CN115006573B - Multifunctional degerming nano-pore COF aerogel and preparation method thereof - Google Patents
Multifunctional degerming nano-pore COF aerogel and preparation method thereof Download PDFInfo
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- CN115006573B CN115006573B CN202210587990.8A CN202210587990A CN115006573B CN 115006573 B CN115006573 B CN 115006573B CN 202210587990 A CN202210587990 A CN 202210587990A CN 115006573 B CN115006573 B CN 115006573B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
- A61L2/235—Solid substances, e.g. granules, powders, blocks, tablets cellular, porous or foamed
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
- A61L9/012—Deodorant compositions characterised by being in a special form, e.g. gels, emulsions
Abstract
The invention discloses a multifunctional degerming nano-pore COF aerogel and a preparation method thereof, the multifunctional degerming nano-pore COF aerogel comprises porous COFs, wherein the porous COFs are provided with metal ions, guanidino and polyimide, the metal ions are Ag+ and an organic ligand I of the COFs is placed in an organic solvent to prepare an organic ligand I-organic solvent solution, a guanidino polymer and polyimide precursor polyamic acid are added to stir, then a silane coupling agent is added to form a mixed solution, a gel accelerator is added to the mixed solution to form a precursor wet sol, the precursor wet sol is placed in an organic solvent of an organic ligand II for synthesizing the COFs to be converted into the COFs wet sol, the functional Ag+ nano ions are loaded in the COFs wet sol by a post-synthesis modification method, the guanidino/polyimide/Ag+ COFs wet sol is generated, then the guanidino/polyimide/Ag+ COFs wet sol is prepared by a gel reaction, and the guanidine/polyimide/Ag+ multifunctional COFs aerogel is obtained after aging and drying.
Description
Technical Field
The invention relates to the technical field of aerogel, in particular to a multifunctional degerming nano-pore COF aerogel and a preparation method thereof.
Background
The common degerming aerogel has a component with degerming function, such as an inorganic degerming component, typically represented by nano Ag+ with excellent performance, and organic degerming components such as organic mercury, organic zinc, chlorophenols, organic bromides and the like, but the organic mercury, the organic zinc and the phenolic bactericides have high sterilization effect, but have extremely toxicity, the irritation of the organic bromides is too large, and the degerming rate is always a problem to be improved.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a multifunctional sterilization nano-pore COF aerogel and a preparation method thereof.
In order to achieve the technical effects, the invention adopts the following scheme:
a multifunctional degerming nano-pore COF aerogel comprises a porous COFs, wherein metal ions, guanidine groups and polyimide are arranged on the porous COFs, and the metal ions are Ag+.
A preparation method of a multifunctional sterilized nano-pore COF aerogel comprises the following steps:
s1, placing an organic ligand I of COFs in an organic solvent, and preparing an organic ligand I-organic solvent solution on a mechanical stirrer at 18-25 ℃ by controlling the rotation speed of a stirring rod to be 250-350 rpm and stirring for 3-5 min;
s2, adding precursor polyamic acid of guanidyl polymer and polyimide into the organic ligand I-organic solvent solution system, and then stirring for 3-5 min at 20-25 ℃ on a magnetic stirrer at a rotating speed of 350-500 rpm;
s3, adding a silane coupling agent into the solution obtained after stirring in the step S2 to form a mixed solution, and then performing ultrasonic reaction in an ultrasonic disperser at 20-25 ℃ for 10-15 min;
s4, adding a gel accelerator into the mixed solution obtained in the step S3, and then homogenizing the mixed solution in an ultrasonic dispersing instrument at 20-25 ℃ for 5-15 min to form precursor wet sol;
s5, placing the precursor wet sol prepared in the step S4 in an organic solvent for synthesizing the organic ligand II of the COFs, stirring for 15-20 min to white emulsion, standing for 3-5 min, then carrying out microwave local heating for 2-4 h to enable the organic ligand I and the organic ligand II of the COFs to complete self-assembly reaction, and converting the precursor wet sol into the COFs wet sol;
s6, carrying out functional Ag+ nano ion loading in the COFs wet sol by a post-synthesis modification method to generate guanidino/polyimide/Ag+ -COFs wet sol;
s7, placing the prepared guanidino/polyimide/Ag+ -COFs wet sol into a baking oven for gel reaction at the temperature of 40-60 ℃ for 1-3 hours to prepare the guanidino/polyimide/Ag+ -COFs wet gel;
s8, aging the guanidino/polyimide/Ag+ -COFs wet gel in an organic solvent for 48-72 hours;
s9, drying the aged guanidino/polyimide/Ag+ -COFs wet gel to obtain the guanidino/polyimide/Ag+ multifunctional COF aerogel.
According to the preferred technical scheme, in the step S1, the ratio of the organic ligand I to the organic solvent is 0.01-1: 1, a step of;
according to a preferred technical scheme, the organic solvent in the step S1 is as follows: a mixed organic solvent of tetrahydrofuran and N, N-dimethylacetamide; the organic ligand I of the COFs is one of trimellitic aldehyde, terephthalaldehyde, tetra (4-formylphenyl) methane, tetra-aldehyde phenyl porphyrin, 3', 5' -tetra-aldehyde biphenyl, 1,2,4, 5-tetra (4-formylphenyl) benzene, 2 '-bipyridine-5, 5' -dicarboxaldehyde, 2, 5-dihydroxyterephthalic acid, 2, 5-dimethoxybenzene-1, 4-dicarboxaldehyde, 2, 6-naphthalene dicarboxaldehyde and 1,3, 5-tri (4-aminophenyl) benzene.
In a preferred embodiment, the guanidino polymer in step S2 is polyhexamethylene biguanide hydrochloride.
According to a preferred technical scheme, the guanidino polymer and polyimide precursor polyamic acid added in the step S2 accounts for 0.1% -10% of the organic ligand I-organic solvent solution system according to the volume ratio.
According to the preferred technical scheme, in the step S3, the dosage of the added silane coupling agent is 0.1-5% of the volume of the stirred solution obtained in the step S2 according to the volume ratio.
According to a preferred technical scheme, the silane coupling agent added in the step S3 is as follows: one of propyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecylmethyldimethoxysilane and hexadecyltrimethoxysilane.
According to the preferred technical scheme, in the step S4, the dosage of the gel accelerator is controlled to be 10-40% of that of the mixed solution according to the volume ratio.
In a preferred technical scheme, the gel accelerator in the step S4 is propylene oxide.
According to the preferred technical scheme, in the step S5, the volume ratio of the organic ligand II to the organic ligand I is 0.8-1.2: 1.
in a preferred embodiment, the organic ligand ii of COFs used in step S5 is: one of phenylenediamine, melem, 1,3, 5-triaminobenzene, biphenyldiamine, 5,15- (aminophenyl) -10, 20-phenylporphyrin, tetrakis (4-aminophenyl) methane, tris (4-aminophenyl) amine, 5 '-diamino-2, 2' -bipyridine, 2,4, 6-tris (4-aminophenoxy) -1,3, 5-triazine, 1,3, 5-tris (4-aminophenyl) benzene, 4,4,4,4-tetraethyl-tetraaniline, 2,3,5, 6-tetrafluoroterephthalic acid formaldehyde; the organic solvents used were: one of ethanol, methanol and dimethylformamide.
According to the preferred technical scheme, the specific operation steps for carrying out the loading of the functional Ag+ nano ions in the step S6 are as follows: placing the prepared COFs wet sol into an organic solution containing Ag salt, carrying out ultrasonic treatment for 2-5 min, vibrating the mixed solution on a shaking table for 15-25 min, then placing the mixed solution into a microwave reactor, controlling the microwave reaction rate, reacting for 45min, and heating in a water bath at 45-60 ℃ for 6-12 h, so that Ag+ is fully loaded on the COFs, and forming the guanidino/polyimide/Ag+ -COFs wet gel.
In a preferred technical scheme, the silver salt in the step S6 is silver nitrate.
In a preferred embodiment, the organic solvent used in step S8 is methanol.
The preferred technical scheme is that the drying method used in the step S9 is as follows: one of freeze drying and supercritical drying.
Compared with the prior art, the beneficial effects are as follows:
1. the concept of the metal-covalent organic framework (M-COF) is creatively applied to the aerogel field, and a new material structure of synergistic sterilization of organic and inorganic multiple components is prepared by using guanidino and comparing and selecting metal ions M (Ag+), so that the maximization of the sterilization effect and the optimal solution are sought, and the result of 1+1>2 is realized;
2. the prepared new material endows the conventional gel with microporous characteristics which are difficult to have, increases the porosity and the surface area of the gel material, improves the adsorption performance of the gel material and enhances the sterilization efficiency;
3. the COFs gel light material prepared from the light element (B, C, O, N) has the advantage of low self weight of the structure;
4. the introduction of polyimide, which is a high-performance material, makes up the defect of guanidine physical and chemical properties, and in addition, the material has the advantages of heat resistance and sustainable use, and the recycling of the material can be realized through ultrasonic water washing.
Drawings
FIG. 1 is a flow chart of a preparation method in the present invention;
FIG. 2 is a process for preparing the present invention;
FIG. 3 is a graph of antimicrobial test results;
fig. 4 is a graph of the results of a persistent antimicrobial test.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
A multifunctional degerming nano-pore COF aerogel comprises a porous COFs, wherein metal ions, guanidine groups and polyimide are arranged on the porous COFs, and the metal ions are Ag+.
A preparation method of a multifunctional sterilized nano-pore COF aerogel comprises the following steps:
s1, placing an organic ligand I of COFs in an organic solvent, and preparing an organic ligand I-organic solvent solution on a mechanical stirrer at 18-25 ℃ by controlling the rotation speed of a stirring rod to be 250-350 rpm and stirring for 3-5 min;
s2, adding precursor polyamic acid of guanidyl polymer and polyimide into the organic ligand I-organic solvent solution system, and then stirring for 3-5 min at 20-25 ℃ on a magnetic stirrer at a rotating speed of 350-500 rpm;
s3, adding a silane coupling agent into the solution obtained after stirring in the step S2 to form a mixed solution, and then performing ultrasonic reaction in an ultrasonic disperser at 20-25 ℃ for 10-15 min;
s4, adding a gel accelerator into the mixed solution obtained in the step S3, and then homogenizing the mixed solution in an ultrasonic dispersing instrument at 20-25 ℃ for 5-15 min to form precursor wet sol;
s5, placing the precursor wet sol prepared in the step S4 in an organic solvent for synthesizing the organic ligand II of the COFs, stirring for 15-20 min to white emulsion, standing for 3-5 min, then carrying out microwave local heating for 2-4 h to enable the organic ligand I and the organic ligand II of the COFs to complete self-assembly reaction, and converting the precursor wet sol into the COFs wet sol;
s6, carrying out functional Ag+ nano ion loading in the COFs wet sol by a post-synthesis modification method to generate guanidino/polyimide/Ag+ -COFs wet sol;
s7, placing the prepared guanidino/polyimide/Ag+ -COFs wet sol into a baking oven for gel reaction at the temperature of 40-60 ℃ for 1-3 hours to prepare the guanidino/polyimide/Ag+ -COFs wet gel;
s8, aging the guanidino/polyimide/Ag+ -COFs wet gel in an organic solvent for 48-72 hours;
s9, drying the aged guanidino/polyimide/Ag+ -COFs wet gel to obtain the guanidino/polyimide/Ag+ multifunctional COF aerogel.
According to the preferred technical scheme, in the step S1, the ratio of the organic ligand I to the organic solvent is 0.01-1: 1, a step of;
according to a preferred technical scheme, the organic solvent in the step S1 is as follows: a mixed organic solvent of tetrahydrofuran and N, N-dimethylacetamide; the organic ligand I of the COFs is one of trimellitic aldehyde, terephthalaldehyde, tetra (4-formylphenyl) methane, tetra-aldehyde phenyl porphyrin, 3', 5' -tetra-aldehyde biphenyl, 1,2,4, 5-tetra (4-formylphenyl) benzene, 2 '-bipyridine-5, 5' -dicarboxaldehyde, 2, 5-dihydroxyterephthalic acid, 2, 5-dimethoxybenzene-1, 4-dicarboxaldehyde, 2, 6-naphthalene dicarboxaldehyde and 1,3, 5-tri (4-aminophenyl) benzene.
In a preferred embodiment, the guanidino polymer in step S2 is polyhexamethylene biguanide hydrochloride.
According to a preferred technical scheme, the guanidino polymer and polyimide precursor polyamic acid added in the step S2 accounts for 0.1% -10% of the organic ligand I-organic solvent solution system according to the volume ratio.
According to the preferred technical scheme, in the step S3, the dosage of the added silane coupling agent is 0.1-5% of the volume of the stirred solution obtained in the step S2 according to the volume ratio.
According to a preferred technical scheme, the silane coupling agent added in the step S3 is as follows: one of propyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecylmethyldimethoxysilane and hexadecyltrimethoxysilane.
According to the preferred technical scheme, in the step S4, the dosage of the gel accelerator is controlled to be 10-40% of that of the mixed solution according to the volume ratio.
In a preferred technical scheme, the gel accelerator in the step S4 is propylene oxide.
According to the preferred technical scheme, in the step S5, the volume ratio of the organic ligand II to the organic ligand I is 0.8-1.2: 1.
in a preferred embodiment, the organic ligand ii of COFs used in step S5 is: one of phenylenediamine, melem, 1,3, 5-triaminobenzene, biphenyldiamine, 5,15- (aminophenyl) -10, 20-phenylporphyrin, tetrakis (4-aminophenyl) methane, tris (4-aminophenyl) amine, 5 '-diamino-2, 2' -bipyridine, 2,4, 6-tris (4-aminophenoxy) -1,3, 5-triazine, 1,3, 5-tris (4-aminophenyl) benzene, 4,4,4,4-tetraethyl-tetraaniline, 2,3,5, 6-tetrafluoroterephthalic acid formaldehyde; the organic solvents used were: one of ethanol, methanol and dimethylformamide.
According to the preferred technical scheme, the specific operation steps for carrying out the loading of the functional Ag+ nano ions in the step S6 are as follows: placing the prepared COFs wet sol into an organic solution containing Ag salt, carrying out ultrasonic treatment for 2-5 min, vibrating the mixed solution on a shaking table for 15-25 min, then placing the mixed solution into a microwave reactor, controlling the microwave reaction rate, reacting for 45min, and heating in a water bath at 45-60 ℃ for 6-12 h, so that Ag+ is fully loaded on the COFs, and forming the guanidino/polyimide/Ag+ -COFs wet gel.
In a preferred technical scheme, the silver salt in the step S6 is silver nitrate.
In a preferred embodiment, the organic solvent used in step S8 is methanol.
The preferred technical scheme is that the drying method used in the step S9 is as follows: one of freeze drying and supercritical drying.
The covalent organic frameworks (Covalent Organic Frameworks, COFs) are new materials which are newly developed after inorganic porous materials and MOFs, are novel crystalline porous organic framework materials which are formed by connecting light elements (such as B, C, O and N) through covalent bonds in 2005 and are found by Yaghi and other colleagues, have the advantages of high specific surface area, adjustable porosity, precise periodicity, high chemical stability, easiness in functional design of molecular layers and the like, and in addition, the materials are composed of light elements only, have low weight density, are widely focused in recent years and have potential in the fields of gas storage and energy storage, semiconductor catalysis, molecular screening/capturing, novel electrode materials, conduction sensing, biomedical and the like.
The COFs has micropores and good adjustable modification performance, so that the COFs and the aerogel are combined to prepare the material with the micropore-mesopore hierarchical pore structure. In addition, compared with common porous materials, such as MOFs, molecular sieves and the like, the COF further shows a highly stable structure in severe chemical environments such as boiling water, strong acid, strong alkali, oxidation and reduction conditions and the like, so that the defects of single composition, poor crystal form and the like of the inorganic porous material are overcome, and meanwhile, the problems of high-temperature stability phase difference and easy collapse in water of the MOFs are solved, so that the novel material prepared from the MOFs has a wider application range.
Example 1
(1) A solution of organic ligand I of COFs was prepared, 0.5ml of 2, 5-dihydroxyterephthalic acid was added to 10ml of a mixed organic solvent of tetrahydrofuran and DMAc (5 ml each), and stirred at 22℃on a mechanical stirrer at 250 rpm for 3min to form a clear solution.
(2) Adding 0.30ml of polyhexamethylene biguanide hydrochloride and 0.30ml of PAAs into the clear solution, controlling the rotating speed to 400 revolutions per minute in a magnetic stirrer at 20 ℃, and stirring for 5min until the solution is uniformly stirred;
(3) Adding 0.106ml of silane coupling agent propyl triethoxysilane into the obtained solution, and dispersing in an ultrasonic dispersing instrument at 20 ℃ for 10min to form a mixed solution;
(4) Adding 1.07ml of gel accelerator propylene oxide into the obtained solution, and carrying out ultrasonic treatment in an ultrasonic dispersing instrument at 25 ℃ for 10min to homogenize the solution to form precursor wet sol;
(5) Adding the precursor wet sol obtained in the step (4) into a solution containing 20ml of methanol, adding 0.5ml of organic ligand II 5,5 '-diamino-2, 2' -bipyridine of COFs, stirring for 15min to white emulsion, standing for 3min until the solution is stable, then locally heating for 2h by microwaves, allowing two organic ligands of the COFs to self-assemble to form covalent organic framework COFs, and converting the precursor wet sol into the COFs wet sol;
(6) Carrying out Ag+ loading in sol by a post-synthesis modification method, putting the COFs wet sol into 50ml of methanol solution, adding 1.02g of AgNO3, carrying out ultrasonic treatment for 2min, then putting the mixture on a shaking table for shaking for 20min, putting the mixture into a microwave reactor for reacting for 45min, and heating the mixture in a water bath at 50 ℃ for 6h to fully complete the loading of Ag+ on the COFs to generate guanidino/polyimide/Ag+ -COFs wet sol;
(7) Placing the guanidino/polyimide/Ag+ -COFs wet sol obtained in the step (6) into a closed mold, and performing gel reaction in an oven at 60 ℃ to form guanidino/polyimide/Ag+ -COFs wet gel;
(8) Adding methanol solution into the guanidino/polyimide/Ag+ -COFs wet gel obtained in the step (7) for aging, wherein the volume of the aging solution is 100mL, and the aging time is 72 hours;
(9) Placing the guanidino/polyimide/Ag+ -COFs wet gel obtained after aging in the step (8) into a high-pressure reaction kettle of a supercritical drying device, pumping CO2 into the high-pressure reaction kettle when the temperature of the high-pressure reaction kettle reaches 45 ℃, and drying the system in a supercritical state for 120 minutes when the pressure of the high-pressure reaction kettle reaches 15 MPa; and slowly discharging CO2 in the high-pressure reaction kettle after the drying is finished, opening the kettle in a normal pressure state, and cooling the reaction kettle to room temperature to obtain the guanidino/polyimide/Ag+ multifunctional COF aerogel.
Example 2
(1) A solution of organic ligand I of COFs was prepared, and 0.6ml of tetra-aldehyde phenyl porphyrin was added to 10ml of a mixed organic solvent of tetrahydrofuran and DMAc (wherein each of tetrahydrofuran and DMAc was 5 ml), and stirred for 3min at 20℃on a mechanical stirrer at a stirring rod rotation speed of 20 rpm to form a clear solution.
(2) Adding 0.31ml of polyhexamethylene biguanide hydrochloride and 0.29ml of PAAs into the clear solution, controlling the rotating speed to 400 revolutions per minute in a magnetic stirrer at 22 ℃, and stirring for 5min until the solution is uniformly stirred;
(3) Adding 0.108ml of silane coupling agent dodecyl trimethoxy silane into the obtained solution, and dispersing in an ultrasonic dispersing instrument at 20 ℃ for 10min to form a mixed solution;
(4) Adding 1.17ml of gel accelerator propylene oxide into the obtained solution, and carrying out ultrasonic treatment in an ultrasonic dispersing instrument at 25 ℃ for 10min to homogenize the solution to form precursor wet sol;
(5) Adding the precursor wet sol obtained in the step (4) into a methanol solution containing 20ml, adding 0.5ml of organic ligand II 2,4, 6-tris (4-aminophenoxy) -1,3, 5-triazine of COFs, stirring for 15min to white emulsion, standing for 3min until the solution is stable, then locally heating for 3h by microwaves, allowing two organic ligands of the COFs to self-assemble to form covalent organic framework COFs, and converting the precursor wet sol into the COFs wet sol;
(6) Carrying out Ag+ loading in the COFs wet sol by a post-synthesis modification method, putting the COFs wet sol liquid into 50ml of methanol solution, adding 1.02g of AgNO3, carrying out ultrasonic treatment for 3min, then placing the mixture on a shaking table, shaking for 15min, placing the mixture into a microwave reactor, reacting for 45min, and then heating the mixture in a water bath at 60 ℃ for 8h to fully complete the loading of the Ag+ on the COFs and generate guanidino/polyimide/Ag+ -COFs wet sol;
(7) Placing the guanidino/polyimide/Ag+ -COFs wet sol obtained in the step (6) into a closed mold, and performing gel reaction in an oven at 60 ℃ to form guanidino/polyimide/Ag+ -COFs wet gel;
(8) Adding methanol solution into the guanidino/polyimide/Ag+ -COFs wet gel obtained in the step (7) for aging, wherein the volume of the aging solution is 100mL, and the aging time is 72 hours;
(9) Placing the guanidino/polyimide/Ag+ -COFs wet gel obtained after aging in the step (8) into a high-pressure reaction kettle of a supercritical drying device, pumping CO2 into the high-pressure reaction kettle when the temperature of the high-pressure reaction kettle reaches 45 ℃, and drying the system in a supercritical state for 120 minutes when the pressure of the high-pressure reaction kettle reaches 15 MPa; and slowly discharging CO2 in the high-pressure reaction kettle after the drying is finished, opening the kettle in a normal pressure state, and cooling the reaction kettle to room temperature to obtain the guanidino/polyimide/Ag+ multifunctional COF aerogel.
Example 3
(1) Preparing a solution of organic ligand I of COFs, adding 0.55ml of 2,2 '-bipyridine-5, 5' -dicarboxaldehyde into 10ml of mixed organic solvent of tetrahydrofuran and DMAc (wherein 5ml of tetrahydrofuran and DMAc are respectively) and stirring for 5min at 20 ℃ on a mechanical stirrer at the rotation speed of a stirring rod of 250 rpm to form a clear solution;
(2) Adding 0.27ml of polyhexamethylene biguanide hydrochloride and 0.27ml of PAAs into the clear solution, controlling the rotating speed to 450 r/min in a magnetic stirrer at 22 ℃, and stirring for 5min until the solution is uniformly stirred;
(3) Adding 0.105ml of silane coupling agent octyl trimethoxy silane into the obtained solution, and dispersing in an ultrasonic dispersing instrument at 20 ℃ for 10min to form a mixed solution;
(4) Adding 1.10ml of gel accelerator propylene oxide into the obtained solution, and carrying out ultrasonic treatment in an ultrasonic dispersing instrument at 22 ℃ for 10min to homogenize the solution to form precursor wet sol;
(5) Adding the precursor wet sol obtained in the step (4) into a methanol solution containing 20ml, adding 0.56ml of organic ligand II 5,15- (aminophenyl) -10, 20-phenylporphyrin of COFs, stirring for 20min to white emulsion, standing for 3min until the solution is stable, then locally heating for 4h by microwaves, allowing two organic ligands of the COFs to self-assemble to form covalent organic framework COFs, and converting the precursor wet sol into the COFs wet sol;
(6) Carrying out Ag+ loading in the COFs wet sol by a post-synthesis modification method, putting the COFs wet sol liquid into 50ml of methanol solution, adding 1.23g of AgNO3, carrying out ultrasonic treatment for 2min, then placing the mixture on a shaking table, shaking for 15min, placing the mixture into a microwave reactor, reacting for 45min, and then heating the mixture in a water bath at 45 ℃ for 6h to fully complete the loading of the Ag+ on the COFs and generate guanidino/polyimide/Ag+ -COFs wet sol;
(7) Placing the guanidino/polyimide/Ag+ -COFs wet sol obtained in the step (6) into a closed mold, and performing gel reaction in an oven at 60 ℃ to form guanidino/polyimide/Ag+ -COFs wet gel;
(8) Adding methanol solution into the guanidino/polyimide/Ag+ -COFs wet gel obtained in the step (7) for aging, wherein the volume of the aging solution is 100mL, and the aging time is 72 hours;
(9) Placing the guanidino/polyimide/Ag+ -COFs wet gel obtained after aging in the step (8) into a high-pressure reaction kettle of a supercritical drying device, pumping CO2 into the high-pressure reaction kettle when the temperature of the high-pressure reaction kettle reaches 45 ℃, and drying the system in a supercritical state for 120 minutes when the pressure of the high-pressure reaction kettle reaches 15 MPa; and slowly discharging CO2 in the high-pressure reaction kettle after the drying is finished, opening the kettle in a normal pressure state, and cooling the reaction kettle to room temperature to obtain the guanidino/polyimide/Ag+ multifunctional COF aerogel.
Example 4
(1) Preparing a solution of organic ligand I of COFs, adding 0.58ml of 3,3', 5' -tetra-aldehyde biphenyl to 10ml of mixed organic solvent of tetrahydrofuran and DMAc (5 ml each), stirring at 22 ℃ on a mechanical stirrer at a stirring rod rotation speed of 250 revolutions per minute for 3min to form a clear solution.
(2) Adding 0.31ml of polyhexamethylene biguanide hydrochloride and 0.31ml of PAAs into the clear solution, controlling the rotating speed to be 350 revolutions per minute in a magnetic stirrer at 20 ℃, and stirring for 5min until the solution is uniformly stirred;
(3) Adding 0.109ml of silane coupling agent octyl triethoxysilane into the obtained solution, and dispersing in an ultrasonic dispersing instrument at 20 ℃ for 10min to form a mixed solution;
(4) Adding 1.08ml of gel accelerator propylene oxide into the obtained solution, and carrying out ultrasonic treatment in an ultrasonic dispersing instrument at 25 ℃ for 10min to homogenize the solution to form precursor wet sol;
(5) Adding 20ml of methanol solution into the precursor wet sol obtained in the step (4), adding 0.59ml of organic ligand II 4,4,4,4-methyl ethane tetralin of COFs, stirring for 15min to white emulsion, standing for 3min until the solution is stable, then locally heating for 3h by microwaves, allowing two organic ligands of the COFs to self-assemble to form covalent organic framework COFs, and converting the precursor wet sol into the COFs wet sol;
(6) Carrying out Ag+ loading in the COFs wet sol by a post-synthesis modification method, putting the COFs wet sol liquid into 50ml of methanol solution, adding 1.18g of AgNO3, carrying out ultrasonic treatment for 2min, then placing the mixture on a shaking table, shaking for 20min, placing the mixture into a microwave reactor, reacting for 45min, and then heating the mixture in a water bath at 60 ℃ for 6h to fully complete the loading of the Ag+ on the COFs to generate guanidino/polyimide/Ag+ -COFs wet sol;
(7) Placing the guanidino/polyimide/Ag+ -COFs wet sol obtained in the step (6) into a closed mold, and performing gel reaction in an oven at 60 ℃ to form guanidino/polyimide/Ag+ -COFs wet gel;
(8) Adding methanol solution into the guanidino/polyimide/Ag+ -COFs wet gel obtained in the step (7) for aging, wherein the volume of the aging solution is 100mL, and the aging time is 72 hours;
(9) Placing the guanidino/polyimide/Ag+ -COFs wet gel obtained after aging in the step (8) into a high-pressure reaction kettle of a supercritical drying device, pumping CO2 into the high-pressure reaction kettle when the temperature of the high-pressure reaction kettle reaches 45 ℃, and drying the system in a supercritical state for 120 minutes when the pressure of the high-pressure reaction kettle reaches 15 MPa; and slowly discharging CO2 in the high-pressure reaction kettle after the drying is finished, opening the kettle in a normal pressure state, and cooling the reaction kettle to room temperature to obtain the guanidino/polyimide/Ag+ multifunctional COF aerogel.
The antibacterial test and the lasting antibacterial test are carried out on the guanidyl/polyimide/Ag+ multifunctional COF aerogel obtained in the embodiment, and the prepared guanidyl/polyimide/Ag+ COFs aerogel has almost 100% of antibacterial rate, is subjected to ultrasonic water washing, has basically unchanged antibacterial effect after repeated use, has greatly improved antibacterial effect and antibacterial lasting compared with a single-component antibacterial material, and has wide application fields in the field of sterilization.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "top", "bottom", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, or the directions or positional relationships conventionally put in place when the inventive product is used, or the directions or positional relationships conventionally understood by those skilled in the art are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific direction, be configured and operated in a specific direction, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (9)
1. The preparation method of the multifunctional sterilization nano-pore COF aerogel is characterized in that the sterilization nano-pore COF aerogel comprises porous COFs, wherein metal ions, guanidino and polyimide are arranged on the porous COFs, the metal ions are Ag+, and the preparation method comprises the following steps:
s1, placing an organic ligand I of a COFs in an organic solvent, and stirring for 3-5 minutes on a mechanical stirrer at 18-25 ℃ at the rotation speed of a stirring rod of 250-350 rpm to prepare an organic ligand I-organic solvent solution;
s2, adding precursor polyamic acid of guanidine polymer and polyimide into the organic ligand I-organic solvent solution system, and then stirring for 3-5 min at 20-25 ℃ on a magnetic stirrer at a rotating speed of 350-500 rpm;
s3, adding a silane coupling agent into the solution obtained after stirring in the step S2 to form a mixed solution, and then performing ultrasonic reaction in an ultrasonic disperser at 20-25 ℃ for 10-15 min;
s4, adding a gel accelerator into the mixed solution obtained in the step S3, and carrying out ultrasonic treatment in an ultrasonic dispersing instrument at 20-25 ℃ for 5-15 min to homogenize the mixed solution to form precursor wet sol;
s5, placing the precursor wet sol prepared in the step S4 in an organic solvent for synthesizing the organic ligand II of the COFs, stirring for 15-20 min to white emulsion, standing for 3-5 min, then carrying out microwave local heating for 2-4 h to enable the organic ligand I and the organic ligand II of the COFs to complete self-assembly reaction, and converting the precursor wet sol into the COFs wet sol;
s6, carrying out functional Ag+ nano ion loading in the COFs wet sol by a post-synthesis modification method to generate guanidino/polyimide/Ag+ -COFs wet sol;
s7, placing the prepared guanidino/polyimide/Ag+ -COFs wet sol into an oven for a gel reaction at 40-60 ℃ for 1-3 hours to prepare guanidino/polyimide/Ag+ -COFs wet gel;
s8, aging the guanidino/polyimide/Ag+ -COFs wet gel in an organic solvent for 48-72 hours;
s9, drying the aged guanidino/polyimide/Ag+ -COFs wet gel to obtain the guanidino/polyimide/Ag+ multifunctional COF aerogel.
2. The method for preparing the multifunctional sterilized nano-pore COF aerogel according to claim 1, wherein in the step S1, the ratio of the organic ligand i to the organic solvent is 0.01-1: 1, a step of; the organic solvent in the step S1 is: a mixed organic solvent of tetrahydrofuran and N, N-dimethylacetamide; the organic ligand I of the COFs is one of trimellitic aldehyde, terephthalaldehyde, tetra (4-formylphenyl) methane, tetra-aldehyde phenyl porphyrin, 3', 5' -tetra-aldehyde biphenyl, 1,2,4, 5-tetra (4-formylphenyl) benzene, 2 '-bipyridine-5, 5' -dicarboxaldehyde, 2, 5-dihydroxyterephthalic acid, 2, 5-dimethoxybenzene-1, 4-dicarboxaldehyde, 2, 6-naphthalene dicarboxaldehyde and 1,3, 5-tri (4-aminophenyl) benzene.
3. The method for preparing a multifunctional sterilized nano-pore COF aerogel according to claim 1, wherein the precursor polyamic acid of the guanidine-based polymer and polyimide added in the step S2 is 0.1% -10% of the organic ligand i-organic solvent solution system according to the volume ratio.
4. The method for preparing a multifunctional sterilized nano-pore COF aerogel according to claim 1, wherein the silane coupling agent is added in the step S3 in an amount of 0.1% -5% of the volume of the stirred solution obtained in the step S2 according to the volume ratio.
5. The method for preparing the multifunctional sterilized nano-pore COF aerogel according to claim 1, wherein the silane coupling agent added in the step S3 is: one of propyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecylmethyldimethoxysilane and hexadecyltrimethoxysilane.
6. The method for preparing the multifunctional sterilized nano-pore COF aerogel according to claim 1, wherein the amount of the gel accelerator is controlled to be 10-40% of the mixed solution according to the volume ratio in the step S4.
7. The method for preparing the multifunctional sterilized nano-pore COF aerogel according to claim 1, wherein in the step S5, the volume ratio of the organic ligand ii to the organic ligand i is 0.8-1.2: 1.
8. the method for preparing the multifunctional sterilized nano-pore COF aerogel according to claim 1, wherein the organic ligand ii of COFs used in the step S5 is: one of phenylenediamine, melem, 1,3, 5-triaminobenzene, biphenyldiamine, 5,15- (aminophenyl) -10, 20-phenylporphyrin, tetrakis (4-aminophenyl) methane, tris (4-aminophenyl) amine, 5 '-diamino-2, 2' -bipyridine, 2,4, 6-tris (4-aminophenoxy) -1,3, 5-triazine, 1,3, 5-tris (4-aminophenyl) benzene, 4,4,4,4-tetraethyl-tetraaniline, 2,3,5, 6-tetrafluoroterephthalic acid formaldehyde; the organic solvents used were: one of ethanol, methanol and dimethylformamide.
9. The method for preparing the multifunctional sterilized nano-pore COF aerogel according to claim 1, wherein the specific operation steps of carrying out the loading of the functional ag+ nano ions in the step S6 are as follows: and (3) placing the prepared COFs wet sol into an organic solution containing Ag salt, carrying out ultrasonic treatment for 2-5 min, vibrating the mixed solution on a shaking table for 15-25 min, then placing the mixed solution into a microwave reactor, controlling the microwave reaction rate, reacting for 45min, and heating in a water bath at 45-60 ℃ for 6-12 h, so that Ag+ is fully loaded on the COFs, and thus the guanidino/polyimide/Ag+ -COFs wet gel is generated.
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