CN113441168B - Core-shell structure hierarchical pore catalytic material for adsorbing inactivated virus and application thereof - Google Patents
Core-shell structure hierarchical pore catalytic material for adsorbing inactivated virus and application thereof Download PDFInfo
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- CN113441168B CN113441168B CN202010217712.4A CN202010217712A CN113441168B CN 113441168 B CN113441168 B CN 113441168B CN 202010217712 A CN202010217712 A CN 202010217712A CN 113441168 B CN113441168 B CN 113441168B
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- 239000000463 material Substances 0.000 title claims abstract description 76
- 241000700605 Viruses Species 0.000 title claims abstract description 64
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- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 18
- 239000011258 core-shell material Substances 0.000 title claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 124
- 238000009826 distribution Methods 0.000 claims abstract description 40
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000415 inactivating effect Effects 0.000 claims abstract description 15
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 229960005486 vaccine Drugs 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000450599 DNA viruses Species 0.000 description 1
- 108010014303 DNA-directed DNA polymerase Proteins 0.000 description 1
- 102000016928 DNA-directed DNA polymerase Human genes 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
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- 230000010534 mechanism of action Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- 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
- B01J29/14—Iron group metals or copper
- B01J29/143—X-type faujasite
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- 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
- B01J29/087—X-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- 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
- B01J29/088—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- 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
- B01J29/405—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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- 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
- B01J29/44—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- 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
- B01J29/46—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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
- B01J29/74—Noble metals
- B01J29/7407—A-type
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- B01J35/647—
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- B01J35/651—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- 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 inactivated viruses, which consists of a shell and a core, wherein the shell consists of an oxygen storage material SiO 2 ‑CeO 2 The composition is 1:1-100:1 in mass ratio, the pore diameter of macropores is in the range of 50-500nm, the average pore diameter of macropores is 60-300nm, the pore volume of macropores is 0.3-1.0ml/g, and the thickness of a shell layer is 60-500nm; the core is a hierarchical pore molecular sieve; the pore size distribution comprises mesopores and micropores which are respectively 2-less than 50nm and 0.3-less than 2nm, the average pore diameter is respectively 0.5-1.9nm and 5-40nm, the pore volume is respectively 0.05-0.25ml/g and 0.25-0.4ml/g, and the particle size is in the range of 100nm-10 mu m. The core-shell structured hierarchical pore catalytic material can be used for adsorbing and inactivating viruses including coronaviruses.
Description
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 inactivated viruses and application thereof.
Background
The transmission of the novel coronavirus (covd-19) is a serious threat to the safety of human life. Development of drugs and vaccines is currently under tightening, but related products are difficult to quickly enter a clinical practical stage in a short time according to the rules of drug and vaccine development. In order to prevent virus transmission, there is an urgent need for a long-term and efficient virus-inactivating material for protection of hospitals, large public places, families and individuals, controlling the spread of highly infectious diseases.
According to reports, the novel coronavirus is mainly carried and transmitted by spray, aerosol, dust and the like in the air, and the sterilization and disinfection methods adopted by different air purifying equipment are different, so that the main sterilization and disinfection materials related to the invention comprise photocatalyst and silver-loaded active carbon.
At present, most of the traditional inorganic antibacterial agents in the market comprise titanium dioxide photocatalysts, silver-loaded activated carbon and the like.
The photocatalyst is a photo-semiconductor material having a photocatalytic function, typified by nano-scale titanium dioxide. Under the irradiation of light (especially ultraviolet light), a photocatalytic reaction similar to photosynthesis is generated, free hydroxyl and active oxygen with strong oxidizing ability are generated, the photocatalytic reaction has strong photooxidation-reduction function, various organic compounds and partial inorganic matters can be oxidized and decomposed, and cell membranes of bacteria and proteins of solidified viruses can be damaged. However, the photocatalyst has a certain limitation in application because of the need of a matched ultraviolet light source device and the defects of low catalytic efficiency, unstable long-term purification effect and the like in practical application.
The silver-loaded activated carbon has the effect of inactivating bacteria mainly by compositing an activated carbon material with excellent adsorption performance with silver particles with a sterilizing effect. But the silver loaded by the silver-loaded activated carbon is combined with the activated carbon mainly through physical adsorption, so that the active components are easy to lose, and the service life is short; silver is unevenly distributed and particle size, so that the sterilization performance is unstable, and most of the silver can only play a role in bacteriostasis. Another major drawback of silver-loaded activated carbon is the difficulty in firmly loading onto carriers for honeycomb and mesh filters for air purification systems.
Although the traditional inorganic antibacterial agent has better antibacterial effect, the antiviral effect is not clear. This is because inorganic antibacterial agents are mainly composed of metal compounds, and silver, copper, and the like, which are effective components of the metal compounds, 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 necessarily link between the antibacterial and antiviral effects of the metal-based compounds. Bacteria are organisms composed of cell walls, cell membranes, cytoplasm, and nuclei, and are capable of metabolism; the virus is a small, simple, non-cellular organism which contains only one nucleic acid (DNA or RNA) and must be parasitic and replicated in living cells, and is composed of a long chain of nucleic acids and a protein shell, without its own metabolic mechanism and enzyme system, which is not defined by the organism. If the mechanism of action of the antimicrobial metal is to inhibit the metabolism of the bacteria, the inactivation effect is not ideal for non-metabolizing viruses.
In conclusion, the development of an inorganic antiviral material with better inactivation performance on highly infectious disease viruses such as novel coronaviruses (COVID-19) is a key technology for effectively inactivating viruses in air.
At present, inorganic antiviral materials with better inactivation effect on high-infectious disease viruses such as novel coronaviruses (COVID-19) and the like and related patents have not been reported and disclosed.
Disclosure of Invention
The invention aims to provide a hierarchical pore catalytic material with a core-shell structure, which has a better adsorption and inactivation function on viruses including coronaviruses, and can be applied to the manufacturing fields of protective materials, equipment and the like, so that the transmission 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 multistage pore catalytic material with a core-shell structure for adsorbing inactivated 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 a porous oxygen storage material SiO 2 -CeO 2 The composition or composition material comprises oxygen storage material SiO with holes 2 -CeO 2 ，SiO 2 With CeO 2 The mass ratio of (3) is 1:1-100:1, preferably 2:1-10:1, more preferably 3:1, a step of; wherein the pores in the shell comprise macropores and mesopores, wherein the macropore pore diameter in the shell is distributed in the range of 50-500nm, the average pore diameter of the macropores is 60-300nm, the macropore pore volume is 0.3-1.0ml/g, preferably 0.35-0.7ml/g, the mesopore pore diameter is distributed in the range of 2-less than 50nm, the average pore diameter of the mesopores is 5-40nm, the mesopore volume is 0.05-0.3ml/g, preferably 0.1-0.25ml/g, and the thickness of the shell is 60-500nm;
the core is a multi-level 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, preferably 0.1-0.2ml/g and 0.3-0.35ml/g, and the particle size is 100nm-10 mu m, preferably 300nm-1 mu m. The hierarchical pore molecular sieve is one or more of ZSM-5, A type, X type and Y type. The molecular sieve is allowed to be subjected to structural and surface modification, and 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, Y. The mass of the modifying element accounts for 0.01-20% of the mass of the catalytic material core, and is preferably 0.05-10%.
The oxygen storage material of the shell also contains p-SiO 2 -CeO 2 Modified modifier, the modifier is ZrO 2 、La 2 O 3 、Pr 2 O 3 、Nd 2 O 3 、Y 2 O 3 One or two or more of them. The addition amount of the modifier is 0.01-2% of the mass of the shell layer, preferably 0.05-1%.
The core-shell structured hierarchical pore catalytic material can be used for adsorbing and inactivating viruses including coronaviruses, and further can be used in the manufacturing fields of protective materials or equipment and the like through loading and forming of structured carriers such as honeycomb ceramics, metal meshes, non-woven fabrics and the like. Can also be used as a material for adsorbing and inactivating viruses in the field of air purification and water purification. The preparation method of the core-shell structured hierarchical pore catalytic material comprises the following steps:
1. preparation of the core
A. Mixing molecular sieve with NaOH solution of 0.1-0.5mol/L according to the volume ratio of 1:5-1:30, heating and stirring at 50-80 ℃, filtering the mixed solution, washing solid with deionized water to neutrality, drying at 100-150 ℃ and roasting at 400-550 ℃ for more than 1 hour in sequence to obtain the multistage pore molecular sieve, namely the core of the catalytic material.
Or B, mixing the hierarchical porous molecular sieve with an aqueous solution containing 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. Nano CeO 2 Hydroxypropyl methylcellulose, triblock copolymer P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide, EO 20 PO 70 EO 20 ) Adding the mixture into silica sol, homogenizing, soaking the nuclear material obtained in the step 1 by using the liquid, and obtaining the nuclear shell structured hierarchical pore catalytic material of the invention after centrifugal separation, drying and roasting at 450-550 ℃ for more than 1 hour.
Or B, with a nitrate solution of a modifier (e.g. Zr (NO) 3 ) 4 ·5H 2 Aqueous O) impregnated with CeO 2 Drying, roasting at 400-550 deg.c for over 1 hr to obtain product to replace nano CeO in the step 2A 2 And (3) preparing a shell layer, and finally obtaining the shell layer modified catalytic material.
The principle of the invention is as follows: the shell with a macroporous structure can effectively adsorb microorganism aerosol (0.1-20 mu m) related to diseases in the air at room temperature, further coronavirus particles (0.08-0.2 mu m) in the aerosol are adsorbed into mesoporous channels of a multistage pore molecular sieve core, a shell layer oxygen storage material activates and migrates oxygen in the air into the core, and simultaneously a modification element loaded on the core dissociates oxygen in the air to form oxygen anions with stronger oxidizing ability, and under the synergistic effect of the shell layer activated oxygen and oxygen anions in the core and adsorption active sites of the molecular sieve in the core, the hydrolysis and the oxidation of organisms (protein shells and nucleic acids of viruses) are catalyzed, so that the viruses are inactivated. In addition, the shell not only has the functions of adsorbing and activating oxygen, but also can prevent loss of the modification components 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 modification components loaded on the core. Such activated oxygen oxidizes viral proteins or nucleic acids (DNA or RNA), destroying their structure, resulting in their inactivation;
2. the core of the catalytic material has a hierarchical pore structure, is suitable for the passage of virus particles, is beneficial to the full contact of the virus particles with adsorption active sites on the core, and can provide more bulk adsorption active sites and negative oxygen ions. The increased adsorption sites allow the-SH groups in the surface proteins of viruses, DNA polymerase (DNA viruses), RNA polymerase or reverse transcriptase (RNA viruses) to bind more readily to the molecular sieve backbone cations, thereby altering the structure of the proteins and enzymes and losing biological activity. On the other hand, the molecular sieve can activate oxygen in water and air under the promotion of the modification element to generate more active oxygen anions (O) 2 - ) And hydroxyl radical (. OH), active oxygen ions have a strong oxidizing ability, and oxidize and destroy proteins or nucleic acids (DNA or RNA) in a short time to inactivate viruses.
3. The unique core-shell structured hierarchical pore catalytic material 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 through the synergistic effect of active oxygen formed by a shell layer, rich adsorption active sites of mesoporous cores and negative oxygen ions, the catalytic efficiency of the material is higher, the inactivation effect is better, and the adsorption and inactivation rate of the material to novel coronaviruses (COVID-19) can reach 100%. The inactivated virus catalytic material with the special structure not only solves the technical problems of poor virus inactivating effect, unstable performance and short service life of the existing material, but also reduces the content of metal elements in the material and reduces the cost of the catalytic material. Compared with silver-carrying active carbon, silver-carrying titanium oxide and other silver-carrying materials with simple structures, the material has the advantages that the unique pore size distribution of the multi-level pore structure is wider, the porous and mesoporous pores in the shell layer are more, the mesoporous and microporous pores are also nuclear, the virus nucleic acid molecules are facilitated to diffuse and adsorb in the molecular sieve core, the contact with active sites is more sufficient, and the adsorption and inactivation of the virus active sites and the oxygen activation sites are more, so that the virus inactivation performance of the material can be greatly improved, and the material has more excellent performance than the traditional silver-carrying bactericidal material.
4. Compared with photocatalyst, the adsorption and inactivation method does not depend on other light sources and other equipment, has wider application range and simpler assembly integration process;
5. the raw materials are easy to obtain, the cost is low, the synthetic route is mature, and the industrialization is easy to realize.
Drawings
The structure of the catalytic material in FIG. 1 is schematically shown, wherein 1 is a micropore on a catalyst core, 2 is a mesopore on the catalyst core, 3 is a macropore on a catalyst shell, 4 is an active site on the catalyst core for adsorbing virus nucleic acid or protein, 5 is a catalyst core, 6 is a catalyst shell, and 7 is an oxygen activation site.
Detailed Description
The invention is further illustrated by the following examples.
1. The preparation of the catalytic material comprises the following steps:
1. preparation of the core
NH is added to 4 ZSM-5 molecular Sieve (SiO) 2 /Al 2 O 3 =25, specific surface area 550m 2 Per gram, the grain diameter is 2.3 mu m, the average pore diameter is 0.54 nm) and 0.35mol/L NaOH solution are mixed according to the volume ratio of 1:30, the mixture is heated and stirred for 2 hours in a water bath at 75 ℃, the mixture is filtered, the solid is washed to be neutral, and the multistage pore molecular sieve is obtained after drying at 120 ℃ for 6 hours and roasting at 500 ℃ for 2 hours, namely the core of the catalytic material. The average mesoporous pore diameter was measured by a full-automatic physical adsorption instrument (ASAP 2460, micromeritics Co., USA) capable of measuring the distribution of mesopores and micropores, the average mesoporous pore diameter was 24.3nm, the pore distribution was 2.0-49.9nm, the average microporous pore diameter was 0.55nm, the pore distribution was 0.3-1.99nm, the mesoporous volume was 0.18ml/g, and the microporous volume was 0.32ml/g. The average particle diameter was measured with a nanolaser particle sizer (Malvern, UK, ZETASIZER Nano ZS) and found to be 2.1 μm with a particle size distribution of 0.07-10.0. Mu.m.
By type A (SiO 2 /Al 2 O 3 =2, specific surface area 750m 2 /g, particle size 3.6 μm, average pore diameter 0.48 nm), type X (SiO 2 /Al 2 O 3 =2.8, specific surface area 650m 2 /g, particle size 6.2 μm, average pore diameter 1.04 nm), Y-type (SiO 2 /Al 2 O 3 =5, specific surface area 886m 2 Per g, particle size 8.5 μm, average pore size 1.25 nm) molecular sieve instead of NH 4 ZSM-5 moleculesAnd (3) screening, and repeating the operation of the step (1) to obtain the corresponding hierarchical pore molecular sieve core.
The average mesoporous pore diameter of the A-type multistage porous molecular sieve core is measured to be 33.2nm, the pore distribution is 2.9-42.3nm, the average microporous pore diameter is 0.48nm, the pore distribution is 0.47-0.50nm, the mesoporous volume is 0.16ml/g, the microporous 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 multi-stage porous molecular sieve nuclear material has the average mesoporous pore diameter of 27.1nm, the pore distribution of 4.2-40.2nm, the average microporous pore diameter of 1.04nm, the pore distribution of 1.02-1.06nm, the mesoporous volume of 0.13ml/g, the microporous volume of 0.33ml/g, the average particle diameter of 6.1 mu m and the particle size distribution of 0.07-10.0 mu m.
The average mesoporous pore diameter of the Y-type multi-level porous molecular sieve nuclear material is measured to be 38.1nm, the pore distribution is 4.5-42.3nm, the average microporous pore diameter is 1.22nm, the pore distribution is 1.20-1.26nm, the mesoporous volume is 0.23ml/g, and the microporous volume is 0.39ml/g. The average particle diameter is 8.4 μm, and the particle size distribution is 0.0,6-10.0 μm.
Alternatively, further, 7.8g Zn (NO 3 ) 2 ·6H 2 And (3) dissolving O in 300ml of deionized water, weighing 100g of the hierarchical pore molecular sieve obtained in the step (1), stirring at room temperature overnight, filtering, washing, drying and roasting at 500 ℃ for 2 hours to obtain the nuclear material containing the modified element Zn. The method for preparing the core material containing Ag and other modification elements is the same as the method except that Zn (NO 3 ) 2 ·6H 2 O is replaced by nitrate of other modifying elements such as Ag.
2. Preparation of the shell
Nanometer CeO 2 Preparing a shell layer: 1.3g of nano CeO 2 (specific surface area 234 m) 2 Per gram, average particle size 23.5 nm), 0.057g hydroxypropyl methylcellulose, 0.067g 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 10.1 nm), homogenizing at high speed, soaking 30.7g of Zn-ZSM-5 porous molecular sieve core material obtained in step 1 with the liquid, centrifuging, drying, and calcining at 550deg.C for 2 hr to obtain SiO-containing material 2 -CeO 2 Shell-coated Zn-ZSM-5 hierarchical pore catalystChemical material Zn-ZSM-5@SiO 2 -CeO 2 。
Measuring the average macropore pore diameter of the shell layer to 87nm by using a full-automatic mercury porosimeter (Micromeritics company, autoPore V) capable of measuring macropore pore diameter and macropore pore volume, wherein the macropore pore volume is 0.52ml/g, and the macropore pore diameter distribution is 50-201nm; measuring the average mesoporous aperture of 27nm with a full-automatic physical adsorption instrument (ASAP 2460, micromeritics Co., USA) capable of measuring mesoporous aperture and mesoporous volume, wherein the mesoporous volume is 0.19ml/g, and the mesoporous aperture distribution is 4-40nm; the shell thickness distribution was determined by resin embedding and cutting and then by transmission electron microscopy (JMS-800D, japanese electronics Co.) to be 85-204nm, and the average shell thickness was 156nm.
Alternatively, the modifier is dissolved in a nitrate solution (e.g., zr (NO) 3 ) 4 ·5H 2 Nitrate of O aqueous solution and/or other shell modifier, wherein the modifier is ZrO 2 、La 2 O 3 、Pr 2 O 3 、Nd 2 O 3 、Y 2 O 3 One or two or more) of which is impregnated with CeO 2 Drying and roasting at 500 ℃ for 2 hours to obtain modified nano CeO 2 Material, replacing nano CeO in the step 2 by the modified material 2 And (3) preparing a shell layer, and finally obtaining the shell layer modified catalytic material.
The composition and the corresponding parameters of the specific catalytic materials obtained according to the preparation method are shown in the following table. (the numerical meanings in brackets in the following tables are SiO 2 With CeO 2 The mass ratio of the modified element is the mass of the core of the catalytic material, the addition of the modifier is 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
2. Adsorption inactivation test for viruses
1. Virus preparation:
preparing TCIDs respectively 50 Is a virus liquid of (COVID-19) (4.37X10) 8 copies/ml) and TCID 50 Is (pLenti) virus solution (7×10) 9 cobies/ml) was used for adsorption inactivation tests of powder catalytic materials for novel coronaviruses and lentiviruses;
2.3 powder catalytic materials were prepared, each having a number of AX-1 to AX-3, and two sample amounts of 200mg and 50mg, respectively, and control glass microspheres (particle size 10 μm, total 2 parts) having the same mass as the catalytic materials were weighed, placed in sterile 1.5mL EP tubes, and 0.8mL of TCID was added dropwise 50 The mixed powder catalytic material and the virus liquid mixture are stirred and mixed once every 5 minutes in the period of 30 minutes at room temperature, so that the sufficient effect of the material and the virus is ensured. A blank (containing only 0.8mL TCID was prepared 50 3 parts of the COVID-19 virus liquid of (A) were placed in sterile 1.5ml EP tubes, respectively, and left at room temperature for 30 minutes at 5 minutes intervals, with stirring.
3. After 30 minutes of action, 250ul of supernatant was pipetted into a new sterile EP tube (ensuring that the supernatant was pipetted into each tube an equal amount) by centrifugation at 3000rpm for 5 minutes
4. RNA was extracted from 250ul of supernatant based on the nucleic acid isolation method. The specific method comprises the following steps: 750ul TRIzol was added to the 250ul sample after treatment, and the mixture was repeatedly blown with a gun to lyse the virus. After standing at room temperature for 5 minutes, 200ul of chloroform was added to the EP tube, the EP tube was capped and left 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 water phase into a new EP pipe, adding 500ul of isopropanol, standing at room temperature (15-30 ℃) for 10 minutes, and centrifuging at 12000rpm (2-8 ℃) for 10 minutes; carefully discarding the supernatant, adding 1ml of 75% ethanol with volume concentration along the pipe wall for washing, mixing by short (2-5S) vortex, centrifuging at 7500rpm (2-8 ℃) for 5 minutes, and discarding the supernatant; allowing the precipitated RNA to naturally dry at room temperature; RNA pellet was dissolved in RNase-free water.
5. Quantitative PCR (qRT-PCR) experiments (operating according to the AM1728 kit specific methods and procedures) were performed using the extracted RNA and Invitrogen-Taqman kit (AM 1728). The RNA extracted from each tube was repeated 3 times, and the number of viruses in the supernatant was obtained by taking an average.
9 powder catalytic materials are prepared, the serial numbers are AX-1 to AX-9, 200mg of each material is weighed, tool lentivirus (pLenti) virus liquid is used for replacing the COVID-19 virus liquid, and the steps 2 to 5 are repeated to obtain the number of viruses in the supernatant.
6. Investigation of different catalytic materials for reducing viral conditions in the supernatant
Assuming that the virus content in the supernatant of the non-treated group is 100%, if the virus content in the supernatant of the treated group is 0, the virus content of the treated group is considered to be reduced by 100% compared with that of the non-treated group, and the corresponding adsorption inactivation rate is 100%.
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 the glass microsphere control group and the blank control group is not detected.
Virus adsorption inactivation rate (%) = {1- (number of viruses in supernatant of blank control-number of viruses in supernatant of test material)/number of viruses in supernatant of blank control } ×100%
Examples 17 to 31
Comparative example 1
Silver-loaded activated carbon (Ag content 2.67wt.% and specific surface area 1235 m) was used 2 /g，Average particle diameter 57.2m, average pore diameter 1.3nm, pore volume 0.88 ml/g) and the procedure was the same as in examples 22-30, showing a 50% reduction in virus content in the remaining supernatant relative to the untreated fraction.
Comparative example 2
Silver-loaded zeolite (Ag content 3.25wt.%, specific surface area 325 m) was used 2 The adsorption and inactivation tests of the above lentivirus were carried out per gram, with an average particle size of 5.3 μm, an average pore size of 0.66nm and a pore volume of 0.27ml/g, and the procedure was the same as in comparative example 1, showing a 65% reduction in virus content in the remaining supernatant relative to the untreated group.
Comparative example 3
Purchase of commercial SiO 2 (specific surface area 436m 2 /g, pore size 6.9nm, particle size 430 nm), ceO 2 (specific surface area 57.2m 2 Per g, average pore size 23.4nm, particle size 1.7 μm) for the above lentiviruses, the procedure was the same as in comparative example 1, and the results showed a 9% and 13% reduction in virus content in the remaining supernatant, respectively, compared to the untreated group.
Comparative example 4
Commercial mordenite (specific surface area 325 m) 2 Each gram of the obtained extract had an average particle diameter of 6.2 μm, an average pore diameter of 0.67nm and a pore volume of 0.27ml/g, and the lentivirus was adsorbed and inactivated by the same procedure as in comparative example 1, and the result showed that the virus content in the remaining supernatant was reduced by 23% relative to that in the untreated group.
Comparative example 5
Pt-loaded 5A molecular sieve (Pt content 1.93wt.%, specific surface 536 m) was used 2 Each gram of the obtained extract was subjected to adsorption and inactivation tests of lentivirus, wherein the average pore diameter was 0.5nm, the average particle diameter was 2.7 μm and the pore volume was 0.38ml/g, and the method steps were the same as those of comparative example 1, and the result showed that the virus content in the remaining supernatant was reduced by 59% relative to that in the untreated group.
Comparative example 6
The multistage ZSM-5 molecular sieve core (average mesoporous pore diameter 24.3nm, pore distribution is 3.2-48.7nm, average microporous pore diameter 0.55nm, pore distribution is 0.51-0.58nm, mesoporous pore volume is 0.18ml/g, microporous pore volume is 0.32 ml/g) prepared in the step 1 is adopted for carrying out slow virus adsorption and inactivation test, the method steps are the same as those of the comparative example 1, and the result shows that the virus content in the residual supernatant is reduced by 70% compared with that in the untreated group.
Comparative example 7
The shell layer material CeO prepared by the step 2 is adopted 2 -SiO 2 (average macropore pore diameter is 87nm, macropore pore volume is 0.52ml/g, macropore pore diameter distribution is 50-201nm, average mesopore pore diameter is 27nm, mesopore pore volume is 0.19ml/g, mesopore pore diameter distribution is 4-40 nm) for adsorbing and inactivating slow virus, and the method steps are the same as comparative example 2, and the result shows that the virus content in the residual supernatant is reduced by 45% compared with the untreated group.
Comparative example 8
The shell layer material CeO prepared by the step 2 is adopted 2 -SiO 2 (average macropore pore diameter is 87nm, macropore pore volume is 0.52ml/g, macropore pore diameter distribution is 50-201nm; average mesopore pore diameter is 27nm, mesopore pore volume is 0.19ml/g, mesopore pore diameter distribution is 4-40 nm) coated mordenite (specific surface area 325 m) 2 Per gram, average particle size 6.2 μm, average pore size 0.67nm, pore volume 0.27 ml/g) and the procedure was the same as that of comparative example 2, and the result showed a 37% reduction in virus content in the remaining supernatant compared to the untreated group.
Comparative example 9
The shell layer material CeO prepared by the step 2 is adopted 2 -SiO 2 (average macropore pore diameter is 87nm, macropore pore volume is 0.52ml/g, macropore pore diameter distribution is 50-201nm, average mesopore pore diameter is 27nm, mesopore pore volume is 0.19ml/g, mesopore pore diameter distribution is 4-40 nm) coated silver-loaded silk optical zeolite (Ag content 3.25wt.%, specific surface area 325 m) 2 Per gram, average particle size 5.3 μm, average pore size 0.66nm, pore volume 0.27 ml/g) and the procedure was the same as that of comparative example 2, and the result showed a 41% 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 /g, pore size 6.9nm, particle size 430 nm), ceO 2 (specific surface area 57.2m 2 Per gram, the average pore diameter is 23.4nm, the grain diameter is 1.7 mu m) Bao Fushang the silver-loaded multistage-pore ZSM-5 molecular sieve core (Ag content) prepared in the step 11.52wt.%, average mesoporous pore diameter 24.3nm, pore distribution of 3.2-48.7nm, average microporous pore diameter 0.55nm, pore distribution of 0.51-0.58nm, mesoporous pore volume of 0.18ml/g, microporous pore volume of 0.32 ml/g) and the method steps are the same as those of comparative example 2, and the result shows that the virus content in the residual supernatant is reduced by 53% compared with the untreated group.
Claims (9)
1. The application of a hierarchical pore catalytic material with a core-shell structure in adsorbing and inactivating 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 a porous oxygen storage material SiO 2 -CeO 2 The composition or composition material comprises oxygen storage material SiO with holes 2 -CeO 2 ，SiO 2 With CeO 2 The mass ratio of (2) is 1:1-100:1; wherein the pores in the shell comprise macropores and mesopores, wherein the macropore pore diameter in the shell is distributed in the range of 50-500nm, the average pore diameter of the macropores is 60-300nm, the pore volume of the macropores is 0.3-1.0mL/g, the pore diameter of the mesopores is distributed in the range of 2-less than 50nm, the average pore diameter of the mesopores is 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 multi-level 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 synthesis process of the hierarchical pore molecular sieve comprises the following steps: mixing 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 solid with deionized water to neutrality, drying at 100-150 ℃ and roasting at 400-550 ℃ for more than 1 hour to obtain the multi-stage pore molecular sieve,
adopting a modifying element to modify the structure and the surface of the molecular sieve, wherein the modifying element is one or more than two of Pt, au, ag, ba, cu, co, ti, zn, la; the mass of the modifying element accounts for 0.01-20% of the mass of the catalytic material core;
the oxygen storage material of the shell also contains p-SiO 2 -CeO 2 Modified modifier, the 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 modifying agents are added in an amount of 0.01-2% of the mass of the shell layer.
2. The use according to claim 1, wherein: the oxygen storage material SiO 2 -CeO 2 SiO of (B) 2 With CeO 2 The mass ratio of the catalyst is 2:1-10:1, the average pore diameter of macropores in the shell is 70-200nm, the pore volume of macropores is 0.35-0.7mL/g, the average pore diameter of mesopores is 10-30nm, the pore volume of mesopores is 0.1-0.25mL/g, and the thickness of the shell is 80-300 nm;
the core is a multi-level pore molecular sieve, the pore size distribution comprises mesopores and micropores, the average pore diameter of the micropores is 0.6-1.6nm, the average pore diameter of the mesopores is 7-30nm, the pore volume of the mesopores and the micropores is 0.1-0.2mL/g and 0.3-0.35mL/g, and the particle size is 300nm-1 mu m.
3. The use according to claim 1, wherein: the addition amount of the modifier is 0.05-1% of the mass of the shell layer.
4. The use according to claim 1, wherein: the molecular sieve is one or more than two of ZSM-5, A type, X type and Y type.
5. The use according to claim 1, wherein: the mass of the modifying element accounts for 0.05-10% of the mass of the catalytic material core.
6. The use according to claim 1, wherein: the catalytic material is used for adsorbing and/or inactivating novel coronavirus COVID-19.
7. Use according to claim 1, wherein the catalytic material is used for air purification and/or water purification as a material for adsorbing and/or inactivating viruses.
8. The use according to any one of claims 1, 6 or 7, wherein the catalytic material is first supported on one of a porous ceramic, a mesh and a non-woven structured carrier, and the catalytic material is then applied.
9. The use according to any one of claims 1 or 6 or 7, wherein the catalytic material is applied at atmospheric pressure, -10-50 ℃ temperature, 0-100% air relative humidity.
Priority Applications (1)
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