CN113441168A - Core-shell structure hierarchical pore catalytic material for adsorbing inactivated viruses and application - Google Patents

Core-shell structure hierarchical pore catalytic material for adsorbing inactivated viruses and application Download PDF

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CN113441168A
CN113441168A CN202010217712.4A CN202010217712A CN113441168A CN 113441168 A CN113441168 A CN 113441168A CN 202010217712 A CN202010217712 A CN 202010217712A CN 113441168 A CN113441168 A CN 113441168A
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catalytic material
core
pore
shell
mesopores
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CN113441168B (en
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马磊
任晓光
朴海龙
吴春田
侯宝林
王稳
李林
许磊
冯璐
张万生
黄延强
王晓东
张涛
张晨
蔡睿
刘中民
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Dalian Institute of Chemical Physics of CAS
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    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention provides a core-shell structure hierarchical pore catalytic material for adsorbing and inactivating viruses, which consists of a shell and a core, wherein the shell is formed by a storage shellOxygen material SiO2‑CeO2The composition comprises the components with the mass ratio of 1:1-100:1, the macropore aperture is 50-500nm, the average macropore aperture is 60-300nm, the macropore volume is 0.3-1.0ml/g, and the shell layer thickness is 60-500 nm; the core is a hierarchical pore molecular sieve; the pore size distribution comprises mesopores and micropores with the sizes of 2-50 nm and 0.3-2 nm, the average pore sizes of 0.5-1.9nm and 5-40nm, the pore volumes of 0.05-0.25ml/g and 0.25-0.4ml/g, and the particle diameters of 100nm-10 μm. The core-shell structure hierarchical pore catalytic material can be used for adsorbing and inactivating viruses including coronavirus.

Description

Core-shell structure hierarchical pore catalytic material for adsorbing inactivated viruses and application
Technical Field
The invention relates to a protection technology of epidemic virus diseases, in particular to a core-shell structure hierarchical pore catalytic material 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, a long-term and efficient virus-inactivating material is urgently needed for the protection of hospitals, large public places, families and individuals and the control of the spread of highly infectious diseases.
According to reports, the novel coronavirus is mainly carried and spread by droplets, aerosol, dust and the like in the air, different sterilization and disinfection methods adopted by different air purification equipment are different, and main sterilization and disinfection materials related to the invention comprise photocatalyst and silver-loaded activated carbon.
At present, most of the traditional inorganic antibacterial agents in the market comprise titanium dioxide photocatalyst, silver-loaded activated carbon and the like.
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 inactivating 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 silver is unevenly distributed and the particle size is uneven, so that the sterilization performance is unstable, and most of the silver particles can only play a role in bacteriostasis. Another major drawback of silver-loaded activated carbon is the difficulty in firmly loading onto the support for the honeycomb and mesh filters of air purification systems.
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.
At present, inorganic antiviral materials and related patents which have better inactivation effect on high infectious disease viruses such as novel coronavirus (COVID-19) are not reported and disclosed.
Disclosure of Invention
The invention aims to provide a core-shell structure hierarchical pore catalytic material which has a better adsorption and inactivation function on viruses including coronavirus, and can be applied to the manufacturing fields of protective materials, equipment and the like, so that the propagation of the viruses is effectively restrained or reduced, and public health events are prevented.
The technical scheme of the invention comprises the following steps: providing a core-shell structure hierarchical pore catalytic material for adsorbing and inactivating viruses, which consists of a granular core and a shell layer coated on the outer surface of the granular 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 hierarchical pore 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%, preferably 0.05-10% of the mass of the catalytic material core.
The oxygen storage material of the shell also contains p-SiO2-CeO2A modified modifier is ZrO2、La2O3、Pr2O3、Nd2O3、Y2O3One or more than two of them. The addition amount of the modifier is 0.01-2% of the shell mass, preferably 0.05-1%.
The core-shell structure hierarchical pore catalytic material can be used for adsorbing and inactivating viruses including coronavirus, and further can be used for the manufacturing field of protective materials or equipment and the like by carrying and forming structural carriers such as honeycomb ceramics, metal nets, non-woven fabrics and the like. Can also be used as a material for adsorbing and inactivating viruses in the fields of air purification and water purification. The preparation method of the core-shell structure hierarchical pore catalytic material comprises the following steps:
1. preparation of the core
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 100-150 ℃ and roasting at 400-550 ℃ for more than 1 hour 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 ℃ for more than 1 hour to obtain the core of the catalytic material containing the modified element.
2. Preparation of the Shell
A. Mixing the nano CeO2Hydroxypropyl methylcellulose, triblock copolymer P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide, EO)20PO70EO20) Adding the core-shell structure hierarchical pore catalytic material into silica sol, homogenizing, soaking the core material obtained in the step 1 with the liquid, and performing centrifugal separation, drying and roasting at 550 ℃ for more than 1 hour 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 ℃ for more than 1 hour replaces the nano CeO in the step 2A2And (4) preparing a shell layer to finally obtain the shell layer modified catalytic material.
The principle of the invention is as follows: the shell with a macroporous structure can effectively adsorb microbe aerosol (0.1-20 μm) related to diseases in air at room temperature, furthermore, coronavirus particles (0.08-0.2 μm) in the aerosol are adsorbed into mesoporous channels 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 modifying element loaded on the core to form oxygen anions with strong oxidation capacity, and the hydrolysis and oxidation of organisms (protein shells and nucleic acid of viruses) are catalyzed under the synergistic action of the shell layer activated oxygen, the oxygen anions in the core and 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.
Compared with the prior art, the invention has the following beneficial effects:
1. the shell of the catalytic material has multiple functions, can adsorb aerosol and spray carrying viruses, can store and activate more oxygen, and can prevent loss of the modification components loaded on the core. This activated oxygen can oxidize viral proteins or nucleic acids (DNA or RNA), destroying their structure, leading to their inactivation;
2. the core of the catalytic material has a hierarchical pore structure, is suitable for virus particles to pass through, is beneficial to fully contact with the 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 structure hierarchical pore catalytic material is different from the traditional silver-loaded metal ion sterilization material in that the traditional silver-loaded bactericide action mechanism 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 catalytic efficiency of the material is higher, the inactivation effect is better, and the adsorption inactivation rate of the material on novel coronavirus (COVID-19) can reach 100%. The inactivated virus catalytic material with the special structure not only solves the technical problems of poor virus inactivation 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 cost of the catalytic material. 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 abundant mesopores and micropores are provided in a core, so that virus nucleic acid molecules are favorably diffused and adsorbed in a molecular sieve core, the material is more fully contacted with active sites, and more virus-inactivating 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 a photocatalyst, the method has the advantages that the virus is adsorbed and inactivated without depending on other light sources and other equipment, the application range is wider, and the assembly integration process is simpler;
5. the raw materials are easy to obtain, the cost is low, the synthetic route is mature, and the industrialization is easy.
Drawings
Fig. 1 is a schematic structural diagram of a catalytic material, wherein 1, micropores on a catalyst core, 2, mesopores on the catalyst core, 3, macropores on a catalyst shell, 4, active sites on the catalyst core for adsorbing viral nucleic acid or protein, 5, the catalyst core, 6, a catalyst shell, 7, and oxygen activation sites.
Detailed Description
The invention is further illustrated by the following examples.
Firstly, the preparation of the catalytic material of the invention comprises the following steps:
1. preparation of the 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. Measurement was carried out by using a fully automatic physical adsorption apparatus (ASAP 2460, Micromeritics, USA) capable of measuring the distribution and pore volume of mesopores and microporesThe average mesoporous aperture is 24.3nm, the pore distribution is 2.0-49.9nm, the average micropore aperture is 0.55nm, the pore distribution is 0.3-1.99nm, the mesoporous pore volume is 0.18ml/g, and the micropore pore volume is 0.32 ml/g. 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 ═ 52G, particle diameter 8.5 μm, average pore diameter 1.25nm) molecular sieve instead of 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. Preparation of the 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 catalytic material Zn-ZSM-5@ SiO coated with shell layer2-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.
Composition of the specific catalytic Material obtained according to the above preparation methodAnd the corresponding parameters are shown in the following table. (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 microporous distribution of the core is 0.3-less than 2nm, and the particle size distribution of the core is 100nm-10 microns)
Examples 1 to 16
Figure BDA0002424949690000061
Figure BDA0002424949690000071
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 the adsorption inactivation test of powder catalytic materials for novel coronaviruses and lentiviruses;
2. preparing 3 powdered catalytic materials (number is AX-1-AX-3), weighing two samples (200 mg and 50 mg) and control glass microspheres (particle size is 10 μm, 2 parts in total) with the same mass as the catalytic material, respectively placing into a sterile 1.5mL EP tube, and dropwise adding 0.8mL of TCID50The COVID-19 virus solution acts for 30 minutes at room temperature, and the mixture of the catalytic material powder and the virus solution is stirred and mixed once every 5 minutes, so that the full action of the material and the virus is ensured. A blank control (containing only 0.8mL of TCID) was also prepared503 parts of COVID-19 virus solution) were placed in sterile 1.5ml EP tubes, and left at room temperature for 30 minutes with 5 minutes intervals, and stirred once.
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 abandoning the supernatant, adding 1ml of 75% ethanol with volume concentration along the tube wall for washing, carrying out vortex mixing for a short time (2-5S), centrifuging for 5 minutes at 7500rpm (2-8 ℃), 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 (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.
Preparing 9 powder catalytic materials with the numbers of AX-1 to AX-9, weighing 200mg of each material, replacing COVID-19 virus liquid with tool lentivirus (pLenti) virus liquid, and repeating the steps 2-5 to obtain the virus number in the supernatant.
6. Investigation of different catalytic 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.
The results show that the catalytic materials AX-1, AX-2 and AX-3 have the effect of directly adsorbing and inactivating the novel coronavirus (COVID-19), and the effect of adsorbing and inactivating the novel coronavirus (COVID-19) by the glass microsphere control group and the blank control group is not detected.
The catalytic materials AX-1 to AX-9 have the effect of directly adsorbing and inactivating the lentivirus (pLenti), and the effect of adsorbing and inactivating the lentivirus (pLenti) by a glass microsphere control group and a blank control group 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 17 to 31
Figure BDA0002424949690000081
Figure BDA0002424949690000091
Comparative example 1
Silver-loaded activated carbon (Ag content 2.67 wt.%, specific surface area 1235 m) is adopted2Per g, mean particle size 57.2m, mean pore diameter 1.3nm, pore volume 0.88ml/g) was tested for the adsorption and inactivation of lentiviruses by the same procedure as in examples 22-30, showing a 50% reduction in virus content in the remaining supernatant compared to the untreated group.
Comparative example 2
Silver-loaded mordenite (Ag content 3.25 wt.%, specific surface area 325 m) is adopted2G, average particle size 5.3 μm, average pore size 0.66nm, pore volume 0.27ml/g) were tested for the adsorption and inactivation of the above lentiviruses, as in comparative example 1, and the results showed a 65% reduction in virus content in the remaining supernatant compared to the untreated group.
Comparative example 3
Purchase of 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, mean pore diameter 23.4nm, particle size 1.7 μm) were tested for the adsorption and inactivation of the above lentiviruses, respectively, by the same procedure as in comparative example 1, and the results showed that the virus content in the remaining supernatant was reduced by 9% and 13%, respectively, relative to the untreated group.
Comparative example 4
Commercial mordenite (specific surface area 325 m)2G, average particle size of 6.2 μm, average pore size of 0.67nm, pore volume of 0.27ml/g) was tested for the adsorption and inactivation of lentiviruses by the same procedure as in comparative example 1, and the results showed relative virus content in the remaining supernatantThe untreated group was reduced by 23%.
Comparative example 5
5A molecular sieve loaded with Pt (Pt content 1.93 wt.%, specific surface area 536 m) is used2Per g, mean pore diameter 0.5nm, mean particle size 2.7 μm, pore volume 0.38ml/g) was tested for the adsorption and inactivation of lentiviruses, as in comparative example 1, and the results showed a 59% reduction in virus content in the remaining supernatant compared to the untreated group.
Comparative example 6
The multistage pore ZSM-5 molecular sieve core prepared in the step 1 (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 adopted to carry out the adsorption and inactivation test of the lentivirus, and 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 compared with that in the non-treated group.
Comparative example 7
Adopting the shell layer material CeO prepared in the step 22-SiO2(the average macropore diameter is 87nm, the macropore capacity is 0.52ml/g, the macropore diameter distribution is 50-201 nm; the average mesopore diameter is 27nm, the mesopore capacity is 0.19ml/g, the mesopore diameter distribution is 4-40 nm.) the slow virus adsorption and inactivation test is carried out, the method steps are the same as the comparative example 2, and the result shows that the virus content in the residual supernatant is reduced by 45 percent compared with that in the non-treated group.
Comparative example 8
Adopting the shell layer material CeO prepared in the step 22-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)2G, mean particle size 6.2 μm, mean pore diameter 0.67nm, pore volume 0.27ml/g) was tested for the adsorption and inactivation of lentiviruses by the same procedure as in comparative example 2, showing a 37% reduction in the virus content of the remaining supernatant compared to the untreated group.
Comparative example 9
Adopting the shell layer material CeO prepared in the step 22-SiO2(average macropore diameter 87nm, macropores)The pore volume is 0.52ml/g, and the pore size distribution of macropores is 50-201 nm; the average mesoporous diameter is 27nm, the mesoporous volume is 0.19ml/g, the mesoporous diameter distribution is 4-40nm), and silver-loaded mordenite is coated (the Ag content is 3.25 wt.%, the specific surface area is 325 m)2G, average particle size 5.3 μm, average pore size 0.66nm, pore volume 0.27ml/g) was tested for the adsorption and inactivation of lentiviruses by the same procedure as in comparative example 2, showing a 41% reduction in the virus content of 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)2(g, average pore size 23.4nm, particle size 1.7 μm) coated on the silver-loaded hierarchical pore ZSM-5 molecular sieve core (Ag content 1.52 wt.%, average mesoporous pore size 24.3nm, pore distribution 3.2-48.7nm, average microporous pore size 0.55nm, pore distribution 0.51-0.58nm, mesoporous pore volume 0.18ml/g, microporous pore volume 0.32ml/g) prepared in step 1, and the method steps were the same as in comparative example 2, and the results showed that the virus content in the remaining supernatant was reduced by 53% compared to the untreated group.

Claims (10)

1. A core-shell structure hierarchical pore catalytic material for adsorbing inactivated viruses is characterized in that: the catalytic material consists of a granular core and a shell layer coated on the outer surface of the granular 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, 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.
2. The catalytic material of claim 1, wherein: the oxygen storage material of the shell also contains p-SiO2-CeO2A modified modifier is ZrO2、La2O3、Pr2O3、Nd2O3、Y2O3One or more than two of them.
3. The catalytic material of claim 2, wherein: the addition amount of the modifier is 0.01-2% of the mass of the shell layer, and preferably 0.05-1%.
4. The catalytic material of claim 1, wherein: the molecular sieve is one or more than two of ZSM-5, A type, X type and Y type.
5. The catalytic material of claim 1 or 4, wherein: the molecular sieve is allowed to be subjected to structure and surface modification by adopting modification elements, 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.
6. The catalytic material of claim 5, wherein: the mass of the modifying element accounts for 0.01-20%, preferably 0.05-10% of the mass of the catalytic material core.
7. Use of a catalytic material according to any of claims 1-6, wherein: the catalytic material is used for adsorbing and/or inactivating viruses, preferably for adsorbing and/or inactivating novel coronaviruses (COVID-19).
8. Use of a catalytic material according to any of claims 1-6 for air purification and/or water purification as a material for adsorbing and/or inactivating viruses.
9. The use of the catalytic material of claim 7 or 8, wherein the catalytic material is first supported or formed on one of the structured carriers such as porous ceramic, mesh and non-woven fabric, and then the application process of the catalytic material is performed.
10. Use of a catalytic material according to claim 7 or 8 or 9, wherein the environment or conditions of use of the catalytic material is atmospheric pressure, -a temperature of-10-50 ℃, and a relative humidity of 0-100% air.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115041218A (en) * 2022-06-27 2022-09-13 昆明理工大学 Hierarchical zeolite core-shell catalyst, preparation method thereof and application thereof in purification of organic sulfur in blast furnace gas

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1552205A (en) * 2003-05-30 2004-12-08 中国科学院大连化学物理研究所 Nanometer catalyst with adsorbing and virus killing activity
CN105712367A (en) * 2014-12-02 2016-06-29 中国科学院大连化学物理研究所 Core/shell-type micropore /mesoporous composite titanium silicon molecular sieve and preparation method thereof
WO2018157042A1 (en) * 2017-02-27 2018-08-30 Sabic Global Technologies B.V. Encapsulated hierarchical zeolite catalyst composition, method of manufacture and use
CN109070068A (en) * 2016-03-09 2018-12-21 巴斯夫公司 core/shell type hydrocarbon trap catalyst and its manufacturing method
CN109529523A (en) * 2018-11-26 2019-03-29 吉林大学 Molecular sieve core-mesoporous organosilicon hollow shell multi-stage porous composite material and preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1552205A (en) * 2003-05-30 2004-12-08 中国科学院大连化学物理研究所 Nanometer catalyst with adsorbing and virus killing activity
CN105712367A (en) * 2014-12-02 2016-06-29 中国科学院大连化学物理研究所 Core/shell-type micropore /mesoporous composite titanium silicon molecular sieve and preparation method thereof
CN109070068A (en) * 2016-03-09 2018-12-21 巴斯夫公司 core/shell type hydrocarbon trap catalyst and its manufacturing method
WO2018157042A1 (en) * 2017-02-27 2018-08-30 Sabic Global Technologies B.V. Encapsulated hierarchical zeolite catalyst composition, method of manufacture and use
CN109529523A (en) * 2018-11-26 2019-03-29 吉林大学 Molecular sieve core-mesoporous organosilicon hollow shell multi-stage porous composite material and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEN ZHIQIANG等: ""The effect of CeO2 dispersity and active oxygen species on the SCR reaction over Fe-ZSM-5@Ce/meso-SiO2"", 《CATALYSIS LETTERS》 *
颜婷婷、喜冬阳、王俊海著: "《多级孔沸石分子筛合成及其催化性能研究》", 30 April 2019 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115041218A (en) * 2022-06-27 2022-09-13 昆明理工大学 Hierarchical zeolite core-shell catalyst, preparation method thereof and application thereof in purification of organic sulfur in blast furnace gas

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