CN114950407B - Preparation method of multifunctional flexible photocatalytic film - Google Patents
Preparation method of multifunctional flexible photocatalytic film Download PDFInfo
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- CN114950407B CN114950407B CN202210545615.7A CN202210545615A CN114950407B CN 114950407 B CN114950407 B CN 114950407B CN 202210545615 A CN202210545615 A CN 202210545615A CN 114950407 B CN114950407 B CN 114950407B
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004744 fabric Substances 0.000 claims abstract description 69
- 239000011521 glass Substances 0.000 claims abstract description 68
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000002121 nanofiber Substances 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- 238000001523 electrospinning Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 38
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 22
- 239000004917 carbon fiber Substances 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000012855 volatile organic compound Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- -1 hydroxyl radicals Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/59—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a preparation method of a multifunctional flexible photocatalytic film. The preparation method of the invention comprises the following steps: 1. preparing electrostatic spinning precursor liquid; 2. preparing a polymer nanofiber membrane/glass cloth by electrostatic spinning, and drying and calcining; 3. preparing an electrostatic spinning precursor solution containing a photocatalyst; 4. preparing a photocatalyst-polymer nanofiber membrane-carbon nanofiber/glass cloth composite material by electrostatic spinning, and sequentially carrying out vacuum drying, tube furnace inert atmosphere calcination and muffle furnace air atmosphere calcination for proper time. The multifunctional flexible photocatalytic film material can greatly improve the separation and transmission efficiency of photo-generated electron holes, and the photocatalyst has abundant oxygen vacancies under the support of carbon fibers to provide a large number of catalytic active sites, thereby having remarkable photocatalytic activity; the obtained material can not only reduce CO 2 The multifunctional organic light-emitting diode also has multiple functions of degrading indoor VOCs, purifying air and the like, and has good application prospect.
Description
Technical Field
The invention relates to a preparation method of a multifunctional flexible photocatalytic film, and belongs to the technical field of photocatalytic materials.
Background
The photocatalytic oxidation method for eliminating volatile organic pollutants (VOCs) in air is a new pollution control technology which is increasingly paid attention in recent years. The photocatalytic treatment of VOCs is to generate electrons and holes under illumination by using photocatalyst, and the generated electrons can be combined with O in the environment 2 Reaction to give O 2－ (superoxide radical), the photogenerated holes can react with water molecules in air to generate hydroxyl radicals (.OH). The superoxide ion free radical, the hydroxyl radical and the photo-generated hole have strong oxidizing ability and react with VOCs in the air to decompose the VOCs into CO 2 And H 2 Substances such as O; the process does not need other chemical auxiliary agents, the reaction condition is mild, and the final product is usually CO only 2 And H 2 O, which does not produce secondary pollution, is one of the most potential application novel technologies aiming at indoor air pollution at present. However, the high-activity photocatalytic material is mainly in nano powder structure, which limits practical application and is urgentIt is necessary to develop a novel fixing technology of the photocatalysis nano material.
In recent years, the nanofiber membrane material prepared by the electrostatic spinning method not only keeps the smaller grain size of the nanomaterial, and the macroscopic size of the material is increased through the fiber membrane structure, so that the fiber membrane structure is easier to integrate into various environment treatment equipment in practical application. However, unlike organic nanofiber membranes, inorganic nanofiber membrane materials prepared by conventional electrospinning techniques have poor toughness, which is caused by the rigid crystal structure of the inorganic material itself. In order to increase the toughness, the bending resistance and the like of the inorganic nano material, a large amount of organic additives are generally added in the spinning process, and the organic additives are carbonized in the subsequent high-temperature treatment process to prepare the carbon fiber composite flexible nano fiber membrane material. If the process is adopted to prepare the fiber membrane material for photocatalysis, the catalytic activity of the photocatalysis material can be greatly reduced, because the carbonization of organic matters into carbon fibers requires a high temperature of more than 700 ℃, the added nano photocatalysis material can be melted and recrystallized to generate micron-sized grains at the high temperature, and the high activity of the nano material is lost. On the other hand, the surface of the photocatalytic material prepared under the condition is covered with a thicker carbon film, so that direct contact between reactant molecules and the surface of the photocatalytic material is hindered, and the photocatalytic activity is greatly reduced compared with that of the original nano catalytic material. In addition, photons with energy higher than the band gap of the semiconductor penetrate into the surface of the photocatalytic material to a depth of tens of nanometers, and the photocatalytic film material with the thickness of micrometers obtained by the electrospinning technology cannot effectively exert the catalytic performance on the mass unit, so that the cost problem in practical application is increased.
Based on the technical problems, the invention provides a method for preparing the high-activity ultrathin photocatalytic film material loaded by the flexible substrate by combining the electrostatic spinning technology with the nano material composite technology. In a plurality of high-strength flexible substrates, glass cloth is high-temperature resistant, widely applied and low in cost, so that the glass cloth is selected as a flexible substrate material to prepare a high-strength and high-activity photocatalytic film material loaded on the glass cloth. Although many studies have been reported on supporting photocatalytic materials on the surface of glass fiber cloth, few practical applications are currently possible. The reason for this is mainly limited by the material loading technology. For example, the commonly used in-situ growth method is adopted to load the photocatalytic material on the surface of the glass cloth, and the glass cloth is required to be subjected to acid washing, alkali washing and subsequent in-situ chemical growth processes, so that the treatment cost is high, and the stability of the growth process of the loaded material is difficult to ensure. Another common loading method is to use a coating mode, the catalyst coating obtained by the method is thicker, the mechanical strength is low, the photocatalytic film material can fall off on the surface of the glass cloth due to external force factors such as collision, although the use of the adhesive can improve the falling-off condition of the material, the application problem of the material under the environment with external friction and collision can not be fundamentally solved, and the high-molecular adhesive can be gradually degraded by the photocatalytic material in the use process, so that the photocatalytic coating finally falls off completely. The electrostatic spinning technology provides possibility for preparing the glass cloth-loaded high-activity ultrathin film material by adjusting the concentration of spinning precursors, the spinning time, the spinning temperature and humidity, the subsequent heat treatment conditions and the like. The main problems faced by this technology at present are: after the nano catalytic material is sprayed on the surface of the glass cloth by an electrospinning technology, the catalytic material is very easy to fall off from the surface layer of the glass cloth due to the large difference of thermal expansion coefficients of the nano catalytic material and the glass cloth in the calcination treatment process, so that the composite material is difficult to prepare successfully. In view of the above, the invention provides a preparation method for loading a high-strength, high-stability and high-activity photocatalytic film material on glass cloth. The preparation of the flexible film on the carbon fiber coated glass cloth is realized, so that the method has higher scientific value and practical significance for purifying indoor air.
Disclosure of Invention
The purpose of the invention is that: the preparation method for loading the high-strength, high-stability and high-activity photocatalytic film material on the glass cloth is provided, and the preparation of the flexible film on the carbon fiber coated glass cloth is realized, so that the preparation method has high scientific value and practical significance for purifying indoor air.
In order to achieve the above object, the present invention provides a method for preparing a multifunctional flexible photocatalytic film, comprising the steps of:
step 1: preparing a polymer precursor solution for electrostatic spinning;
step 2: filling the polymer precursor solution obtained in the step 1 into an injector, and carrying out electrostatic spinning under the condition of setting spinning conditions by taking glass cloth as a carrier to obtain a polymer nanofiber membrane/glass cloth;
step 3: vacuum drying the polymer nanofiber membrane/glass cloth at a certain temperature, and calcining in a tube furnace for a certain time to obtain carbon nanofiber/glass cloth;
step 4: mixing the polymer precursor solution obtained in the step 1 with a photocatalyst according to a certain proportion, stirring for a certain time, uniformly dispersing by ultrasonic to obtain a precursor solution containing the photocatalyst, loading a proper volume into an injector, taking the carbon nanofiber/glass cloth obtained in the step 3 as a carrier, setting spinning conditions, and carrying out electrostatic spinning to obtain the photocatalyst-polymer nanofiber membrane-carbon nanofiber/glass cloth composite material;
step 5: vacuum drying the photocatalyst-polymer nanofiber-carbon nanofiber/glass cloth composite material obtained in the step 4 at a certain temperature, and calcining for a certain time in the inert atmosphere of the tube furnace to obtain the photocatalyst-carbon nanofiber 1 Carbon nanofibers 2 Calcining the glass cloth composite material in the atmosphere of a muffle furnace, and removing the carbon nanofiber on the outermost surface of the glass cloth composite material by controlling the calcining temperature and time to obtain the photocatalyst-carbon nanofiber 2 The glass cloth flexible photocatalytic film is the multifunctional flexible photocatalytic film.
Preferably, the polymer used for preparing the polymer precursor solution in the step 1 is at least one of PVP, PAN and PVA, and the used solvent is an alcohol solvent or a carboxylic acid solvent; the mass fraction of the polymer precursor solution is 1-15%.
Preferably, the method comprises the steps of, the process conditions of the electrostatic spinning in the step 2 and the step 4 are as follows: the feeding speed is 0.1-20 mL/h, the electrospinning voltage is 15-20 kV, the distance between the nozzle and the collector is 15-20 cm, the rotating speed of the roller is 60r/min, the relative humidity is 30% +/-5%, and the ambient temperature is 23+/-2 ℃.
Preferably, the calcination temperature of the tube furnace in the step 3 is 300-800 ℃ and the time is 0.5-12 h.
Preferably, the temperature of the vacuum drying in the step 3 and the step 5 is 40-80 ℃ and the time is 0.5-12 h.
Preferably, the ratio of the photocatalyst to the polymer in the step 4 is 0.01 to 1:1.
preferably, the calcination temperature of the tube furnace in the step 5 is 300-800 ℃ and the time is 0.5-12 h.
Preferably, the calcination temperature of the muffle furnace in the step 5 is controlled to be 300-800 ℃, and the calcination time is controlled to be not more than 2 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) The carbon nano-fibers firmly loaded on the glass cloth provide a large number of growth attachment points and active sites for the photocatalyst, so that the firm loading of the catalytic material on the surface of the glass cloth is ensured, the composite photocatalytic material has extremely high photocatalytic activity and use stability, and the flexible thin film photocatalytic material can be used for CO 2 The functions of reducing and degrading indoor VOCs, purifying other pollutants in the air and the like are achieved, and the method has wide application prospects;
(2) The preparation method disclosed by the invention does not need special equipment and harsh conditions, is simple in process, strong in controllability, easy to realize large-scale production and has practicability.
Drawings
FIG. 1 is a photograph of electrospun PVP nanofiber membrane/glass cloth obtained in example 1;
FIG. 2 is a photograph of a carbon nanofiber coated glass cloth obtained in example 1;
FIG. 3 shows Bi obtained in example 2 2 WO 6 -a photograph of a carbon nanofiber-glass cloth composite;
FIG. 4 is a graph showing the performance of the flexible bismuth tungstate film obtained in example 2 in photocatalytic reduction of CO 2;
FIG. 5 is a degradation curve of photocatalytic degradation of acetaldehyde by the bismuth tungstate flexible film obtained in example 2, wherein C/CO represents a post-reaction concentration/initial concentration;
FIG. 6 shows Bi obtained in example 3 2 WO 6 -a photograph of glass cloth composite material.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Example 1
Preparation of carbon fiber/glass cloth:
(1) 1g of polyvinylpyrrolidone PVP is weighed and dissolved in 9g of ethanol, and is magnetically stirred for 12 hours at room temperature of 20 ℃ to form uniform and transparent polymer precursor solution;
(2) Burning glass cloth with proper size in a muffle furnace at 450 ℃ for 2h in an air state, soaking in 1mol/L NaOH solution for 12h, leaching with deionized water and ethanol, and drying for later use;
(3) The 5mL precursor solution is taken and filled into a 10mL injector, and placed into an electrostatic spinning machine. The positive voltage of the spinning is 15kv, the distance between the tip and the receiving plate is 15cm, the spraying speed is 1.5mL/h, the temperature is 23 ℃, and the humidity is 33%; PVP nanofiber membrane/glass cloth was prepared using the treated glass cloth as a carrier, as shown in FIG. 1.
Putting the spun PVP nanofiber membrane/glass cloth into a constant temperature oven at 60 ℃ for drying and stabilizing treatment under vacuum conditions, and naturally cooling after 4 hours; n (N) 2 Calcining at 500 ℃ for 2 hours in the atmosphere to obtain the carbon fiber/glass cloth, as shown in figure 2.
The detection analysis shows that: the result of example 1 is a carbon fiber/glass cloth with PVP nanofiber membrane in N 2 And calcining in the atmosphere to form carbon nano fibers which are tightly combined with the glass cloth, wherein the carbon fibers are firmly loaded in the pores of the glass cloth.
Example 2
Bi 2 WO 6 -preparation of carbon nanofiber-glass cloth composite material:
(1) 1g of polyvinylpyrrolidone PVP is weighed and dissolved in 9g of ethanol, and is magnetically stirred for 12 hours at room temperature of 20 ℃ to form uniform and transparent polymer precursor solution;
(2) 0.26g Bi 2 WO 6 Dispersing the nano powder into 1mL of ethanol, adding 10mL of 10wt% PVP solution, stirring at 20 ℃ for 12h, and carrying out electrostatic spinning by taking the carbon fiber/glass cloth prepared in the example 1 as a carrier to obtain Bi 2 WO 6 PVP-carbon fiber/glass cloth, vacuum drying, and drying in advance in a tube furnace N 2 Calcining for 2 hours at 500 ℃ in atmosphere to obtain Bi 2 WO 6 -carbon fiber 1 -carbon fiber 2 Glass cloth; calcining in muffle furnace at 400 deg.C for not more than 3 hr, and burning off the carbon fiber to obtain Bi 2 WO 6 -carbon fiber 2 Glass cloth flexible photocatalytic film as shown in fig. 3.
The detection analysis shows that: EXAMPLE 2 Bi is obtained 2 WO 6 -carbon fiber 2 The glass cloth flexible photocatalysis film, the photocatalyst is firmly supported on carbon fiber of the glass cloth. CO is carried out on the obtained material 2 Reduction Properties (the products are CO and CH 4 ) And performance test of degrading acetaldehyde, the material is found to have better CO 2 The reduction performance, as shown in fig. 4, can also effectively degrade indoor VOCs (such as acetaldehyde, etc.), as shown in fig. 5, and has good air purifying performance.
Example 3
This embodiment differs from embodiment 2 only in that: directly replacing the carbon fiber/glass cloth carrier obtained in example 1 with glass cloth, bi was added to the glass cloth 2 WO 6 The nano powder is sprayed on the glass cloth carrier through electrospinning.
The remainder was exactly the same as described in example 1.
The detection analysis shows that: example 3 such Bi obtained by the method 2 WO 6 A nanofiber membrane/glass cloth composite material, bi after calcination 2 WO 6 The fiber membrane is separated from the glass cloth, as shown in fig. 6.
Example 4
This embodiment differs from embodiment 2 in that: bi to be obtained 2 WO 6 -carbon fiber 1 -carbon fiber 2 Calcining glass cloth in muffle furnace air atmosphere, and preventing carbon fiber on the surfaceControlling the time to obtain Bi 2 WO 6 Glass cloth photocatalytic film.
The detection analysis shows that: bi obtained in example 4 2 WO 6 In comparison with example 2, the carbon fibers on the glass cloth are partially or completely burned off, and the photocatalyst-formed film and the glass cloth are partially or completely separated.
Claims (8)
1. The preparation method of the multifunctional flexible photocatalytic film is characterized by comprising the following steps of:
step 1: preparing a polymer precursor solution for electrostatic spinning;
step 2: filling the polymer precursor solution obtained in the step 1 into an injector, and carrying out electrostatic spinning under the condition of setting spinning conditions by taking glass cloth as a carrier to obtain a polymer nanofiber membrane/glass cloth;
step 3: vacuum drying the polymer nanofiber membrane/glass cloth at a certain temperature, and calcining in a tube furnace for a certain time to obtain carbon nanofiber/glass cloth;
step 4: mixing the polymer precursor solution obtained in the step 1 with a photocatalyst according to a certain proportion, stirring for a certain time, uniformly dispersing by ultrasonic to obtain a precursor solution containing the photocatalyst, loading a proper volume into an injector, taking the carbon nanofiber/glass cloth obtained in the step 3 as a carrier, and setting spinning conditions for electrostatic spinning to obtain a photocatalyst-polymer nanofiber membrane-carbon nanofiber/glass cloth composite material;
step 5: vacuum drying the photocatalyst-polymer nanofiber-carbon nanofiber/glass cloth composite material obtained in the step 4 at a certain temperature, and calcining for a certain time in the inert atmosphere of a tube furnace to obtain the photocatalyst-carbon nanofiber 1 Carbon nanofibers 2 Calcining the glass cloth composite material in the atmosphere of a muffle furnace, and removing the carbon nanofiber on the outermost surface of the glass cloth composite material by controlling the calcining temperature and time to obtain the photocatalyst-carbon nanofiber 2 The glass cloth flexible photocatalytic film is the multifunctional flexible photocatalytic film.
2. The method for preparing a multifunctional flexible photocatalytic film according to claim 1, wherein the polymer used for preparing the polymer precursor solution in step 1 is at least one of PVP, PAN and PVA, and the solvent used is an alcohol solvent or a carboxylic acid solvent; the mass fraction of the polymer precursor solution is 1-15%.
3. The method for preparing the multifunctional flexible photocatalytic film according to claim 1, wherein the process conditions of the electrospinning in the step 2 and the step 4 are as follows: the feeding speed is 0.1-20 mL/h, the electrospinning voltage is 15-20 kV, the distance between the nozzle and the collector is 15-20 cm, the rotating speed of the roller is 60r/min, the relative humidity is 30% +/-5%, and the ambient temperature is 23+/-2 ℃.
4. The method for preparing a multifunctional flexible photocatalytic film according to claim 1, wherein the calcination temperature in the tube furnace in the step 3 is 300-800 ℃ and the time is 0.5-12 hours.
5. The method for preparing a multifunctional flexible photocatalytic film according to claim 1, wherein the vacuum drying temperature in step 3 and step 5 is 40-80 ℃ and the time is 0.5-12 hours.
6. The method for preparing a multifunctional flexible photocatalytic film according to claim 1, wherein the ratio of photocatalyst to polymer in step 4 is 0.01-1: 1.
7. the method for preparing a multifunctional flexible photocatalytic film according to claim 1, wherein the calcination temperature in the tube furnace in step 5 is 300-800 ℃ and the time is 0.5-12 hours.
8. The method for preparing a multifunctional flexible photocatalytic film according to claim 1, wherein the calcination temperature of the muffle furnace in step 5 is controlled to 300-800 ℃, and the calcination time is controlled to not more than 2 hours.
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