CN115448376A - Preparation method of cobalt-based nanosheet, cobalt-based nanosheet and application - Google Patents
Preparation method of cobalt-based nanosheet, cobalt-based nanosheet and application Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 55
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 53
- 239000010941 cobalt Substances 0.000 title claims abstract description 53
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 150000001868 cobalt Chemical class 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 239000000376 reactant Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 44
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 30
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 30
- 239000012266 salt solution Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 13
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
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- 238000000034 method Methods 0.000 claims description 6
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- 244000005700 microbiome Species 0.000 claims description 5
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- 239000000463 material Substances 0.000 abstract description 21
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- 239000003125 aqueous solvent Substances 0.000 abstract description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 abstract description 2
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- A—HUMAN NECESSITIES
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- 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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- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
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Abstract
The cobalt-based nanosheet and the preparation method provided by the application are characterized in that ZIF-67 is dissolved in an aqueous solution of cobalt salt, the aqueous solution reacts for 2-7 hours at the temperature of 25 ℃, the obtained reactant is cleaned and dried to obtain the cobalt-based nanosheet, and the cobalt-based nanosheet is synthesized into a-Co (OH) stably existing at room temperature under simple stirring conditions by taking the ZIF-67 as a sacrificial template and carrying out ion etching and layered cobalt hydroxide in-situ growth on the basis of the material of the ZIF-67 2 (CHN) does not favor beta-Co (OH) during synthesis 2 The transition is carried out, the hexagonal nanosheet has uniform particle size and sharp edge, the positive potential in the aqueous solvent is stable, and the microscopic thickness is within the range of 10-50 nm; the preparation method has the advantages of low reaction temperature, simple preparation process, low cost, large-scale synthesis, larger product size and easier control,the specific surface area is larger, the active sites are more, and the like, and the biological safety is certain, so that the antimicrobial agent can be applied to the aspect of antimicrobial.
Description
Technical Field
The application relates to the technical field of new material preparation, in particular to a preparation method of a cobalt-based nanosheet, the cobalt-based nanosheet and application of the cobalt-based nanosheet.
Background
For a long time, bacterial infection threatens the global human health, and antibiotics are effective medicines for resisting the bacterial infection, and the overabuse of the antibiotics can cause serious bacterial drug resistance while certain antibacterial effect is achieved. According to the world health organization conjecture, antibiotic-resistant bacteria cause about 70 million deaths worldwide each year, and this number is expected to increase to 1000 million people by 2050. However, the development cycle of new antibiotics is long and far behind the pace of bacterial evolution, so that the development of effective antibacterial agents is still slow.
The nano material has been widely applied to the field of biological medicine due to its special physical and chemical properties and good biocompatibility, and many nano materials have been proved to have antibacterial effect, and exert antibacterial effect by mechanisms of influencing the integrity of bacterial cell membranes, releasing antibacterial metal ions, generating Reactive Oxygen Species (ROS), inhibiting enzyme activity, DNA synthesis and the like, and the probability of inducing bacterial drug resistance by the inorganic metal nano material is low, so that the nano material is expected to become a powerful means for treating bacterial infection. Wherein, the hydrotalcite and the hydrotalcite-like compound can be used as drugs and drug carriers to realize antimicrobial application due to the unique structural characteristics, the interchangeability of interlayer anions, the controllability of grain size distribution and other characteristics.
a-Co(OH) 2 Has a hydrotalcite-like structure, exposes more active sites due to its large layered structure and specific surface area, but a-Co (OH) 2 Belonging to the metastable state, and beta-Co (OH) 2 Belongs to a thermally stable phase, so that under elevated temperature or strong alkaline conditions, a-Co (OH) 2 Readily converted to beta-Co (OH) 2 This makes a-Co (OH) 2 Controllable preparation becomes difficult.
Disclosure of Invention
In view of the above, it is necessary to provide a cobalt-based nanosheet with good stability and a preparation method thereof, aiming at the defects existing in the prior art.
In order to solve the above problems, the following technical solutions are adopted in the present application:
one of the purposes of the application is to provide a preparation method of a cobalt-based nanosheet, which comprises the following steps:
dissolving ZIF-67 in an aqueous solution of cobalt salt, carrying out mixed reaction for 2-7h at the temperature of 25-80 ℃, and cleaning and drying the obtained reactant to obtain the cobalt-based nanosheet.
In some of these embodiments, the ZIF-67 is prepared by:
and mixing the 2-methylimidazole solution and a cobalt salt solution at the temperature of 25-80 ℃ for reaction for 2-7h, and cleaning and drying the obtained reactant to obtain the ZIF-67.
In some embodiments, in the step of mixing and reacting the 2-methylimidazole solution with the cobalt salt solution at 25-80 ℃ for 2-7h and cleaning and drying the obtained reactant to obtain the ZIF-67, the concentration of the 2-methylimidazole solution is 10-100mg/ml.
In some of these embodiments, the concentration of the 2-methylimidazole solution is 45mg/ml.
In some embodiments, in the step of mixing and reacting the 2-methylimidazole solution with the cobalt salt solution at 25-80 ℃ for 2-7h, and cleaning and drying the obtained reactant to obtain the ZIF-67, the concentration of the cobalt ion solution in the cobalt salt solution is 1-100mg/ml.
In some embodiments, the cobalt salt in the cobalt salt solution comprises cobalt nitrate, cobalt acetate or cobalt chloride, and the solvent comprises deionized water, methanol, ethanol, or a mixed solution of methanol and ammonia.
In some of these embodiments, the cobalt salt solution is a cobalt nitrate methanol solution having a concentration of 20mg/ml.
In some embodiments, the ZIF-67 is dissolved in an aqueous solution of cobalt salt, the mixture is reacted for 2-7 hours at the temperature of 25-80 ℃, and the cobalt-based nanosheet is obtained after the obtained reactant is cleaned and dried, wherein the ZIF-67 content is 7mg/ml.
In some embodiments, in the step of dissolving the ZIF-67 in an aqueous solution of a cobalt salt, reacting at 25-80 ℃ for 2-7h, and washing and drying the obtained reactant to obtain the cobalt-based nanosheet, the cobalt ion solution in the cobalt salt solution has a concentration of 1-100mg/ml.
In some embodiments, the cobalt salt in the cobalt salt solution comprises cobalt nitrate, cobalt acetate or cobalt chloride, and the solvent comprises deionized water, methanol, ethanol, or a mixed solution of methanol and ammonia.
In some of these embodiments, the cobalt salt solution is an aqueous cobalt nitrate solution having a concentration of 24mg/ml.
The second purpose of the application is to provide a cobalt-based nanosheet, which is prepared by any one of the preparation methods of the cobalt-based nanosheets.
The third object of the application provides an application of the cobalt-based nanosheet in resisting microorganisms.
The fourth purpose of the application is to provide an application of the cobalt-based nanosheet in evaluating cell proliferation.
This application adopts above-mentioned technical scheme, its beneficial effect as follows:
the cobalt-based nanosheet and the preparation method thereof are characterized in that ZIF-67 is dissolved in a cobalt salt aqueous solution and reacts for 2-7h at the temperature of 25-80 ℃, and the obtained reactant is cleaned and dried to obtain the cobalt-based nanosheet 2 (CHN) does not favor beta-Co (OH) during synthesis 2 The transition is carried out, the hexagonal nanosheet has uniform particle size and sharp edge, the positive potential in the aqueous solvent is stable, and the microscopic thickness is within the range of 10-50 nm; the preparation method has the advantages of low reaction temperature, simple and convenient preparation process, low cost, large-scale synthesis, larger and more controllable product size, larger specific surface area, more active sites and the like, has certain biological safety, and can be applied to the aspect of microorganism resistance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the description of the embodiments of the present application or the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM topography of a sample prepared in example 1 of the present application.
FIG. 2 is an SEM topography of a sample prepared in example 2 of the present application.
FIG. 3 is an SEM topography of a sample prepared according to example 3 of the present application.
FIG. 4 is an SEM topography of a sample prepared in example 4 of the present application.
FIG. 5 is an SEM topography of a sample prepared according to example 5 of the present application.
FIG. 6 is an SEM topography of a sample prepared in example 6 of the present application.
FIG. 7 is an SEM topography of a sample prepared in example 7 of the present application.
FIG. 8 is an SEM topography of a sample prepared in example 8 of the present application.
FIG. 9 is an SEM topography of a sample prepared according to example 9 of the present application.
FIG. 10 is an SEM topography of a sample prepared in example 10 of the present application.
Fig. 11 is an XRD spectrum of the nanosheet prepared in example 11 of the present application.
Fig. 12 (a) is a graph showing the results of anti-staphylococcus aureus (s. Aureus) provided in example 12 of the present application.
Fig. 12 (b) is a schematic diagram of the results of the anti-escherichia coli (e.coli) provided in example 12 of the present application.
FIG. 13 is a graph showing the results of 293T cytotoxicity provided in example 13 of the present application.
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary and intended to be used for explaining the present application and should not be construed as limiting the present application.
In the description of the present application, it is to be understood that the terms "upper", "lower", "horizontal", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present application and simplifying the description, and do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
In order to make the objects, technical solutions and advantages of the present application more clearly understood, the present application is further described in detail below with reference to the accompanying drawings and embodiments.
The preparation method of the cobalt-based nanosheet provided by an embodiment of the application includes the following step S110, and specific implementation manners of the steps are described in detail below.
Step S110: dissolving ZIF-67 in an aqueous solution of cobalt salt, reacting for 2-7h at 25-80 ℃, and cleaning and drying the obtained reactant to obtain the cobalt-based nanosheet.
In some embodiments, the ZIF-67 specifically comprises the following steps: and (2) mixing the 2-methylimidazole solution and the cobalt salt solution at the temperature of 25-80 ℃ for reaction for 2-7h, and cleaning and drying the obtained reactant to obtain the ZIF-67.
In some of these embodiments, the concentration of the 2-methylimidazole solution is 10-100mg/ml.
Preferably, the concentration of the 2-methylimidazole solution is 45mg/ml.
It should be noted that: based on the concentration, hexagonal ZIF-67 nano particles with uniform size are obtained, if the concentration is too low, the size of the obtained material is not uniform, and if the concentration is too high, imidazole ligand is redundant, and unnecessary medicines are consumed.
In some of these embodiments, the cobalt ion solution concentration in the cobalt salt solution is 1-100mg/ml.
In some embodiments, the cobalt salt in the cobalt salt solution comprises cobalt nitrate, cobalt acetate or cobalt chloride, and the solvent comprises deionized water, methanol, ethanol, or a mixed solution of methanol and ammonia.
Preferably, the cobalt salt solution is a cobalt nitrate methanol solution, and the concentration of the cobalt nitrate methanol solution is 20mg/ml.
It should be noted that: the cobalt ions and the imidazole ligand are controlled to synthesize the hexagonal ZIF-67 nano particles with uniform size under the condition of the proportion, if the cobalt ions and the imidazole ligand are too low, the size of the obtained material is not uniform, and if the cobalt ions are too high, the cobalt ions are redundant, and unnecessary medicines are consumed.
It is understood that ZIFs, i.e., zeolitic imidazolate framework materials, are porous crystalline materials. A ZIF-67 zeolite imidazole ester framework material cas:46201-07-4 is an MOF material, and the synthesis and application research of metal organic framework Materials (MOFs) are one of the hot fields of modern porous material research. In the embodiment, the cobalt-based ZIFs are used as the sacrificial template, and the ZIF-67 is synthesized by using the sacrificial template material, so that the preparation process is simple.
In some of these embodiments, the ZIF-67 is present in an amount of 7mg/ml.
In some of these embodiments, the cobalt ion solution in the cobalt salt solution has a concentration of 1 to 100mg/ml.
In some embodiments, the cobalt salt in the cobalt salt solution comprises cobalt nitrate, cobalt acetate or cobalt chloride, and the solvent comprises deionized water, methanol, ethanol, or a mixed solution of methanol and ammonia.
Preferably, the cobalt salt solution is an aqueous cobalt nitrate solution, and the concentration of the aqueous cobalt nitrate solution is 24mg/ml.
It should be noted that: and controlling cobalt ions and water ions in the proportion to simultaneously etch and regenerate the nanosheets for the ZIF-67 nanoparticles so as to form cobalt-based nanosheets with clear edges, uniform sizes and uniform thicknesses, wherein if the cobalt-based nanosheets are too low or too high, irregular steps and incomplete stripping appear on the surface of the obtained material, and the uneven etching and growth rate of the nanosheets is displayed.
It can be understood that in the ZIF-67 reaction process of cobalt ion and water ion etching, the free hydroxyl group and cobalt ion have strong coordination, so that the cobalt-based nanosheet grows in a certain direction, and finally a hexagonal sheet structure is formed, and the structure is stable.
It should be noted that: the application is not limited to ZIF-67, and the corresponding cobalt-based nanosheets are obtained under the action of other metal salts, such as zinc nitrate, copper nitrate and the like.
According to the preparation method of the cobalt-based nanosheet, provided by the embodiment of the application, the cobalt-based ZIFs is used as a sacrificial template, and a-Co (OH) is synthesized at room temperature under the stirring condition through ion etching and in-situ growth of layered cobalt hydroxide 2 So that the prepared cobalt-based nanosheet can exist stably and does not tend to beta-Co (OH) in the synthesis process 2 The nano-composite material has the advantages of uniform particle size, sharp hexagonal nano-sheet appearance of edges, stable positive potential in a water solvent, and microscopic thickness in the range of 10-50 nm, further increases the specific surface area of the material, provides more microorganism contact areas and active sites, has good stability, and provides a new idea for the synthesis of the layered double hydroxide.
The cobalt-based nanosheet provided by the embodiment of the application can be obtained under different concentrations and room temperature conditions, the reaction time is short, and the stable alpha-Co (OH) can be obtained without extra continuous temperature rise and strict acid-base regulation conditions 2 The method can realize batch production, and the synthesis method is simple and convenient to operate.
According to the cobalt-based nanosheet provided by the embodiment of the application, the positive potential of the material is further improved on the basis that the ZIF-67 has the positive potential, so that the cobalt-based nanosheet is more easily contacted with a negatively charged cell membrane, a certain antimicrobial effect is achieved, and a new thought is provided for the antibacterial design of the nanomaterial.
The cobalt-based nanosheet provided by the embodiment of the application can be applied to resisting microorganisms and evaluating cell proliferation, and has a good market prospect.
The technical solutions of the present application are described in detail below with reference to specific examples.
Synthesis of sacrificial template material ZIF-67:
example 1: preparing an organic ligand 2-methylimidazole (2-MI) methanol solution required by growth of ZIF-67, and selecting the concentration of the 2-MI methanol solution to be 45mg/ml; preparing a cobalt nitrate methanol solution required by ZIF-67 growth, selecting the concentration of the cobalt nitrate methanol solution to be 20mg/ml, mixing and reacting for 3 hours under the action of a magnetic stirrer, centrifuging at 10000rpm/s for 10min, washing with methanol for three times, and drying in vacuum at 60 ℃.
Ion etching the template and growing the layered nanosheets:
example 2: preparing an aqueous solution of cobalt nitrate for ion etching, selecting the aqueous solution of cobalt nitrate with the concentration of 24mg/ml and the aqueous solution of cobalt nitrate with the concentration of ZIF-67 of 7mg/ml, mixing and reacting the two solutions for 5 hours under the action of a magnetic stirrer, centrifuging at 4000rpm/s for 5 minutes, washing with methanol for three times, and drying in vacuum at 40 ℃.
Example 3: preparing an aqueous solution of cobalt nitrate for ion etching, selecting the aqueous solution of cobalt nitrate with the concentration of 12mg/ml and the aqueous solution of cobalt nitrate with the concentration of 7mg/ml of ZIF-67, mixing and reacting the two solutions for 5 hours under the action of a magnetic stirrer, centrifuging at 4000rpm/s for 5 minutes, washing with methanol for three times, and drying in vacuum at 40 ℃.
Example 4: preparing a cobalt nitrate aqueous solution for ion etching, selecting the cobalt nitrate aqueous solution with the concentration of 120mg/ml and the cobalt nitrate aqueous solution with the concentration of 7mg/ml of ZIF-67, mixing and reacting the two solutions for 5 hours under the action of a magnetic stirrer, centrifuging at 4000rpm/s for 5 minutes, washing with methanol for three times, and drying in vacuum at 40 ℃.
Example 5: preparing a cobalt nitrate aqueous solution for ion etching, selecting the cobalt nitrate aqueous solution with the concentration of 24mg/ml and the cobalt nitrate aqueous solution with the concentration of 7mg/ml of ZIF-67, mixing and reacting the two solutions for 2min under the action of a magnetic stirrer, centrifuging at 4000rpm/s for 5min, washing with methanol for three times, and drying in vacuum at 40 ℃.
Example 6: preparing an aqueous solution of cobalt nitrate for ion etching, selecting the aqueous solution of cobalt nitrate with the concentration of 24mg/ml and the aqueous solution of cobalt nitrate with the concentration of ZIF-67 of 7mg/ml, mixing and reacting the two solutions for 10min under the action of a magnetic stirrer, centrifuging at 4000rpm/s for 5min, washing with methanol for three times, and drying in vacuum at 40 ℃.
Example 7: preparing a cobalt nitrate aqueous solution for ion etching, selecting the cobalt nitrate aqueous solution with the concentration of 24mg/ml and the cobalt nitrate aqueous solution with the concentration of 7mg/ml of ZIF-67, mixing and reacting the two solutions for 1h under the action of a magnetic stirrer, centrifuging at 4000rpm/s for 5min, washing with methanol for three times, and drying in vacuum at 40 ℃.
Example 8: preparing zinc nitrate aqueous solution for ion etching, selecting the zinc nitrate aqueous solution with the concentration of 24mg/ml and the zinc nitrate aqueous solution with the concentration of 7mg/ml of ZIF-67, mixing and reacting the two solutions for 5 hours under the action of a magnetic stirrer, centrifuging at 4000rpm/s for 5 minutes, washing with methanol for three times, and drying in vacuum at 40 ℃.
Example 9: preparing a copper nitrate aqueous solution for ion etching, selecting a cobalt nitrate aqueous solution with the concentration of 24mg/ml and a copper nitrate aqueous solution with the concentration of 7mg/ml, mixing and reacting the two solutions for 5 hours under the action of a magnetic stirrer, centrifuging at 4000rpm/s for 5 minutes, washing with methanol for three times, and drying in vacuum at 40 ℃.
Example 10: preparing ceric amine nitrate aqueous solution for ion etching, selecting ceric amine nitrate aqueous solution with the concentration of 1mg/ml and selecting cerium amine nitrate aqueous solution with the concentration of 7mg/ml, mixing and reacting the ceric amine nitrate aqueous solution and the ceric amine nitrate aqueous solution under the action of a magnetic stirrer for 5 hours, centrifuging at 4000rpm/s for 5 minutes, washing with methanol for three times, and drying in vacuum at 40 ℃.
Observation of material surface morphology:
example 11: after spraying gold on the sample, observing the surface morphology of the nanomaterial by using a field emission scanning electron microscope (FE-SEM, ZEISS, germany, SUPRA 55), wherein the surface morphologies of the samples of examples 1-10 are shown in FIGS. 1-10, and it can be seen that the formed nanomaterial shows a lamellar nanosheet structure as the reaction time is prolonged.
And (3) analyzing the material components:
example 12: FIG. 11 is an XRD spectrum of Co (OH) 2 thus prepared. As can be seen from fig. 11, the XRD spectrum has diffraction peaks 2 θ =10.000 °, 19.316 ° and 59.195 ° corresponding to a-Co (OH) 2 standard card (PDF card No. 74-1057) and crystal planes (003), (006) and (110), respectively, indicating successful synthesis of a-Co (OH) 2 phase.
And (3) antibacterial experiments:
example 13: dissolving the nano material in a culture solution, mixing Escherichia coli (E.coli) and staphylococcus aureus (S.aureus) with the material at a density of 1 × 107CFU/mL, inoculating the mixture into a pore plate, placing the pore plate in an incubator at 37 ℃ for 24 hours, detecting the activity of bacteria by using MTT (methyl thiazolyl tetrazolium), and evaluating the antibacterial performance of the material. The results of the antibacterial test are shown in fig. 12 (a) and (b). As can be seen from fig. 12 (a) and (b), the nanosheets exhibited a certain antibacterial performance against e.coli and s.aureus at a concentration of 500 mg/ml.
Cell experiments:
example 14: the prepared material was dissolved in a medium and placed in a 24-well plate with kidney epithelial cells (293T) at 1X 10 4 cell/well Density plated on well plates, at 37 ℃ 5% 2 After 2 days in the incubator, the absorbance values were measured using CCK-8 to evaluate the proliferation of cells on different materials. Cell proliferation is shown in figure 13. As can be seen from the figure, 20mg/ml of nanosheets inhibited cell proliferation to some extent with the extension of culture time, but 5mg/ml,10mg/ml and 15mg/ml did not affect cell bioactivity.
Virus experiments: HEK-293T (ACE 2-OE) cells with over-expressed ACE2-GFP and SC2-P or VOC-SC2-P carrying Flag are incubated for 2 hours in the presence of different nano materials and then fixed, and the amount of pseudovirus in the cells is detected by anti-Flag immunofluorescence. Finally, the inhibition experiment of the nano material on the true SARS-CoV-2 and VOC virus is carried out in a biosafety level 3 laboratory according to the standard. The Vero-E6 cell is infected in a 96-well plate for 2 hours in the presence or absence of a nano material, redundant virus is washed away, and the culture is continued for 48 hours by adding a nano antiviral material; the culture supernatants were collected and analyzed for virus loading by real-time quantitative PCR using a commercial COVID19 detection kit.
It is to be understood that various features of the above-described embodiments may be combined in any combination, and for the sake of brevity, all possible combinations of features in the above-described embodiments may not be described in detail, but rather, all combinations of features may be considered to fall within the scope of the present disclosure unless there is a conflict between such combinations.
The foregoing is considered as illustrative only of the preferred embodiments of the invention, and is presented only for the purpose of illustrating the principles of the invention and not in any way to limit its scope. Any modifications, equivalents and improvements made within the spirit and principles of the present application and other embodiments of the present application without the exercise of inventive faculty will occur to those skilled in the art and are intended to be included within the scope of the present application.
Claims (14)
1. A preparation method of a cobalt-based nanosheet is characterized by comprising the following steps:
dissolving ZIF-67 in an aqueous solution of cobalt salt, reacting for 2-7h at 25-80 ℃, and cleaning and drying the obtained reactant to obtain the cobalt-based nanosheet.
2. A method of making cobalt-based nanoplatelets as in claim 1, wherein the ZIF-67 is prepared by:
and mixing the 2-methylimidazole solution and a cobalt salt solution at the temperature of 25-80 ℃ for reaction for 2-7h, and cleaning and drying the obtained reactant to obtain the ZIF-67.
3. The preparation method of cobalt-based nanosheets as defined in claim 2, wherein in the step of mixing and reacting the 2-methylimidazole solution with the cobalt salt solution at 25 ℃ -80 ℃ for 2-7h, and washing and drying the obtained reactant to obtain the ZIF-67, the concentration of the 2-methylimidazole solution is 10-100mg/ml.
4. A process for the preparation of cobalt-based nanoplatelets as in claim 3, wherein the concentration of the 2-methylimidazole solution is 45mg/ml.
5. The preparation method of cobalt-based nanosheets as defined in claim 2, wherein in the step of mixing and reacting the 2-methylimidazole solution with the cobalt salt solution at 25-80 ℃ for 2-7h, and washing and drying the obtained reactant to obtain the ZIF-67, the concentration of the cobalt ion solution in the cobalt salt solution is 1-100mg/ml.
6. A preparation method of cobalt-based nanosheets as defined in claim 5, wherein the cobalt salt in the cobalt salt solution comprises cobalt nitrate or cobalt acetate or cobalt chloride, and the solvent comprises deionized water or methanol or ethanol or a mixed solution of methanol and ammonia.
7. A process for the preparation of cobalt-based nanoplatelets of claim 6 wherein the cobalt salt solution is a cobalt nitrate methanolic solution having a concentration of 20mg/ml.
8. The preparation method of cobalt-based nanosheets as defined in claim 1, wherein in the step of dissolving the ZIF-67 in an aqueous solution of a cobalt salt, reacting at 25-80 ℃ for 2-7h, and washing and drying the obtained reactant to obtain the cobalt-based nanosheets, the ZIF-67 content is 7mg/ml.
9. The preparation method of cobalt-based nanosheets as defined in claim 1, wherein in the step of dissolving the ZIF-67 in an aqueous solution of a cobalt salt, reacting at 25-80 ℃ for 2-7h, and washing and drying the obtained reactant to obtain the cobalt-based nanosheets, the cobalt ion solution in the cobalt salt solution has a concentration of 1-100mg/ml.
10. The preparation method of cobalt-based nanosheets of claim 7, wherein the cobalt salt in the cobalt salt solution comprises cobalt nitrate or cobalt acetate or cobalt chloride, and the solvent comprises deionized water or methanol or ethanol or a mixed solution of methanol and ammonia.
11. A process for the preparation of cobalt-based nanoplatelets of claim 10 wherein the cobalt salt solution is an aqueous cobalt nitrate solution having a concentration of 24mg/ml.
12. Cobalt-based nanosheet characterized by being produced by the method of producing a cobalt-based nanosheet of any one of claims 1 to 11.
13. Cobalt-based nanoplatelets as in claim 12 for use in combating microorganisms.
14. Use of cobalt-based nanoplatelets as defined in claim 12 for evaluating the proliferation of a cell.
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