CN115007145B - Preparation method and application of Ag-loaded layered double hydroxide - Google Patents
Preparation method and application of Ag-loaded layered double hydroxide Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 8
- 239000011550 stock solution Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000047 product Substances 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 4
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 37
- 241000700605 Viruses Species 0.000 description 21
- 230000005540 biological transmission Effects 0.000 description 10
- 230000000840 anti-viral effect Effects 0.000 description 9
- 239000011701 zinc Substances 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 7
- 230000002147 killing effect Effects 0.000 description 6
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 5
- 239000000645 desinfectant Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 208000015181 infectious disease Diseases 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 241001678559 COVID-19 virus Species 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010166 immunofluorescence Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000009385 viral infection Effects 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- 208000025721 COVID-19 Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 108091006197 SARS-CoV-2 Nucleocapsid Protein Proteins 0.000 description 1
- 208000037847 SARS-CoV-2-infection Diseases 0.000 description 1
- 201000003176 Severe Acute Respiratory Syndrome Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 238000002651 drug therapy Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000007918 pathogenicity Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229960005486 vaccine Drugs 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- 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
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/08—Radiation
- A61L2/088—Radiation using a photocatalyst or photosensitiser
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
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Abstract
The invention relates to a preparation method of double metal hydroxide, in particular to a preparation method and application of Ag-loaded layered double metal hydroxide, comprising the following steps: s1: dissolving zinc nitrate hexahydrate, aluminum nitrate nonahydrate and silver nitrate in deionized water to obtain a mixed solution; s2: dropwise adding the mixed solution obtained in the step S1 into a formamide solution, and then stirring at a low temperature under an inert gas atmosphere to obtain a reaction stock solution; s3: and (2) dropwise adding a sodium hydroxide solution into the reaction stock solution obtained in the step (S2) to control the pH value and react, and centrifuging and washing a reaction product to obtain the Ag-supported layered double hydroxide. Compared with the prior art, the synthesis method provided by the invention is simple, simple and convenient to operate, mild in condition, high in purity of target products, safe and nontoxic, and capable of synthesizing in a large scale at low cost.
Description
Technical Field
The invention relates to a preparation method of double metal hydroxide, in particular to a preparation method and application of Ag-loaded layered double metal hydroxide.
Background
The severe acute respiratory syndrome, coronavirus-2 (SARS-CoV-2), is still an urgent threat to public health worldwide by high pathogenicity. New virus variants continue to appear, and the key to preventing transmission is to prevent transmission of the virus in the population and to destroy the virus in the environment. Current vaccine and drug therapies still cannot completely suppress the spread of infection; the virus cannot be killed by wearing non-drug intervention measures such as mask and keeping social distance; physical disinfection methods often require special equipment and energy sources; toxic gases may be generated during the application of chemical disinfectants, which can also harm the human body, corrode metals or destroy the environment.
The current situation of virus epidemic is urgent to develop a green sterilizing material which is safe, energy-saving and capable of safely and effectively sterilizing viruses and reducing virus transmission. Unlike traditional chemical disinfectants, inorganic nano disinfectant has good safety, stability and sustainability, does not produce secondary pollution, and has wide application prospect.
Layered double hydroxides (layered double hydroxide, LDHs), also known as hydrotalcite-like materials, are a class of earth-abundant two-dimensional layered compounds, typically formed by overlapping positively charged brucite-like layers with anions and water molecules occupying the space between the layers. In recent years, LDH has attracted attention in the fields of catalysis, energy, biology and the like because of advantages such as easy modulation of its composition (types and ratios of metal ions on the laminate, types of anions and the like), easy regulation of its structure (number of layers, interlayer spacing and the like), easy realization of functionalization by being composited with other materials and the like.
Besides inorganic nano materials, the metal disinfectant containing Ag, cu, zn and other metals and ions thereof also has good antiviral performance. Among them, ag-containing disinfectants have the advantages of high efficiency, broad spectrum, high safety, difficult generation of drug resistance and the like, and have the most extensive research. The Ag-loaded layered double hydroxide exhibits a stronger killing effect against viruses than the pure-phase layered double hydroxide. Therefore, the preparation of the multifunctional nano material compounded by the layered double hydroxide and Ag is expected to show potential application value in antiviral property. The currently developed nano Ag composite LDH sterilization and antiviral materials are mainly concentrated on simple load of nano Ag on a plurality of layers of LDH, and the preparation process is complex and the product quality is poor.
Disclosure of Invention
The invention aims to solve at least one of the problems and provide a preparation method and application of Ag-supported layered double hydroxide, wherein the preparation method is simple and has low cost; the prepared nano material has excellent virus killing effect; and in the synthesis process, complex instruments are not needed, the operation is simple, and the large-scale production is facilitated.
The aim of the invention is achieved by the following technical scheme:
the first aspect of the invention discloses a preparation method of Ag-supported layered double hydroxide, which comprises the following steps:
S1: dissolving zinc nitrate hexahydrate, aluminum nitrate nonahydrate and silver nitrate in deionized water to obtain a mixed solution;
s2: dropwise adding the mixed solution obtained in the step S1 into a formamide solution, and then stirring at a low temperature under an inert gas atmosphere to obtain a reaction stock solution;
s3: and (2) dropwise adding a sodium hydroxide solution into the reaction stock solution obtained in the step (S2) to control the pH value and react, and centrifuging and washing a reaction product to obtain the Ag-supported layered double hydroxide.
Preferably, the mass ratio of zinc nitrate hexahydrate, aluminum nitrate nonahydrate and silver nitrate in the step S1 is 100-500:50-500:1-50. Because Zn and Al elements have strong photocatalytic performance, the Zn and Al elements are basically harmless to human bodies and have abundant reserves, so the Zn and Al elements are often used as reaction elements in the biomedical field. The mass ratio range proposed here firstly ensures the formation of a layered double hydroxide structure and secondly the mass of Ag is greater which results in: 1. the cost becomes high, 2, precipitation of Ag oxide is generated instead of being supported on LDH; thus, the amount of Ag used needs to be controlled.
Preferably, the dosage ratio of the formamide solution to the zinc nitrate hexahydrate in the step S2 is 10 to 100mL:100-500mg.
Preferably, the formamide solution has a volume fraction of 15 to 33%.
Preferably, the temperature of the low-temperature stirring in the step S2 is-5-5 ℃ for 10-30min. The reaction rate can be reduced due to the low temperature and the existence of inert gas, so that stacking image caused by rapid synthesis of LDH is avoided, and the synthesis of ultrathin LDH is possible; further, in addition to providing more loading sites for Ag, it is possible to shorten the carrier transport distance and expose rich antiviral reaction site sites. In addition, the inert gas can also effectively avoid intercalation of carbonate radical (the interlayer binding force of carbonate radical is relatively strong) in the coprecipitation process, thereby preparing the ultrathin structure.
Preferably, the inert gas in step S2 is nitrogen.
Preferably, the concentration of the sodium hydroxide solution in step S3 is 0.5-4M and the pH is 9-12.
Preferably, the reaction in step S3 is carried out at a temperature of-5 to 5℃for a period of 10 to 40 minutes under nitrogen.
Preferably, the rotational speed of the centrifugation described in step S3 is 6000-8000r/min.
Preferably, the washing in step S3 is three times each using deionized water and absolute ethanol.
The LDH carrier with a quasi-single-layer ultrathin structure has a short migration path, and the recombination rate of photo-generated hole electron pairs can be reduced; meanwhile, the high specific surface area of the silver-activated carbon can be fully combined with Ag, so that abundant antiviral reaction sites are provided, and the antiviral performance can be obviously improved.
The invention discloses an application of the preparation method of the Ag-supported layered double hydroxide in the antiviral field.
The excellent performance of the Ag-loaded layered double hydroxide prepared by the invention is probably due to the following characteristics: under irradiation of light, electrons can be excited from the valence band to the conduction band of LDH. In general, these carriers are very complex and only a small fraction of the electrons can participate in the photocatalytic reaction. When silver nanoparticles are supported on LDH nanoplatelets, schottky barriers are formed. Because the fermi level of Ag is lower than the conduction band of LDH, photo-generated electrons may be transferred from LDH to deposited silver nanoparticles, thereby promoting carrier separation, inhibiting recombination, and extending carrier lifetime, accelerating interfacial charge transport; on the other hand, due to the surface plasmon resonance effect of the Ag nano-particles, the ZnAl-LDH loaded with Ag can be more easily excited by light under visible light, so that surface electron excitation and interface electron transfer are enhanced. The transferred electrons can be captured by the adsorbed O 2 to form O 2-,·O2- which can further react with H + or H 2 O to generate OH, and active free radicals such as OH, O 2- and the like generated under the excitation of ultraviolet or visible light can act with viruses to destroy internal tissues and influence the growth and metabolism of cells, so that the purpose of resisting viruses is achieved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The layered double hydroxide loaded with Ag is prepared by adopting a low-temperature formamide coprecipitation method in one step. The obtained layered double hydroxide has a nano lamellar structure, wherein Ag particles are uniformly distributed on the layered double hydroxide. The synthesis method is simple, the operation is simple and convenient, the condition is mild, the purity of the target product is high, the synthesis method is safe and nontoxic, and the synthesis method can be used for synthesizing the target product in a large scale at low cost.
(2) The Ag-loaded layered double hydroxide material is used for killing viruses, and the result shows that the Ag-loaded layered double hydroxide material has excellent virus killing effect. In the application of virus inactivation, the ZnAl-LDH-Ag treatment group can obviously inhibit infection of the SARS-CoV-2 virus on Vero-E6 cells under the conditions of natural illumination and ultraviolet.
(3) In the preparation process, all reagents are commercial products and no further treatment is needed.
(4) The synthesis method is simple, and the obtained material is easy to apply.
Drawings
FIG. 1 is a physical diagram of layered double hydroxide and Ag-supported layered double hydroxide materials prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of layered double hydroxide and Ag-supported layered double hydroxide materials prepared in example 1;
FIG. 3 is an X-ray photoelectron spectrum of layered double hydroxide and Ag-supported layered double hydroxide materials prepared in example 1; wherein (a) is the X-ray photoelectron spectrum of Zn; (b) X-ray photoelectron spectroscopy of Al; (c) X-ray photoelectron spectroscopy of Ag;
FIG. 4 is a transmission electron microscope image of the Ag-supported layered double hydroxide material prepared in example 1; wherein (a) is a transmission electron microscope image of the Ag-loaded layered double hydroxide material; (b) A high-resolution transmission electron microscope image of the Ag-loaded layered double hydroxide material; (c) A transmission electron microscope image for reflecting the distribution state of Zn on the surface of the Ag-loaded layered double hydroxide material; (d) A transmission electron microscope image of the distribution state of reaction Al on the surface of the Ag-loaded layered double hydroxide material; (e) A transmission electron microscope image of the distribution state of the reaction O on the surface of the Ag-loaded layered double hydroxide material; (f) A transmission electron microscope image of the distribution state of the reaction Ag on the surface of the Ag-loaded layered double hydroxide material;
FIG. 5 is an ultraviolet-visible absorption spectrum of the layered double hydroxide and Ag-supported layered double hydroxide material prepared in example 1.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The commercially available products, which are conventionally available, can be used by those skilled in the art unless the experimental reagents are specifically described in the following examples.
Example 1
1. Preparation of Ag-supported layered double hydroxide material (ZnAl-LDH-Ag)
223Mg of zinc nitrate hexahydrate and 94mg of aluminum nitrate nonahydrate and 2mg of silver nitrate were dissolved in 20mL of deionized water. The above mixed solution was then dropped into a three-necked flask containing 20mL of a 23% by volume formamide solution. Then the three-neck flask is transferred into a low-temperature reaction tank, the temperature is controlled to be 0 ℃, and nitrogen is introduced into the three-neck flask to be stirred for 10 minutes. Finally, the prepared 2.5M sodium hydroxide solution was slowly dropped into the three-necked flask to maintain the pH at 10. The reaction was completed within 15 minutes while maintaining a low temperature nitrogen atmosphere. The product was collected by centrifugation, repeatedly washed with deionized water and absolute ethanol, and then kept in a wet state for use.
2. Test of Severe acute respiratory syndrome-coronavirus-2 (SARS-CoV-2) inactivating Property
Virus inactivation: the ZnAl-LDH and ZnAl-LDH-Ag powder is dissolved by using a DMEM culture medium, and 1mg/ml of storage solution is prepared. In the experiment, znAl-LDH and ZnAl-LDH-Ag stock solutions are diluted into working solutions with final concentrations of 50 mug/mL, 10 mug/mL, 2 mug/mL, 0.4 mug/mL, 0.08 mug/mL and 0.016 mug/mL respectively by using a DMEM culture medium. SARS-CoV-2 (10 5 PFU) was incubated with varying concentrations of compound for 0.5 hours at room temperature. Each compound was divided into three groups, one group incubated under light-protected conditions, one group incubated under natural light, and one group incubated under uv light. The mixture was then added to Vero-E6 cells. After 24 hours, the infection rate of each group of SARS-CoV-2 was measured by immunofluorescence.
The method for judging the killing effect on viruses by using the Ag-loaded layered double hydroxide material comprises the following steps: the virus killing effect of the Ag-loaded layered double hydroxide material is evaluated by detecting the infection rate of SARS-CoV-2 virus to Vero-E6 cells by an immunofluorescence method.
The experimental steps are as follows:
The ZnAl-LDH and ZnAl-LDH-Ag powder is dissolved by using a DMEM culture medium, and 1mg/mL of storage solution is prepared.
The time is 12 hours in advance, vero-E6 cells are planted in a 24-hole plate, and the cell density is ensured to reach 80% -90% when the virus is infected.
In the experiment, znAl-LDH and ZnAl-LDH-Ag stock solutions are diluted into working solutions with final concentrations of 50 mug/mL, 10 mug/mL, 2 mug/mL, 0.4 mug/mL, 0.08 mug/mL and 0.016 mug/mL respectively by using a DMEM culture medium.
SARS-CoV-2 (10 5 PFU) was incubated with varying concentrations of compound for 0.5 hours at room temperature. ZnAl-LDH and ZnAl-LDH-Ag were each grouped into three groups, one group incubated under light-protected conditions, one group incubated under natural light, and one group incubated under uv light.
100. Mu.L of the mixed solution of the viruses, znAl-LDH and ZnAl-LDH-Ag of each treatment group is added into prepared Vero-E6 cells, and the mixture is gently mixed and placed in an incubator at 37 ℃ and 5% CO 2 for culture.
After 2h, the supernatant was discarded and fresh DMEM broth was added.
After 24h of virus infection, an immunofluorescence experiment is carried out by utilizing SARS-CoV-2N protein antibody, the SAR-CoV-2 virus infection rate of each group is detected, the half effective inhibition concentration (EC 50) of different materials on SARS-CoV-2 is calculated, and the inhibition effect of ZnAl-LDH and ZnAl-LDH-Ag on SARS-CoV-2 infection is evaluated.
Experimental results: under natural illumination condition, the EC50 of the Ag-loaded layered double hydroxide material for resisting SARS-CoV-2 is 0.1637 mug/mL, which is far lower than the EC 50=4.158 mug/mL of the Ag-unloaded layered double hydroxide material, and has more excellent SARS-CoV-2 resisting effect. In addition, after ultraviolet irradiation treatment, the EC50 of the Ag-loaded layered double hydroxide material for resisting SARS-CoV-2 is 0.01258 mug/mL, which has better antiviral effect than natural light.
FIG. 1 is a digital photograph of layered double hydroxide and Ag-supported layered double hydroxide materials prepared in example 1, and it can be seen that both materials have a Tyndall effect, which indicates that the materials have an ultra-thin structure;
FIG. 2 is an X-ray diffraction pattern of the layered double hydroxide and Ag-supported layered double hydroxide material prepared in example 1 at a scanning speed of 4 DEG/min and a scanning range of 5 DEG to 75 deg. The two are highly consistent with the layered double hydroxide standard card (PDF#48-1022), in addition, the layered double hydroxide loaded with Ag has ZnO phase (PDF#36-1451), and the synergistic effect of ZnO and the layered double hydroxide material loaded with Ag is beneficial to antivirus;
FIG. 3 is an X-ray photoelectron spectrum of (a) Zn, (b) Al and (c) Ag element of the layered double hydroxide and Ag-supported layered double hydroxide material prepared in example 1, from which it can be seen that 1) after Ag is supported, two chemical bonds occur due to Zn element generated by ZnO, 2) the Al element does not change much before and after the supporting, and 3) the Ag element is successfully supported;
FIG. 4 is a transmission electron micrograph of (a) a Ag-supported layered double hydroxide material prepared in example 1, (b) a high resolution transmission electron micrograph, corresponding to the (100) crystal plane of ZnO, showing the uniform distribution of (c) Zn, (d) Al, (e) O, and (f) Ag by an energy dispersive X-ray spectroscopical element map of the Ag-supported layered double hydroxide;
FIG. 5 is an ultraviolet-visible absorption spectrum of the layered double hydroxide and Ag-supported layered double hydroxide material prepared in example 1, and it can be seen that the light absorption performance is improved after Ag is supported, and the improvement of the light absorption performance is beneficial to the improvement of the photocatalytic performance, and more active free radicals with antiviral performance are generated;
Table 1 shows the contents of the elements of the layered double hydroxide and Ag-supported layered double hydroxide materials prepared in example 1, as measured by inductively coupled plasma mass spectrometry, and the concentrations of the layered double hydroxide solutions were 2mg/mL.
TABLE 1 content of elements of layered double hydroxide and Ag-supported layered double hydroxide Material
Example 2
1. Preparation of Ag-loaded layered double hydroxide material
446Mg of zinc nitrate hexahydrate, 188mg of aluminum nitrate nonahydrate and 4mg of silver nitrate were dissolved in 40mL of deionized water. The above mixed solution was then dropped into a three-necked flask containing 40mL of a 23% by volume formamide solution. Then the three-neck flask is transferred into a low-temperature reaction tank, the temperature is controlled to be 0 ℃, and nitrogen is introduced into the three-neck flask to be stirred for 10 minutes. Finally, the prepared 2.5M sodium hydroxide solution was slowly dropped into the three-necked flask to maintain the pH at 10. The reaction was completed within 15 minutes while maintaining a low temperature nitrogen atmosphere. The product was collected by centrifugation, repeatedly washed with deionized water and absolute ethanol, and then kept in a wet state for use.
2. The severe acute respiratory syndrome-coronavirus-2 (SARS-CoV-2) inactivation performance test was similar to example 1.
Example 3
1. Preparation of Ag-loaded layered double hydroxide material
112Mg of zinc nitrate hexahydrate, 48mg of aluminum nitrate nonahydrate and 1mg of silver nitrate were dissolved in 10mL of deionized water. The above mixed solution was then dropped into a three-necked flask containing 10mL of a 23% by volume formamide solution. Then the three-neck flask is transferred into a low-temperature reaction tank, the temperature is controlled to be 0 ℃, and nitrogen is introduced into the three-neck flask to be stirred for 10 minutes. Finally, the prepared 0.25M sodium hydroxide solution was slowly dropped into the three-necked flask to maintain the pH at 10. The reaction was completed within 15 minutes while maintaining a low temperature nitrogen atmosphere. The product was collected by centrifugation, repeatedly washed with deionized water and absolute ethanol, and then kept in a wet state for use.
2. The severe acute respiratory syndrome-coronavirus-2 (SARS-CoV-2) inactivation performance test was similar to example 1.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (6)
1. The preparation method of the Ag-supported layered double hydroxide is characterized by comprising the following steps of:
S1: dissolving zinc nitrate hexahydrate, aluminum nitrate nonahydrate and silver nitrate in deionized water to obtain a mixed solution;
s2: dropwise adding the mixed solution obtained in the step S1 into a formamide solution, and then stirring at a low temperature under an inert gas atmosphere to obtain a reaction stock solution;
S3: dropwise adding a sodium hydroxide solution into the reaction stock solution obtained in the step S2 to control the pH value and react, and centrifuging and washing a reaction product to obtain the Ag-loaded layered double hydroxide;
The mass ratio of the zinc nitrate hexahydrate, the aluminum nitrate nonahydrate and the silver nitrate in the step S1 is 100-500:50-500:1-50;
The dosage ratio of the formamide solution to the zinc nitrate hexahydrate in the step S2 is 10-100mL:100-500mg; the temperature of the low-temperature stirring is-5-5 ℃ and the time is 10-30min;
the temperature of the reaction in the step S3 is-5-5 ℃ and the time is 10-40min.
2. The method for preparing the Ag-supported layered double hydroxide according to claim 1, wherein the volume fraction of the formamide solution is 15-33%.
3. The method for producing a supported Ag layered double hydroxide according to claim 1, wherein the inert gas in step S2 is nitrogen.
4. The method for preparing Ag-supported layered double hydroxide according to claim 1, wherein the concentration of the sodium hydroxide solution in the step S3 is 0.5-4M and the pH value is 9-12.
5. The method for producing an Ag-supported layered double hydroxide according to claim 1, wherein the reaction in step S3 is performed under a nitrogen atmosphere.
6. The method for producing an Ag-supported layered double hydroxide according to claim 1, wherein the rotational speed of the centrifugation in step S3 is 6000-8000r/min.
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