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CN107754493B - Photocatalytic transparent PM2.5 filtering membrane and preparation method thereof - Google Patents

Photocatalytic transparent PM2.5 filtering membrane and preparation method thereof Download PDF

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CN107754493B
CN107754493B CN201711058790.9A CN201711058790A CN107754493B CN 107754493 B CN107754493 B CN 107754493B CN 201711058790 A CN201711058790 A CN 201711058790A CN 107754493 B CN107754493 B CN 107754493B
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tio
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CN107754493A (en
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张静
熊叶
薛朝华
张明明
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Shaanxi University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/54Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
    • B01D46/543Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8678Removing components of undefined structure
    • B01D53/8687Organic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079Manufacture of membranes comprising organic and inorganic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58Fabrics or filaments
    • B01J35/59Membranes

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Abstract

The invention discloses a transparent PM2.5 filtering membrane with photocatalysis and a preparation method thereof, wherein the PM2.5 filtering membrane is a composite nanofiber membrane with a sandwich-like structure and comprises polyacrylonitrile @ TiO2And polyamide-6, wherein the diameter distribution of the nano-fibers of the composite nano-fiber membrane is 60-100 nm. The reticular crosslinked compactness of complex film has photocatalysis function, high transparency and efficient PM2.5 filtering performance simultaneously, and the application is prevented that nanometer screen window not only can effectually block outdoor PM2.5 and get into indoorly, and the low concentration harmful gas in the photocatalysis atmosphere keeps good daylighting, ventilation effect simultaneously under the effect of sunlight moreover.

Description

Photocatalytic transparent PM2.5 filtering membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of filtering materials, and particularly relates to a transparent PM2.5 efficient filtering membrane with photocatalysis and a preparation method thereof.
Background
With the development of industrialization, environmental and air pollution is further increased, and the harm brought by PM2.5 has attracted worldwide attention. PM2.5 is called as 'lung-accessible particulate matter', can directly enter human lungs, and has negative effects on the quality of the atmospheric environment and the health of human bodies due to the fact that the PM contains toxic and harmful substances, is long in residence time in air and long in conveying distance. In addition, the indoor air quality also arouses people's concern, and especially in the severe haze period, PM2.5 value in the indoor air is even higher than outdoor air, and simultaneously because the indoor VOCs concentration that indoor decoration brought obviously increases, seriously influences people's healthy. Therefore, the research and development of the high-efficiency PM2.5 filter material capable of efficiently degrading VOCs in the air are widely regarded. WuRui et al prepared a PM2.5 preventing nanometer window screening with photocatalytic function, the window screening is composed of nanometer air filtration membrane, photocatalytic membrane and carbon-sandwiched non-woven fabric, wherein the nanometer air filtration membrane is composed of dispersed nanometer vinegar cellulose fibers, a plurality of nanometer pores with the pore diameter of 0.5-1 μm are formed, and the porosity of the nanometer filtration membrane is 85% -98%; the photocatalytic film is formed by TiO2/SiO2 composite nanotubes. The nanometer window screen is respectively composed of a photocatalysis membrane and a nanometer filtering membrane with filtering performance, the process flow of the preparation process is relatively long, the aperture of the nanometer vinegar cellulose fiber is large, the PM2.5 filtering efficiency is only about 75%, and the light transmittance is not high.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a photocatalytic transparent PM2.5 filtering membrane and a preparation method thereof, aiming at overcoming the defects in the prior art, solving the problems of low light transmittance, poor air permeability and single function of the conventional air filtering membrane, and being suitable for the fields of indoor air purification devices, window screening materials and the like.
The invention adopts the following technical scheme:
a transparent PM2.5 filtering membrane with photocatalysis performance is disclosed, wherein the PM2.5 filtering membrane is a composite nanofiber membrane with a sandwich-like structure and comprises polyacrylonitrile @ TiO2And polyamide-6, polyamide-6 being arranged on the upper and lower layers of the sandwich-like structure, polyacrylonitrile @ TiO2The composite nanofiber membrane is arranged in the middle layer of the sandwich-like structure, and the diameter of the nanofiber of the composite nanofiber membrane is 60-100 nm.
Further, the polyacrylonitrile @ TiO2The porosity of the porous material is 80-85%, and the surface pore diameter is 0.05-0.1 μm.
Further, the light transmittance of the composite nanofiber membrane is 70-75%, and the air permeability is 14450-14912 mL/(cm)2·h)。
A preparation method of a photocatalytic transparent PM2.5 filtering membrane comprises the following steps:
s1, respectively preparing 6-10 mass percent of PAN @ TiO2The spinning solution and 12-16% of polyamide-6 spinning solution by mass percent, wherein the PAN @ TiO2The spinning solution is doped with 20 mass percent of TiO2
S2, mixing the PAN @ TiO prepared in the step S12Respectively injecting the spinning solution and the polyamide-6 spinning solution into two liquid storage cylinders of a spinning nozzle in an electrostatic spinning machine, arranging the spinning nozzle on the left side of a receiving device of the electrostatic spinning machine, controlling the flow rate of the spinning solution through an injection pump, arranging tin foil paper on the receiving device of the electrostatic spinning machine, starting single-needle spinning to respectively spin different polymers in the liquid storage cylinders, and obtaining a layer of uniform and transparent PAN @ TiO @ on the surface of the receiving device2a/PA 6 nanocomposite fibre membrane;
s3, adding the PAN @ TiO obtained in the step S22the/PA 6 nano composite fiber membrane is dried in vacuum for 18 to 24 hours at the temperature of 60 ℃ together with the tinfoil paper, and the transparent PM2.5 filter membrane with the photocatalytic-like sandwich structure is prepared.
Further, in step S1, slowly adding polyacrylonitrile powder into the N, N-dimethylformamide solution, magnetically stirring for 8-12 h at 20-25 ℃, and slowly adding nano TiO powder2Continuously stirring for 8-12 h at 20-25 ℃ to obtain PAN @ TiO 6-10 wt% of the total spinning solution2And (4) spinning solution.
Furthermore, the molecular weight of the polyacrylonitrile powder is 150,000, and the average particle size of the nano titanium dioxide powder is 40-50 nm.
Further, in step S1, dissolving polyamide-6 particles in a formic acid solution, magnetically stirring at 25 ℃ for 18-24 hours until the polyamide-6 particles are completely dissolved, and preparing a polyamide-6 spinning solution with a mass percentage of 12-16% for later use.
Furthermore, the molecular weight of the polyamide-6 particles is 18000-20000.
Further, in step S2, the polyamide-6 spinning solution is first opened for spinning, and a layer of polyamide-6 nanofiber membrane is obtained as a substrate after collection for 20-30 min; reopening PAN/TiO2Spinning the spinning solution, and collecting for 15-20 min; finally, opening the polyamide-6 spinning solution for spinning,collecting for 20-30 min.
Furthermore, the spinning voltage is 18-20 kV, the spinning distance is 18-20 cm, and the feeding speed is 0.5-0.8 mL/h.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention relates to a transparent PM2.5 filtering membrane with photocatalysis, which is prepared from polyacrylonitrile/TiO by a simple electrostatic spinning method2The composite nanometer air filtering material with the sandwich-like structure formed by the nanometer fibers and the polyamide-6 nanometer fibers has the advantages that the reticular cross-linking of the composite membrane is tight, the photocatalytic function is realized, the transparency is high, the efficient PM2.5 filtering performance is realized, the composite nanometer air filtering material is applied to a nanometer screen window, the outdoor PM2.5 can be effectively prevented from entering a room, low-concentration harmful gas in atmosphere can be effectively prevented from being subjected to photocatalysis under the action of sunlight, and meanwhile, good lighting and ventilation effects are kept.
Further, polyacrylonitrile @ TiO2The porosity of the composite material is 80-85%, the average surface pore diameter is 0.05-0.1 mu m, the specific area is large, the porosity is high, the filtration rate on PM2.5 in air is high, the transparency is high, and the air permeability is good.
Further, the light transmittance of the composite nanofiber membrane is 70-75%, and the air permeability is 14450 mL/(cm)2·h)~14912mL/(cm2H), has good filtering performance, high light transmittance and good air permeability, has the filtering efficiency of 97.97-99.89% on PM2.5 in air, and has good photocatalytic effect on indoor VOCs.
The invention also discloses a method for preparing the photocatalytic transparent PM2.5 filter membrane, and PAN @ TiO @ is respectively prepared2Spinning the spinning solution and the polyamide-6 spinning solution by a double-needle electrostatic spinning machine to obtain uniform and transparent PAN @ TiO2And finally, drying the/PA 6 nano composite fiber membrane in vacuum at 60 ℃ for 18-24 hours to prepare the transparent PM2.5 filtering membrane with the photocatalytic-like sandwich structure.
Furthermore, in the method, hydrophilic nano TiO is directly added2Added into PAN spinning solution, the preparation process is simple and easy to implement, and the prepared PAN @ TiO is2The spinning solution is homogeneous and transparent and has stable properties.
Further, in the method, PA6 particles are directly dissolved in a formic acid solvent, and the mixture is stirred for a certain time at 25 ℃ to obtain the homogeneous and transparent PA6 spinning solution, so that the method is simple and feasible, and the raw materials are easy to obtain.
Further, the method comprises the steps of carrying out alternate spinning through a double-needle spinning machine, respectively controlling the spinning time of needles of different pipelines, starting PA6 spinning, collecting the spinning for 20-30 min, starting PAN/TiO2 spinning solution, collecting the spinning for 15-20 min, finally starting polyamide-6 spinning, collecting the spinning for 20-30 min, and obtaining the nanofiber filtering membrane with good light transmittance and filtering effect.
Furthermore, when the spinning voltage is 18-20 kV, the spinning distance is 18-20 cm, and the feeding speed is 0.5-0.8 mL/h, the spinning process is stable, the average diameter of the obtained nano-fiber is small, the pore diameter is small, the porosity is high, the thickness of the obtained nano-fiber film is uniform, and the performance is stable.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic view of an electrostatic spinning apparatus according to the production method of the present invention;
FIG. 2 is a scanning electron microscope image of the composite nanofiber air filtration membrane obtained in example 3 of the present invention.
Wherein: 1. a high voltage power supply; 2. an injector; 3. a micro two-channel injection pump; 4. a spinneret; 5. and a receiving device.
Detailed Description
The invention discloses a transparent PM2.5 filtering membrane with photocatalysis, wherein the PM2.5 filtering membrane is a composite nanofiber membrane with a sandwich-like structure and sequentially comprises polyamide-6 and polyacrylonitrile @ TiO from top to bottom2And the polyamide-6, PM2.5 filter membrane is PAN @ TiO2the/PA 6 composite nanofiber membrane has the diameter distribution of nanofibers of 60 nm-100 nm.
Wherein PAN @ TiO2/PA6 compositeThe light transmittance of the nanofiber membrane is 70-75%, and the air permeability is 14450 mL/(cm)2·h)~14912mL/(cm2H), the porosity is about 80-85%, and the surface aperture is 0.05-0.1 μm.
The invention also discloses a method for preparing the photocatalytic transparent PM2.5 filtering membrane, which comprises the following steps:
s1, respectively preparing 6-10% by mass of PAN @ TiO2The spinning solution and 12-16% of polyamide 6 spinning solution by mass percent, wherein the PAN @ TiO2The spinning solution is doped with 20 mass percent of TiO2
Wherein polyacrylonitrile Powder (PAN) is slowly added into N, N-Dimethylformamide (DMF) solution, magnetic stirring is carried out for 8-12 h at 25 ℃, and then nano titanium dioxide powder (TiO) is added2) Slowly adding the mixture into the solution, and continuously stirring for 8-12 h at 25 ℃ to prepare PAN @ TiO @ with the mass fraction of 6-10%2Spinning solution;
preferably, polyacrylonitrile has a molecular weight of 150,000, and hydrophilic nano TiO2The average particle diameter of (A) is 40nm to 50 nm;
dissolving polyamide-6 particles (PA6) in a formic acid solution, magnetically stirring for 18-24 hours at 25 ℃ until the polyamide-6 particles are completely dissolved, and preparing a polyamide-6 (PA6) spinning solution with the mass percent of 12-16% for later use;
preferably, the molecular weight of the polyamide-6 is 18000 to 20000.
S2, mixing PAN @ TiO2And PA6 spinning solution is respectively injected into two liquid storage cylinders of a spinning nozzle of the electrostatic spinning machine, the spinning nozzle is arranged on the left side of a receiving device of the electrostatic spinning machine, the flow rate of the spinning solution is controlled by an injection pump, tin foil paper is arranged on the receiving device of the electrostatic spinning machine, then single-needle spinning is started to respectively spin different polymers in the liquid storage cylinders, and a layer of uniform and transparent PAN @ TiO @ can be obtained on the surface of the receiving device2A sandwich-like structure nano composite fiber membrane of/PA 6;
wherein, the PA6 spinning solution is firstly started for spinning and collected for 20min to 30 min; reopening PAN/TiO2Spinning the spinning solution and collecting15 min-20 min; then starting PA6 spinning solution for spinning, and collecting for 20-30 min;
preferably, the spinning voltage is 18-20 kV, the spinning distance is 18-20 cm, and the feeding speed is 0.5-0.8 mL/h.
S3, adding the PAN @ TiO obtained in the step S22the/PA 6 nano composite fiber membrane with the tin foil paper is dried for 18 to 24 hours in vacuum at the temperature of 60 ℃, and the PAN @ TiO with stable sandwich structure and performance is obtained2the/PA 6 composite nanofiber PM2.5 filter material.
Example 1:
s1 preparation of spinning solution
3g of polyacrylonitrile Powder (PAN) and 0.6g of nano titanium dioxide powder (TiO) are weighed respectively2) 47g N, N-dimethyl formamide (DMF), adding PAN powder slowly into DMF solution, magnetically stirring at 25 deg.C for 8 hr, and adding nanometer TiO2Slowly adding the mixture into the solution, and continuously stirring the mixture for 8 hours at 25 ℃ to prepare PAN @ TiO with the mass fraction of 6%2Spinning solution; 6g of polyamide-6 particles (PA6) are weighed and dissolved in 44g of formic acid solution, and the mixture is magnetically stirred for 18 hours at 25 ℃ until PA6 particles are completely dissolved to prepare PA6 spinning solution with the mass percent of 12% for later use.
S2、PAN@TiO2Preparation of/PA 6 composite nanofiber
Mixing the above PAN @ TiO2The spinning solution and the PA6 spinning solution are respectively injected into two liquid cylinders of an injector 2 in a micro-injection pump 3, the tin foil paper is placed on a receiving device 5, a high-voltage power supply 1 is started, and a spinning nozzle 4 starts to work (shown in figure 1).
Firstly, starting PA6 spinning solution for spinning, wherein the spinning voltage is 18KV, the spinning distance is 18cm, the feeding speed of the spinning solution is 0.5mL/h, and collecting for 30 min; reopening PAN/TiO2Spinning the spinning solution, adjusting the spinning voltage to be 20KV, the spinning distance to be 18cm, the feeding speed of the spinning solution to be 0.5mL/h, and collecting for 15 min; finally, starting PA6 spinning solution for spinning, wherein the spinning voltage is 18KV, the spinning distance is 18cm, the feeding speed of the spinning solution is 0.5mL/h, and collecting for 30 min;
S3、PAN@TiO2post-treatment of/PA 6 composite nanofiber
After the shutdown, willObtained PAN @ TiO2the/PA 6 composite electrostatic spinning fiber membrane with the tin foil paper is dried for 24 hours in vacuum at 60 ℃ to ensure that the solvent is fully volatilized, thus obtaining the PAN @ TiO with a sandwich-like structure and stable performance2the/PA 6 composite nanofiber PM2.5 filter material.
The PAN @ TiO2the/PA 6 composite nanofiber membrane is tightly crosslinked in a net shape, the average diameter of the nanofiber is 70nm, the porosity is 80%, the average surface pore size is 0.06 mu m, the filtration efficiency on PM2.5 in air is 97.97%, the light transmittance is 72%, and the air permeability is 14688 mL/(cm)2H) and has better photocatalysis effect on indoor VOCs.
Example 2:
s1 preparation of spinning solution
Respectively weighing 4g of polyacrylonitrile Powder (PAN) and 0.8g of nano titanium dioxide powder (TiO)2) 46g N, N-Dimethylformamide (DMF). Slowly adding PAN powder into DMF solution, magnetically stirring at 25 deg.C for 12 hr, and adding nanometer TiO2Slowly adding the solution into the solution, and continuously stirring the solution for 12 hours at 25 ℃ to prepare PAN @ TiO with the mass fraction of 8%2Spinning solution; 7g of polyamide-6 particles (PA6) are weighed and dissolved in 43g of formic acid solution, and the solution is magnetically stirred for 24 hours at 25 ℃ until PA6 particles are completely dissolved, so as to prepare PA6 spinning solution with the mass percent of 14%.
S2、PAN@TiO2Preparation of/PA 6 composite nanofiber
Mixing the above PAN @ TiO2The spinning solution and the PA6 spinning solution are respectively injected into two liquid cylinders of an injector 2 in a micro-injection pump 3, the tin foil paper is placed on a receiving device 5, a high-voltage power supply 1 is started, and a spinning nozzle 4 starts to work (shown in figure 1).
Firstly, starting PA6 spinning solution for spinning, wherein the spinning voltage is 20KV, the spinning distance is 20cm, the feeding speed of the spinning solution is 0.6mL/h, and collecting for 20 min; reopening polyacrylonitrile/TiO2Blending the spinning solution for spinning, wherein the spinning voltage is 20KV, the spinning distance is 18cm, the feeding speed of the spinning solution is 0.6mL/h, and collecting for 10 min; finally, starting PA6 spinning solution for spinning, wherein the spinning voltage is 20KV, the spinning distance is 20cm, the feeding speed of the spinning solution is 0.6mL/h, and collecting for 20 min;
S3、PAN@TiO2post-treatment of/PA 6 composite nanofiber
After the machine is stopped, the obtained composite electrostatic spinning fiber membrane and the tin foil paper are dried for 24 hours in vacuum at the temperature of 60 ℃ to ensure that the solvent is fully volatilized, and the PAN @ TiO with a sandwich-like structure and stable performance is obtained2the/PA 6 composite nanofiber PM2.5 filter material.
The PAN @ TiO2the/PA 6 composite nanofiber membrane is tightly crosslinked in a net shape, the average diameter of the nanofiber is 60nm, the porosity is 83%, the average surface pore size is 0.1 mu m, the filtration efficiency on PM2.5 in air is 98.89%, the light transmittance is 75%, and the air permeability is 14912 mL/(cm)2H) and has better photocatalysis effect on indoor VOCs.
Example 3:
s1 preparation of spinning solution
5g of polyacrylonitrile Powder (PAN) and 1g of nano titanium dioxide powder (TiO) are weighed respectively2) 45g N, N-Dimethylformamide (DMF). Slowly adding PAN powder into DMF solution, magnetically stirring at 25 deg.C for 12 hr, and adding nanometer TiO2Slowly adding the solution into the solution, and continuously stirring the solution for 12 hours at 25 ℃ to prepare a PAN @ TiO2 spinning solution with the mass fraction of 10%; 8g of polyamide-6 particles (PA6) are weighed and dissolved in 42g of formic acid solution, and the mixture is magnetically stirred for 24 hours at 25 ℃ until PA6 particles are completely dissolved to prepare the PA6 spinning solution with the mass percent of 16%.
S2、PAN@TiO2Preparation of/PA 6 composite nanofiber
Mixing the above PAN @ TiO2And polyamide-6 spinning solution are respectively injected into two liquid cylinders of an injector 2 in a micro-injection pump 3, the tin foil paper is placed on a receiving device 5, a high-voltage power supply 1 is started, and a spinning nozzle 4 starts to work (shown in figure 1).
Firstly, starting a polyamide-6 spinning solution for spinning, wherein the spinning voltage is 20KV, the spinning distance is 20cm, the feeding speed of the spinning solution is 0.8mL/h, and collecting for 20 min; reopening PAN/TiO2Blending the spinning solution for spinning, wherein the spinning voltage is 20KV, the spinning distance is 20cm, the feeding speed of the spinning solution is 0.5mL/h, and collecting for 10 min; and finally, starting the polyamide-6 spinning solution for spinning, wherein the spinning voltage is 20KV, the spinning distance is 20cm, and the feeding speed of the spinning solution is 08mL/h, collecting for 20 min;
S3、PAN@TiO2post-treatment of/PA 6 composite nanofiber
After the machine is stopped, the obtained composite electrostatic spinning fiber membrane and the tin foil paper are dried for 24 hours in vacuum at the temperature of 60 ℃ to ensure that the solvent is fully volatilized, and the PAN @ TiO with a sandwich-like structure and stable performance is obtained2the/PA 6 composite nanofiber PM2.5 filter material.
The PAN @ TiO2the/PA 6 composite nanofiber membrane is tightly crosslinked in a net shape, the average diameter of the nanofiber is 100nm, the porosity is 85%, the average pore diameter is 0.05 mu m, the filtration efficiency on PM2.5 in air is 99.89%, the light transmittance is 70%, and the air permeability is 14450 mL/(cm)2H) and has better photocatalysis effect on indoor VOCs.
Table 1 shows the comparison of the effect of the composite nanofiber air filter material of example 3 of the present invention on several indoor Vocs
Figure BDA0001454254390000081
Figure BDA0001454254390000091
The PAN @ TiO obtained in example 3 was used2The scanning electron microscope image of the/PA 6 composite nanofiber membrane is shown in FIG. 2, in the image, the network crosslinking of the nanofibers is tight, the average diameter is 100nm, the porosity is 85%, and the average pore diameter is 0.05 μm.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (4)

1. The preparation method of the photocatalytic transparent PM2.5 filtering membrane is characterized in that the PM2.5 filtering membrane is a composite nanofiber membrane with a sandwich-like structure and comprises polyacrylonitrile @ TiO2And polyamide-6, polyamide-6 being arranged in a sandwich-like structureUpper and lower layers of (A) polyacrylonitrile @ TiO2The composite nanofiber membrane is arranged in the middle layer of a sandwich-like structure, the diameter of the nanofiber of the composite nanofiber membrane is 60-100 nm, and polyacrylonitrile @ TiO2The porosity of the composite nanofiber membrane is 80-85%, the surface aperture is 0.05-0.1 mu m, the light transmittance of the composite nanofiber membrane is 70-75%, and the air permeability is 14450-14912 mL/(cm)2H) comprising the steps of:
s1, respectively preparing PAN @ TiO2Dope and polyamide-6 dope, wherein the PAN @ TiO2PAN @ TiO doped spinning solution2TiO with spinning solution mass percentage of 20%2Slowly adding polyacrylonitrile powder into an N, N-dimethylformamide solution, magnetically stirring for 8-12 h at 20-25 ℃, and slowly adding nano titanium dioxide powder TiO2Continuously stirring for 8-12 h at 20-25 ℃ to obtain PAN @ TiO 6-10 wt% of the total spinning solution2Dissolving polyamide-6 particles in a formic acid solution, magnetically stirring at 25 ℃ for 18-24 hours until the polyamide-6 particles are completely dissolved, and preparing the polyamide-6 spinning solution with the mass percent of 12-16% for later use;
s2, mixing the PAN @ TiO prepared in the step S12Respectively injecting the spinning solution and the polyamide-6 spinning solution into two liquid storage cylinders of a spinning nozzle of an electrostatic spinning machine, arranging the spinning nozzle at one side of a receiving device of the electrostatic spinning machine, controlling the flow rate of the spinning solution through an injection pump, arranging tin foil paper on the receiving device of the electrostatic spinning machine, starting single-needle spinning to respectively spin different polymers in the liquid storage cylinders, and obtaining a layer of uniform and transparent PAN @ TiO on the surface of the receiving device2The method comprises the following steps of (1) starting a polyamide-6 spinning solution to spin a/PA 6 nano composite fiber membrane, and collecting for 20-30 min to obtain a layer of polyamide-6 nano fiber membrane as a substrate; reopening PAN/TiO2Spinning the spinning solution, and collecting for 15-20 min; finally, starting the polyamide-6 spinning solution for spinning, and collecting for 20-30 min;
s3, adding the PAN @ TiO obtained in the step S22the/PA 6 nano composite fiber membrane is dried in vacuum for 18 to 24 hours at the temperature of 60 ℃ together with the tinfoil paper, and the transparent PM2.5 filter membrane with the photocatalytic-like sandwich structure is prepared.
2. The method for preparing a photocatalytic transparent PM2.5 filter membrane according to claim 1, wherein in step S1, the molecular weight of the polyacrylonitrile powder is 150,000, and the average particle size of the nano titanium dioxide powder is 40-50 nm.
3. The method for producing a photocatalytic transparent PM2.5 filtration membrane according to claim 1, wherein in step S1, the molecular weight of the polyamide-6 particles is 18000 to 20000.
4. The method for preparing the photocatalytic transparent PM2.5 filter membrane according to claim 1, wherein in step S2, the spinning voltage is 18-20 kV, the spinning distance is 18-20 cm, and the feeding speed is 0.5-0.8 mL/h.
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