an air conditioner, a fresh air system and the like.
The application environment or condition of the honeycomb ceramic is normal pressure, the temperature of-10-50 ℃ and the relative humidity of 0-100% air.
The preparation method of the honeycomb ceramic for adsorbing and inactivating viruses comprises the following steps:
1. preparation of powdery core-shell structure hierarchical pore material
(1) Mixing a molecular sieve with 0.1-0.5mol/L NaOH solution according to the volume ratio of 1. Or 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 core-shell structure hierarchical pore material containing the modified element.
(2) Mixing the nano CeO 2 Hydroxypropyl methylcellulose, triblock copolymer P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide, EO) 20 PO 70 EO 20 ) And (2) adding the core-shell structure hierarchical porous material into silica sol, homogenizing, then soaking the core material obtained in the step (1) with the liquid, and obtaining the core-shell structure hierarchical porous material after centrifugal separation, drying and roasting. Alternatively, a nitrate solution of a modifier (e.g., zr (NO) 3 ) 4 ·5H 2 Aqueous solution of O) impregnated CeO 2 After drying, the product obtained after roasting at 400-550 ℃ replaces the nano CeO in the step 2 2 And preparing a shell layer to finally obtain the powdery core-shell structure hierarchical pore material.
2. Preparation of the coating
(1) Slurry synthesis: preparing 100% slurry, including 0.1-54wt.% of the powder core-shell structure hierarchical pore material prepared in the step 1, 0.1-99.87wt.% of a liquid inorganic binder (solid content is 5-50%, aluminum dihydrogen phosphate accounts for 0.1-50% of solid mass), 0.01-40wt.% of ethanol, 0.01-2wt.% of glycerol and 0.01-1wt.% of polyethylene glycol, and adding water for supplementing when the sum of the mass fractions of the components is less than 100%. And performing ball milling for 0.1-24 hours at the rotating speed of 50-1000 r/min to obtain coating slurry, wherein the mass ratio of the powdery core-shell structure hierarchical pore material to the inorganic binder is 1-19. Or, any one of aluminum sol, titanium sol and zirconium sol is combined into the inorganic binder instead of the silica sol.
(2) Coating (dip coating): dipping the coating slurry prepared in the step 2 (1) into 200-1075-hole/square inch square-hole cordierite honeycomb ceramic for 1-60 minutes, blowing out redundant slurry in honeycomb ceramic pore channels by using high-pressure gas of 0.1-0.8MPa, drying at 80-150 ℃ for 3-24 hours and roasting at 300-700 ℃ for 1-10 hours to obtain a coating on the honeycomb ceramic body; repeating the coating process for 1-5 times to finally obtain the honeycomb ceramic with the nuclear shell structure hierarchical pore material coating and capable of adsorbing and inactivating viruses, wherein the coating accounts for 5-50% of the total mass of the honeycomb ceramic; or, the cordierite honeycomb ceramic is replaced by one of mullite, cordierite-mullite and aluminum titanate honeycomb ceramic; or the square hole honeycomb ceramics is replaced by one of hexagonal, triangular and circular hole honeycomb ceramics.
The principle of the invention is as follows: the virus killing material coating on the honeycomb ceramic pore wall is composed of a core-shell structure hierarchical pore material, wherein a shell with a large pore 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) and the like in the aerosol are adsorbed into a mesoporous channel of a hierarchical pore molecular sieve core, oxygen in the air is activated and transferred into the core by a shell layer oxygen storage material, meanwhile, oxygen in the air is dissociated by a modification element loaded on the core to form oxygen anions with stronger oxidation capacity, and the hydrolysis and oxidation of organisms (protein shells and nucleic acids of 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 prevent the loss of the modification components loaded on the core, stabilize the inactivation performance of the material and prolong the service life of the material.
The combined inorganic binder and the organic additive adopted in the preparation of the coating on the honeycomb ceramic can remarkably promote the high firm combination between the core-shell structure hierarchical pore material particles and the honeycomb ceramic matrix and between the particles, so that the honeycomb ceramic has excellent vibration resistance and scouring resistance, and can keep the super strong virus adsorption and inactivation performance of the honeycomb ceramic. The honeycomb ceramic for adsorbing and inactivating viruses is suitable for inactivating bacteria and viruses in air of an air purifier, an air conditioner, a fresh air system and the like, and can obviously reduce the flow resistance and pressure drop of a bed layer.
Compared with the prior art, the invention has the following beneficial effects:
1. the shell of the virus-inactivating core-shell structure hierarchical porous material particles in the honeycomb ceramic coating 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 the oxygen activation and inactivation material;
2. the core of the hierarchical pore material particle with the core-shell structure in the honeycomb ceramic coating 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 material particle in the core-shell structure in the honeycomb ceramic coating 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 the shell layer, rich adsorption active sites of the mesoporous and microporous core and negative oxygen ions, and the material has higher catalytic efficiency and better disinfection effect. The inactivated virus catalytic material with the special structure not only solves the technical problems of poor sterilization and disinfection effects, 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 the granular material, the honeycomb ceramic has smaller bed flow resistance and pressure drop, and is easy to be applied to high-flow-rate air purification equipment.
5. Compared with the particle material, the honeycomb ceramic has high mechanical strength, the coating is firmly combined with the matrix, the coating is not easy to fall off, and the honeycomb ceramic is not easy to damage in the using process.
6. Compared with photocatalyst, the honeycomb ceramic adsorption inactivation virus does not depend on other light sources and other equipment, has wider application range and simpler assembly integration process.
7. The honeycomb ceramic has the advantages of easily obtained 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 NH 4 ZSM-5 molecular Sieve (SiO) 2 /Al 2 O 3 =25, specific surface area 550m 2 Per g, particle size 2.3 μm, average pore size 0.54 nm) and 0.35mol/L NaOH solution in a volume ratio of 1. The average mesoporous diameter of 24.3nm, the pore distribution of 3.2-48.7nm, the average micropore diameter of 0.55nm, the pore distribution of 0.51-0.58nm, 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).
By type A (SiO) 2 /Al 2 O 3 =2, specific surface area 750m 2 G, particle diameter of 3.6 μm, average pore diameter of 0.48 nm), X-type (SiO) 2 /Al 2 O 3 =2.8, specific surface area 650m 2 G, particle diameter of 6.2 μm, average pore diameter of 1.04 nm), Y-type (SiO) 2 /Al 2 O 3 =5, specific surface area 886m 2 G, particle size 8.5 μm, average pore diameter 1.25 nm) molecular sieve instead of NH 4 And (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 measured to be 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, and the average particle size is 3.4 mu m.
The average mesoporous aperture of the X-type hierarchical pore molecular sieve core material is 27.1nm, the pore distribution is 4.2-40.2nm, the average micropore aperture is 1.04nm, the pore distribution is 1.02-1.06nm, the mesoporous pore volume is 0.13ml/g, and the micropore pore volume is 0.33ml/g. The average particle size was 6.1. 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 0.39ml/g. The average particle size was 8.4. Mu.m.
Alternatively, further, 7.8g of Zn (NO) may be added 3 ) 2 ·6H 2 Dissolving 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 added 3 ) 2 ·6H 2 O is replaced by nitrate of other modifying elements such as Ag.
(2) Preparing a shell: 1.3g of nano CeO 2 (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, EO 20 PO 70 EO 20 ) Adding into 88.7g of 2.6wt.% silica sol (average particle diameter of 10.1 nm), 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 2 2 -CeO 2 Zn-ZSM-5 multi-stage hole material Zn-ZSM-5@ SiO coated with shell layer 2 -CeO 2 。
Measuring the average macropore diameter of the shell layer to be 87nm, the macropore volume to be 0.52ml/g and the macropore pore diameter distribution to be 50-201nm by using a full-automatic mercury porosimeter (AutoPore V, micromeritics, USA) capable of measuring the macropore diameter and the macropore volume; measuring the average mesoporous diameter of 27nm, the mesoporous volume of 0.19ml/g and the mesoporous pore size distribution of 4-40nm by using a full-automatic physical adsorption instrument (ASAP 2460, micromeritics corporation, USA) 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, a nitrate solution of a modifier (e.g., zr (NO) 3 ) 4 ·5H 2 Aqueous solution of O) impregnated with CeO 2 Drying and roasting at 500 deg.c for 2 hr to obtain modified nanometer CeO 2 Material, using the modified material to replace the nano CeO in the step 2 2 Preparing a shell layer to finally obtain the shell layerA modified material.
2. Preparation of adsorbed inactivated Virus coating
(1) Slurry synthesis: 20.0wt.% of the powdery core-shell structure hierarchical pore material prepared in the step 1 and 16.67wt.% of aluminum dihydrogen phosphate and silica sol combined inorganic binder (the mass solid content is 30%, the mass content of the aluminum dihydrogen phosphate is 15%, and the SiO content is 2 15 percent of ethanol, 2.0 percent of glycerol and 1 percent of polyethylene glycol by weight are uniformly mixed with the balance of deionized water, the mixture is ball-milled for 1 hour at the rotating speed of 600 r/min to obtain coating slurry, and the average particle size of the slurry is 1.2 mu m by using a Nano laser particle sizer (Zetasizer Nano ZS, british Mark). Or, replacing the silica sol in the combined inorganic binder by aluminum sol, titanium sol and zirconium sol, and repeating the operation of the step 2 (1) to obtain coating slurry. The average grain diameter of the slurry is 1.5 mu m after the aluminum sol is used; the average grain diameter of the slurry is measured to be 1.1 mu m after titanium sol is used; the average particle size of the slurry was 1.6 μm as measured after using the zirconium sol.
(2) Coating: dipping the 400-hole/square-inch square-hole cordierite honeycomb ceramic by using the coating slurry prepared in the step 2 (1) for 1 minute, blowing redundant slurry in the honeycomb ceramic pore channel by using high-pressure gas of 0.8MPa, drying for 3 hours at 150 ℃ and roasting for 3 hours at 500 ℃ to obtain an upper coating of the honeycomb ceramic body; repeating the coating process for 1 time to finally obtain the honeycomb ceramic with the core-shell structure hierarchical pore material coating and adsorbing inactivated viruses, wherein the coating accounts for 20.3 percent of the total mass of the honeycomb ceramic, the thickness of the coating is measured to be 25.2 mu m by SEM, and the specific surface area of the obtained honeycomb ceramic material is 96.7m 2 The average macropore aperture is 735nm, the macropore distribution is 0.05-12.1 μm, the macropore capacity is 0.24ml/g, the average mesopore aperture is 24.3nm, the mesopore distribution is 3.2-48.7nm, the mesopore capacity is 0.042ml/g, the average micropore aperture is 0.55nm, the micropore distribution is 0.51-0.58nm, and the micropore capacity is 0.064ml/g; the weight loss rate of the coating after aqueous phase ultrasonic treatment for 60 minutes at 250W and 53kHz is 3.62%.
Or, replacing the cordierite honeycomb ceramic with mullite, cordierite-mullite and aluminum titanate honeycomb ceramic, and repeating the operation of the step 2 (2) to obtain the virus-adsorbed inactivated honeycomb ceramic with the core-shell structure hierarchical pore material coating. The coating obtained by the mullite honeycomb ceramic accounts for 18.3 percent of the total mass of the honeycomb ceramic, the thickness of the coating is 19.7 mu m, and the weight loss rate of the coating is 2.12 percent; the coating obtained by the cordierite-mullite honeycomb ceramic accounts for 22.6 percent of the total mass of the honeycomb ceramic, the thickness of the coating is 25.1 mu m, and the weight loss rate of the coating is 1.08 percent; the coating obtained by the aluminum titanate honeycomb ceramic accounts for 19.5 percent of the total mass of the honeycomb ceramic, the thickness of the coating is 20.7 mu m, and the weight loss rate of the coating is 0.93 percent. Or, replacing the square-hole cordierite honeycomb ceramic with hexagonal, triangular and circular-hole honeycomb ceramic, and repeating the operation of the step 2 (2) to obtain the virus-adsorbing inactivated honeycomb ceramic with the core-shell structure hierarchical-hole material coating. The coating obtained by the hexagonal-hole cordierite honeycomb ceramic accounts for 23.3 percent of the total mass of the honeycomb ceramic, the thickness of the coating is 24.7 mu m, and the weight loss rate of the coating is 1.65 percent; the coating obtained by the triangular-hole cordierite honeycomb ceramic accounts for 21.4 percent of the total mass of the honeycomb ceramic, the thickness of the coating is 20.5 mu m, and the weight loss rate of the coating is 3.02 percent; the coating obtained by the circular-hole cordierite honeycomb ceramic accounts for 18.6 percent of the total mass of the honeycomb ceramic, the thickness of the coating is 19.6 mu m, and the weight loss rate of the coating is 0.78 percent.
According to the preparation method, the specific composition and corresponding parameters of the obtained powdery core-shell structure hierarchical pore material are shown in the following table 1, and the specific composition and corresponding parameters of the honeycomb ceramic are shown in the following table 2.
Examples 1 to 4
TABLE 1
TABLE 2
Examples 5 to 20
2. Adsorption inactivation test for viruses
1. Virus preparation:
separately preparing TCIDs 50 The COVID-19 virus liquid (75 ng/ul) and TCID 50 The tool lentivirus (pLenti) virus liquid (100 ng/ul) is used for the adsorption inactivation test of powder materials and honeycomb ceramics on novel coronavirus and lentivirus;
2. preparing 9 honeycomb ceramic blocks with the number of HX-1-9, weighing 0.5g of each material and 0.5g of honeycomb ceramic matrix not loaded with the core-shell structure hierarchical pore material, respectively placing into a sterile 1.5mL EP tube, and dropwise adding 1.0mL of TCID 50 The lentivirus (pLenti) virus solution is acted at room temperature for 30 minutes, and the mixture of the test object and the virus solution is mixed by shaking a shaking table once every 5 minutes, so that the material and the virus are fully acted. A blank control (containing only 1.0mL of LTCID) was also prepared 50 3 parts of lentivirus (pLenti) virus solution) were placed in sterile 1.5ml EP tubes, respectively, and left at room temperature for 30 minutes with shaking at 5 minute intervals. The results are given in examples 23 to 31;
two sets of 3 powdered materials, designated AX-1-3, were prepared, and 200mg of control glass microspheres (10 μm in size) and 200mg of COVID-19 virus solution and tool lentivirus (pLenti) solution were weighed out for each material, and the above procedure was repeated, as shown in examples 20-22;
3. after 30 minutes of action, centrifuge for 5 minutes at 3000rpm, aspirate 250ul of supernatant into each tube into fresh sterile EP tubes (ensure equal aspiration of supernatant 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 allowed to stand at room temperature for 2 to 3 minutes, followed by centrifugation at 12000rpm (2 to 8 ℃ C.) 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 abandoning 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 abandoning 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 (AM 1728) (according to the AM1728 kit protocol). The RNA extracted from each tube was repeated 3 times, and the average value was taken to obtain the number of viruses in the supernatant.
6. Examination of the reduction of the virus in the supernatant of the different test groups
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.
The results are shown in Table 3, the powder material AX-1-3 has the adsorption inactivation effect on both the novel coronavirus (COVID-19) and the lentivirus (pLenti), the honeycomb ceramic HX-1-9 has the effect of directly adsorbing and inactivating the lentivirus (pLenti), and the adsorption inactivation effect on the novel coronavirus (COVID-19) and/or the lentivirus (pLenti) by the honeycomb ceramic control, the glass microsphere control and the blank control group which are not loaded with the core-shell structure hierarchical pore material is not detected.
Viral adsorption inactivation rate (%) = {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 2.67wt.%, specific surface area 1235 m) is adopted 2 Lentivirus adsorption and inactivation tests were performed on honeycomb ceramic (400 pores per square inch, square pores, cordierite material, 0.15mm wall thickness) loaded with particles of 57.2 μm average particle size, 1.3nm average pore diameter, 0.88ml/g pore volume, following the same procedure as in examples 16-24, and showed a 41% reduction in virus content in the remaining supernatant relative to the untreated group.
Comparative example 2
Silver-loaded mordenite (Ag content 3.25wt.%, specific surface area 325 m) is adopted 2 Lentivirus adsorption and inactivation test was performed on honeycomb ceramic (400 pores per square inch, square pores, cordierite material, 0.15mm wall thickness) loaded with 5.3 μm average particle size, 0.66nm average pore diameter, 0.27ml/g pore volume, using the same procedure as in comparative example 1, and the results showed a 62% reduction in virus content in the remaining supernatant compared to the untreated group.
Comparative example 3
By means of SiO 2 (specific surface area 436 m) 2 (g), pore diameter of 6.9nm, particle diameter of 430 nm)) supported honeycomb ceramic, ceO 2 (specific surface area 57.2 m) 2 (g, mean pore diameter 23.4nm, particle size 1.7 μm) slow virus adsorption and inactivation in honeycomb ceramic (400 pores per square inch, square pores, cordierite material, 0.15mm wall thickness) were tested, respectively, as in comparative example 1, and the results showed a 10% and 13% reduction in virus content in the remaining supernatant relative to the untreated group, respectively.
Comparative example 4
Mordenite (with the specific surface area of 325 m) 2 Lentivirus adsorption and inactivation tests were performed on honeycomb ceramic (400 pores per square inch, square pores, cordierite material, 0.15mm wall thickness) loaded with particles having a particle size of 6.2 μm, an average pore diameter of 0.67nm, and a pore volume of 0.27ml/g, using the same procedure as in comparative example 1, and the results showed a 23% reduction in the virus content in the remaining supernatant relative to the untreated group.
Comparative example 5
Pt-loaded 5A molecular sieves (Pt content 1.93wt.%, table) were usedArea 536m 2 Lentivirus adsorption and inactivation test was performed on honeycomb ceramic (400 pores per square inch, square pores, cordierite material, 0.15mm wall thickness) loaded with 0.38ml/g (average pore diameter 0.5nm, average particle size 2.7 μm) and the procedure of comparative example 1 showed a 64% reduction in virus content in the remaining supernatant compared to the untreated group.
Comparative example 6
The lentivirus adsorption and inactivation test was performed using a honeycomb ceramic (400 pores/square inch, square pores, cordierite material, wall thickness 0.15 mm) loaded with hierarchical pore ZSM-5 molecular sieve cores (average mesopore diameter 24.3nm, pore distribution 3.2-48.7nm, average micropore pore diameter 0.55nm, pore distribution 0.51-0.58nm, mesopore volume 0.18ml/g, micropore volume 0.32 ml/g), the procedure of the method was the same as that of comparative example 1, and the results showed that the virus content in the remaining supernatant was reduced by 70% compared to the untreated group.
Comparative example 7
Using shell material CeO 2 -SiO 2 (the average macropore diameter is 87nm, the macropore volume is 0.52ml/g, the macropore diameter distribution is 50-201nm; the average mesopore diameter is 27nm, the mesopore volume is 0.19ml/g, the mesopore diameter distribution is 4-40 nm) is carried out on the honeycomb ceramic (400 pores/square inch, square hole, cordierite material, wall thickness is 0.15 mm) loaded, 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 54 percent relative to that in a non-treated group.
Comparative example 8
Adopting the shell material CeO prepared in the second step 2 -SiO 2 (the average macropore aperture is 87nm, the macropore volume is 0.52ml/g, the macropore aperture distribution is 50-201nm; the average mesopore aperture is 27nm, the mesopore volume is 0.19ml/g, the mesopore aperture distribution is 4-40 nm) coating mordenite (the specific surface area is 325 m) 2 Per g, mean particle size of 6.2 μm, mean pore diameter of 0.67nm, pore volume of 0.27 ml/g) porous particle-loaded honeycomb ceramic (400 pores per square inch, square pores, cordierite material, 0.15mm wall thickness) was tested for lentivirus adsorption and inactivation, as per comparative example 2, and the results showed a reduction in 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 step 2 -SiO 2 (the average macropore diameter is 87nm, the macropore volume is 0.52ml/g, the macropore aperture distribution is 50-201nm; the average mesopore diameter is 27nm, the mesopore volume is 0.19ml/g, the mesopore aperture distribution is 4-40 nm) is coated with silver-loaded mordenite (the Ag content is 3.25 wt%, the specific surface area is 325 m) 2 Per g, average particle size 5.3 μm, average pore size 0.66nm, pore volume 0.27 ml/g) particle-loaded honeycomb ceramic (400 pores per square inch, square pores, cordierite material, 0.15mm wall thickness) was tested for lentivirus adsorption and inactivation, using the same procedure as in comparative example 2, and the results showed a 44% reduction in virus content in the remaining supernatant compared to the untreated group.
Comparative example 10
Using commercial SiO 2 (specific surface area 436m 2 Perg, pore diameter of 6.9nm, particle diameter of 430 nm), ceO 2 (specific surface area 57.2 m) 2 (g, average pore diameter 23.4nm, particle size 1.7 μm) coating the silver-loaded hierarchical pore ZSM-5 molecular sieve core (Ag content 1.52wt.%, average mesoporous pore diameter 24.3nm, pore distribution 3.2-48.7nm, average microporous pore diameter 0.55nm, pore distribution 0.51-0.58nm, mesoporous pore volume 0.18ml/g, microporous pore volume 0.32 ml/g) prepared in step one, and particle-loaded honeycomb ceramic (400 pores/square inch, square pores, cordierite material, wall thickness 0.15 mm) was subjected to lentiviral adsorption and inactivation test, the same procedure as in comparative example 2, showing that the virus content in the remaining supernatant was reduced by 47% relative to that in the untreated group.
Claims (12)
1. A honeycomb ceramic for adsorbing inactivated viruses is characterized in that: the honeycomb ceramic is composed of a honeycomb ceramic matrix and a coating coated on the inner wall of a pore channel of the honeycomb ceramic matrix;
the coating is composed of porous particles for adsorbing inactivated viruses and an inorganic binder roasting product, and the porous particles account for 50-95% of the mass of the coating; the coating accounts for 1-50% of the mass of the honeycomb ceramic for adsorbing and inactivating viruses; the thickness range of the coating is 0.5-60 μm, and the average thickness is 0.7-55 μm;
the porous 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 SiO 2 -CeO 2 The composition or composition material comprising a porous oxygen storage material SiO 2 -CeO 2 ，SiO 2 With CeO 2 1-100 in a mass ratio of 1; wherein the pores in the shell comprise macropores and mesopores, the pore size distribution of the macropores in the shell is within the range of 50-500nm, the average pore size of the macropores is within the range of 60-300nm, the pore volume of the macropores is 0.3-1.0ml/g, the pore size distribution of the mesopores is within the range of 2-less than 50nm, the average pore size of the mesopores is within the range of 5-40nm, the pore volume of the mesopores is 0.05-0.3ml/g, and the thickness of the shell is 60-500nm;
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 0.3 nm-less than 2nm, the average pore size of the micropores is 0.5-1.9nm, the pore size distribution range of the mesopores is 2 nm-less than 50nm, the average pore size of the mesopores is 5-40nm, the pore volumes of the mesopores and the micropores are 0.05-0.25ml/g and 0.25-0.4ml/g respectively, and the particle size is 100nm-10 mu m;
the oxygen storage material of the porous particle shell also contains p-SiO 2 -CeO 2 A modified modifier is ZrO 2 、La 2 O 3 、Pr 2 O 3 、Nd 2 O 3 、Y 2 O 3 One or more than two of (a); the addition amount of the modifier is 0.01-2% of the mass of the shell layer;
carrying out structure and surface modification on the molecular sieve, wherein the modification elements are one or more than two of Pt, ir, au, ag, ba, mg, ca, cs, cu, co, ni, ti, ga, fe, zn, la, pr, nd and Y; the mass of the modifying element accounts for 0.01-20% of the mass of the catalytic material core.
2. The honeycomb ceramic of claim 1, wherein:
the firmness of the coating is that the weight loss rate of the coating after the water phase ultrasonic oscillation for 60 minutes is less than 5 percent of the mass of the coating before the ultrasonic oscillation under the conditions of 250W and 53 kHz.
3. The honeycomb ceramic of claim 1, wherein: the honeycomb ceramic substrate is made of one or more than two of cordierite, mullite, cordierite-mullite and aluminum titanate, the pore density is 200-1075 pores per square inch, the wall thickness is 0.1-0.2mm, and the radial section of each pore channel is one or more than two of square, hexagon, circle and triangle.
4. The honeycomb ceramic of claim 1, wherein: the porous 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 SiO 2 -CeO 2 The composition or composition material comprises a porous oxygen storage material SiO 2 -CeO 2 ，SiO 2 With CeO 2 The mass ratio of (A) to (B) is 2; wherein the pores in the shell comprise macropores and mesopores, the pore size of the macropores in the shell is distributed in the range of 50-500nm, the average pore size of the macropores is 70-200nm, the pore volume of the macropores is 0.35-0.7ml/g, the pore size of the mesopores is distributed in the range of 2-less than 50nm, the average pore size of the mesopores is 10-30nm, the pore volume of the mesopores is 0.1-0.25ml/g, and the thickness of the shell is 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 0.3 nm-less than 2nm, the average pore size of the micropores is 0.6-1.6nm, the pore size distribution range of the mesopores is 2 nm-less than 50nm, the average pore size of the mesopores is 7-30nm, the pore volumes of the mesopores and the micropores are respectively 0.1-0.2ml/g and 0.3-0.35ml/g, and the particle size is 300nm-1 mu m.
5. The honeycomb ceramic of claim 4, wherein: the addition amount of the modifier is 0.05-1% of the mass of the shell layer.
6. The honeycomb ceramic of claim 4, wherein: the molecular sieve is one or more than two of ZSM-5, A type, X type and Y type;
carrying out structure and surface modification on the molecular sieve, wherein the mass of the modification element accounts for 0.05-10% of the mass of the catalytic material core.
7. The honeycomb ceramic of claim 1, wherein: the inorganic binder is a composition of aluminum dihydrogen phosphate and one or more than two of silica sol, aluminum sol, titanium sol and zirconium sol, wherein the aluminum dihydrogen phosphate accounts for 0.1-50% of the solid content of the binder.
8. The honeycomb ceramic of claim 1, wherein: the porous particles account for 60-90% of the mass of the coating; the coating accounts for 5-20% of the mass of the honeycomb ceramic for adsorbing and inactivating the viruses; the thickness of the coating ranges from 5 to 20 μm, with an average thickness of 0.7 to 55 μm.
9. Use of a honeycomb ceramic according to any one of claims 1 to 7, wherein: the honeycomb ceramic is used for adsorbing and/or inactivating viruses.
10. Use of a honeycomb ceramic according to any one of claims 1 to 8 as a material for the adsorption inactivation of viruses for air purification and/or water purification.
11. The use of the honeycomb ceramic of claim 10 as a component in an air purifier, an air conditioner, and a high flow rate air purification device for a fresh air system.
12. The use of the honeycomb ceramic according to claim 9, 10 or 11, wherein the application environment or condition of the honeycomb ceramic is atmospheric pressure, a temperature of-10 to 50 ℃, and a relative humidity of 0 to 100% air.
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