CN111955478A - Slow-release carbon-based antibacterial and antiviral composite material and preparation method and application thereof - Google Patents
Slow-release carbon-based antibacterial and antiviral composite material and preparation method and application thereof Download PDFInfo
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- CN111955478A CN111955478A CN202010874986.0A CN202010874986A CN111955478A CN 111955478 A CN111955478 A CN 111955478A CN 202010874986 A CN202010874986 A CN 202010874986A CN 111955478 A CN111955478 A CN 111955478A
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
The invention belongs to the field of antiviral materials, and relates to a sustained-release carbon-based antibacterial and antiviral composite material as well as a preparation method and application thereof. The slow-release carbon-based antibacterial and antiviral composite material contains a component A and a component B, wherein the component A is activated carbon loaded with nano zero-valent iron and nano silver, and the component B is activated carbon loaded with graphene. The slow-release carbon-based antibacterial and antiviral composite material provided by the invention can slow down the release rate of nano silver, perfectly solve the problem of high release rate of silver ions, realize safe, lasting and effective antibacterial and antiviral effects, and can be applied to antibacterial and antiviral protection of water outlet ends of water works, inlet ends of district tap water pipe networks, water for livestock and poultry farms, air purification systems of livestock and poultry farms, household drinking water and the like through a certain structure and a certain product form, so that the microbial safety of the water and the drinking water is ensured.
Description
Technical Field
The invention belongs to the field of antiviral materials, and particularly relates to a sustained-release carbon-based antibacterial and antiviral composite material as well as a preparation method and application thereof.
Background
The widespread spread of viral infections worldwide has become one of the most serious public health and social problems worldwide, such as SARS coronavirus, avian influenza virus, H1N1 influenza a virus, and new coronavirus, among others. Viruses may also be transmitted through showers or pipes, in addition to airborne and contact transmission. Therefore, it is important to prevent virus invasion from productive life, especially to kill viruses from media (such as water and air) which human beings contact, thereby ensuring the health and safety of human beings. The development and application of antiviral materials is one of the important pathways for inhibiting and destroying viruses. With the prevalence of new viruses, the traditional antiviral materials cannot meet the requirements, and the development of new efficient antiviral materials is crucial.
Metal and carbon-based nano materials have been widely applied to the field of antibacterial and antiviral by virtue of the characteristics of highly adjustable structural performance, excellent antibacterial performance and the like, and particularly, nano silver and graphene-based antibacterial and antiviral materials have attracted extensive attention. Nano silver has been widely studied and applied as a nano antibacterial and antiviral material. The low toxicity and non-selective inhibition of the nano silver to various viruses have important significance for preventing and treating infection of various viruses. The unpaired electrons on the surface of the nano silver and the nano size effect greatly improve the virus adsorption capacity of the nano silver, and enhance the chemical reaction capacity with the virus. The nano silver can inhibit the combination of virus and cell receptor, virus nucleic acid and release Ag through mechanical adsorption+The virus structure is forced to realize the aim of effective virus resistance. However, the nano-silver antibacterial and antiviral material has the problem that the nano-silver is easy to run off. In addition to nano silver antibacterial and antiviral materials, carbon-based nanomaterials, particularly materials such as graphene or graphene oxide, are antiviral materials that have attracted attention in recent years. Graphene and derivatives thereof are important novel two-dimensional multifunctional nano materials, and have the advantages of excellent broad-spectrum antibacterial and antiviral capacity, no induction of bacteria to generate drug resistance, simple preparation process, good biocompatibility and the like. Graphene is subjected to sharp physical edges, membrane surface component extraction, physical capture, oxidative stress, charge transfer and the likeIn a manner that is effective in killing viruses, either directly or indirectly. However, the cost of graphene materials is relatively high, and similar problems of nano-environment application exist, so it is necessary to fully exert the antiviral ability of graphene in a composite manner, and reduce environmental risks and application cost.
Some antibacterial and antiviral materials based on nano silver and graphene have been disclosed. For example, CN111328831A discloses a composite antibacterial and antiviral material with nano-diamond loaded with nano-silver, which can stably and durably maintain a suspended state in a saline solution and has excellent antibacterial and antiviral capabilities. However, the composite antibacterial and antiviral material is made of nano materials, and the dispersibility of particles cannot be guaranteed, so that the antibacterial and antiviral performance of the composite antibacterial and antiviral material is affected; secondly, the nano particles are easy to run off when the nano particles are used for cloth. CN111418607A discloses a composite nano-silver antiviral agent with higher stability and timeliness, which consists of ester quaternary ammonium salt cationic surfactant, dodecyl trimethyl ammonium chloride, nano-silver sol, polyethylene glycol and water. The composite nano silver antiviral agent is applied to non-woven fabrics, and the antiviral performance of the non-woven fabrics can be improved. However, the above two nano-silver antibacterial and antiviral materials all have the problem that nano-silver is easy to run off, and since the two nano-silver antibacterial and antiviral materials are both liquid phase nano-materials, the nano-silver antibacterial and antiviral materials can be dispersed in water to cause water pollution by being directly put into water for antibacterial and antiviral, and need to be loaded on a carrier and then used, and the steps are complicated.
Disclosure of Invention
The invention aims to overcome the defects of easy loss and high release rate of nano-silver in the existing nano-silver antibacterial and antiviral material, and provides a sustained-release carbon-based antibacterial and antiviral composite material which can slow down the loss and the release rate of nano-silver and is lasting and effective, and a preparation method and application thereof.
The invention provides a slow-release carbon-based antibacterial and antiviral composite material, which comprises a component A and a component B, wherein the component A is activated carbon loaded with nano zero-valent iron and nano silver, and the component B is activated carbon loaded with graphene.
In a preferred embodiment, the mass ratio of the component A to the component B is (0.5-10): 1, and the two components can be perfectly matched to achieve better synergistic slow-release antibacterial and antiviral effects.
In a preferred embodiment, the particle size of the activated carbon in the component A is 0.8-1.5 mm or 0.01-0.2 mm, and the particle size of the activated carbon in the component B is less than 0.05mm, so that after the activated carbon and the activated carbon are mixed according to the particle size distribution, the water pressure resistance is small during use, and the subsequent use is more facilitated.
In a preferred embodiment, the mass ratio of the nano zero-valent iron in the component A is 0.1-1.0%, and the mass ratio of the nano silver is 0.03-2.00%, at this time, the nano silver can realize uniform and firm loading, and simultaneously cooperate with the nano zero-valent iron to efficiently convert chemical pollutants.
In a preferred embodiment, the mass ratio of the graphene in the component B is 0.1% to 20%, and in this case, the adsorption capacity of the activated carbon and the antibacterial and antiviral capacity of the dispersed graphene can be well cooperated.
In a preferred embodiment, the component a is prepared according to the following steps:
s11, acidifying the activated carbon and then drying to obtain acidified activated carbon;
s12, dissolving ferrous sulfate in a mixed solvent of ethanol and water, and then adding polyethylene glycol to mix uniformly to obtain a steeping liquor;
s13, adding the acidified activated carbon into the impregnation liquid, uniformly stirring, adding a sodium borohydride solution, carrying out in-situ reduction reaction, and washing to obtain activated carbon loaded with nano zero-valent iron;
s14, adding the activated carbon loaded with the nano zero-valent iron into the silver salt solution under the protection of nitrogen to perform redox reaction to obtain the component A.
In a preferred embodiment, in step S11, the activated carbon is soaked in a high-grade hydrochloric acid solution with a mass concentration of 2-10% for 20-30 h according to a solid-to-liquid ratio of 1 (3-10), and then washed with deionized water until the pH value is unchanged, and dried.
In a preferred embodiment, in step S12, the volume ratio of ethanol to water is 2:8 to 8: 2.
In a preferred embodiment, in step S12, the polyethylene glycol has a number average molecular weight of 200 to 4000.
In a preferred embodiment, in the step S12, the mass ratio of the polyethylene glycol to the ferrous sulfate is 1 (2-5).
In a preferred embodiment, in step S12, the mass ratio of iron in the ferrous sulfate to the acidified activated carbon is 1 (5-200).
In a preferred embodiment, in step S13, the sodium borohydride solution is present in an amount in a molar ratio of nFe2+/nBH4 -The addition is 1: 3-1: 8.
In a preferred embodiment, in step S13, the in-situ reduction reaction conditions include a stirring rate of 300 to 800r/min, a reaction temperature of room temperature, and a reaction time of 20 to 40 min.
In a preferred embodiment, in step S14, the silver salt is silver nitrate.
In a preferred embodiment, in step S14, the concentration of the silver salt solution is C(Ag+)＝0.2～10mmol/L。
In a preferred embodiment, in step S14, the redox reaction conditions include a stirring rate of 300 to 800r/min, a reaction temperature of room temperature, and a reaction time of 10 to 40 min.
In a preferred embodiment, the component B is prepared according to the following steps:
s21, crushing the activated carbon powder, performing acidification treatment and drying to obtain acidified activated carbon powder;
s22, ultrasonically dispersing graphene oxide in ultrapure water to obtain a uniform graphene oxide solution;
and S23, adding the acidified activated carbon powder into the graphene oxide solution, stirring, adding ascorbic acid for reduction reaction, and filtering, washing and drying after the reaction is finished to obtain the graphene-loaded activated carbon.
In a preferred embodiment, in step S21, the activated carbon is added into deionized water according to a solid-to-liquid ratio of 1 (50-100), and the mixture is ball milled for 180-300 min by using a planetary ball mill at a rotation speed of 230-300 r/min, washed by deionized water, and dried.
In a preferred embodiment, in step S21, the acidification treatment method includes soaking the substrate in a 0.5-3M high-grade hydrochloric acid solution at a solid-to-liquid ratio of 1 (3-10) for 20-30 hours, washing the substrate with deionized water until the pH value is unchanged, and drying the substrate.
In a preferred embodiment, in step S22, the graphene oxide and the ultrapure water are used in amounts such that the concentration of the obtained graphene oxide solution is 0.3-2 mg/mL.
In a preferred embodiment, in step S23, the mass ratio of the acidified activated carbon powder to the graphene oxide is (2.5-20): 1.
In a preferred embodiment, in step S23, the stirring speed is 250 to 500r/min, and the time is 12 to 24 hours.
In a preferred embodiment, in step S23, the mass ratio of the ascorbic acid to the graphene oxide is (0.5-10): 1.
In a preferred embodiment, in step S23, the reduction reaction is performed in a water bath at 70-100 ℃ for 2-6 h. Furthermore, the reduction reaction usually requires the introduction of N2As a shielding gas.
The preparation method of the slow-release carbon-based antibacterial and antiviral composite material provided by the invention comprises the step of uniformly mixing the component A and the component B.
In addition, the invention also provides application of the slow-release carbon-based antibacterial and antiviral composite material in antiviral protective equipment and antiviral water purification and filtration filter elements.
In the common silver-loaded activated carbon, the acting force between silver or silver ions and the activated carbon is mainly van der waals force, complexing force and the like. Compared with the active carbon loaded with the nano zero-valent iron and the nano silver, the active carbon loaded with the nano zero-valent iron and the nano silver has stronger acting force due to larger difference between oxidation-reduction potentials of the zero-valent iron and the silver, the strong acting force between the nano zero-valent iron and the nano silver provides favorable conditions for slow release of silver ions, the loss risk of the nano silver can be reduced, and the release amount and the release rate of the silver ions after the silver ions are contacted with water are lower. And in the graphene-loaded activated carbon, the graphene has extremely strong adsorption force on free silver ions in water, so that part of the free silver ions in the water can be adsorbed to the solid surface again, and the silver ions in the water can be further reduced. According to the invention, the active carbon loaded with nano zero-valent iron and nano silver and the active carbon loaded with graphene are compounded for use, the active carbon loaded with nano zero-valent iron and nano silver can reduce the release rate of silver ions at one time through the interaction between molecular atoms in the material, the active carbon loaded with graphene can re-adsorb the silver ions released in a water body to the solid surface through the strong adsorption effect of the graphene on the silver ions so as to achieve the purpose of reducing the release rate of the silver ions at the second time, and the internal and external cooperative mode can perfectly solve the problem of high release rate of the silver ions, thereby realizing safe, lasting and effective antibacterial and antiviral effects.
The slow-release carbon-based antibacterial and antiviral composite material provided by the invention can be applied to antibacterial and antiviral protection of water and drinking water microorganisms by a certain structure and a certain product form, such as a water outlet end of a tap water plant, an inlet end of a tap water pipe network of a community, water for a livestock and poultry farm, an air purification system of the livestock and poultry farm, domestic drinking water and the like, and the safety of the water and the drinking water is ensured.
In addition, compared with the simply mixed nano zero-valent iron, nano silver and graphene, the nano zero-valent iron and nano silver loaded active carbon and the graphene loaded active carbon load zero-valent iron, nano silver and graphene on the active carbon from the molecular and atomic levels, so that the nano material can be firmly fixed, the uniformity of the nano material can be ensured, the effects of low load and proper antibacterial and antiviral performances are achieved, the antibacterial and antiviral activity of the composite material is promoted, and the use cost is reduced.
Drawings
Fig. 1 is an XRD pattern of the nano zero-valent iron and nano silver-supported activated carbon prepared in example 1.
Fig. 2 is an SEM image of the nano zero-valent iron and nano silver-loaded activated carbon prepared in example 1.
Fig. 3 is an XRD pattern of graphene-supported activated carbon prepared in example 1.
Fig. 4 is an SEM image of graphene-supported activated carbon prepared in example 1.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) Preparing the activated carbon loaded with nano zero-valent iron and nano silver:
s11, screening 1.0-1.5 mm of activated carbon, washing and drying with deionized water, adding into 5% hydrochloric acid to soak for 24 hours, washing with deionized water until the pH value is unchanged, and drying to obtain acidified activated carbon;
s12, weighing FeSO according to the mass ratio of iron to acidified active carbon of 1:1004·7H2O, adding 100mL of mixed solvent of ultrapure water and absolute ethyl alcohol with the volume ratio of 8:2 for dissolving, then adding 0.1g of polyethylene glycol with the number average molecular weight of 200 (the mass ratio of the polyethylene glycol to the ferrous sulfate is 1:2), and introducing N2Stirring and reacting at room temperature for 120min under the condition that the rotating speed is 400r/min to obtain an impregnation liquid;
s13, adding 20g of acidified activated carbon into the impregnation solution, stirring for 120min, and slowly adding 100mL of NaBH with the concentration of 0.29mol/L4Solution, passing N through2Stirring and reacting for 30min at the room temperature under the condition that the rotating speed is 450 r/min; carrying out suction filtration on the obtained reaction product, wherein the filter paper is medium-speed filter paper, and the obtained solid is washed with ultrapure water for three times to obtain activated carbon loaded with nano zero-valent iron;
s14, adding the activated carbon loaded with the nano zero-valent iron to 100mL of AgNO with the concentration of 5mmol/L3In the solution, N is introduced2Stirring and reacting at room temperature for 30min under the condition that the rotating speed is 500r/min, carrying out suction filtration on the obtained reaction product, washing the separated solid particles for 3 times respectively by using ultrapure water and absolute ethyl alcohol, and carrying out vacuum drying at constant temperature of 70 ℃ and 0.06MPa to obtain the activated carbon loaded with nano zero-valent iron and nano silver.
Fig. 1 is an XRD chart of the activated carbon loaded with nano zero-valent iron and nano silver prepared in this example. As can be seen from fig. 1, the activated carbon loaded with nanoscale zero-valent iron and nanoscale silver prepared in this example is composed of amorphous carbon, nanoscale zero-valent iron, and crystalline nanoscale elemental silver.
Fig. 2 is an SEM image of the activated carbon loaded with nano zero-valent iron and nano silver prepared in this example. As can be seen from fig. 2, in the activated carbon loaded with nano zero-valent iron and nano silver prepared in this embodiment, the nano zero-valent iron and the nano silver are uniformly dispersed in the activated carbon, the nano zero-valent iron exists in a chain form, the nano silver exists in small spherical particles, and the particle size of most of the nano zero-valent iron and the nano silver is between 10nm and 20 nm.
Digesting the active carbon solid loaded with the nano zero-valent iron and the nano silver, and determining the iron content and the silver content in the active carbon solid after constant volume. The detection result shows that the mass ratio of the nano zero-valent iron in the sample is 0.84%, and the mass ratio of the nano silver is 0.29%.
(2) Preparing a graphene-loaded powder activated carbon composite material:
s21, grinding the activated carbon to about 1000 meshes, washing and drying the activated carbon by using deionized water, adding the washed and dried activated carbon into a 1M hydrochloric acid solution, soaking for 24 hours, washing until the pH value is unchanged, and drying for 24 hours in a drying oven at 105 ℃ to obtain acidified activated carbon powder;
s22, ultrasonically dispersing graphene oxide in 100mL of ultrapure water for 4 hours according to the mass ratio of the activated carbon to the graphene oxide of 10:1 to obtain a graphene oxide solution with the concentration of 0.3 mg/mL;
s23, adding 0.3g of acidified activated carbon powder into the graphene oxide solution, stirring for 12 hours, slowly adding ascorbic acid with the amount of 5 times of the mass of the graphene oxide, and introducing N2Reacting in water bath at 80 deg.C for 4 hr, filtering with sand core funnel, washing with water, and vacuum-drying at constant temperatureAnd drying to obtain the graphene-loaded activated carbon, wherein the mass ratio of the graphene is 9.1%.
Fig. 3 is an XRD pattern of the graphene-supported activated carbon prepared in this example. As can be seen from fig. 3, the graphene-supported activated carbon prepared in this embodiment is composed of amorphous carbon and graphene.
Fig. 4 is an SEM image of the graphene-supported activated carbon prepared in this example. As can be seen from fig. 4, the graphene is distributed on the surface of the activated carbon in a dispersed form.
(3) Uniformly mixing the active carbon loaded with nano zero-valent iron and nano silver and the powdered active carbon composite loaded with graphene according to the proportion of 8.5 parts by weight to 1.5 parts by weight to obtain the slow-release carbon-based antibacterial and antiviral composite. The sustained-release carbon-based antibacterial and antiviral composite material is subjected to antiviral test, the specific process of the test is carried out according to the method disclosed in GB/T21510 appendix A, wherein three groups of parallel test groups and control groups are respectively selected, the test group sample is the sustained-release carbon-based antibacterial and antiviral composite material obtained in the embodiment, and the control group sample is silicon dioxide powder with the powder size of not more than 10nm and the purity of 98-99%. The results are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the slow-release carbon-based antibacterial and antiviral composite material can kill 99.89% of H1N1 viruses.
The slow release carbon-based antibacterial and antiviral composite material is subjected to a slow release performance test, which comprises the following specific steps: adding 2g of the slow-release carbon-based antibacterial and antiviral composite material into 6mL of pure water, and soaking for 24 +/-1 h at 25 +/-5 ℃ in a dark condition; filling pure water into another container with the same volume to serve as a blank control; after soaking, sampling by using a filter and testing by using an ICP-MS; before testing, standard samples with different concentration gradients are prepared to draw a standard curve. The test result shows that the concentration of silver ions in the water sample after 24 hours of soaking is 19.2 ppb.
It should be noted that, in this embodiment, the H1N1 virus is taken as a research object, but the invention is not limited to this in practical application, and the sustained-release carbon-based antibacterial and antiviral composite material prepared by the present invention can also be used for killing other newly prevalent viruses, etc.
Example 2
(1) Preparing the activated carbon loaded with nano zero-valent iron and nano silver:
s11, screening 1.0-1.5 mm of activated carbon, washing and drying with deionized water, adding into 5% hydrochloric acid to soak for 24 hours, washing with deionized water until the pH value is unchanged, and drying to obtain acidified activated carbon;
s12, weighing FeSO according to the mass ratio of iron to acidified active carbon of 1:2004·7H2O, adding 100mL of mixed solvent of ultrapure water and absolute ethyl alcohol with the volume ratio of 8:2 for dissolving, then adding 0.1g of polyethylene glycol with the number average molecular weight of 200 (the mass ratio of the polyethylene glycol to the ferrous sulfate is 1:5), and introducing N2Stirring and reacting at room temperature for 120min under the condition that the rotating speed is 400r/min to obtain an impregnation liquid;
s13, adding 40g of activated carbon into the impregnation liquid, stirring for 120min, and slowly adding 100mL of NaBH with the concentration of 0.29mol/L4Solution, passing N through2Stirring and reacting for 30min at the room temperature under the condition that the rotating speed is 450 r/min; carrying out suction filtration on the obtained reaction product, wherein the filter paper is medium-speed filter paper, and the obtained solid is washed with ultrapure water for three times to obtain activated carbon loaded with nano zero-valent iron;
s14, adding the activated carbon loaded with the nano zero-valent iron to 100mL of AgNO with the concentration of 6mmol/L3In the solution, N is introduced2Stirring and reacting at room temperature for 30min under the condition that the rotating speed is 500r/min, carrying out suction filtration on the obtained reaction product, washing the separated solid particles for 3 times respectively by using ultrapure water and absolute ethyl alcohol, and carrying out vacuum drying at the constant temperature of 70 ℃ and at the constant temperature of 0.06MPa to obtain the activated carbon loaded with nano zero-valent iron and nano silver.
XRD detection shows that the active carbon loaded with nano zero-valent iron and nano silver consists of amorphous carbon, nano zero-valent iron and crystalline nano simple substance silver.
SEM detection shows that in the activated carbon loaded with the nano zero-valent iron and the nano silver, the nano zero-valent iron and the nano silver are uniformly dispersed in the activated carbon, the nano zero-valent iron exists in a chain form, the nano silver exists in small spherical particles, and the particle size of most of the nano zero-valent iron and the nano silver is 10-20 nm.
Digesting the active carbon solid loaded with the nano zero-valent iron and the nano silver, and determining the iron content and the silver content in the active carbon solid after constant volume. The detection result shows that the mass ratio of the nano zero-valent iron in the sample is 0.39%, and the mass ratio of the nano silver is 0.07%.
(2) Preparing a graphene-loaded powder activated carbon composite material:
s21, grinding the activated carbon to about 1000 meshes, washing and drying the activated carbon by using deionized water, adding the washed and dried activated carbon into a 1M hydrochloric acid solution, soaking for 24 hours, washing until the pH value is unchanged, and drying for 24 hours in a drying oven at 105 ℃ to obtain acidified activated carbon powder;
s22, ultrasonically dispersing graphene oxide in 100mL of ultrapure water for 4 hours according to the mass ratio of the activated carbon to the graphene oxide of 5:1 to obtain a graphene oxide solution with the concentration of 0.6 mg/mL;
s23, adding 0.3g of acidified activated carbon powder into the graphene oxide solution, stirring for 12 hours, slowly adding ascorbic acid with the amount of 5 times of the mass of the graphene oxide, and introducing N2Reacting for 4 hours in a water bath at 80 ℃, then filtering by using a sand core funnel, washing with water, and drying in vacuum at constant temperature to obtain the graphene-loaded activated carbon, wherein the mass ratio of graphene is 16.7%.
XRD detection shows that the graphene-loaded activated carbon is composed of amorphous carbon and graphene.
SEM detection shows that in the graphene-loaded activated carbon, graphene is distributed on the surface of the activated carbon in a dispersed mode.
(3) Uniformly mixing the active carbon loaded with nano zero-valent iron and nano silver and the powdered active carbon composite loaded with graphene according to the proportion of 6 parts by weight to 4 parts by weight to obtain the slow-release carbon-based antibacterial and antiviral composite. The sustained-release carbon-based antibacterial and antiviral composite material is subjected to antiviral test, the specific test process is the same as that in example 1, and the result shows that the sustained-release carbon-based antibacterial and antiviral composite material can kill 99.89% of H1N1 virus.
The slow release performance test of the slow release type carbon-based antibacterial and antiviral composite material is carried out, the specific test process is the same as that in example 1, and the result shows that the concentration of silver ions in an upper water sample after 24 hours of soaking is 14.3 ppb.
Comparative example 1
The activated carbon loaded with nano zero-valent iron and nano silver was prepared according to the method of example 1, and the graphene-loaded powdered activated carbon was not added, that is, the sustained-release carbon-based antibacterial and antiviral composite material of the comparative example was composed of only the activated carbon loaded with nano zero-valent iron and nano silver.
The sustained-release carbon-based antibacterial and antiviral composite material is subjected to antiviral test, the specific test process is the same as that in example 1, and the result shows that the sustained-release carbon-based antibacterial and antiviral composite material can kill 90% of H1N1 viruses.
The slow release performance test of the slow release type carbon-based antibacterial and antiviral composite material is carried out, the specific test process is the same as that in example 1, and the result shows that the concentration of silver ions in an upper water sample after 24 hours of soaking is 24.1 ppb.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. The slow-release carbon-based antibacterial and antiviral composite material is characterized by comprising a component A and a component B, wherein the component A is activated carbon loaded with nano zero-valent iron and nano silver, and the component B is activated carbon loaded with graphene.
2. The slow-release carbon-based antibacterial and antiviral composite material as claimed in claim 1, wherein the mass ratio of the component A to the component B is (0.5-10): 1.
3. The slow-release carbon-based antibacterial and antiviral composite material as claimed in claim 1, wherein the particle size of the activated carbon in the component A is 0.8-1.5 mm or 0.01-0.2 mm, and the particle size of the activated carbon in the component B is less than 0.05 mm.
4. The slow-release carbon-based antibacterial and antiviral composite material as claimed in claim 1, wherein the mass ratio of the nano zero-valent iron in the component A is 0.1-1.0%, and the mass ratio of the nano silver is 0.03-2.00%; the mass ratio of the graphene in the component B is 0.1-20%.
5. The slow-release carbon-based antibacterial and antiviral composite material as claimed in claim 1, wherein the component A is prepared by the following steps:
s11, acidifying the activated carbon and then drying to obtain acidified activated carbon;
s12, dissolving ferrous sulfate in a mixed solvent of ethanol and water, and then adding polyethylene glycol to mix uniformly to obtain a steeping liquor;
s13, adding the acidified activated carbon into the impregnation liquid, uniformly stirring, adding a sodium borohydride solution, carrying out in-situ reduction reaction, and washing to obtain activated carbon loaded with nano zero-valent iron;
s14, adding the activated carbon loaded with the nano zero-valent iron into the silver salt solution under the protection of nitrogen to perform redox reaction to obtain the component A.
6. The sustained-release carbon-based antibacterial and antiviral composite material according to claim 5,
in the step S11, the acidification treatment mode is that the activated carbon is soaked in a high-grade hydrochloric acid solution with the mass concentration of 2-10% for 20-30 h according to the solid-to-liquid ratio of 1 (3-10), and then washed by deionized water until the pH value is unchanged, and dried;
in the step S12, the volume ratio of the ethanol to the water is 2: 8-8: 2; the number average molecular weight of the polyethylene glycol is 200-4000; the mass ratio of the polyethylene glycol to the ferrous sulfate is 1 (2-5); the mass ratio of iron in the ferrous sulfate to the acidified active carbon is 1 (5-200);
in step S13, the amount of sodium borohydride solution is nFe2+/nBH4 -Adding the mixture in a ratio of 1: 3-1: 8; the conditions of the in-situ reduction reaction comprise that the stirring speed is 300-800 r/min, the reaction temperature is room temperature, and the reaction time is 20-40 min;
in step S14, the silver salt is silver nitrate; the concentration of the silver salt solution is C(Ag+)0.2-10 mmol/L; the redox reaction conditions comprise that the stirring speed is 300-800 r/min, the reaction temperature is room temperature, and the reaction time is 10-40 min.
7. The slow-release carbon-based antibacterial and antiviral composite material as claimed in claim 1, wherein the component B is prepared by the following steps:
s21, crushing the activated carbon powder, performing acidification treatment and drying to obtain acidified activated carbon powder;
s22, ultrasonically dispersing graphene oxide in ultrapure water to obtain a uniform graphene oxide solution;
and S23, adding the acidified activated carbon powder into the graphene oxide solution, stirring, adding ascorbic acid for reduction reaction, and filtering, washing and drying after the reaction is finished to obtain the graphene-loaded activated carbon.
8. The sustained-release carbon-based antibacterial and antiviral composite material according to claim 7,
in the step S21, the crushing method comprises the steps of adding activated carbon into deionized water according to a solid-liquid ratio of 1 (50-100), ball-milling for 180-300 min by using a planetary ball mill at a rotating speed of 230-300 r/min, washing by using the deionized water, and drying; soaking the mixture for 20-30 hours by using a high-grade hydrochloric acid solution with the molar concentration of 0.5-3M according to the solid-to-liquid ratio of 1 (3-10), washing the mixture by using deionized water until the pH value is unchanged, and drying the mixture;
in the step S22, the graphene oxide and the ultrapure water are used in amounts such that the concentration of the obtained graphene oxide solution is 0.3-2 mg/mL;
in step S23, the mass ratio of the acidified activated carbon powder to the graphene oxide is (2.5-20) to 1; the stirring speed is 250-500 r/min, and the stirring time is 12-24 h; the mass ratio of the ascorbic acid to the graphene oxide is (0.5-10) to 1; the reduction reaction is carried out in a water bath at 70-100 ℃ for 2-6 h.
9. The preparation method of the slow-release carbon-based antibacterial and antiviral composite material as claimed in any one of claims 1 to 8, characterized in that the method comprises uniformly mixing the component A and the component B.
10. The use of the slow-release carbon-based antibacterial and antiviral composite material as claimed in any one of claims 1 to 8 in antiviral protective equipment and antiviral water purification and filtration filter elements.
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