CN112626718A - Method for preparing MOF (Metal organic framework)/cellulose/polyacrylonitrile mask filter layer - Google Patents

Method for preparing MOF (Metal organic framework)/cellulose/polyacrylonitrile mask filter layer Download PDF

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CN112626718A
CN112626718A CN202011125446.9A CN202011125446A CN112626718A CN 112626718 A CN112626718 A CN 112626718A CN 202011125446 A CN202011125446 A CN 202011125446A CN 112626718 A CN112626718 A CN 112626718A
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cellulose
polyacrylonitrile
solution
mil
spinning
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张辉
陈天宇
张雅宁
陈文豆
谷豪帅
王泳智
张文文
杨瑞瑞
王珊
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Xian Polytechnic University
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Xian Polytechnic University
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
    • A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
    • A41D13/1192—Protective face masks, e.g. for surgical use, or for use in foul atmospheres with antimicrobial agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2509/00—Medical; Hygiene

Abstract

The invention discloses a method for preparing a MOF/cellulose/polyacrylonitrile mask filter layer, which comprises the following steps: step 1, preparing MIL-53(Fe) nanoparticles; step 2, synthesizing cellulose nanocrystals; step 3, mixing polyacrylonitrile and the cellulose nanocrystalline obtained in the step 2 to obtain a mixed solution; step 4, adding the product obtained in the step 1 into the mixed solution obtained in the step 3 to obtain a spinning solution; and 5, performing electrostatic spinning on the spinning solution obtained in the step 4 to obtain the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane. The invention uses metal organic framework MIL-53(Fe) as an adsorption and photocatalyst and cellulose as a moisture absorption material, and adopts an electrostatic spinning method to prepare the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane with the functions of antibiosis, high-efficiency filtration and natural degradation.

Description

Method for preparing MOF (Metal organic framework)/cellulose/polyacrylonitrile mask filter layer
Technical Field
The invention belongs to the technical field of textile engineering, and relates to a method for preparing a MOF/cellulose/polyacrylonitrile mask filter layer.
Background
The mask is divided into two types, namely KN and KP, according to the filtering effect. The KN is only suitable for filtering non-oily particles and comprises three grades of KN90 (more than or equal to 90%), KN95 (more than or equal to 95%) and KN100 (more than or equal to 99.97%); and KPs are suitable for filtering oily and non-oily particles and comprise three grades of KP90 (more than or equal to 90%), KP95 (more than or equal to 95%) and KP100 (more than or equal to 99.97%). The numbers of KN and KP suffixes represent the level of filtering efficiency, the higher the number, the better the filtering effect. Since the KN mask does not test the penetration of synthetic blood and the moisture resistance of the surface, the mask can block viruses when used for a short time, but cannot be used for contacting a patient who may be splashed or contacted with the patient for a long time.
In recent years, iron-based MOFs materials with Fe as the central metal ion, such as MIL-53(Fe), MIL-100(Fe), MIL-101(Fe), etc., have been widely studied in the aspect of environmental pollutant degradation and adsorption. The MIL-53(Fe) is a three-dimensional metal organic framework material which is assembled by taking Fe (III) as a metal center and taking terephthalic acid as an organic ligand, has good visible light responsiveness and excellent chemical stability, is simple in preparation method, low in cost and low in environmental toxicity, and has good application prospect in the aspect of removing organic pollutants and heavy metal ions in sewage through photocatalysis. Binding sites in textiles make them promising substrates for incorporation into MOFs, providing a basis for the preparation of better effective composites.
The cellulose is a natural polymer material, has stable chemical property and rich sources, the basic structural unit is D-glucopyranosyl, linear long-chain macromolecules consisting of beta- (1-4) -D-glucosyl, and hydroxyl on the 2 nd, 3 rd and 6 th carbon atoms has more active polarity and has obvious influence on hydrogen bonds and hygroscopicity among cellulose molecules.
Disclosure of Invention
The invention aims to provide a method for preparing a filter layer of an MOF (organic metal framework)/cellulose/polyacrylonitrile mask, which uses a metal organic framework MIL-53(Fe) as an adsorption and photocatalyst and cellulose as a moisture absorption material, and adopts an electrostatic spinning method to prepare the MOF/cellulose/polyacrylonitrile blended nanofiber composite membrane with the functions of antibiosis, high-efficiency filtration and natural degradation.
The invention adopts the technical scheme that a method for preparing an MOF/cellulose/polyacrylonitrile mask filter layer specifically comprises the following steps:
step 1, preparing MIL-53(Fe) nanoparticles;
step 2, preparing cellulose nanocrystals;
step 3, mixing polyacrylonitrile and the cellulose nanocrystalline obtained in the step 2 to obtain a mixed solution;
step 4, adding the product obtained in the step 1 into the mixed solution obtained in the step 3 to obtain a spinning solution;
and 5, performing electrostatic spinning on the spinning solution obtained in the step 4 to obtain an MIL-53 (Fe)/cellulose/polyacrylonitrile blended nanofiber composite membrane, and drying the MIL-53 (Fe)/cellulose/polyacrylonitrile blended nanofiber composite membrane in a drying oven at 35 ℃ for 4-6 hours to obtain the composite membrane.
The present invention is also characterized in that,
the specific process of step 1 is as follows:
measuring 50-100 mL of N, N-Dimethylformamide (DMF) solution as a solvent, and FeCl according to a molar ratio3·6H2O, terephthalic acid (H)2BDC) and DMF in a molar ratio of 1: 1: treating the mixture of 280-500 at room temperature with 40KHz and 300W ultrasonic oscillation for 10-30 min until a clear solution is formed; then mechanically stirring for 3-6 h at the speed of 200-500 r/min; then transferring the reaction mixture into a reaction kettle, heating at 120-180 ℃ for 12-24 h, naturally cooling to room temperature, cooling, and centrifuging at the speed of 11000r/min for 15-30 min to obtain a precipitate, namely MIL-53 (Fe); according to the bath ratio of 1: 10-30, soaking the obtained precipitate for 15-30 min at normal temperature by using a methanol solution and deionized water, repeating the soaking for 3 times, finally reheating for 8-12 h at 100-150 ℃, and cooling to room temperature to obtain the final MIL-53(Fe) nanoparticles.
The specific process of the step 2 is as follows:
step 2.1, pretreating cotton fibers;
according to the bath ratio of 1: 7-10, adding 10-20 g of cotton fibers into 70-140 mL of 3 mass percent sodium hydroxide solution, slowly stirring for 6-8 h at 80-100 ℃, repeatedly washing with deionized water after cooling until the pH value of the solution is 7-8, then adding the filtered cotton fibers into 140-200 mL of 0.6 mass percent sodium hypochlorite solution, treating for 30-60 min at 100-120 ℃, repeatedly rinsing with deionized water after cooling until the pH value of the solution is 7;
step 2.2, preparing cellulose nanocrystals by a sulfuric acid method;
according to the volume ratio of 1: 2: 2-3, mixing 50-60% of sulfuric acid by mass concentration, 37% of hydrochloric acid by mass fraction and deionized water to prepare 200mL, adding the cotton fiber treated by the sodium hypochlorite in the step 2.1, and mixing the obtained mixture according to a solid-liquid ratio of 1: 8-10 g/mL, treating for 1-3 h at 40-60 ℃, filtering, repeatedly cleaning with ionized water until the pH value of the solution is neutral, then washing with absolute ethyl alcohol for 2-3 times until the filtrate is colorless, finally cleaning with deionized water for 1-2 times, drying at 80-100 ℃, and grinding to obtain the cellulose nanocrystal.
The specific process of the step 3 is as follows:
step 3.1, preparing an electrostatic spinning solution;
adding 30-80 g/L PAN powder and 3-8 g/L polyvinylpyrrolidone (PVP) powder into 10-100 mL DMF solution, and stirring at room temperature for 15-24 h to obtain a light yellow transparent liquid, namely a polyacrylonitrile spinning solution;
step 3.2: according to the following steps of 1: and 16, mixing the cellulose nanocrystals obtained in the step 2 with the polyacrylonitrile spinning solution obtained in the step 3.1, carrying out ultrasonic oscillation treatment for 10-30 min, and violently stirring at the speed of 200-500 r/min for 2-4 h to fully mix the solution.
The specific process of the step 4 is as follows:
and (3) adding 5-40% by mass of MIL-53(Fe) particles into the mixed solution obtained in the step (3), and ultrasonically stirring for 2-4 hours to obtain a spinning solution.
The parameters of the spinning process in step 5 are set as follows: the distance between the syringe needle and the receiving plate is 10-15 cm, and the flow rate of the spinning solution is 0.1-0.5 mL/h.
The invention has the following beneficial effects:
(1) the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane medical mask filter layer prepared by electrostatic spinning can be used for uniformly distributing MIL-53(Fe) in polyacrylonitrile/polyvinylpyrrolidone blended fibers, and has a certain photocatalytic sterilization effect. The adsorption capacity of the blended nanofiber membrane can be enhanced by regulating the dosage ratio of polyacrylonitrile to polyvinylpyrrolidone, MIL-53(Fe) powder or metal element doping and other modes, cellulose is a natural polymer material, the chemical property is stable, the source is rich, the basic structural unit is D-glucopyranosyl, beta- (1-4) -D-glucosyl forms linear long-chain macromolecules, the polarity of hydroxyl on the 2, 3 and 6-position carbon atoms is active, and the hydroxyl has obvious influence on hydrogen bonds and hygroscopicity among cellulose molecules. Therefore, the nano-fiber composite filtering membrane with good antibacterial performance can be obtained by better adsorbing bacteria.
(2) The common medical mask has protection capability and is mainly characterized in that the electrostatic adsorption effect is achieved, the middle filter layer of the medical mask is a layer of melt-blown non-woven fabric which is made of polypropylene and belongs to superfine fibers, and the medical mask is characterized in that the medical mask has electrostatic adsorption capability after electret treatment. When the air flow breathed by the human body passes through the non-woven fabric, the air can normally pass through, and the dust and the virus droplets can be adsorbed by static electricity. After the dust in the air is adsorbed by static electricity, the dust is extremely difficult to separate and cannot be cleaned, and the dust and pathogenic bacteria can be remained as long as the static electricity exists. However, if the static electricity disappears, the mask does not work. The static electricity is most afraid of water, the static electricity disappears when the ordinary disposable mask is soaked in water, and the KN95 grade protective mask has a shelf life because the static electricity disappears after a long time. The product breaks through electrostatic adsorption, utilizes physical adsorption to protect and isolate dust and germs, utilizes the photocatalytic activity of MIL-53(Fe) to kill germs, can be repeatedly utilized by washing, and reasonably utilizes resources. In addition, once the mask is discarded, the filter layer of the MOF/cellulose/polyacrylonitrile mask can be quickly decomposed, MIL-53(Fe) and cellulose cannot pollute the environment, and only a small part of polyacrylonitrile remains.
Drawings
FIG. 1 is a scanning electron micrograph of MIL-53(Fe) powder obtained in example 2 of a method for preparing a MOF/cellulose/polyacrylonitrile mask filter layer according to the present invention;
FIG. 2 is an X-ray diffraction pattern of MIL-53(Fe) powder obtained in example 2 of a method for preparing a MOF/cellulose/polyacrylonitrile mask filter layer according to the present invention;
FIG. 3 is a UV-diffuse reflectance spectrum of MIL-53(Fe) powder obtained in example 2 of a method of making a MOF/cellulose/polyacrylonitrile mask filter layer according to the present invention;
FIG. 4 is a scanning electron microscope image of a cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane prepared by electrostatic spinning according to example 2 of a method for preparing a MOF/cellulose/polyacrylonitrile mask filter layer of the present invention;
FIG. 5 is a scanning electron microscope image of an electrostatic spinning prepared MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane obtained in example 2 of a method for preparing a MOF/cellulose/polyacrylonitrile mask filter layer according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention discloses a method for preparing an MOF (Metal-organic framework)/cellulose/polyacrylonitrile mask filter layer, which is characterized in that PAN (Polyacrylonitrile) and PVP (polyvinyl pyrrolidone) are taken as substrate spinning solutions, cellulose and MOF (Metal-organic framework) are added to endow the mask filter layer with moisture absorption and photocatalytic sterilization functions, and meanwhile, the dust and germ adsorption capacity of the filter layer is improved, and the specific process is as follows:
step 1, preparing a metal organic framework MIL-53 (Fe):
weighing 50-100 mL of dimethylformamide solution as a solvent and then FeCl according to a molar ratio3·6H2O、H2The molar ratio of BDC to DMF was 1: 1: 280-1: 1: the mixture of 500 is treated by ultrasonic oscillation of 40KHz and 300W for 10-30 min at room temperature until a clear solution is formed, and then mechanically stirred at the speed of 200-500 r/min for 3-6 h. And then transferring the reactant mixture into a reaction kettle, heating at 120-180 ℃ for 12-24 h, naturally cooling to room temperature, cooling, and centrifuging at the speed of 11000r/min for 15-30 min to obtain a precipitate, namely MIL-53 (Fe). According to the bath ratio of 1: 10-30, soaking for 15-30 min at normal temperature by using a methanol solution and deionized water, repeating the soaking for 3 times, finally reheating for 8-12 h at 100-150 ℃, and cooling to room temperature to obtain the final MIL-53(Fe) nanoparticles.
Step 2, synthesizing cellulose nanocrystals:
step 2.1: pre-treated cotton fiber
According to the bath ratio of 1: 7-10, adding 10-20 g of cotton fibers into 70-140 mL of 3 mass percent sodium hydroxide solution, slowly stirring for 6-8 h at 80-100 ℃, cooling, repeatedly washing with deionized water until the pH value of the solution is 7-8, then adding the filtered cotton fibers into 140-200 mL of 0.6 mass percent sodium hypochlorite solution, treating for 30-60 min at 100-120 ℃, cooling, and repeatedly rinsing with deionized water until the pH value of the solution is 7.
Step 2.2: preparation of Cellulose Nanocrystalline (CNC) by sulfuric acid process
According to the volume ratio of 1: 2: 2-1: 2: mixing 50-60% of sulfuric acid, 37% of hydrochloric acid and deionized water to prepare 200mL, adding sodium hypochlorite-treated cotton fibers, and mixing the cotton fibers according to a solid-liquid ratio of 1: 8-1: 10(g/mL), treating for 1-3 h at 40-60 ℃, filtering, repeatedly washing with ionized water until the pH value of the solution is neutral, then washing with absolute ethyl alcohol for 2-3 times until the filtrate is colorless, finally washing with deionized water for 1-2 times, drying at 80-100 ℃, and grinding to obtain the cellulose nanocrystal.
Step 3, mixing polyacrylonitrile and the cellulose nanocrystalline obtained in the step 2 to obtain a mixed solution;
step 3.1: preparation of electrospinning solution
Adding 30-80 g/L PAN powder and 3-8 g/L PVP powder into 10-100 ml DMF solution, and stirring at room temperature for 15-24 h to obtain light yellow transparent liquid, namely the polyacrylonitrile spinning solution.
Step 3.2: adding cellulose to the solution obtained in step 3.1
According to the proportion of 1: and 16, mixing the cellulose and polyacrylonitrile spinning solution, carrying out ultrasonic oscillation treatment for 10-30 min at room temperature by using 40KHz and 300W, and violently stirring for 2-4 h at the speed of 200-500 r/min until the solution is fully mixed.
Step 4, adding the product obtained in the step 1 into the mixed solution obtained in the step 3 to obtain a spinning solution;
and (3) adding 5-40% by mass of MIL-53(Fe) particles into the mixed solution obtained in the step (3), and ultrasonically stirring for 2-4 hours to obtain a spinning solution.
And 5, performing electrostatic spinning on the spinning solution obtained in the step 4 to obtain an MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane, and drying the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane in a drying oven at 35 ℃ for 4-6 hours to obtain the composite membrane.
The operating parameters of the spinning process were as follows: the spinning voltage is 20kV, the receiving distance (namely the distance between the needle head of the injector and the receiving plate) is 10-15 cm, and the flow rate of the spinning solution obtained in the step 4 is 0.2 mL/h.
Example 1
According to FeCl3·6H2O、H2The molar ratio of BDC to DMF was 1: 1: 364, 1g of FeCl was weighed3·6H2O, 0.5g of H2And (3) preparing a mixed solution from BDC and 80ml of DMF, carrying out ultrasonic oscillation treatment for 30min at room temperature by using 40KHz and 300W until a clear solution is formed, and mechanically stirring for 3h at the speed of 200-500 r/min. Then, the reaction mixture is transferred into an autoclave, heated for 24 hours at 120 ℃, naturally cooled to room temperature, and centrifuged for 15 minutes at the speed of 11000r/min to obtain a precipitate, namely MIL-53 (Fe). According to the bath ratio of 1: 30, soaking the mixture for 15min at normal temperature by using a methanol solution and deionized water, repeating the soaking for 3 times, finally reheating the mixture for 10h at the temperature of 100 ℃, and cooling the mixture to the room temperature to obtain the final MIL-53(Fe) photocatalyst. According to the bath ratio of 1: 10, adding 10g of cotton fibers into 70mL of sodium hydroxide solution with the mass fraction of 3%, slowly stirring for 8h at 80 ℃, repeatedly washing with deionized water after cooling until the pH value of the solution is 7, then adding the filtered cotton fibers into 200mL of sodium hypochlorite solution with the mass fraction of 0.6%, treating for 30min at 100 ℃, repeatedly rinsing with deionized water after cooling until the pH value of the solution is 7. According to the volume ratio of 1: 2: mixing 50% sulfuric acid, 37% hydrochloric acid and deionized water to prepare 200mL, adding sodium hypochlorite-treated cotton fiber, and mixing according to a solid-liquid ratio of 1: 8(g/mL), treating for 1h at 60 ℃, filtering, repeatedly washing with ionized water until the pH value of the solution is neutral, then washing with absolute ethyl alcohol for 2 times until the filtrate is colorless, finally washing with deionized water for 2 times, drying at 100 ℃, and grinding to obtain the cellulose nanocrystal. Taking PAN powder with the concentration of 40g/L and PVP powder with the concentration of 5g/LAnd adding the mixture into a certain amount of DMF solution, and stirring for 15 hours at room temperature to obtain light yellow transparent liquid, namely the polyacrylonitrile spinning solution. According to the proportion of 1: 16 mixing the spinning solution of cellulose and PAN/PVP, treating for 30min at room temperature with 40KHz 300W ultrasonic vibration, and vigorously stirring at 500r/min for 4h until the solution is fully mixed. Adding 20 mass percent of MIL-53(Fe) powder into the uniform cellulose/polyacrylonitrile spinning solution, and ultrasonically stirring the MIL-53 (Fe)/cellulose/polyacrylonitrile spinning solution for 4 hours for later use. The operating parameters of the spinning process were as follows: the spinning voltage was 20kV, the take-up distance (i.e., the distance between the syringe needle and the take-up plate) was 15cm, and the flow rate of the spinning solution obtained in step 4 was 0.5 mL/h. And after spinning is finished, preparing the MIL-53 (Fe)/cellulose/polyacrylonitrile blended nanofiber composite membrane by electrostatic spinning, drying the composite membrane for 4 hours in a drying oven at the temperature of 35 ℃, and storing the composite membrane for later experiments.
Example 2
According to FeCl3·6H2O、H2The molar ratio of BDC to DMF was 1: 1: 280, 0.811g of FeCl was weighed3·6H2O, 0.498g of H2And preparing a mixed solution from BDC and 64.93ml of DMF, carrying out ultrasonic oscillation treatment at room temperature for 10min by using 40KHz and 300W until a clear solution is formed, and mechanically stirring at the speed of 500r/min for 3-6 h. Transferring the reactant mixture into an autoclave, heating at 150 ℃ for 12h, naturally cooling to room temperature, cooling, and centrifuging at the speed of 11000r/min for 15min to obtain a precipitate, namely MIL-53 (Fe). According to the bath ratio of 1: and 10, soaking the substrate for 15min at normal temperature by using a methanol solution and deionized water, repeating the soaking for 3 times, finally reheating the substrate for 12h at the temperature of 150 ℃, and cooling the substrate to room temperature to obtain the final MIL-53(Fe) photocatalyst. According to the bath ratio of 1: and 7, adding 20g of cotton fibers into 140mL of sodium hydroxide solution with the mass fraction of 3%, slowly stirring for 6h at 100 ℃, repeatedly washing with deionized water after cooling until the pH value of the solution is 7, then adding the filtered cotton fibers into 140mL of sodium hypochlorite solution with the mass fraction of 0.6%, treating for 30min at 100 ℃, repeatedly rinsing with deionized water after cooling until the pH value of the solution is 7. According to the volume ratio of 1: 2: 2, sulfuric acid with the mass concentration of 54 percent, hydrochloric acid with the mass fraction of 37 percent and deionized waterMixing ions to prepare 200mL, adding sodium hypochlorite-treated cotton fibers, and mixing the cotton fibers according to a solid-liquid ratio of 1: 8(g/mL), treating at 60 ℃ for 3h, filtering, repeatedly washing with ionized water until the pH value of the solution is neutral, then washing with absolute ethyl alcohol for 3 times until the filtrate is colorless, finally washing with deionized water for 2 times, drying at 80 ℃, and grinding to obtain the cellulose nanocrystal. 0.862g of PAN powder and 0.1034g of PVP powder are added into 16ml of DMF, and stirred for 15 hours at room temperature to obtain light yellow transparent liquid, namely the polyacrylonitrile spinning solution. According to the proportion of 1: 16 mixing the spinning solution of cellulose and polyacrylonitrile, treating with 40KHz 300W ultrasonic vibration at room temperature for 30min, and vigorously stirring at 500r/min for 4h until the solution is fully mixed. Adding 10% MIL-53(Fe) powder by mass into the uniform cellulose/polyacrylonitrile spinning solution, and ultrasonically stirring the MIL-53 (Fe)/cellulose/polyacrylonitrile spinning solution for 4 hours for later use. The operating parameters of the spinning process were as follows: the spinning voltage was 20kV, the take-up distance (i.e., the distance between the syringe needle and the take-up plate) was 15cm, and the flow rate of the spinning solution obtained in step 4 was 0.2 mL/h. And after spinning is finished, preparing the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane by electrostatic spinning, drying the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane in a drying oven at 35 ℃ for 6 hours, and storing the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane for later experiments.
Example 3
According to FeCl3·6H2O、H2The molar ratio of BDC to DMF was 1: 1: 456, 0.5g of FeCl was weighed respectively3·6H2O, 0.3g of H2A mixed solution of BDC and 60ml DMF was treated with 40KHz 300W ultrasonic agitation at room temperature for 20min until a clear solution was formed, and mechanically stirred at 200r/min for 6 h. And then transferring the reactant mixture into an autoclave, heating for 15h at 150 ℃, naturally cooling to room temperature, cooling, and centrifuging for 15min at the speed of 11000r/min to obtain a precipitate, namely MIL-53 (Fe). According to the bath ratio of 1: and 10, soaking the substrate for 15min at normal temperature by using a methanol solution and deionized water, repeating the soaking for 3 times, finally reheating the substrate for 10h at the temperature of 150 ℃, and cooling the substrate to room temperature to obtain the final MIL-53(Fe) photocatalyst. According to the bath ratio of 1: 7, adding 15g of cotton fiber into 100mL of the mixture with the mass fraction of 3%Slowly stirring the solution in sodium hydroxide solution for 8 hours at the temperature of 100 ℃, repeatedly washing the solution with deionized water until the pH value of the solution is 7 after cooling, then adding the filtered cotton fibers into 140mL of sodium hypochlorite solution with the mass fraction of 0.6%, treating the solution for 60min at the temperature of 100 ℃, and repeatedly rinsing the solution with deionized water until the pH value of the solution is 7 after cooling. According to the volume ratio of 1: 2: mixing 56% sulfuric acid, 37% hydrochloric acid and deionized water to prepare 200mL, adding sodium hypochlorite-treated cotton fiber, and mixing according to a solid-liquid ratio of 1: 8(g/mL), treating for 1h at 40 ℃, filtering, repeatedly washing with ionized water until the pH value of the solution is neutral, then washing with absolute ethyl alcohol for 3 times until the filtrate is colorless, finally washing with deionized water for 2 times, drying at 100 ℃, and grinding to obtain the cellulose nanocrystal. Adding 36g/L PAN powder and 6g/L PVP powder into 25mL DMF solution, and stirring at room temperature for 15h to obtain light yellow transparent liquid, namely the polyacrylonitrile spinning solution. According to the proportion of 1: 16 mixing the spinning solution of cellulose and polyacrylonitrile, treating with 40KHz 300W ultrasonic vibration at room temperature for 10min, and vigorously stirring at 200r/min for 4h until the solution is fully mixed. Adding MIL-53(Fe) powder with the mass fraction of 40% into the uniform cellulose/polyacrylonitrile spinning solution, and ultrasonically stirring the MIL-53 (Fe)/cellulose/polyacrylonitrile spinning solution for 4 hours for later use. The operating parameters of the spinning process were as follows: the spinning voltage was 20kV, the take-up distance (i.e., the distance between the syringe needle and the take-up plate) was 12cm, and the flow rate of the spinning solution obtained in step 4 was 0.1 mL/h. And after spinning is finished, preparing the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane by electrostatic spinning, drying the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane in a drying oven at 35 ℃ for 4 hours, and storing the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane for later experiments.
Example 4
According to FeCl3·6H2O、H2The molar ratio of BDC to DMF was 1: 1: 454, 0.6g of FeCl was weighed respectively3·6H2O, 0.365g of H2A mixture of BDC and 73.09ml of DMF was treated with 40KHz 300W ultrasonic agitation at room temperature for 30min until a clear solution formed and mechanically stirred at 500r/min for 6 h. Then, the reactant mixture is transferred toTransferring into autoclave, heating at 180 deg.C for 15h, naturally cooling to room temperature, cooling, centrifuging at 11000r/min for 20min to obtain precipitate MIL-53 (Fe). According to the bath ratio of 1: 30, soaking the mixture for 30min at normal temperature by using a methanol solution and deionized water, repeating the soaking for 3 times, finally reheating the mixture for 12h at the temperature of 150 ℃, and cooling the mixture to the room temperature to obtain the final MIL-53(Fe) photocatalyst. According to the bath ratio of 1: and 7, adding 10g of cotton fibers into 70mL of sodium hydroxide solution with the mass fraction of 3%, slowly stirring for 6h at 80 ℃, cooling, repeatedly washing with deionized water until the pH value of the solution is 7, then adding the filtered cotton fibers into 140mL of sodium hypochlorite solution with the mass fraction of 0.6%, treating for 30-60 min at 100-120 ℃, cooling, and repeatedly rinsing with deionized water until the pH value of the solution is 7. According to the volume ratio of 1: 2: mixing 60% sulfuric acid, 37% hydrochloric acid and deionized water to prepare 200mL, adding sodium hypochlorite-treated cotton fiber, and mixing according to a solid-liquid ratio of 1: 10(g/mL), treating for 2h at 50 ℃, filtering, repeatedly washing with ionized water until the pH value of the solution is neutral, then washing with absolute ethyl alcohol for 3 times until the filtrate is colorless, finally washing with deionized water for 2 times, drying at 80 ℃, and grinding to obtain the cellulose nanocrystal. Adding 80g/L PAN powder and 8g/L PVP powder into 20mL DMF solution, and stirring at room temperature for 24h to obtain light yellow transparent liquid, namely PAN/PVP spinning solution. According to the proportion of 1: 16 mixing the spinning solution of cellulose and polyacrylonitrile, treating with 40KHz 300W ultrasonic vibration at room temperature for 30min, and vigorously stirring at 500r/min for 4h until the solution is fully mixed. MIL-53(Fe) powder with the mass fraction of 40 percent is ultrasonically stirred for 4 hours in the uniform cellulose/Polyacrylonitrile (PAN) spinning solution for standby. The operating parameters of the spinning process were as follows: the spinning voltage is 20kV, the receiving distance (namely the distance between the needle head of the injector and the receiving plate) is 10-15 cm, and the flow velocity of the spinning solution obtained in the step 4 is 0.1-0.5 mL/h. And after spinning is finished, preparing the MIL-53 (Fe)/cellulose/polyacrylonitrile blended nanofiber composite membrane by electrostatic spinning, drying the composite membrane for 4 hours in a drying oven at the temperature of 35 ℃, and storing the composite membrane for later experiments.
Comparative example 1
According to the bath ratio of 1: and 10, soaking the substrate for 15min at normal temperature by using a methanol solution and deionized water, repeating the soaking for 3 times, finally reheating the substrate for 10h at the temperature of 100 ℃, and cooling the substrate to room temperature to obtain the final MIL-53(Fe) photocatalyst. According to the bath ratio of 1: 10, adding 10g of cotton fibers into 100mL of sodium hydroxide solution with the mass fraction of 3%, slowly stirring for 10h at 80 ℃, cooling, repeatedly washing with deionized water until the pH value of the solution is 7, then adding the filtered cotton fibers into 200mL of sodium hypochlorite solution with the mass fraction of 0.6%, treating for 30min at 100 ℃, cooling, and repeatedly rinsing with deionized water until the pH value of the solution is 7. According to the volume ratio of 1: 2: mixing 50% sulfuric acid, 37% hydrochloric acid and deionized water to prepare 200mL, adding sodium hypochlorite-treated cotton fibers, and mixing the cotton fibers with the mass concentration of 50%, the mass fraction of hydrochloric acid and the deionized water according to a solid-liquid ratio of 1: 9(g/mL), treating for 1h at 60 ℃, filtering, repeatedly washing with deionized water until the pH value of the solution is neutral, then washing with absolute ethyl alcohol for 3 times until the filtrate is colorless, finally washing with absolute ethyl alcohol for 3 times, drying at 100 ℃, and grinding to obtain the cellulose nanocrystal. Adding PAN powder with the concentration of 40g/L and PVP powder with the concentration of 5g/L into a certain amount of DMF solution, and stirring for 15 hours at room temperature to obtain light yellow transparent liquid, namely the polyacrylonitrile spinning solution. According to the proportion of 1: 16 mixing the spinning solution of cellulose and polyacrylonitrile, treating for 60min at room temperature with 28KHz 300W ultrasonic oscillation, and vigorously stirring at 500r/min for 4h until the solution is fully mixed. The operating parameters of the spinning process were as follows: the spinning voltage was 20kV, the take-up distance (i.e., the distance between the syringe needle and the take-up plate) was 15cm, and the flow rate of the spinning solution obtained in step 4 was 0.5 mL/h. And after spinning is finished, preparing the cellulose/polyacrylonitrile blended nanofiber composite membrane by electrostatic spinning, drying the composite membrane for 4 hours in a drying oven at 35 ℃, and storing the composite membrane for subsequent experiments.
The filtering capacity of the prepared MIL-53 (Fe)/cellulose/polyacrylonitrile blended nanofiber composite membrane is evaluated through an air permeability test. The test results are shown in table 1: the air permeability of the general medical mask was 101.38mm/s, the sample of comparative example 1 was 11.24mm/s, and the result obtained in example 2 was that the inner core layer was changed to our prepared MIL-53 (Fe)/cellulose/polyacrylonitrile blended nanofiber composite membrane, which had an air permeability of 105.56mm/s, and was close to that of the general medical mask. Therefore, the mask without MIL-53(Fe) has poor air permeability and is not suitable for wearing. The MIL-53(Fe) has adsorption and photocatalysis effects, does not depend on static electricity to play a role, and under the condition of similar air permeability, the MIL-53 (Fe)/cellulose/polyacrylonitrile blended nanofiber composite membrane is used as a mask core layer, so that the mask can be recycled. The mask core layer prepared in example 2 facilitates recycling of the mask.
FIG. 1 is a scanning electron micrograph of MIL-53(Fe) powder obtained in example 2 of the present invention. As can be seen, the MIL-53(Fe) surface is smooth and clean, and has irregular shape, which is in the shape of rhombus with different sizes.
FIG. 2 is an X-ray diffraction pattern of MIL-53(Fe) powder obtained in example 2 of the present invention. The sample obtained by powder X-ray diffraction of MIL-53(Fe) was crystalline. Diffraction peaks at diffraction angles 2 θ of 9.3 °, 12.7 °, 17.6 °, 18.5 °, 25.5 °, and 27.3 ° were consistent with the previously reported MIL-53 and simulated samples, confirming the successful synthesis of MIL-53 (Fe).
FIG. 3 is a UV-visible diffuse reflectance spectrum, denoted by (alpha hv), of MIL-53(Fe) powder prepared according to example 2 of the present invention2/nAnd forbidden band width EgAnd (4) a functional relation graph. Obtaining (alpha hv) according to Kubelka-Munk function (formula 1)2/nAnd EgAnd (4) functional relation. The calculated forbidden band width of the MIL-53(Fe) powder is 2.06 eV. The MIL-53(Fe) has narrow forbidden band width and small energy required by electron transition, so that more electrons can be excited into a conduction band, and the photocatalytic activity is high.
αhν＝A(h-Eg)n/2 (1)
Where α is the absorption coefficient of the material, h is the planck constant, ν is the frequency of light, Eg is the forbidden bandwidth, and a is a constant.
FIG. 4 is a scanning electron microscope image of a cellulose/polyacrylonitrile blended nanofiber composite membrane prepared by electrostatic spinning according to example 1 of the present invention. It can be seen that the fiber film without MIL-53(Fe) has clear and smooth surface, small diameter, uniform shape, gaps and certain air permeability.
FIG. 5 is a scanning electron microscope image of the MIL-53 (Fe)/cellulose/polyacrylonitrile blended nanofiber composite membrane prepared by electrostatic spinning obtained in example 2 of the present invention. It can be seen that after MIL-53(Fe) is added, the fiber surface is convex, not smooth, porous and sparsely distributed.
Table 1 shows the results of the air permeability test of the sample of example 2 of the present invention. The protective effect of the mask mainly depends on the inner core layer, the air permeability of the outer layer and the inner layer of the mask is 1109.97mm/s, the air permeability of the single core layer is 120.60mm/s, the air permeability of the common medical mask is 101.38mm/s, and the air permeability of the sample of the comparative example 1 is 11.24mm/s, the result obtained in the example 2 is that the inner core layer is replaced by the MIL-53 (Fe)/cellulose/polyacrylonitrile blended nanofiber composite membrane prepared by us, the air permeability is 105.56mm/s, the composite membrane is close to the common medical mask, but the mask without the MIL-53(Fe) is poor in air permeability and is not suitable for wearing. The sample prepared in this example 2 is optimal.
TABLE 1
Figure BDA0002733466410000161

Claims (6)

1. A method for preparing a filter layer of an MOF/cellulose/polyacrylonitrile mask is characterized by comprising the following steps: the method specifically comprises the following steps:
step 1, preparing MIL-53(Fe) nanoparticles;
step 2, synthesizing cellulose nanocrystals;
step 3, mixing polyacrylonitrile and the cellulose nanocrystalline obtained in the step 2 to obtain a mixed solution;
step 4, adding the product obtained in the step 1 into the mixed solution obtained in the step 3 to obtain a spinning solution;
and 5, performing electrostatic spinning on the spinning solution obtained in the step 4 to obtain an MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane, and drying the MIL-53 (Fe)/cellulose/Polyacrylonitrile (PAN) blended nanofiber composite membrane in a drying oven at 35 ℃ for 4-6 hours to obtain the composite membrane.
2. A method of making a MOF/cellulose/polyacrylonitrile facemask filter layer according to claim 1, wherein: the specific process of the step 1 is as follows:
weighing 50-100 mL of dimethylformamide solution as a solvent; according to FeCl3·6H2O、H2The molar ratio of BDC to DMF was 1: 1: treating the mixture of 280-500 at room temperature with 40KHz and 300W ultrasonic oscillation for 10-30 min until a clear solution is formed; then mechanically stirring for 3-6 h at the speed of 200-500 r/min; then transferring the reactant mixture into a reaction kettle, heating at 120-180 ℃ for 12-24 h, naturally cooling to room temperature, cooling, and centrifuging at the speed of 11000r/min for 15-30 min to obtain a precipitate, namely MIL-53 (Fe); according to the bath ratio of 1: 10-30, soaking the obtained precipitate for 15-30 min at normal temperature by using a methanol solution and deionized water, repeating the soaking for 3 times, finally reheating for 8-12 h at 100-150 ℃, and cooling to room temperature to obtain the final MIL-53(Fe) nanoparticles.
3. A method of making a MOF/cellulose/polyacrylonitrile facemask filter layer according to claim 2, wherein: the specific process of the step 2 is as follows:
step 2.1, pretreating cotton fibers;
according to the bath ratio of 1: 7-10, adding 10-20 g of cotton fibers into 70-140 mL of 3 mass percent sodium hydroxide solution, slowly stirring for 6-8 h at 80-100 ℃, repeatedly washing with deionized water after cooling until the pH value of the solution is 7-8, then adding the filtered cotton fibers into 140-200 mL of 0.6 mass percent sodium hypochlorite solution, treating for 30-60 min at 100-120 ℃, repeatedly rinsing with deionized water after cooling until the pH value of the solution is 7;
step 2.2, preparing cellulose nanocrystals by a sulfuric acid method;
according to the volume ratio of 1: 2: 2-3, mixing 50-60% of sulfuric acid by mass concentration, 37% of hydrochloric acid by mass fraction and deionized water to prepare 200mL, adding the cotton fiber treated by the sodium hypochlorite in the step 2.1, and mixing the obtained mixture according to a solid-liquid ratio of 1: 8-10 g/mL, treating for 1-3 h at 40-60 ℃, filtering, repeatedly cleaning with ionized water until the pH value of the solution is neutral, then washing with absolute ethyl alcohol for 2-3 times until the filtrate is colorless, finally cleaning with absolute ethyl alcohol for 1-2 times, drying at 80-100 ℃, and grinding to obtain the cellulose nanocrystal.
4. A method of making a MOF/cellulose/polyacrylonitrile facemask filter layer according to claim 3, wherein: the specific process of the step 3 is as follows:
step 3.1, preparing an electrostatic spinning solution;
adding 30-80 g/L PAN powder and 3-8 g/L PVP powder into 10-100 ml DMF solution, and stirring at room temperature for 15-24 h to obtain light yellow transparent liquid, namely polyacrylonitrile spinning solution;
step 3.2: according to the following steps of 1: and 16, mixing the cellulose nanocrystals obtained in the step 2 and the polyacrylonitrile spinning solution obtained in the step 3.1, carrying out ultrasonic oscillation treatment for 10-30 min, and violently stirring at the speed of 200-500 r/min for 2-4 h until the solutions are fully mixed to obtain a mixed solution.
5. A method of making a MOF/cellulose/polyacrylonitrile facemask filter layer according to claim 3, wherein: the specific process of the step 4 is as follows:
and (3) adding 5-40% by mass of MIL-53(Fe) particles into the mixed solution obtained in the step (3), and ultrasonically stirring for 2-4 hours to obtain a spinning solution.
6. A method of making a MOF/cellulose/polyacrylonitrile facemask filter layer according to claim 5, characterized in that: the parameters of the spinning process in the step 5 are set as follows: the distance between the syringe needle and the receiving plate is 10-15 cm, and the flow rate of the spinning solution is 0.1-0.5 mL/h.
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Application publication date: 20210409