CN108251970A - TiO2The preparation method of/PAN nanofiber membrane - Google Patents
TiO2The preparation method of/PAN nanofiber membrane Download PDFInfo
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- CN108251970A CN108251970A CN201810064151.1A CN201810064151A CN108251970A CN 108251970 A CN108251970 A CN 108251970A CN 201810064151 A CN201810064151 A CN 201810064151A CN 108251970 A CN108251970 A CN 108251970A
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- tio
- nanofiber membrane
- pan nanofiber
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- nanocrystal
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 82
- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 145
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 106
- 239000002159 nanocrystal Substances 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 36
- 238000009987 spinning Methods 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 78
- 239000007788 liquid Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000975 dye Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 230000001699 photocatalysis Effects 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000001523 electrospinning Methods 0.000 abstract description 10
- 239000005030 aluminium foil Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 56
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000835 fiber Substances 0.000 description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 238000005253 cladding Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007786 learning performance Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a kind of TiO2The preparation method of/PAN nanofiber membrane, specific preparation process are：Polyacrylonitrile powder is dissolved to obtain polymer solution；By TiO2Nanocrystal is scattered in polymer solution, obtains spinning solution；It will be fixed on the syringe pump of electrospinning device in spinning solution inhalation syringe and by syringe, while spinning head connected into high-voltage power cathode, receiver board connection high voltage power supply cathode, receiver board is covered with aluminium foil, carries out electrostatic spinning, obtain TiO2/ PAN nanofiber membrane.Preparation method of the present invention is easy to operate, technological process is short, is suitble to wide popularization and application, while also have excellent catalytic performance and mechanical property, has broad application prospects.
Description
Technical field
The present invention relates to electrostatic spinning fields, belong to a kind of TiO available for photocatalytically degradating organic dye2/ PAN nanometers
The preparation method of tunica fibrosa.
Background technology
Polyacrylonitrile (PAN) is obtained by monomers acrylonitrile through Raolical polymerizable, mainly for the preparation of polyacrylonitrile
Fiber.On polyacrylonitrile film there is undersaturated itrile group, by the way that itrile group is hydrolyzed into carboxyl, the parent of polypropylene fibre film is adjusted
It is aqueous can be to meet the needs of practical application, in addition to this, polypropylene fibre film also has weatherability and good excellent of sun-resistant property
Point, meanwhile, it also has good tolerance to chemical attack.Based on above-mentioned advantage, polypropylene fibre film is widely used
In the field for being separated by filtration dyeing wastewater.But often containing the organic substances such as dyestuff, single filtering in dyeing waste water
Membrane technology can not remove such organic pollution from source, moreover, when Organic Pollutants in Wastewater too high levels, meeting
The separated pore of filter membrane is blocked, water yield is caused to decline, the operational efficiency of entire cleaning system is directly affected, ideal is not achieved
Clean-up effect, cause serious environmental pollution.
TiO2Have many advantages, such as it is nontoxic, cheap, be easy to get, be a kind of very promising catalysis material.TiO2Light
Catalytic degradation reaction is a kind of efficient deep oxidation process, is irradiated by the light of certain wavelength, TiO2Photocatalyst surface is produced
Raw a large amount of active materials, by the organic pollutions oxygenolysis such as halogenated hydrocarbon, fat, itrogenous organic substance, carboxylic acid, surfactant
For water and carbon dioxide, to achieve the purpose that disinfection, decoloration, deodorization.Therefore, based on TiO2Photocatalysis technology to thoroughly degrading
Organic pollution in environment purification has a very wide range of applications.It is traditional but with constantly further investigation and application
Nano-TiO2The shortcomings that suspended phase photochemical catalyst easy in inactivation, easily cohesion, difficult recycling, is gradually exposed so that single nanometer
TiO2Material is restricted when in use.
Electrostatic spinning is exactly the special shape of polymeric fluid electrostatic atomization, and the substance that atomization is divided out at this time is not small
Drop, but the small jet stream of polymer, can run considerably long distance, finally be solidified into fiber.Electrostatic spinning is a kind of spy
Different fiber fabrication process, polymer solution or melt carry out jet spinning in highfield.Under electric field action, at syringe needle
Drop can be become conical (i.e. " taylor cone ") from spherical shape, and extend from conical tip to obtain fiber filaments.This mode can be with
Produce the polymer filaments of nanometer grade diameter.Electrostatic spinning and with its manufacturing device is simple, cost of spinning is cheap, can spin substance
The advantages that type is various, technique is controllable, it has also become effectively prepare one of main path of composite nano-fiber material.
At present, TiO is prepared in electrostatic spinning2During/polymer nanofibre film, most commonly used is polyethylene pyrrole
Pyrrolidone (PVP), cellulose acetate (PVAC), and prepare TiO by the use of polyacrylonitrile (PAN) as polymeric substrates2/ PAN receives
Rice tunica fibrosa passes through the TiO obtained by the prior art using less2/ PAN nanofiber membrane photocatalysis performance with it is anti-aging
Performance is relatively low, can not be repeatedly circulated, this causes its use cost to rise, and has seriously affected the promotion of economic benefit, has not had
Standby market application foreground.
Invention content
The present invention is in order to overcome the above-mentioned deficiencies of the prior art, and it is an object of the present invention to provide a kind of use electrostatic spinning technique system
Standby TiO2The method of/PAN nanofiber membrane, the nano fibrous membrane being prepared in this way have the energy of good photocatalytic degradation
Power, longer service life are recycled Reusability, have saved cost, improved economic benefit.
In order to achieve the above objectives, the present invention provides following technical solution：A kind of TiO2The preparation side of/PAN nanofiber membrane
Method, specific preparation process are：
S1, at room temperature, polyacrylonitrile powder is dissolved by a certain percentage in a solvent, and heating stirring is to being completely dissolved to obtain
Polymer solution；
S2, by TiO2Nanocrystal is scattered in polymer solution by a certain percentage, completely every light, ultrasonic oscillation 0.5-
After 1h, 1-12h is at the uniform velocity stirred, obtains spinning solution；
S3, it will be fixed on the syringe pump of electrospinning device in spinning solution inhalation syringe and by syringe, simultaneously
Spinning head is connected into high-voltage power cathode, receiver board connection high voltage power supply cathode, receiver board is covered with aluminium foil, in room temperature 10-30
DEG C and relative humidity 40-60% under conditions of, carry out electrostatic spinning, obtain TiO2/ PAN nanofiber membrane.
Further, in step S2, TiO2Nanocrystal is made by method comprising the following steps：By colloidal sol-solidifying
Glue method prepares TiO2Colloidal sol, then the TiO that will be obtained2TiO is made in colloidal sol2Powder, the TiO that then will be obtained2Powder, in 450 DEG C-
Calcining obtains TiO at 600 DEG C2Nanocrystal to get.By preparing TiO in regulating step S22The calcination temperature of nanocrystal, can
Control TiO2The crystallinity and particle size of nanocrystal, so as to further adjust TiO2The mechanical property of/PAN nanofiber membrane
Energy.
Further, TiO2The specific preparation process of nanocrystal is：
S21. a certain amount of absolute ethyl alcohol is measured, adds in butyl titanate and acetic acid, A liquid is made in sealing stirring；
S22. deionized water is added in absolute ethyl alcohol, B liquid is made；
S23. and then under agitation B liquid is added dropwise in A liquid, then closed stirs to get TiO2Colloidal sol；Again will
TiO2Colloidal sol is put into baking oven, and set temperature is 60-100 DEG C, so that TiO2Colloidal sol crystallizes to obtain TiO2Crystal is ground and sieved by crystal
Filter, obtains TiO2Powder；Then by TiO2Powder is put into Muffle furnace, and set temperature is 450 DEG C -600 DEG C, calcines 2-3h, will calcine
TiO afterwards2Powder regrinds sieving, obtains TiO2Nanocrystal.
Further, in step S21, absolute ethyl alcohol：Butyl titanate：The volume ratio of acetic acid is (8-9):(6-8):1.
Further, in step S22, absolute ethyl alcohol：The volume ratio of deionized water is 2:1.
Further, TiO in step S22The average grain diameter of nanocrystal is 25nm, is the mixing of anatase and rutile
Crystal form.
Further, it is 4 to mix the mass values of anatase and rutile in crystal form.Detitanium-ore-type structure has best
Photocatalytic activity, Rutile structure can be very good to absorb the ultraviolet light in sunlight, sharp by optimizing as anti-aging materials
The ratio of titanium ore and rutile can make TiO2/ PAN nanofiber membrane has best photocatalysis and anti-aging property.
Further, solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, acetone, chloroform, four in step S1
One kind in hydrogen furans, chloroform, dichloromethane；A concentration of 8-12wt% of polymer solution；TiO in step S22Nanometer
The mass values of crystal and acrylonitrile powder are 0.1-0.5.
Further, the spinning process mesohigh of step S3 is set as 5-25KV, and flow velocity is set as 0.1-2.0mL/h, spray
Silk head is away from receiver board 5-25cm.
In addition to this, the present invention also provides one kind TiO as made from above-mentioned preparation method2/ PAN nanofiber membrane light is urged
Change the method for degradating organic dye, the specific steps are by TiO2/ PAN nanofiber membrane is put into photochemical reactor and has engine dyeing
Material uniformly mixing, opens light source and carries out photocatalytic degradation.After reusing 3 times, TiO2/ PAN nanofiber membrane is to 20mg/L
Methylene blue solution degradation efficiency be maintained at 88.16%, maintain higher catalytic activity.
The beneficial effects of the present invention are：The present invention provides a kind of TiO2The preparation method of/PAN nanofiber membrane is led to
Crossing nano fibrous membrane made from the preparation method of the present invention has larger specific surface area, stronger absorption and photocatalytic degradation
Can, so as to more efficiently adsorbing separation organic pollution, and more thoroughly degraded and purified, it is dirty preferably to solve environment
Dye problem；Meanwhile there is undersaturated itrile group on polyacrylonitrile film, by the way that itrile group is hydrolyzed into carboxyl, it is fine that polypropylene is adjusted
The hydrophilicity of film is tieed up, in addition polypropylene fibre film also has the advantages that weatherability and sun-resistant property are good, while it is rotten to chemistry
Erosion also has good tolerance, based on above-mentioned advantage, using polyacrylonitrile as the TiO of carrier2/ PAN nanofiber membrane is not only
Its hydrophilicity can be adjusted according to actual application environment, efficiency is separated by filtration to improve, also there is longer service life, it can
It is repeatedly circulated, has saved cost, improve economic benefit.In addition to this, TiO of the invention2/ PAN nanofiber membrane
Preparation method is easy to operate, technological process is short, is suitble to wide popularization and application, and then promote China's Green Sustainable strategy
Implement, comply with the trend of new world technology change.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be implemented in accordance with the contents of the specification, below with presently preferred embodiments of the present invention and after attached drawing is coordinated to be described in detail such as.
Description of the drawings
Fig. 1-1 is the TiO obtained by embodiment one in the present invention2(P25)/PAN nanofiber membrane SEM figures
Fig. 1-2 is the TiO obtained by embodiment one in the present invention2(P25) distribution of fiber diameters of/PAN nanofiber membrane
Figure.
Fig. 2 is the TiO obtained by embodiment one in the present invention2(P25)/PAN nanofiber membrane Mechanics Performance Testing figure.
Fig. 3 is the TiO obtained by embodiment one in the present invention2(P25) the photocatalytic degradation efficiency figure of/PAN nanofibers.
Fig. 4-1 is the TiO obtained by embodiment two in the present invention2(450 DEG C)/PAN nanofiber membrane SEM schemes.
Fig. 4-2 is the TiO obtained by embodiment two in the present invention2The fibre diameter of (450 DEG C)/PAN nanofiber membrane point
Butut.
Fig. 5-1 is the TiO obtained by embodiment three in the present invention2(500 DEG C)/PAN nanofiber membrane SEM schemes.
Fig. 5-2 is the TiO obtained by embodiment three in the present invention2The fibre diameter of (500 DEG C)/PAN nanofiber membrane point
Butut.
Fig. 6-1 is the TiO obtained by example IV in the present invention2(600 DEG C)/PAN nanofiber membrane SEM schemes.
Fig. 6-2 is the TiO obtained by example IV in the present invention2(600 DEG C)/PAN nanofiber membrane distribution of fiber diameters
Figure.
Fig. 7 is the TiO obtained by embodiment two to four in the present invention2The XRD diagram of/PAN nanofiber membrane, wherein 72-TiO2
(450 DEG C) particle, 73-TiO2(500 DEG C) particle, 74-TiO2(600 DEG C) particle.
Fig. 8 is the TiO obtained by embodiment two to four in the present invention2/ PAN nanofiber membrane Mechanics Performance Testing figure,
Middle 82-TiO2(450 DEG C)/PAN nanofiber membrane, 83-TiO2(500 DEG C)/PAN nanofiber membrane, 84-TiO2(600℃)/PAN
Nanofiber.
Specific embodiment
With reference to the accompanying drawings and examples, the specific embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but be not limited to the scope of the present invention.
Embodiment one
The first step：At room temperature, quantitative polyacrylonitrile powder is weighed as solute, and selecting DMF, configuration concentration is as solvent
Above-mentioned solution is placed on magnetic stirring apparatus and at the uniform velocity stirs 3h by the polymer solution of 12wt%, treats that polyacrylonitrile powder is completely molten
Xie Hou obtains the polymer solution of faint yellow clear.
Second step：Weigh the TiO that appropriate average grain diameter is 25nm2Nanocrystal, the TiO that will be weighed up2Nanocrystal is scattered in
In obtained polymer solution, wherein TiO2The mass values of nanocrystal and polyacrylonitrile powder are 0.5；With tinfoil paper paper bag
Solution obtained above is wrapped up in so that it is completely every light, ultrasonic vibration 30min at the uniform velocity stirs 3h, obtains TiO2Nanocrystal is uniform
The milky spinning solution of dispersion.
Third walks：Controlling temperature, relative humidity sucks injection 50% or so, by spinning solution obtained at 20 DEG C or so
It is fixed on the syringe pump of electrospinning device in device and by syringe, while the spinning head in electrospinning device is connected into height
Voltage source anode, receiver board connection high voltage power supply cathode, receiver board are covered with aluminium foil, the distance between receiver board and spinning head tune
It saves and carries out electrostatic spinning for 17cm, voltage 18kv, flow velocity 0.5mL/h when adjusting spinning, TiO is made2/ PAN nanofibers
Film.
TiO in second step2Nanocrystal is the mixed crystal type nanometer crystal (P25) that commercially available average grain diameter is 25nm, is led to
The weight ratio to control anatase crystal and rutile crystal type is overregulated as 4.
The present embodiment additionally provides a kind of by TiO obtained2(P25)/PAN nanofiber membrane is used for photocatalytic degradation methylene
The method of base indigo plant solution, the specific steps are：The methylene based sols of a concentration of 20mg/L of 200mL is taken to be injected into reaction vessel first
It is interior, add the TiO of 0.12g2(P25) reaction solution is made in/PAN nanofiber membrane；Secondly above-mentioned reaction solution is being protected from light condition
Lower ultrasonic vibration 15min, magnetic agitation 30min make catalyst be sufficiently mixed with methylene blue solution；Later on CEL-
HXUV300 instruments, start timing after light stability, every 1h, are drawn in 5mL degradation solutions to centrifuge tube with needle tubing；Finally will
Above-mentioned degradation solution centrifuges, and supernatant liquor is taken to measure its light absorption value with UV-1240 type ultraviolet-visible spectrophotometers, with
To photocatalytic activity.
Please refer to Fig.1-1 and Fig. 1-2, TiO2(P25) particle is randomly dispersed in the TiO obtained by embodiment one2(P25)/
PAN nanofiber membrane surface inlays hetero-junctions is formed in fiber, TiO2(P25)/PAN nanofiber membrane diameter range mainly divides
For cloth between 140-220nm, these features have more close relationship with its photocatalysis and mechanical property.It is referring to Fig. 2, real
Apply the TiO obtained by example one2(P25) tensile strength of/PAN nanofiber membrane is 3.0MPa.Referring to Fig. 3, in 10h, implement
TiO obtained by example one2(P25)/PAN nanofibers are to light of the volume for the methylene blue solution of a concentration of 20mg/L of 200mL
Catalytic degradation efficiency is 100%.
By TiO made from embodiment one2(P25)/PAN nanofiber membrane is reused 3 times, to the methylene blue of 20mg/L
Solution degradation efficiency is as shown in the table：
The content according to listed by upper table is it is found that use TiO after 3 times2(P25)/PAN nanofiber membrane is to the methylene of 20mg/L
Base indigo plant solution degradation efficiency is maintained at 88.16%, maintains higher catalytic activity.
Embodiment two
The first step：At room temperature, quantitative polyacrylonitrile powder is weighed as solute, and selecting DMF, configuration concentration is as solvent
Above-mentioned solution is placed on magnetic stirring apparatus and at the uniform velocity stirs 3h by the polymer solution of 12wt%, treats that polyacrylonitrile powder is completely molten
Xie Hou obtains the polymer solution of faint yellow clear.
Second step：Weigh suitable TiO2Nanocrystal, the TiO that will be weighed up2Nanocrystal is scattered in obtained polymer
In solution, wherein TiO2The mass values of nanocrystal and polyacrylonitrile powder are 0.5；It is wrapped up with masking foil obtained above molten
Liquid so that its completely every light, ultrasonic vibration 30min at the uniform velocity stirs 3h, obtains TiO2The milky that nanocrystal uniformly disperses is spun
Silk solution.
Third walks：Controlling temperature, relative humidity sucks injection 50% or so, by spinning solution obtained at 20 DEG C or so
It is fixed on the syringe pump of electrospinning device in device and by syringe, while the spinning head in electrospinning device is connected into height
Voltage source anode, receiver board connection high voltage power supply cathode, receiver board are covered with aluminium foil, the distance between receiver board and spinning head tune
It saves and carries out electrostatic spinning for 17cm, voltage 18kv, flow velocity 0.5mL/h when adjusting spinning, TiO is made2/ PAN nanofibers
Film.
TiO in second step2Nanocrystal is prepared using sol-gel method, the specific steps are：
60mL absolute ethyl alcohols are measured, add in 40mL butyl titanates and 6.68mL acetic acid, A liquid is made in sealing stirring 1h；
6.32mL deionized waters are added in 12mL absolute ethyl alcohols, B liquid is made；
B liquid is added dropwise in A liquid under the conditions of high-speed stirred, control rate of addition be 1drop/3s, closed stirring 1h,
It stands for 24 hours, obtains TiO2Colloidal sol.
By TiO obtained2Colloidal sol is put into baking oven, and set temperature is 80 DEG C, so that TiO2Colloidal sol crystallizes to obtain TiO2Crystal,
Crystal is ground, and with 160 mesh standard sieve sievings, obtain TiO2Powder；By TiO2Powder is put into Muffle furnace, set temperature 450
DEG C, 2h is calcined, by the TiO after calcining2Powder regrinds sieving, obtains TiO2(450 DEG C) nanocrystal.
The present embodiment additionally provides a kind of by TiO obtained2(450 DEG C)/PAN nanofiber membrane is sub- for photocatalytic degradation
The method of methyl blue solution, the specific steps are：The methylene based sols of a concentration of 20mg/L of 200mL is taken to be injected into reaction first to hold
In device, the TiO of 0.10g is added2(450 DEG C)/PAN nanofiber membrane is with obtained reaction solution；Secondly above-mentioned reaction solution is being kept away
Ultrasonic vibration 15min under the conditions of light, magnetic agitation 30min, makes catalyst be sufficiently mixed with methylene blue solution；It is later on
CEL-HXUV300 instruments after light stability, carry out photocatalytic degradation methylene blue reaction.
Embodiment three
The first step：At room temperature, quantitative polyacrylonitrile powder is weighed as solute, and selecting DMF, configuration concentration is as solvent
Above-mentioned solution is placed on magnetic stirring apparatus and at the uniform velocity stirs 3h by the polymer solution of 12wt%, treats that polyacrylonitrile powder is completely molten
Xie Hou obtains the polymer solution of faint yellow clear.
Second step：Weigh suitable TiO2Nanocrystal, the TiO that will be weighed up2Nanocrystal is scattered in obtained polymer
In solution, wherein TiO2The mass values of nanocrystal and polyacrylonitrile powder are 0.5；It is wrapped up with masking foil obtained above molten
Liquid so that its completely every light, ultrasonic vibration 30min at the uniform velocity stirs 3h, obtains TiO2The milky that nanocrystal uniformly disperses is spun
Silk solution.
Third walks：Controlling temperature, relative humidity sucks injection 50% or so, by spinning solution obtained at 20 DEG C or so
It is fixed on the syringe pump of electrospinning device in device and by syringe, while the spinning head in electrospinning device is connected into height
Voltage source anode, receiver board connection high voltage power supply cathode, receiver board are covered with aluminium foil, the distance between receiver board and spinning head tune
It saves and carries out electrostatic spinning for 17cm, voltage 18kv, flow velocity 0.5mL/h when adjusting spinning, TiO is made2/ PAN nanofibers
Film.
TiO in second step2Nanocrystal is prepared using sol-gel method, the specific steps are：
60mL absolute ethyl alcohols are measured, add in 40mL butyl titanates and 6.68mL acetic acid, A liquid is made in sealing stirring 1h；
6.32mL deionized waters are added in 12mL absolute ethyl alcohols, B liquid is made；
B liquid is added dropwise in A liquid under the conditions of high-speed stirred, control rate of addition be 1drop/3s, closed stirring 1h,
It stands for 24 hours, obtains TiO2Colloidal sol.
By TiO obtained2Colloidal sol is put into baking oven, and set temperature is 80 DEG C, so that TiO2Colloidal sol crystallizes to obtain TiO2Crystal,
Crystal is ground, and with 160 mesh standard sieve sievings, obtain TiO2Powder；By TiO2Powder is put into Muffle furnace, set temperature 500
DEG C, 2h is calcined, by the TiO after calcining2Powder regrinds sieving, obtains TiO2(500 DEG C) nanocrystal.
The present embodiment additionally provides a kind of by TiO obtained2(500 DEG C)/PAN nanofiber membrane is sub- for photocatalytic degradation
The method of methyl blue solution, the specific steps are：The methylene based sols of a concentration of 20mg/L of 200mL is taken to be injected into reaction first to hold
In device, the TiO of 0.10g is added2(500 DEG C)/PAN nanofiber membrane is with obtained reaction solution；Secondly above-mentioned reaction solution is being kept away
Ultrasonic vibration 15min under the conditions of light, magnetic agitation 30min, makes catalyst be sufficiently mixed with methylene blue solution；It is later on
CEL-HXUV300 instruments after light stability, carry out photocatalytic degradation methylene blue reaction.
Example IV
The first step：At room temperature, quantitative polyacrylonitrile powder is weighed as solute, and selecting DMF, configuration concentration is as solvent
Above-mentioned solution is placed on magnetic stirring apparatus and at the uniform velocity stirs 3h by the polymer solution of 12wt%, treats that polyacrylonitrile powder is completely molten
Xie Hou obtains the polymer solution of faint yellow clear.
Second step：Weigh suitable TiO2Nanocrystal, the TiO that will be weighed up2Nanocrystal is scattered in obtained polymer
In solution, wherein TiO2The mass values of nanocrystal and polyacrylonitrile powder are 0.5；It is wrapped up with masking foil obtained above molten
Liquid so that its completely every light, ultrasonic vibration 30min at the uniform velocity stirs 3h, obtains TiO2The milky that nanocrystal uniformly disperses is spun
Silk solution.
Third walks：Controlling temperature, relative humidity sucks injection 50% or so, by spinning solution obtained at 20 DEG C or so
It is fixed on the syringe pump of electrospinning device in device and by syringe, while the spinning head in electrospinning device is connected into height
Voltage source anode, receiver board connection high voltage power supply cathode, receiver board are covered with aluminium foil, the distance between receiver board and spinning head tune
It saves and carries out electrostatic spinning for 17cm, voltage 18kv, flow velocity 0.5mL/h when adjusting spinning, TiO is made2/ PAN nanofibers
Film.
TiO in second step2Nanocrystal is prepared using sol-gel method, the specific steps are：
60mL absolute ethyl alcohols are measured, add in 40mL butyl titanates and 6.68mL acetic acid, A liquid is made in sealing stirring 1h；
6.32mL deionized waters are added in 12mL absolute ethyl alcohols, B liquid is made；
B liquid is added dropwise in A liquid under the conditions of high-speed stirred, control rate of addition be 1drop/3s, closed stirring 1h,
It stands for 24 hours, obtains TiO2Colloidal sol.
By TiO obtained2Colloidal sol is put into baking oven, and set temperature is 80 DEG C, so that TiO2Colloidal sol crystallizes to obtain TiO2Crystal,
Crystal is ground, and with 160 mesh standard sieve sievings, obtain TiO2Powder；By TiO2Powder is put into Muffle furnace, set temperature 600
DEG C, 2h is calcined, by the TiO after calcining2Powder regrinds sieving, obtains TiO2(600 DEG C) nanocrystal.
The present embodiment additionally provides a kind of by TiO obtained2(600 DEG C)/PAN nanofiber membrane is sub- for photocatalytic degradation
The method of methyl blue solution, the specific steps are：The methylene based sols of a concentration of 20mg/L of 200mL is taken to be injected into reaction first to hold
In device, the TiO of 0.10g is added2(600 DEG C)/PAN nanofiber membrane is with obtained reaction solution；Secondly above-mentioned reaction solution is being kept away
Ultrasonic vibration 15min under the conditions of light, magnetic agitation 30min, makes catalyst be sufficiently mixed with methylene blue solution；It is later on
CEL-HXUV300 instruments after light stability, carry out photocatalytic degradation methylene blue reaction.
Fig. 4-1,4-2,5-1,5-2,6-1,6-2 are please referred to, using TiO made from different calcination temperatures2Particle electrification is spun
The TiO that silk forms2The main distribution of diameter of/PAN nanofiber membrane is as shown in the table：
The content according to listed by upper table is it is found that with the improve of calcination temperature, TiO2The diameter of/PAN nanofiber membrane increases,
This is because, calcination temperature raising is conducive to TiO2Crystallization nucleation, and disposably generate a large amount of nanocrystals so that TiO2Knot
Crystalline substance improves, and grain size becomes smaller, so as to TiO2Nanocrystal improves the cladding degree of PAN nanofiber membrane, and this feature is to its power
Learning performance has more close relationship.At the same time, TiO2After nanocrystal grain size becomes smaller, TiO is greatly improved2's
Specific surface area contacts conducive to reactive material with catalyst, improves photo-catalysis capability.
Referring to Fig. 7, it is able to observe that TiO in the position of 2 θ=25 °2Apparent diffraction maximum is anatase phase structure, and
And as the rising of calcination temperature, the intensity of diffraction maximum also significantly increase, this shows TiO2The crystallinity enhancing of nanocrystal.Please
Refering to Fig. 8, with TiO2The rising of calcination temperature, obtained TiO2The corresponding peak of curve of/PAN nanofiber membrane increases therewith
Add, show that the normal stress suffered by the area of section of the tunica fibrosa is also significantly increasing, work as TiO2Calcination temperature be 450 DEG C
When, TiO2The tensile strength of/PAN nanofiber membrane is 5.0MPa, works as TiO2Calcination temperature be 500 DEG C when, TiO2/ PAN nanometers
The tensile strength of tunica fibrosa is 5.5MPa, works as TiO2Calcination temperature be 600 DEG C when, TiO2The anti-tensile of/PAN nanofiber membrane is strong
It spends for 8.5MPa, TiO2The raising of calcination temperature is to TiO2The shadow of normal stress suffered by/PAN nanofiber membrane area of section
It rings mainly due to TiO2The crystallinity of nanocrystal improves, and tunica fibrosa mechanical performance is caused to change.In addition every is observed
The abscissa variation of curve is as can be seen that due to TiO2The raising of calcination temperature, leads to TiO2The fracture of/PAN nanofiber membrane is stretched
Long rate further increases, with TiO2Calcination temperature increases to 600 DEG C from 450 DEG C, TiO2The extension at break of/PAN nanofiber membrane
Rate increases to 37.5% from 20%.TiO2The raising of calcination temperature is to TiO2The influence master of/PAN nanofiber membrane elongation at break
If due to TiO2The grain size of nanocrystal becomes smaller, so as to TiO2Nanocrystal is to the cladding degree and cladding of PAN nanofiber membrane
The uniformity improves, and then enhances with PAN based high molecular chains interaction force, makes TiO2/ PAN nanofiber membrane unit cross-sectional area is equal
Even stress, so as to improve TiO2/ PAN nanofiber membrane tensile property, makes TiO2The elongation at break liter of/PAN nanofiber membrane
It is high.At the same time, work as TiO2When nanocrystal improves the cladding degree of PAN nanofiber membrane with degree of being evenly coated, TiO2/PAN
The diameter of nano fibrous membrane is consequently increased, and TiO2The dimensional effect of/PAN nanofiber membrane can also enhance nano fibrous membrane
Mechanical property.In conclusion the TiO obtained by different calcination temperatures2Nanocrystal can enhance poly- as a kind of additive
The mechanical property of object is closed, so as to obtain a kind of high-quality polymer nanofibre film for having both excellent mechanical properties and deformation performance,
To meet the needs of actual application environment.
As the TiO obtained by embodiment two to four2After/PAN nanofiber membrane is reused 3 times, to the Asia of 20mg/L
Methyl blue solution degradation efficiency can be maintained at 88.16%, no longer repeat herein.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that those of ordinary skill in the art are come
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of TiO2The preparation method of/PAN nanofiber membrane, which is characterized in that specifically preparation process is：
S1, at room temperature by polyacrylonitrile powder dissolving in a solvent, obtains polymer solution；
S2, by TiO2Nanocrystal is scattered in the polymer solution, and completely after light, ultrasonic oscillation 0.5-1h, at the uniform velocity
1-12h is stirred, obtains spinning solution；
S3, by the spinning solution under conditions of 10-30 DEG C of room temperature and relative humidity 40-60%, carry out electrostatic spinning, obtain
TiO2/ PAN nanofiber membrane.
2. TiO according to claim 12The preparation method of/PAN nanofiber membrane, which is characterized in that in the step S2,
TiO2Nanocrystal is made by method comprising the following steps：TiO is prepared by sol-gel method2Colloidal sol, then will obtain
TiO2TiO is made in colloidal sol2Powder, the TiO that then will be obtained2Powder is calcined at 450 DEG C -600 DEG C and obtains TiO2Nanocrystal,
To obtain the final product.
3. TiO according to claim 22The preparation method of/PAN nanofiber membrane, which is characterized in that the TiO2Nanometer
The specific preparation process of crystal is：
S21. a certain amount of absolute ethyl alcohol is measured, adds in butyl titanate and acetic acid, A liquid is made in sealing stirring；
S22. deionized water is added in absolute ethyl alcohol, B liquid is made；
S23. and then under agitation B liquid is added dropwise in A liquid, then closed stirs to get TiO2Colloidal sol；Again by TiO2It is molten
Glue is put into baking oven, and set temperature is 60-100 DEG C, so that TiO2Colloidal sol crystallizes to obtain TiO2Crystal is ground sieving, obtained by crystal
TiO2Powder；Then by TiO2Powder is put into Muffle furnace, and set temperature is 450 DEG C -600 DEG C, 2-3h is calcined, after calcining
TiO2Powder regrinds sieving, obtains TiO2Nanocrystal.
4. TiO according to claim 32The preparation method of/PAN nanofiber membrane, which is characterized in that the step S21
In, the absolute ethyl alcohol：Butyl titanate：The volume ratio of acetic acid is (8-9):(6-8):1；In the step S22, the anhydrous second
Alcohol：The volume ratio of deionized water is 2:1.
5. TiO according to claim 12The preparation method of/PAN nanofiber membrane, which is characterized in that in the step S2
TiO2The average grain diameter of nanocrystal is 25nm, is the mixing crystal form of anatase and rutile.
6. TiO according to claim 52The preparation method of/PAN nanofiber membrane, which is characterized in that in the step S2,
The mixing crystal form TiO2Anatase and rutile mass values be 4.
7. TiO according to claim 12The preparation method of/PAN nanofiber membrane, which is characterized in that in the step S1
Solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, chloroform, tetrahydrofuran, chloroform, dichloromethane
In one kind；A concentration of 8-12wt% of the polymer solution；TiO in the step S22Nanocrystal and acrylonitrile powder
Mass values be 0.1-0.5.
8. TiO according to claim 12The preparation method of/PAN nanofiber membrane, which is characterized in that the step S3's
Spinning process mesohigh is set as 5-25KV, and flow velocity is set as 0.1-2.0mL/h, and spinning head is away from receiver board 5-25cm.
9. a kind of TiO prepared according to any one of the claim 1-8 preparation methods2/ PAN nanofiber membrane is used for photocatalysis
The method of degradating organic dye, which is characterized in that the specific steps are：By the TiO2/ that PAN nanofiber membrane is put into photochemistry is anti-
Device is answered uniformly to be mixed with organic dyestuff, opens light source, carries out photocatalytic degradation.
10. a kind of TiO prepared according to any one of the claim 1-8 preparation methods2/ PAN nanofiber membrane, feature exist
In the TiO2/ PAN nanofiber membrane can be repeated for photocatalytically degradating organic dye.
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