CN107287770A - The method that method of electrostatic spinning prepares polyacid/polymer hybridisation nano fibrous membrane - Google Patents
The method that method of electrostatic spinning prepares polyacid/polymer hybridisation nano fibrous membrane Download PDFInfo
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- CN107287770A CN107287770A CN201710428072.XA CN201710428072A CN107287770A CN 107287770 A CN107287770 A CN 107287770A CN 201710428072 A CN201710428072 A CN 201710428072A CN 107287770 A CN107287770 A CN 107287770A
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- polyacid
- electrostatic spinning
- high molecular
- molecular compound
- fibrous membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 43
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 238000009396 hybridization Methods 0.000 title claims abstract description 21
- 239000002121 nanofiber Substances 0.000 claims abstract description 94
- 238000009987 spinning Methods 0.000 claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000001523 electrospinning Methods 0.000 claims abstract description 17
- 229910003091 WCl6 Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910015221 MoCl5 Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims abstract description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 73
- 229910052721 tungsten Inorganic materials 0.000 claims description 66
- 239000010937 tungsten Substances 0.000 claims description 66
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 65
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 37
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims description 19
- 239000011733 molybdenum Substances 0.000 claims description 19
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 33
- 150000002500 ions Chemical class 0.000 abstract description 29
- 239000010865 sewage Substances 0.000 abstract description 22
- 239000000835 fiber Substances 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 44
- 238000002360 preparation method Methods 0.000 description 13
- 239000013068 control sample Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 7
- -1 poly(methacrylic acid) Polymers 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000010970 precious metal Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 5
- 239000002070 nanowire Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- 108010022355 Fibroins Proteins 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 108010022579 ATP dependent 26S protease Proteins 0.000 description 1
- 229920000832 Cutin Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 210000002268 wool Anatomy 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
-
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/04—Filters
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to the method that electrospinning process prepares polyacid/polymer hybridisation nano fibrous membrane, including step are as follows：(1) organic high molecular compound is added in N, N dimethylformamides, stirring is completely dissolved to organic high molecular compound, then adds WCl6Or MoCl5, stir to being completely dissolved, obtain spinning solution；(2) spinning solution is subjected to electrostatic spinning, obtains nanofiber film precursor；(3) by nanofiber film precursor in 40~100 DEG C of heat treatments；Then irradiate, produce under ultraviolet light.Polyacid particle size is stable in Hybrid nanofibers film prepared by the present invention, does not reunite significantly, and be evenly distributed in fiber surface；So as to greatly add color change of the fiber under ultraviolet light and noble metal and heavy metal ion are reduced to the speed of metal simple-substance, the effect that Hybrid nanofibers film removes heavy metal ions in sewage can be farthest played.
Description
Technical field
The present invention relates to a kind of preparation method of macromolecule base load polyacid Hybrid nanofibers film, belong to nano material preparation
Technical field.
Background technology
Water is the part that it is essential that the mankind depend on for existence, but with recent years increasingly serious environmental pollution and
The delimitation of drinking water supply reduces the importance that people just recognize water conservation and exploitation purification water resource new technology.Will
It is imperative that trade effluent and sanitary sewage carry out necessary processing before the Nature is discharged into.These pollutants, as
Industrialization and the accessory substance of social development, severe challenge is constituted to city water technology.These wastewater pollutants mainly include
Heavy metal ion, toxic dye molecule and radioactive element etc..Traditional waste water treatment process inefficiency, simultaneously as day
Excessive use, waste and the pollution of right water, the need for current water pollution handling process can not meet population growth.Therefore
How to set up efficient, quick and long-life New Technology about Wastewater Treatment is one of Present Global every country facing challenges.
Nanometer technology is one of most important technological achievement of twentieth century, nanometer materials (1-100nm) block material therewith
Material is compared to can embody the features such as totally different physicochemical properties are due to itself skin effect, quantum size effect.Utilize
Develop a series of sewage disposals and sewage purification nanometer new technology is expected to replace the sewage disposal technology of inefficiency at this stage.
It is effective that specific surface area, efficient surface-active and the adjustable energy band and electronic structure significantly improved assigns nano material
Sewage treatment capacity.
In recent years, received much concern using electrostatic spinning technique synthesis nano filter membrane material.Fiber filter material is because of tool
There are good machinability, the designability of 26S Proteasome Structure and Function, and as with fastest developing speed in recent years, most popular filter material
Material.Electrostatic spinning is as a new technology for preparing membrane material, with prepared nano fibrous membrane compared with traditional filter membrane,
Have the advantages that aperture is small, porosity is high, hole connective good, film surface roughness is high and low grammes per square metre.Electrostatic spinning nano
Tunica fibrosa has two big outstanding advantages, and filter efficiency is high and water-flowing amount is big.At present, Electrospun nano-fibers film is used for sewage disposal
Key be absorption of the nano fibrous membrane to heavy metal ions in sewage, organic pollution and dye molecule, around Static Spinning
This thin feature of silk fiber, existing more research work.For example：(1) Ki et al. is by fibroin (SF) and poplar cutin (WK)
Carry out electrostatic spinning and obtain a kind of adsorbable Cu2+Composite cellulosic membrane, the tunica fibrosa is to Cu2+Adsorption capacity up to 2.88mg/
G, more than ten times of (references are higher by than common filtering material：Ki C S,Gang E H,Um I C,et al.Nanofibrous
membrane of wool keratose/silk fibroin blend for heavy metal ion
adsorption.Journal of Membrane Science,2007,302(1):20-26.).(2) Kaur et al. passes through right
Electrostatic spinning polyvinylidene fluoride film carries out surface modification, prepares the membrane material that may filter that humic acid, the membrane material exists
Under the effect of 0.25Pa pressure, the filter efficiency to humic acid can reach 92% (reference：Kaur S,Ma Z,Gopal R,et
al.Plasma-induced graft copolymerization of poly(methacrylic acid)on
electrospun poly(vinylidene fluoride)nanofiber membrane.Langmuir,2007,23(26):
13085-13092.)。
Again for example：Chinese patent document CN104587852A (application numbers：201310533222.5) disclose an a kind of huge sum of money
Belong to ion type PS hollow fiber ultrafiltration membranes and preparation method thereof, prepared after spinning solution with the preparation of dry-wet spinning method
Hollow fiber ultrafiltration membrane, the spinning solution composition include polysulfones, additive, solvent and pore-foaming agent.Chinese patent document
CN105268417A (application numbers：201510707679.2) disclose and a kind of there is absorption and separation of heavy metal ions function to answer
The preparation method of film is closed, nylon 6/nanometer tunica fibrosa is prepared for first with electrospinning process；Will be super secondly by physical action
Branched polyamide amine is adsorbed onto the surface of nylon 6 fiber；Over-branched polyamidoamine is crosslinked finally by chemical reaction, shape is allowed to
Into tubular film, the surface of nylon 6 fiber is firmly adhered to.
The major defect that above-mentioned Electrospun nano-fibers film is used for sewage disposal technology is mainly to be inhaled by physical action
Heavy metal ion and organic pollutant molecule are enclosed, is easily come off after absorption from nano fibrous membrane, causes absorption endless
Total efficiency declines.
Noble metal (Au, Ag, Pt, Pd etc.) and heavy metal (Pb, Hg, Cu etc.) in-situ reducing are answered preparation using polyacid
Close on nano-fiber film, metal ion quickly can be reduced to recoverable metal particle of the absorption in fiber surface, fiber
Film in itself can be with recycled for multiple times.So far, heavy metal ion in-situ reducing is not utilized also in the composite Nano of preparation
Patent and document report are seen on fiber membrane.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides method of electrostatic spinning and prepares polyacid/polymer hybridisation nano fibrous membrane
Method, especially with method of the metal ion in-situ reducing on polyacid/high-molecular composite nanometer fiber membrane, solve existing
Have in technology and easily come off, be not easily recycled after adsorption of metal ions, sewage disposal speed is slow, and material property is unstable, Yi Jiwu
The problem of method is mass produced.
Technical scheme is as follows：
The method that method of electrostatic spinning prepares polyacid/polymer hybridisation nano fibrous membrane, including step are as follows：
(1) prepared by spinning solution
Organic high molecular compound is added in DMF (DMF), stirring to organic polymer chemical combination
Thing is completely dissolved, and then adds the highest price salt of transition metal, is stirred to the highest price salt of transition metal and is completely dissolved, obtains spinning
Liquid；
In spinning solution, the concentration of described organic high molecular compound is 4~15wt%；Organic high molecular compound and
The mass ratio of the highest price salt of transition metal is 1：(1~6)；
(2) electrostatic spinning
Spinning solution obtained by step (1) is subjected to electrostatic spinning, condition is：7~20kV of spinning voltage, electrode distance 100~
220mm, 15~50 DEG C of temperature, relative humidity 0~60% obtains nanofiber film precursor；
(3) presoma is reduced
By nanofiber film precursor obtained by step (2) in 40~100 DEG C of heat treatments；Then, under ultraviolet light irradiation 1~
20min, produces polyacid/polymer hybridisation nano fibrous membrane.
, according to the invention it is preferred to, the organic high molecular compound described in step (1) is polyacrylonitrile (PAN) or poly-
Vinylpyrrolidone (PVP)；It is further preferred that the number-average molecular weight of polyacrylonitrile is 100,000~110,000, polyvinylpyrrolidine
The number-average molecular weight of ketone is 1,250,000~1,350,000.
, according to the invention it is preferred to, the transition metal described in step (1) is molybdenum or tungsten；It is further preferred that described
The highest price salt of transition metal is the highest price hydrochloride of transition metal, more preferably WCl6Or MoCl5。
, according to the invention it is preferred to, the concentration of the organic high molecular compound described in step (1) spinning solution for 6~
12wt%；The mass ratio of the highest price salt of organic high molecular compound and transition metal is 1：(1~4)；
When organic high molecular compound is polyacrylonitrile, the spinning solution obtained by step (1) is with WCl6Addition spinning
Liquid is changed into Chinese red and with the smoke creating of white, shows that a large amount of tungsten polyacid have been generated；Spinning solution is with MoCl5Plus
Enter the smoke creating for being changed into blackish green and adjoint white, show that a large amount of molybdenum polyacid have been generated；
When organic high molecular compound is polyvinylpyrrolidone, the spinning solution obtained by step (1) is with WCl6Plus
Enter spinning solution and be changed into blue-green and with the smoke creating of white, show that a large amount of tungsten polyacid have been generated；Spinning solution with
MoCl5Addition be changed into it is blackish green and with white smoke creating, show that a large amount of molybdenum polyacid have been generated.
, according to the invention it is preferred to, in step (2) when organic high molecular compound is polyacrylonitrile, Static Spinning strand
Part is：7~20kV of spinning voltage, 100~220mm of electrode distance, 15~40 DEG C of temperature, relative humidity 15~60%；Further
It is preferred that, 10~15kV of voltage, 150~180mm of electrode distance, 20~30 DEG C of temperature, relative humidity 20~35%；
When organic high molecular compound is polyvinylpyrrolidone, electrospinning conditions are：7~20kV of spinning voltage,
100~220mm of electrode distance, 25~50 DEG C of temperature, relative humidity 0~35%；It is further preferred that spinning voltage be 10~
15kV, the reception distance between spinning syringe needle and metal plate receiver is 20~30cm, the feed rate of electrostatic spinning for 0.5~
1.2mL/h, 30~40 DEG C of temperature, relative humidity 5~25%.
, according to the invention it is preferred to, heating-up temperature is 60~90 DEG C in step (3), and the heat time is 20-40min, ultraviolet
The light irradiation time is 1~10min；It is preferred that, the intensity of ultraviolet light is 30~100mw, and wavelength is 190~360nm.
Polyacid/the PAN or polyacid prepared using the inventive method /PVP Hybrid nanofibers film thicknesses are homogeneous, fiber
Diametrically stable, polyacid even particle distribution just can be reduced to high reduction-state in ultraviolet light lower very short time, can quickly go back
Former special metal ion.
The technical characterstic and excellent results of the present invention is as follows：
1st, in polymer-based polyacid Hybrid nanofibers film prepared by the present invention, tungsten polyacid particle size is stable, not bright
Aobvious reunion, and be uniformly distributed；
2nd, further investigations have shown that polymer-based polyacid Hybrid nanofibers film prepared by the present invention is piezo-electric electret,
Most of many granulates are distributed in the surface of every fiber under electrostatic field, so as to greatly add fiber in ultraviolet light
Color change under irradiation and heavy metal ion is reduced to the speed of metal simple-substance, can farthest play hydridization and receive
Rice tunica fibrosa removes the effect of heavy metal ions in sewage；
3rd, the simple efficiency high of present invention process, stability is good, and will not destroy fiber original while generation reduction reaction
Some appearance structures, can carry out magnanimity preparation；
4th, polymer-based polyacid Hybrid nanofibers film prepared by the present invention can remove a variety of heavy metal ions in sewage
(Cu2+, Hg2+, Pb2+Deng), and when heavy metal ions in sewage concentration is less than 1ppb, Hybrid nanofibers film still can be with
Detection rapidly and efficiently and reduce removing.
Brief description of the drawings
Fig. 1 is the SEM photograph of the gained tungsten polyacid of embodiment 1/PAN Hybrid nanofibers films.
Fig. 2 is the SEM photograph of the gained tungsten polyacid of embodiment 2/PAN Hybrid nanofibers films.
Fig. 3 is the SEM photograph of tungsten polyacid/PAN Hybrid nanofibers films of the gained Argent grain of test example 3 modification.
Fig. 4 is the SEM photograph of tungsten polyacid/PAN Hybrid nanofibers films of the gained Argent grain of test example 4 modification.
Fig. 5 is the SEM photograph of tungsten polyacid/PAN Hybrid nanofibers films of the gained Argent grain of test example 5 modification.
Fig. 6 is the SEM photograph of tungsten polyacid/PAN Hybrid nanofibers films of the gained Argent grain of test example 6 modification.
Fig. 7 is the thermogravimetric of tungsten polyacid/PAN Hybrid nanofibers films obtained by embodiment 1 and embodiment 2 in test example 7
Curve.
Fig. 8 is the XRD of the nano fibrous membrane obtained by embodiment 1 and test example 6 in test example 8.
Fig. 9 is that the gained tungsten polyacid of embodiment 1/PAN Hybrid nanofibers film removing heavy metals ionic natures are utilized in test example 1
Test characterize, regard single PAN Electrospun nano-fibers film as control sample.
Figure 10 is that the gained tungsten polyacid of embodiment 2/PAN Hybrid nanofibers film heavy-metal ion removals are utilized in test example 2
The test of property is characterized, and regard single PAN Electrospun nano-fibers film as control sample.
Figure 11 is the SEM photograph of the gained tungsten polyacid of embodiment 3/PVP Hybrid nanofibers films.
Figure 12 is the SEM photograph of the gained tungsten polyacid of embodiment 4/PVP Hybrid nanofibers films.
Figure 13 is the thermogravimetric of tungsten polyacid/PVP Hybrid nanofibers films obtained by embodiment 3 and embodiment 4 in test example 9
Curve.
Figure 14 is the gained tungsten polyacid of embodiment 4/PVP Hybrid nanofibers film removing heavy metals ionic natures in test example 10
Test is characterized, and regard single PVP Electrospun nano-fibers film as control sample.
Figure 15 is using the gained tungsten polyacid of embodiment 1/PAN Hybrid nanofibers film to remove mercury ion in sewage in test example 11
The test of recycling is characterized.
Figure 16 is the SEM photograph of the gained molybdenum polyacid of embodiment 5/PAN Hybrid nanofibers films.
Figure 17 is the SEM photograph of the gained molybdenum polyacid of embodiment 6/PVP Hybrid nanofibers films.
Figure 18 is that the gained molybdenum polyacid of embodiment 5/PAN Hybrid nanofibers film heavy-metal ion removals are utilized in test example 12
The test of property is characterized, and regard single PAN Electrospun nano-fibers film as control sample.
Embodiment
With reference to embodiment, the present invention will be further described with accompanying drawing, but not limited to this.It is raw materials used in embodiment
It is convenient source, device therefor is conventional equipment.
The efficiency of wherein polyacid/polymer hybridisation nano fibrous membrane heavy metal ions in sewage processing passes through inductive etc.
Gas ions (ICP-MS) are tested.
The number-average molecular weight of polyacrylonitrile used is 106000 in embodiment, and the number-average molecular weight of polyvinylpyrrolidone is
1300000。
Embodiment 1
A kind of tungsten polyacid/PAN Hybrid nanofibers membrane preparation methods, including step are as follows：
(1) prepared by spinning solution
0.5g polyacrylonitrile (PAN) particle is added in 6mL DMFs (DMF), stirring to polypropylene
Nitrile is completely dissolved, and then adds 2g WCl6, stirring to WCl6It is completely dissolved, obtains Chinese red clarification spinning solution；
(2) electrostatic spinning
Using Beijing Yongkang work in peace and contentment Co., Ltd model ss-2535H electrospinning device carry out electrostatic spinning, will walk
Suddenly the spinning solution prepared in (1) is poured into syringe, and spinning is carried out using rotating cylinder receiver board；Electrospinning conditions are：Electricity
Press 15kV, electrode distance 170mm, 20 DEG C of temperature, relative humidity 30%, propulsions pump speed be 0.08ml/min, obtain Nanowire
Tie up film precursor；
(3) presoma is reduced
Nanofiber film precursor obtained by step (2) is put into 80 DEG C of heating 30min in baking oven, then, is in power
8mW/cm2Hand-held uviol lamp under irradiate 10min, produce blue tungsten polyacid/PAN composite hybridization nano fibrous membranes.
Tunica fibrosa is changed into navy blue from yellow-white during ultra violet lamp, shows tungsten polyacid/PAN Hybrid nanofibers
Film is in high reduction-state.The SEM photographs of gained tungsten polyacid/PAN Hybrid nanofibers films as shown in figure 1, as shown in Figure 1,
The uniform diameter of tungsten polyacid/PAN Hybrid nanofibers, average diameter about 400nm.
Test example 1
100ppb standards silver ion, copper ion, mercury ion and lead ion solution are prepared, is experiment sample with embodiment 1, with
Do not contain tungsten polyacid PAN fiber film be control sample, will experiment sample and control sample put into respectively different types of heavy metal from
In sub- solution, the heavy metal ion solution after the daughter such as being coupled to having reduced using inductance carries out Concentration Testing, as a result such as Fig. 9 institutes
Show.As shown in Figure 9, tungsten polyacid made from embodiment 1/PAN Hybrid nanofibers films have removes a variety classes huge sum of money in water very well
Belong to the effect of ion, and the more rates of reduction of amount that tunica fibrosa is added are faster and can be by the heavy metal ion in sewage
100% removes.
Embodiment 2
As described in Example 1, except that：
WCl in step (1)6Addition be 1g；
Step (2) be the same as Example 1；
Step (3) be the same as Example 1.
Tungsten polyacid/PAN Hybrid nanofibers SEM photograph obtained by the present embodiment as shown in Fig. 2 as shown in Figure 2, tungsten polyacid/
PAN Hybrid nanofibers uniform diameters, average diameter about 200nm.
Test example 2
Tungsten polyacid/PAN Hybrid nanofibers film made from embodiment 2 is fine by the reduction-state obtained after ultra violet lamp
Dimension film is slightly below what is obtained in embodiment 1.
100ppb standards silver ion, copper ion, mercury ion and lead ion solution are prepared, is experiment sample with embodiment 2, with
Do not contain tungsten polyacid PAN fiber film be control sample, will experiment sample and control sample put into respectively different types of heavy metal from
In sub- solution, the heavy metal ion solution after the daughter such as being coupled to having reduced using inductance carries out Concentration Testing, as a result such as Figure 10
It is shown.As shown in Figure 10, removing the heavy metal ion sewage of same concentrations needs the gained nanofiber of embodiment 2 of more multimass
Film, and time used relative can improve.But still the heavy metal ion in sewage 100% can almost be removed.
Test example 3, nano-Ag particles in-situ reducing
The gained tungsten polyacid of embodiment 1/PAN Hybrid nanofibers films are put into 0.1M AgNO310 seconds in solution, so
Hybridized nanometer film is pulled out from solution with clean silicon chip rapidly afterwards, is then placed in 80 DEG C of baking ovens and heats, obtain Nano Silver
Tungsten polyacid/PAN Hybrid nanofibers of particle modification.SEM photograph as shown in figure 3, from the figure 3, it may be seen that the time of only 10 seconds just
There are a large amount of silver ions in situ in tungsten polyacid/PAN Hybrid nanofibers films, illustrate your gold the hybrid film that the present invention is synthesized reduces
The speed for belonging to ion is very fast.
Test example 4
As shown in test example 3, the gained tungsten polyacid of embodiment 1/PAN Hybrid nanofibers films are put into 0.1M AgNO3It is molten
30 seconds in liquid, then hybridized nanometer film is pulled out from solution with clean silicon chip rapidly, is then placed in 80 DEG C of baking ovens
Heating, obtains tungsten polyacid/PAN Hybrid nanofibers of nano-Ag particles modification.SEM photograph is as shown in figure 4, as shown in Figure 4,30 seconds
The time of clock, compared to there is within 10 seconds more nano-silver ionics in situ in tungsten polyacid/PAN Hybrid nanofibers films, illustrates that extension is anti-
The hybrid film that the present embodiment is synthesized between seasonable can restore more precious metal ions.
Test example 5
As shown in test example 3, the gained tungsten polyacid of embodiment 1/PAN Hybrid nanofibers films are put into 0.1M AgNO3It is molten
1min in liquid, is then rapidly pulled hybridized nanometer film out with clean silicon chip from solution, is then placed in 80 DEG C of baking ovens and is added
Heat.Obtain tungsten polyacid/PAN Hybrid nanofibers of nano-Ag particles modification.SEM photograph as shown in figure 5, as shown in Figure 5,1min's
Time had more nano-silver ionics in situ in tungsten polyacid/PAN Hybrid nanofibers films again compared to 30 seconds, and substantially
Fiber surface is all covered.Illustrate that the hybrid film for continuing the present embodiment synthesis of extension reaction time can be restored more expensive
Metal ion.
Test example 6
As shown in test example 3, the gained tungsten polyacid of embodiment 1/PAN Hybrid nanofibers films are put into 0.1M AgNO3It is molten
5min in liquid, is then rapidly pulled hybridized nanometer film out with clean silicon chip from solution, is then placed in 80 DEG C of baking ovens and is added
Heat, obtains tungsten polyacid/PAN Hybrid nanofibers of nano-Ag particles modification.SEM photograph is as shown in fig. 6, it will be appreciated from fig. 6 that 5min
Time nano-Ag particles all cover on tungsten polyacid/PAN Hybrid nanofibers surface.Illustrate that the hydridization that the present invention is synthesized is received
The reduction precious metal ion of rice tunica fibrosa energy quick in situ.
Test example 7
By tungsten polyacid made from embodiment 1 and embodiment 2/PAN Hybrid nanofibers film test thermogravimetric curve, such as Fig. 7 institutes
Show.
As shown in Figure 7, as addition 2g WCl6When in spinning liquid as precursor, tungsten in the film after final electrostatic spinning
The content of polyacid is about 60%, and as addition 1g WCl6When in spinning liquid as precursor, the film after final electrostatic spinning
The content of middle tungsten polyacid is about 47%, and more tungsten polyacid can accelerate the rate of reduction and phase homogenous quantities of precious metal ion
Hybrid nanofibers film can restore more precious metal simple substances.
Test example 8
Nano-Ag particles made from tungsten polyacid/PAN Hybrid nanofibers film made from embodiment 1 and test example 6 are modified
Tungsten polyacid/PAN Hybrid nanofibers test XRD, as shown in Figure 8.
As shown in Figure 8, tungsten polyacid/polymer hybridisation nano fibrous membrane that direct electrostatic spinning is obtained is unformed, examination
Test and one layer of thicker silver nano-grain is reduced on the hybridized fiber film that example 6 is obtained, therefore can significantly see from XRD
The diffraction maximum of silver-colored simple substance.
Embodiment 3
A kind of tungsten polyacid/PVP Hybrid nanofibers membrane preparation methods, including step are as follows：
(1) prepared by spinning solution
0.4g polyvinylpyrrolidones (PVP) particle is added in 5mL DMFs (DMF), stirring is extremely
Polyacrylonitrile is completely dissolved, and then adds 0.5g WCl6, stirring to WCl6It is completely dissolved, obtains blue-green clarification spinning solution；
(2) electrostatic spinning
Using Beijing Yongkang work in peace and contentment Co., Ltd model ss-2535H electrospinning device carry out electrostatic spinning, will walk
Suddenly the spinning solution prepared in (1) is poured into syringe, and spinning is carried out using rotating cylinder receiver board；Electrospinning conditions are：Electricity
Press 15kV, electrode distance 170mm, 30 DEG C of temperature, relative humidity 20%, propulsions pump speed be 0.08mL/min, obtain Nanowire
Tie up film precursor；
(3) presoma is reduced
Nanofiber film precursor obtained by step (2) is put into 80 DEG C of heating 30min in baking oven, then, is in power
8mW/cm2Hand-held uviol lamp under irradiate 10min, produce blue tungsten polyacid/PVP Hybrid nanofibers films.
Tunica fibrosa is changed into light blue from yellow-white during ultra violet lamp, shows tungsten polyacid/PVP Hybrid nanofibers
Film is in reduction-state.The SEM photograph of gained tungsten polyacid/PAN Hybrid nanofibers films is as shown in figure 11, as shown in Figure 11,
The uniform diameter of tungsten polyacid/PAN Hybrid nanofibers, average diameter about 200nm.
Embodiment 4
A kind of tungsten polyacid/PVP Hybrid nanofibers membrane preparation methods, including step are as follows：
(1) prepared by spinning solution
0.4g polyvinylpyrrolidones (PVP) particle is added in 5mL DMFs (DMF), stirring is extremely
Polyacrylonitrile is completely dissolved, and then adds 2g WCl6, stirring to WCl6It is completely dissolved, obtains blue-green clarification spinning solution；
(2) electrostatic spinning
Using Beijing Yongkang work in peace and contentment Co., Ltd model ss-2535H electrospinning device carry out electrostatic spinning, will walk
Suddenly the spinning solution prepared in (1) is poured into syringe, and spinning is carried out using rotating cylinder receiver board；Electrospinning conditions are：Electricity
Press 15kV, electrode distance 170mm, 30 DEG C of temperature, relative humidity 20%, propulsions pump speed be 0.08mL/min, obtain Nanowire
Tie up film precursor；
(3) presoma is reduced
Nanofiber film precursor obtained by step (2) is put into 80 DEG C of heating 30min in baking oven, then, is in power
8mW/cm2Hand-held uviol lamp under irradiate 10min, produce blue tungsten polyacid/PVP Hybrid nanofibers films.
Tunica fibrosa is changed into black-and-blue from yellow-white during ultra violet lamp, shows tungsten polyacid/PVP Hybrid nanofibers
Film is in high reduction-state.The SEM photograph of gained tungsten polyacid/PAN Hybrid nanofibers films is as shown in figure 12.Can by Figure 12
Know, with the increase of presoma addition, tungsten polyacid/PAN Hybrid nanofibers become flat, average diameter about 800nm.
Test example 9
By tungsten polyacid made from embodiment 3 and embodiment 4/PVP Hybrid nanofibers film test thermogravimetric curve, such as Figure 13 institutes
Show.
As shown in Figure 13, as addition 2g WCl6When in spinning liquid as precursor, tungsten in the film after final electrostatic spinning
The content of polyacid is about 70%, and as addition 0.5g WCl6It is thin after final electrostatic spinning when in spinning liquid as precursor
The content of tungsten polyacid is then 30% in film.More tungsten polyacid can accelerate the rate of reduction and phase homogenous quantities of precious metal ion
Hybrid nanofibers film can restore more precious metal simple substances.
Test example 10
100ppb standard silver ion, copper ion, mercury ion and lead ion solution is prepared, is experiment sample with embodiment 4,
Experiment sample and control sample are put into different types of heavy metal by the PVP tunica fibrosas not contain tungsten polyacid respectively as control sample
In solion, the heavy metal ion solution after the daughter such as being coupled to having reduced using inductance carries out Concentration Testing, as a result as schemed
Shown in 14.As shown in Figure 14, tungsten polyacid made from embodiment 4/PVP Hybrid nanofibers films have removes variety classes in water very well
The effect of heavy metal ion, and the more rates of reduction of amount that tunica fibrosa is added are faster and can be by the heavy metal ion in sewage
100% removes.
Test example 11
As described in test example 1, mercury ion in sewage is removed using the gained tungsten polyacid of embodiment 1/PAN Hybrid nanofibers film,
Recycling test is carried out, as a result as shown in figure 15.
As shown in Figure 15, tungsten polyacid/PAN Hybrid nanofibers film produced by the present invention remove sewage in heavy metal from
Sub- aspect has good recycling performance.
Embodiment 5
A kind of molybdenum polyacid/PAN Hybrid nanofibers membrane preparation methods, including step are as follows：
(1) prepared by spinning solution
0.5g polyacrylonitrile (PAN) particle is added in 6mL DMFs (DMF), stirring to polypropylene
Nitrile is completely dissolved, and then adds 2g MoCl5, stirring to MoCl5It is completely dissolved, obtains blackish green clarification spinning solution；
(2) electrostatic spinning
Using Beijing Yongkang work in peace and contentment Co., Ltd model ss-2535H electrospinning device carry out electrostatic spinning, will walk
Suddenly the spinning solution prepared in (1) is poured into syringe, and spinning is carried out using rotating cylinder receiver board；Electrospinning conditions are：Electricity
Press 15kV, electrode distance 170mm, 20 DEG C of temperature, relative humidity 30%, propulsions pump speed be 0.08ml/min, obtain Nanowire
Tie up film precursor；
(3) presoma is reduced
Nanofiber film precursor obtained by step (2) is put into 80 DEG C of heating 30min in baking oven, then, is in power
8mW/cm2Hand-held uviol lamp under irradiate 10min, produce blue-green molybdenum polyacid/PAN composite hybridization nano fibrous membranes.
Tunica fibrosa is changed into blue-green from yellow-white during ultra violet lamp, shows molybdenum polyacid/PAN Hybrid nanofibers
Film is in high reduction-state.The SEM photograph of gained molybdenum polyacid/PAN Hybrid nanofibers films as shown in figure 16, can by Figure 16
Know, the uniform diameter of molybdenum polyacid/PAN Hybrid nanofibers, average diameter about 300nm.
Embodiment 6
A kind of molybdenum polyacid/PVP Hybrid nanofibers membrane preparation methods, including step are as follows：
(1) prepared by spinning solution
0.4g polyvinylpyrrolidones (PVP) particle is added in 5mL DMFs (DMF), stirring is extremely
Polyacrylonitrile is completely dissolved, and then adds 2g MoCl5, stirring to MoCl5It is completely dissolved, obtains blackish green clarification spinning solution；
(2) electrostatic spinning
Using Beijing Yongkang work in peace and contentment Co., Ltd model ss-2535H electrospinning device carry out electrostatic spinning, will walk
Suddenly the spinning solution prepared in (1) is poured into syringe, and spinning is carried out using rotating cylinder receiver board；Electrospinning conditions are：Electricity
Press 15kV, electrode distance 170mm, 30 DEG C of temperature, relative humidity 20%, propulsions pump speed be 0.08mL/min, obtain Nanowire
Tie up film precursor；
(3) presoma is reduced
Nanofiber film precursor obtained by step (2) is put into 80 DEG C of heating 30min in baking oven, then, is in power
8mW/cm2Hand-held uviol lamp under irradiate 10min, produce blue-green molybdenum polyacid/PVP Hybrid nanofibers films.
Tunica fibrosa is changed into blue-green from yellow-white during ultra violet lamp, shows molybdenum polyacid/PVP Hybrid nanofibers
Film is in reduction-state.The SEM photograph of gained molybdenum polyacid/PVP Hybrid nanofibers films is as shown in figure 17, as shown in Figure 17,
The uniform diameter of molybdenum polyacid/PVP Hybrid nanofibers, average diameter about 800nm.
Test example 12
100ppb standards silver ion, copper ion, mercury ion and lead ion solution are prepared, is experiment sample with embodiment 5, with
Do not contain molybdenum polyacid PAN fiber film be control sample, will experiment sample and control sample put into respectively different types of heavy metal from
In sub- solution, the heavy metal ion solution after the daughter such as being coupled to having reduced using inductance carries out Concentration Testing, as a result such as Figure 18
It is shown.As shown in Figure 18, molybdenum polyacid made from embodiment 5/PAN Hybrid nanofibers films have removes variety classes weight in water very well
The effect of metal ion, and the more rates of reduction of amount that tunica fibrosa is added are faster and can be by the heavy metal ion in sewage
100% removes.
Claims (10)
1. the method that method of electrostatic spinning prepares polyacid/polymer hybridisation nano fibrous membrane, including step are as follows：
(1) prepared by spinning solution
Organic high molecular compound is added in DMF (DMF), stirred complete to organic high molecular compound
Fully dissolved, then adds the highest price salt of transition metal, stirs to the highest price salt of transition metal and is completely dissolved, obtains spinning solution；
In spinning solution, the concentration of described organic high molecular compound is 4~15wt%；Organic high molecular compound and transition
The mass ratio of the highest price salt of metal is 1：(1~6)；
(2) electrostatic spinning
Spinning solution obtained by step (1) is subjected to electrostatic spinning, condition is：7~20kV of spinning voltage, electrode distance 100~
220mm, 15~50 DEG C of temperature, relative humidity 0~60% obtains nanofiber film precursor；
(3) presoma is reduced
By nanofiber film precursor obtained by step (2) in 40~100 DEG C of heat treatments；Then, under ultraviolet light irradiation 1~
20min, produces polyacid/polymer hybridisation nano fibrous membrane.
2. method of electrostatic spinning according to claim 1 prepares the method for polyacid/polymer hybridisation nano fibrous membrane, its feature
It is, the organic high molecular compound described in step (1) is polyacrylonitrile (PAN) or polyvinylpyrrolidone (PVP).
3. method of electrostatic spinning according to claim 1 prepares the method for polyacid/polymer hybridisation nano fibrous membrane, its feature
It is, the transition metal described in step (1) is molybdenum or tungsten, and the highest price salt of described transition metal is WCl6Or MoCl5。
4. method of electrostatic spinning according to claim 2 prepares the method for polyacid/polymer hybridisation nano fibrous membrane, its feature
It is, the number-average molecular weight of the polyacrylonitrile described in step (1) is 100,000~110,000, the equal molecule of number of polyvinylpyrrolidone
Measure as 1,250,000~1,350,000.
5. method of electrostatic spinning according to claim 1 prepares the method for polyacid/polymer hybridisation nano fibrous membrane, its feature
It is, the concentration of the organic high molecular compound described in step (1) spinning solution is 6~12wt%.
6. method of electrostatic spinning according to claim 1 prepares the method for polyacid/polymer hybridisation nano fibrous membrane, its feature
It is, the mass ratio of the highest price salt of step (1) organic high molecular compound and transition metal is 1：(1~4).
7. method of electrostatic spinning according to claim 1 prepares the method for polyacid/polymer hybridisation nano fibrous membrane, its feature
It is, in step (2) when organic high molecular compound is polyacrylonitrile, electrospinning conditions are：7~20kV of spinning voltage,
100~220mm of electrode distance, 15~40 DEG C of temperature, relative humidity 15~60%；
When organic high molecular compound is polyvinylpyrrolidone, electrospinning conditions are：7~20kV of spinning voltage, electrode
100~220mm of distance, 25~50 DEG C of temperature, relative humidity 0~35%.
8. method of electrostatic spinning according to claim 1 prepares the method for polyacid/polymer hybridisation nano fibrous membrane, its feature
It is, in step (2) when organic high molecular compound is polyacrylonitrile, electrospinning conditions are：10~15kV of voltage, electrode
150~180mm of distance, 20~30 DEG C of temperature, relative humidity 20~35%；
When organic high molecular compound is polyvinylpyrrolidone, electrospinning conditions are：Spinning voltage is 10~15kV, is spun
Reception distance between silk syringe needle and metal plate receiver is 20~30cm, and the feed rate of electrostatic spinning is 0.5~1.2mL/
H, 30~40 DEG C of temperature, relative humidity 5~25%.
9. method of electrostatic spinning according to claim 1 prepares the method for polyacid/polymer hybridisation nano fibrous membrane, its feature
It is, heating-up temperature is 60~90 DEG C in step (3), the heat time is 20-40min, the ultraviolet light time is 1~10min.
10. the method that method of electrostatic spinning according to claim 1 prepares polyacid/polymer hybridisation nano fibrous membrane, it is special
Levy and be, the intensity of ultraviolet light is 30~100mw in step (3), wavelength is 190~360nm.
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