CN117736461B - Preparation method of Zn-MOFs material - Google Patents
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- CN117736461B CN117736461B CN202410186246.6A CN202410186246A CN117736461B CN 117736461 B CN117736461 B CN 117736461B CN 202410186246 A CN202410186246 A CN 202410186246A CN 117736461 B CN117736461 B CN 117736461B
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention relates to a preparation method of Zn-MOFs material, which comprises the steps of mixing solution A and solution B and reacting to obtain Zn-MOFs material; solution A is Zn metal salt solution; the solution B is a mixed solution of the organic ligand I and the organic ligand II. In the preparation method of the Zn-MOFs material, inorganic metal ions (Zn 2+) and organic ligands (halogen-containing organic structural materials) have a certain antibacterial function, and the prepared Zn-MOFs material is easier to adsorb bacteria on the surface of an antibacterial agent and achieves an antibacterial effect through a more stable and durable slow-release process.
Description
Technical Field
The invention belongs to the technical field of antibiosis, and relates to a preparation method of Zn-MOFs material.
Background
MOFs materials are widely studied in the medical and health industries because of the advantages of large specific surface area, multi-stage adjustable aperture, multiple framework structures, good biocompatibility and stability and the like. As typical representatives of MOFs materials, zn-MOFs such as ZIF-8 are favored because of the characteristics of easy synthesis, good chemical stability, good biocompatibility and the like, and in recent years, researches on Zn-MOFs in aspects of drug carriers, slow-release antibacterial and photocatalytic antibacterial have achieved a certain result;
According to the research results obtained at present, the research and development of Zn-MOFs base photocatalysis antibacterial fiber has the following problems: zn-MOFs as a semiconductor material has the problems of large forbidden bandwidth, long photocatalytic reaction time, need of adding auxiliary antibacterial materials or thermal oxygen sensitization, excitation mainly in a near infrared region and the like, and greatly limits the application of the Zn-MOFs in the field of photocatalytic antibacterial disinfection;
For example: document 1 (J Mol Structure, 2021, 1225: 129094-1-129094-7) discloses a novel complex Zn-MOFs material which can be used for antibacterial purposes, but which requires the use of DCFH-DA fluorescent material to assist ROS production and has a long photocatalytic reaction time.
Document 2 (study of preparation and application of ZIF-8 based composite antibacterial material [ D ]. Vinca: jilin university, 2020) discloses a Zn-MOF nanocomposite particle adsorbing Ag + with multiple antibacterial action, but requires synergistic effect of Zn 2+ and reduced Ag under near infrared light irradiation to have antibacterial performance.
Document 3 (Acta Biomaterialia, 2021,122:291) discloses a Zn-MOF nanosystem with photothermal/pH dual stimulus response for antimicrobial treatment, also requiring near infrared excitation at 808 nm.
Therefore, research on a preparation method of a novel Zn-MOFs material is of great significance in order to solve the problems.
Disclosure of Invention
The invention aims to solve the problems existing in the prior art and provides a preparation method of a Zn-MOFs material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of Zn-MOFs material comprises mixing solution A and solution B, and reacting to obtain Zn-MOFs material;
Solution A is Zn metal salt solution;
The solution B is a mixed solution of an organic ligand I and an organic ligand II;
The organic ligand I is 、/>、/>、/>Or/>Wherein X is chloro, bromo or iodo;
The organic ligand II is 、/>、Or/>。
The antibacterial mechanism of the Zn-MOFs material of the invention mainly comprises the following steps:
① Inorganic metal ions (Zn 2+) and organic ligands (halogen-containing organic structural materials) forming the Zn-MOFs material have a certain antibacterial function, when the Zn-MOFs material is in a specific environment (the specific environment is under visible light), coordination bonds between metal centers and the organic ligands are broken to a certain extent, and then the metal ions and the organic ligands with the antibacterial function are slowly released in the environment so as to achieve an antibacterial effect, the permeability of bacterial membranes is changed through contact reaction, nutrient substances in bacteria are lost, and then the bacteria are inactivated, or bacterial propagation and growth are blocked by destroying genetic materials DNA and RNA of the bacteria, and the antibacterial effect is achieved.
② From document 4 (Dalton Trans, 2017:10.1039.C7DT032556K), it is known that the conduction band potential is calculated to be approximately-0.78V (vs. NHE) according to the Mort-Schottky curve of the ZIF-8 of the conventional Zn core MOF structure, which is larger than (O 2/·O2 -: -0.33V vs. NHE), the generation of superoxide radical O 2 - is favorable in thermodynamics, but the generation of photo-generated electrons cannot be satisfied in kinetics due to the fact that the ZIF-8 is difficult to excite under visible light due to the large forbidden bandwidth (4.94 eV). The Zn-MOFs material has a small forbidden bandwidth (2.07-2.34 eV) (the reason for the reduced forbidden bandwidth is that the organic ligand I is introduced with halogen groups in the preparation process, the doping stress of the halogen atoms affects the forbidden bandwidth, the organic ligands are of conjugated structures, pi electrons have large delocalized structures, and can promote electron transfer), and the Zn-MOFs material is easy to drive under visible light and can generate photo-generated electrons more easily. The Zn-MOFs prepared by the method has lower forbidden bandwidth, and the absorbed visible light wavelength is shorter than the near infrared light wavelength, so that the energy is higher, the activity of the photocatalytic reaction is higher, and the photocatalytic reaction time is shortened.
The photocatalysis antibacterial specific process of the Zn-MOFs material comprises the following steps: the Zn-MOFs material generates charge separation under the excitation of visible light to generate a large number of photo-generated electron-hole pairs (Zn-MOFs+hv- & gt e -+h+), photo-generated electrons are transferred to the center of Zn 2+ through LMCT (ligand metal charge transfer), zn 2+ is activated to be Zn +（Zn2++e-→Zn+, a large number of Zn + and redundant e - with strong reducibility are subjected to oxidation-reduction reaction with O 2 in air or water solution, zn + is oxidized to be stable Zn 2+, O 2 is reduced to be ·O2（-Zn++O2→ Zn2++·O2-、e-+O2→·O2 -）,·O2 - which is an anion and a free radical, the photo-generated electron-hole pairs have strong oxidability and reducibility, the photo-generated electron pairs and the hole (h +) with strong oxidability in a valence band act on microorganisms such as bacteria, the cell membrane, protein and genetic materials of the bacteria are destroyed by utilizing the strong oxidation-reduction property of the photo-generated electron pairs, and debris and secretion of the photo-generated electron pairs are decomposed into nontoxic harmless carbon dioxide and water. The antibacterial process is green, clean, efficient and durable, and has broad-spectrum bactericidal property.
In addition, the halogen group is introduced into the organic ligand I, so that the action capability between the material and other components can be enhanced, and a halogen bond is formed; and the existence of halogen can enhance cytotoxicity of the material, and cooperate with a mode of generating active oxygen by photocatalysis to inhibit bacteria, so that the sterilization performance is enhanced.
As a preferable technical scheme:
According to the preparation method of the Zn-MOFs material, the pore volume of the Zn-MOFs material is 1.5-2.7 cm 3/g, the pore diameter is 0.48-0.77 nm, the specific surface area is 1636-1951 m 2/g, the specific surface area is large, the number of reaction sites can be ensured, the pore diameter and the pore volume are large, and a large enough entering channel and reaction space can be ensured, so that reactants can enter specific positions, and the steric hindrance effect can not be caused (the reactants cannot reach the reaction sites).
According to the preparation method of the Zn-MOFs material, the antibacterial rate of the Zn-MOFs material to escherichia coli and staphylococcus aureus is 99.68% -99.99% after the Zn-MOFs material is irradiated by visible light for 20-30 min.
The metal-organic framework material is formed by constructing Zn metal oxygen clusters and organic ligands I, II through coordination, has triangular prism structure unit configuration, and X groups introduced into the organic ligands I are beneficial to forming intermolecular halogen bond action, promote the formation of micropore structures and play a role in stabilizing, and increase pore volume and pore diameter; the microcosmic appearance is triangular prism, and the surface groups are protruded as 'roughness', so that the specific surface area is increased. The Zn-MOFs prepared by the method have larger specific surface area, pore volume and pore diameter, and the organic ligand I, II has halogen groups, aromatic ring hydrogen, metal core Zn and the like, so that more reaction sites can be provided, the probability of acting with O 2 in the environment is increased, and the photocatalytic reaction is promoted.
The preparation method of the Zn-MOFs material comprises the following specific preparation steps:
(1) Respectively putting Zn metal salt in a solvent A to obtain a solution A, and putting an organic ligand I and an organic ligand II in a solvent B to obtain a solution B;
(2) Respectively carrying out ultrasonic treatment on the solution A and the solution B for 15-30 min to uniformly disperse, adding the solution A into the solution B, stirring for 6-12 h at room temperature, and then standing for 18-36 h;
(3) And washing and centrifuging the mixed solution after standing for 3-5 times, and then placing the mixed solution in a 60-80 ℃ oven for drying for 8-12 hours to obtain the Zn-MOFs material.
According to the preparation method of the Zn-MOFs material, in the step (1), the molar ratio of the Zn metal salt to the organic ligand I to the organic ligand II is 6.5-8.0:3.3-3.8:2, the molar ratio is set in the range, the proportion relation of the reactants to form a final product is met, a certain value is too small, the component is lost in a triangular prism structure, and a certain value is too large, so that raw materials are wasted.
According to the preparation method of the Zn-MOFs material, in the step (1), zn metal salt is Zn（NO3）2、Zn（NO3）2·6H2O、ZnSO4·7H2O、ZnCl2 or ZnCl 2·4H2 O.
According to the preparation method of the Zn-MOFs material, in the step (1), the concentration of the solution A is 0.05-0.5 mol/L, and the concentration of the solution B is 0.05-0.5 mol/L.
According to the preparation method of the Zn-MOFs material, in the step (1), the solvent A is DMSO, methanol, ethanol, water or acetonitrile, and the solvent B is DMSO, methanol, ethanol, water or acetonitrile.
The beneficial effects are that:
(1) Compared with the traditional organic and inorganic antibacterial agents, the preparation method of the Zn-MOFs material has a certain antibacterial function by inorganic metal ions (Zn 2+) and organic ligands (halogen-containing organic structural materials), and the prepared Zn-MOFs material is easier to adsorb bacteria on the surface of the antibacterial agents and achieves an antibacterial effect through a more stable and durable slow release process;
(2) Compared with the existing MOF antibacterial material with Zn core, the Zn-MOFs prepared by the invention has lower forbidden bandwidth, and the absorbed visible light wavelength is shorter than the near infrared light wavelength, and the energy is higher, so that the Zn-MOFs have higher photocatalytic reaction activity and shorten the photocatalytic reaction time; and the Zn-MOFs material is not required to be added with auxiliary antibacterial materials or sensitized by thermal oxygen and is excited in a visible light region (more convenient for practical application).
Drawings
FIG. 1 is a schematic diagram of a preparation mechanism of a Zn-MOFs material;
FIG. 2 is a graph showing the specific surface area (BET) test of the Zn-MOF material prepared in example 1;
FIG. 3 is a graph showing the specific surface area (BET) test of the Zn-MOF material prepared in example 2;
FIG. 4 is a graph showing the specific surface area (BET) test of the Zn-MOF material prepared in example 3;
FIG. 5 is a graph showing the specific surface area (BET) test of the Zn-MOF material prepared in example 4;
FIG. 6 is a graph showing the specific surface area (BET) test of the Zn-MOF material prepared in example 5.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The test methods involved in the examples are as follows:
Specific surface area (BET) test: measuring a nitrogen adsorption and desorption isotherm by using a microphone ASAP2460 analyzer, and calculating the specific surface area of the Zn-MOFs material by adopting a Brunauer-Emmett-Teller method;
Photocatalytic test: photocurrent, electrochemical impedance and mote-schottky curve (MS) were measured using a CHI660E electrochemical workstation (CH Instruments, china), an equivalent amount of 10mg Zn-MOFs material was weighed and ultrasonically dispersed in 500 μl of a mixture of absolute ethanol and PVDF (volume ratio of 1:1) during the sample preparation, and then the mixture was uniformly dropped on conductive glass and dried sufficiently for use; fluorescence spectra (PL) were measured using a Hitachi F-4700 fluorescence spectrophotometer.
Photocatalytic antibacterial performance test: the method selects escherichia coli and staphylococcus aureus as detection strains (the activity is kept at 3-9 generations), equipment used in the experiment is subjected to high-pressure sterilization or ultraviolet lamp irradiation treatment, the photocatalysis antibacterial rate of the Zn-MOFs material on the escherichia coli and the staphylococcus aureus under different conditions is researched, and the specific flow is as follows:
(1) Inoculation and activation of bacteria: firstly, respectively weighing 10g/L of yeast peptone, 5g/L of yeast extract and 5g/L of NaCl in a beaker, adding a certain amount of deionized water and a proper amount of NaOH, and preparing a bacterial liquid culture medium with pH=7.4; placing the prepared bacterial liquid culture medium into a high-pressure steam sterilizing pot for high-pressure sterilization (121 ℃ for 30 min) to obtain sterile culture solution; taking 250mL of sterile culture solution in an ultra-clean workbench, inoculating experimental strains in a conical flask, and placing the experimental strains in a constant-temperature shaking table (37 ℃ and 120 rpm) for activation for 24 hours to obtain obviously turbid bacterial stock solution; in order to obtain bacterial liquid with higher activity, 200 mu L of bacterial stock solution is taken and transferred into 100mL of sterile culture solution, and the bacterial liquid is further cultured in a constant temperature shaking table (37 ℃ C., 120 rpm) for 24 hours, and the ultraviolet absorbance of the bacterial liquid at the wavelength of 600nm is ensured to be not lower than 0.5, and finally the bacterial liquid is used as experimental stock solution.
(2) Antibacterial process: firstly, respectively weighing 2.84g/L Na 2HPO4, 1.36g/L KH 2PO4 and a certain amount of water, preparing PBS buffer solution with the concentration of 0.01mol/L, and placing the PBS buffer solution in an autoclave for sterilization treatment to obtain sterile PBS buffer solution; taking a certain amount of experimental original bacterial liquid in a test tube, diluting the experimental original bacterial liquid by 100 times by using a sterile culture solution, and then taking a certain amount of diluted bacterial liquid and further diluting the bacterial liquid by 100 times by using a sterile PBS buffer solution to obtain experimental bacterial liquid; weighing 0.5g of sample, and placing the sample under ultraviolet irradiation for disinfection treatment for 2 hours; placing 3.5mL of experimental bacterial liquid and 50mL of sterile PBS buffer solution in a photocatalytic reactor, adding a sample into the photocatalytic reactor, stirring at a rotation speed of 5000rpm for 10min to enable the sample to be in full contact with the photocatalytic reactor, then turning on a xenon lamp light source (provided with an ultraviolet filter plate, lambda is more than or equal to 420 nm) with power of 35W required by photocatalytic reaction, continuing stirring for 30min, and simultaneously turning on a condensation circulating water device to enable the temperature to be maintained at room temperature; the same liquid and sample were placed in a conical flask and shaken at the same room temperature and rotational speed for the same time, as a dark environment control group.
(3) Colony count: firstly, preparing a liquid culture medium according to the proportion in (1), adding 20g/L agar powder (CAS: 9002-18-0, product number: S33010-500g, brand: source leaf) into the liquid culture medium, heating and stirring uniformly at 50 ℃, sterilizing, measuring 25 mL of the sterilized solution, pouring the solution into an ultraviolet sterilized flat plate, and cooling and solidifying to obtain a solid culture medium; when the xenon lamp irradiates, 100 mu L of reacted liquid is taken in sixteen-hole plates every 10min, then 10 times of sterile water which is sterilized is used in advance for dilution, then 100 mu L of diluted solution is taken on a sterile solid culture medium and uniformly coated, finally the solid culture medium is placed in a constant-temperature incubator at 37 ℃ for culturing for 48h, and after bacteria on the culture medium can be obviously observed, the growth condition of bacterial colonies on a flat plate is photographed and counted; it should be noted that in the experiment, the staphylococcus aureus is found to grow less in colony under the same dilution factor, which is unfavorable for comparison and calculation, and in order to calculate the antibacterial rate more obviously, no sterile water dilution is used in the antibacterial experiment on the staphylococcus aureus.
(4) Antibacterial evaluation: the colonies growing on the solid medium were counted by photographing, and in order to reduce the error, each group of samples was taken three times and the average value was calculated as the final colony count, and the antibacterial ratio was calculated as follows:
×100%；
wherein: AR-antibacterial ratio; CG-control group; EG-experimental group.
Example 1
A preparation method of Zn-MOFs material is shown in figure 1, and comprises the following specific steps:
(1) Preparation of raw materials:
zn metal salt: zn (NO 3）2;
organic ligand I: ；
organic ligand II: ；
Solvent a: DMSO;
Solvent B: DMSO;
(2) Zn metal salt is dissolved in a solvent A to obtain a solution A with the concentration of 0.05mol/L, and an organic ligand I and an organic ligand II are dissolved in a solvent B to obtain a solution B with the concentration of 0.05 mol/L;
Wherein, the mol ratio of Zn metal salt, organic ligand I and organic ligand II is 6.5:3.3:2;
(3) After the solution A and the solution B are respectively and evenly dispersed for 15min, the solution A is added into the solution B, stirred for 12h at room temperature, and then kept stand for 18h;
(4) And washing and centrifuging the mixed solution after standing for 3 times, and then placing the mixed solution in a 60 ℃ oven for drying for 12 hours to prepare the Zn-MOFs material.
The pore volume of the finally prepared Zn-MOFs material is 1.5cm 3/g, the pore diameter is 0.48nm, and the specific surface area is 1636m 2/g as shown in figure 2; the antibacterial rates of the Zn-MOFs material on the escherichia coli and the staphylococcus aureus after 20min of irradiation of visible light are 99.68% and 99.68% respectively; the antibacterial rates of the dark environment control group on the escherichia coli and the staphylococcus aureus are 22.86% and 25.41% respectively.
Example 2
A preparation method of Zn-MOFs material comprises the following specific steps:
(1) Preparation of raw materials:
Zn metal salt: zn (NO 3）2·6H2 O;
organic ligand I: ；
organic ligand II: ；
solvent a: methanol;
solvent B: ethanol;
(2) Zn metal salt is dissolved in a solvent A to obtain a solution A with the concentration of 0.1mol/L, and an organic ligand I and an organic ligand II are dissolved in a solvent B to obtain a solution B with the concentration of 0.1 mol/L;
Wherein, the mol ratio of Zn metal salt, organic ligand I and organic ligand II is 6.5:3.8:2;
(3) After the solution A and the solution B are respectively and evenly dispersed for 20min, the solution A is added into the solution B, stirred for 11h at room temperature, and then kept stand for 22h;
(4) And washing and centrifuging the mixed solution after standing for 3 times, and then placing the mixed solution in a 65 ℃ oven for drying for 11 hours to prepare the Zn-MOFs material.
The pore volume of the finally prepared Zn-MOFs material is 1.8cm 3/g, the pore diameter is 0.54nm, and the specific surface area is 1687m 2/g as shown in figure 3; the antibacterial rates of the Zn-MOFs material on the escherichia coli and the staphylococcus aureus after 22min of visible light irradiation are 99.71 percent and 99.81 percent respectively; the antibacterial rates of the dark environment control group on the escherichia coli and the staphylococcus aureus are 26.55 percent and 27.12 percent respectively.
Example 3
A preparation method of Zn-MOFs material comprises the following specific steps:
(1) Preparation of raw materials:
zn metal salt: znSO 4·7H2 O;
organic ligand I: ；
organic ligand II: ；
solvent a: ethanol;
Solvent B: methanol;
(2) Zn metal salt is dissolved in a solvent A to obtain a solution A with the concentration of 0.2mol/L, and an organic ligand I and an organic ligand II are dissolved in a solvent B to obtain a solution B with the concentration of 0.2 mol/L;
Wherein, the mol ratio of Zn metal salt, organic ligand I and organic ligand II is 7.0:3.5:2;
(3) After the solution A and the solution B are respectively and evenly dispersed for 25min, the solution A is added into the solution B, stirred for 10h at room temperature, and then kept stand for 26h;
(4) And washing and centrifuging the mixed solution after standing for 4 times, and then placing the mixed solution in a 70 ℃ oven for drying for 10 hours to prepare the Zn-MOFs material.
The pore volume of the finally prepared Zn-MOFs material is 2.2cm 3/g, the pore diameter is 0.59nm, and as shown in figure 4, the specific surface area is 1745m 2/g; the antibacterial rates of the Zn-MOFs material on the escherichia coli and the staphylococcus aureus after 24min of visible light irradiation are 99.83% and 99.9% respectively; the antibacterial rates of the dark environment control group on the escherichia coli and the staphylococcus aureus are 31.93% and 33.27%, respectively.
Example 4
A preparation method of Zn-MOFs material comprises the following specific steps:
(1) Preparation of raw materials:
zn metal salt: znCl 2;
organic ligand I: ；
organic ligand II: ；
solvent a: water;
Solvent B: water;
(2) Zn metal salt is dissolved in a solvent A to obtain a solution A with the concentration of 0.35mol/L, and organic ligand I and organic ligand II are dissolved in a solvent B to obtain a solution B with the concentration of 0.35 mol/L;
Wherein, the mol ratio of Zn metal salt, organic ligand I and organic ligand II is 7.5:3.6:2;
(3) After the solution A and the solution B are respectively and evenly dispersed for 28min, the solution A is added into the solution B, stirred for 8h at room temperature, and then kept stand for 30h;
(4) And washing and centrifuging the mixed solution after standing for 4 times, and then placing the mixed solution in a 75 ℃ oven for drying for 9 hours to prepare the Zn-MOFs material.
The pore volume of the finally prepared Zn-MOFs material is 2.5cm 3/g, the pore diameter is 0.68nm, and the specific surface area is 1894m 2/g as shown in figure 5; the antibacterial rates of the Zn-MOFs material on the escherichia coli and the staphylococcus aureus after 27min of irradiation of visible light are 99.95 percent and 99.97 percent respectively; the antibacterial rates of the dark environment control group on the escherichia coli and the staphylococcus aureus are 36.26% and 38.63% respectively.
Example 5
A preparation method of Zn-MOFs material comprises the following specific steps:
(1) Preparation of raw materials:
zn metal salt: znCl 2·4H2 O;
organic ligand I: ；
organic ligand II: ；
Solvent a: acetonitrile;
Solvent B: acetonitrile;
(2) Zn metal salt is dissolved in a solvent A to obtain a solution A with the concentration of 0.5mol/L, and organic ligand I and organic ligand II are dissolved in a solvent B to obtain a solution B with the concentration of 0.5 mol/L;
wherein, the mol ratio of Zn metal salt, organic ligand I and organic ligand II is 8.0:3.7:2;
(3) After the solution A and the solution B are respectively and ultrasonically dispersed for 30min, adding the solution A into the solution B, stirring for 6h at room temperature, and then standing for 36h;
(4) Washing and centrifuging the mixed solution after standing for 5 times, and then placing the mixed solution in an oven at 80 ℃ for drying for 8 hours to prepare the Zn-MOFs material.
The pore volume of the finally prepared Zn-MOFs material is 2.7cm 3/g, the pore diameter is 0.77nm, and the specific surface area is 1951m 2/g as shown in FIG. 6; the antibacterial rates of the Zn-MOFs material on the escherichia coli and the staphylococcus aureus after 30min of irradiation of visible light are 99.99 percent and 99.99 percent respectively; the antibacterial rates of the dark environment control group on the escherichia coli and the staphylococcus aureus are 41.37% and 46.89%, respectively.
Claims (7)
1. A preparation method of Zn-MOFs material is characterized by comprising the following steps: mixing the solution A and the solution B and then reacting to obtain Zn-MOFs material;
Solution A is Zn metal salt solution;
The solution B is a mixed solution of an organic ligand I and an organic ligand II;
The organic ligand I is Wherein X is chloro, bromo or iodo;
The organic ligand II is
The molar ratio of Zn metal salt, organic ligand I and organic ligand II is 6.5-8.0:3.3-3.8:2.
2. The method for preparing Zn-MOFs material according to claim 1, wherein the Zn-MOFs material has a pore volume of 1.5-2.7 cm 3/g, a pore diameter of 0.48-0.77 nm and a specific surface area of 1636-1951 m 2/g.
3. The method for preparing the Zn-MOFs material according to claim 2, wherein the Zn-MOFs material has an antibacterial rate of 99.68-99.99% to coliform bacteria and staphylococcus aureus after irradiation of visible light for 20-30 min.
4. The preparation method of the Zn-MOFs material according to claim 1, wherein the specific preparation steps are as follows:
(1) Respectively putting Zn metal salt in a solvent A to obtain a solution A, and putting an organic ligand I and an organic ligand II in a solvent B to obtain a solution B;
(2) Respectively carrying out ultrasonic treatment on the solution A and the solution B for 15-30 min to uniformly disperse, adding the solution A into the solution B, stirring for 6-12 h at room temperature, and then standing for 18-36 h;
(3) Washing and centrifuging the mixed solution after standing for 3-5 times, and then placing the mixed solution in a baking oven at 60-80 ℃ for drying for 8-12 h to obtain the Zn-MOFs material.
5. The method for producing Zn-MOFs materials according to claim 4, wherein the Zn metal salt in step (1) is Zn(NO3)2、Zn(NO3)2·6H2O、ZnSO4·7H2O、ZnCl2 or ZnCl 2·4H2 O.
6. The method for producing Zn-MOFs materials according to claim 4, wherein the concentration of solution A in step (1) is 0.05-0.5 mol/L and the concentration of solution B is 0.05-0.5 mol/L.
7. The method of preparing Zn-MOFs materials according to claim 4, wherein solvent A in step (1) is DMSO, methanol, ethanol, water or acetonitrile, and solvent B is DMSO, methanol, ethanol, water or acetonitrile.
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| KR20180028756A (en) * | 2016-09-09 | 2018-03-19 | 한국화학연구원 | Bifunctional silver ion-containing metal-organic framework composites with functions of antibiosis and dehumidification, a preparation method thereof, and a biodegradable polymer film comprising the same |
| CN112934201A (en) * | 2021-02-07 | 2021-06-11 | 扬州工业职业技术学院 | Composite waste gas adsorption material and preparation method thereof |
| CN112961366A (en) * | 2021-02-01 | 2021-06-15 | 吉林大学 | Preparation method of halamine-containing metal organic framework material with sterilization function |
| WO2023082508A1 (en) * | 2021-11-10 | 2023-05-19 | 浙江大学 | Sustained-release antibacterial membrane and preparation method therefor |
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| KR20180028756A (en) * | 2016-09-09 | 2018-03-19 | 한국화학연구원 | Bifunctional silver ion-containing metal-organic framework composites with functions of antibiosis and dehumidification, a preparation method thereof, and a biodegradable polymer film comprising the same |
| CN112961366A (en) * | 2021-02-01 | 2021-06-15 | 吉林大学 | Preparation method of halamine-containing metal organic framework material with sterilization function |
| CN112934201A (en) * | 2021-02-07 | 2021-06-11 | 扬州工业职业技术学院 | Composite waste gas adsorption material and preparation method thereof |
| WO2023082508A1 (en) * | 2021-11-10 | 2023-05-19 | 浙江大学 | Sustained-release antibacterial membrane and preparation method therefor |
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