CN105057003B - A kind of nano titania preparation method of composite film - Google Patents
A kind of nano titania preparation method of composite film Download PDFInfo
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- CN105057003B CN105057003B CN201510519203.6A CN201510519203A CN105057003B CN 105057003 B CN105057003 B CN 105057003B CN 201510519203 A CN201510519203 A CN 201510519203A CN 105057003 B CN105057003 B CN 105057003B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 263
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 80
- 239000002121 nanofiber Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 230000008021 deposition Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000002120 nanofilm Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 85
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 62
- 238000009987 spinning Methods 0.000 claims description 56
- 239000007864 aqueous solution Substances 0.000 claims description 53
- 239000010936 titanium Substances 0.000 claims description 52
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 39
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 39
- 229910052709 silver Inorganic materials 0.000 claims description 39
- 239000004332 silver Substances 0.000 claims description 39
- 238000001291 vacuum drying Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 35
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims description 29
- 238000000151 deposition Methods 0.000 claims description 29
- 229960004502 levodopa Drugs 0.000 claims description 29
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 claims description 28
- 239000004793 Polystyrene Substances 0.000 claims description 25
- 229920002223 polystyrene Polymers 0.000 claims description 25
- 229960003638 dopamine Drugs 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 21
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000002114 nanocomposite Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000004425 Makrolon Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 126
- 239000002105 nanoparticle Substances 0.000 abstract description 15
- 239000010409 thin film Substances 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000010041 electrostatic spinning Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000000505 pernicious effect Effects 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 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 36
- 229960000907 methylthioninium chloride Drugs 0.000 description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 34
- 229910052719 titanium Inorganic materials 0.000 description 34
- 229920000747 poly(lactic acid) Polymers 0.000 description 30
- 239000004626 polylactic acid Substances 0.000 description 30
- 206010013786 Dry skin Diseases 0.000 description 21
- 239000004677 Nylon Substances 0.000 description 19
- 229920001778 nylon Polymers 0.000 description 19
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 14
- 229920002292 Nylon 6 Polymers 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 238000001782 photodegradation Methods 0.000 description 12
- 238000007654 immersion Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920001690 polydopamine Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000232 polyglycine polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a kind of titanium dioxide nano-film preparation methods.The present invention prepares polymer nanofibre film template-titania nanoparticles in the attachment of polymeric fiber surface and deposition three steps of postprocessing working procedures including electrostatic spinning, particle will not be caused in use to handling the secondary pollution of medium, and is conducive to repeatedly utilize and recycle.Such nano thin-film can be used for Degradation of Organo-pollutants in Water with Photo-catalysis in water treatment procedure, dye-sensitized solar cell anode, pernicious gas absorption and catalytic decomposition etc..Present invention process is simple, film large specific surface area, mechanical property disclosure satisfy that using the aperture for needing, being distributed between fiber is more uniform, film can directly cut out molding, can be needed to control the load capacity and particle size of titanium dioxide according to application, it can fundamentally solve the problems, such as the recycling of titanium dioxide, and can further load the several functions that other components expand titanium dioxide.
Description
Technical field：
The invention belongs to chemical fields, are related to organic/inorganic composite material, particularly a kind of polymer nanofiber load
The titania nanoparticles organic-inorganic nanocomposite film that then surface modification is formed.
Background technology
Titanium dioxide is as a kind of semi-conducting material with multiple functions characteristic, in photocatalytic degradation, electronic device, light
Electricity conversion, gas detection and biosensor etc. have important use.At present, commercialization titanium dioxide product such as P25 exists
It is usually to be played a role with form of nanoparticles in application process, particle is easy to reunite, and utilization rate can reduce, and the recycling of particle is stranded
Difficulty, the serious secondary pollution that can also cause water body；During air filtration and degradable organic pollutant, titanium dioxide with
Form of nanoparticles is supported on film surface, can be effectively increased the contact area of titanium dioxide and pollutant, and can pass through
The preparation parameter of film is adjusted, to adjust permeability of film etc..In addition, titania nanoparticles are in ultraviolet irradiation following table
Reveal good photo-catalysis capability, however UV energy only accounts for 7% or so of natural light, therefore the broad stopband of titanium dioxide
Usually by noble metal loading in titanium dioxide surface surface occurs for the hot application for limiting it under sunlight irradiation, people
Plasma enhancing acts on, to assist improving absorption of the compound system to visible ray, while inhibit the compound of electron-hole again,
Improve the photocatalytic activity of titanium dioxide.Silver system metal catalytic object is compound with titanium dioxide, is one of Common combinations.Because of titanium dioxide
Titanium and silver are all inorganic matter, compound difficulty, therefore present invention introduces dopamines can two inorganic nano materials be firmly bonded in one
It rises.The present invention prepares polymer nanofiber as template using electrical spinning method, utilizes polymeric fiber surface functional group and tetravalence
Titanium ion (Ti4+) coordination or electrostatic attraction or so, induction titania nanoparticles are in polymer nanofiber Surface Creation
And growth, and then titania nanoparticles is promoted to form continuous titanium dioxide nano-film, polymer in-mold in fiber surface
Plate not only provides a kind of flexible support to film, while can assign its good mechanical strength, greatly expands titanium dioxide
The application range of titanium；It is the phenolic hydroxyl group of dopamine in 8.5 dopamine solutions that polymer/titanium deoxid film is immersed in pH value
It is coordinated with titanium dioxide, a strata dopamine is formed in titanium dioxide surface；It will be through the amine-modified polymer/titanium dioxide of DOPA
Nano compound film is immersed in silver nitrate solution, phenolic hydroxyl group and amino containing week reduction in poly-dopamine, can with silver from
Son is coordinated, and by silver ion reduction and is adhered to titanium dioxide surface, and the silver-colored simple substance being reduced continues as nucleation site
The silver nano-grain grown into.This nano titania composite film preparation technology is simple, cost is relatively low, easy to spread.
Invention content：
It is an object of the invention to introduce a kind of method for preparing nano titania laminated film.The film is with Static Spinning
Silk polymer nanofiber is template, using titanium tetrachloride as presoma, by technology controlling and process, makes titania nanoparticles close
It is deposited on fiber surface and forms continuous inorganic shell layer；Using dopamine solution to polymer/titanium dioxide nanofiber
Surface is modified, and a strata dopamine is formed in fiber surface；It will be fine through the amine-modified polymer of DOPA/nano titania
Dimension film is immersed in silver nitrate solution, due to the reproducibility of dopamine and indifference adhesiveness, by silver ion reduction and is adhered to
Nanofiber surface, forming deposition has polymer/nano titania laminated film of silver nano-grain.Wherein, polymer is fine
The main ingredient of dimension for can electrostatic spinning and with functional group polymer material, the polymer poly third such as containing polar functional group
Alkene nitrile, cellulose, polyvinyl alcohol, polyurethane, makrolon, polyvinyl chloride, pla-pcl, polyester, polyimides, polyamide,
Polylactic acid, polyvinyl chloride, aramid fiber etc. and polymer such as polystyrene, poly- second containing low pole or nonpolar functional group
Alkene, polypropylene, polytetrafluoroethylene (PTFE) etc..Ti4+With the functional group of polymer surfaces coordination or electrostatic attraction can occur for ion, in alkalinity
Under the conditions of generate titanium dioxide, and be used as nucleation site continued growth titanium dioxide nano-crystal, by medium temperature, pH value with
And additional ionic type can regulate and control titanium dioxide crystal form from the transformation between rutile, amorphous, anatase, brockite.
If functional group contained by polymer and Ti4+Interact weak, such as polystyrene, then the titanium dichloride load amount of polymer surfaces compared with
It is few；If functional group contained by polymer and Ti4+Strong coordinate bond, such as polyacrylonitrile are formed, then the titanium dioxide of polymer surfaces is born
Carrying capacity is big, and Load Balanced.In the aqueous dopamine solution for being 8.5 in pH value, phenolic hydroxyl group and the titanium dioxide of dopamine are coordinated, and are gathered
It closes object/titanium dioxide nanofiber surface and forms a strata dopamine, the formation of above-mentioned coordination structure can make titanium dioxide pair can
See that the absorption of light increases.It will be immersed in silver nitrate solution through the amine-modified film of DOPA, weak reduction contained in poly-dopamine
Property phenolic hydroxyl group and amino, can be coordinated, and silver ion reduction and titanium dioxide surface will be adhered to, be reduced with silver ion
Silver-colored simple substance as nucleation site, continue to grow into various sizes of silver nano-grain.The mechanicalness of integrated load effect and film
Can from the point of view of, polyacrylonitrile and the composite membrane effect that titanium dioxide is formed are more excellent.
In photocatalytic degradation field, titania nanoparticles are compared, are kept according to the nano thin-film prepared by the present invention
Good ultraviolet photocatalysis effect convenient for recycling, can avoid the secondary pollution in water treatment procedure.In addition, silver nanoparticle
Grain is deposited in titanium dioxide surface, since noble metal is in the plasma resonance humidification of semiconductor surface, makes titanium dioxide
The absorption of visible ray is increased, conducive to efficiently using green energy resource, reducing energy consumption；Meanwhile titanium dioxide surface and silver nanoparticle
Grain contact, can inhibit compound, the raising quantum efficiency in electronics and hole, and then improve the photocatalytic activity of titanium dioxide.DOPA
Amine was both coordinated with titanium dioxide as adhesive, and titanium dioxide is made to increase the absorption of visible ray, and by silver ion reduction
For silver-colored simple substance, and it is tightly adhered to titanium dioxide surface.The nano titania laminated film that depositing has silver nano-grain can fill
Divide using Visible Light Induced Photocatalytic organic pollution, there is very big actual application value in field of environment protection.
Technical scheme is as follows：
A kind of preparation method of nano titania laminated film, it is characterised in that：The film has Yin Na by surface deposition
The polymer of rice grain/titanium dioxide nanofiber composition, the diameter of fiber can be controlled between tens nanometers to hundreds of nanometers
System, the titanium dioxide shell thickness of load can from several nanometers to hundreds of nanometer regulate and control, the diameter of silver nano-grain is several
Regulate and control in nanometer to tens nanometer ranges, bonded between silver nano-grain and titanium dioxide using poly-dopamine.It is entire fine
The thickness of dimension film can be controlled in micron or nano thickness.
The preparation of the nano titania composite cellulosic membrane, which is characterized in that include the following steps：
(1) method of electrostatic spinning prepares polymer nanofibre film template：
Under magnetic stirring, the organic solvent spinning solution of 7-24wt.% polymer is prepared.In 10-60 DEG C of spinning temperature, spin
Under conditions of silk humidity 20-60%, spinning solution is added in spinning liquid storage device, and nozzle internal diameter is from 0.2-1.0mm, spinning distance
10-20cm, spinning voltage 8-25kV, solution inject speed as 1-4mL/h.After spinning 30-40min, you can obtain a fibre
Polymer nanofibre film of the diameter in the range of 100-500nm is tieed up, is placed on drying at room temperature 20-24h in vacuum drying chamber.
More particularly：
Polyacrylonitrile Electrospun：Under magnetic stirring, the n,N-Dimethylformamide for preparing 8-12wt.% polyacrylonitrile is spun
Silk liquid.Under conditions of 10-60 DEG C of spinning temperature, spinning humidity 20-60%, 3mL spinning solutions is taken to be added to 5mL spinning liquid storage devices
In, nozzle internal diameter is from 0.2-1.0mm, and spinning distance 10-20cm, spinning voltage 8-25kV, the speed of injecting of solution is 1-3mL/
h.After spinning 40min, you can obtain polyacrylonitrile nanofiber film of the fibre diameter in the range of 200-500nm, be placed on
Drying at room temperature is for 24 hours in vacuum drying chamber.
Polylactic acid electrospinning silk：Under magnetic stirring, the trifluoroacetic acid spinning solution of 7-12wt.% polylactic acid is prepared.In spinning
Under conditions of 10-60 DEG C of temperature, spinning humidity 20-60%, 3mL spinning solutions is taken to be added in 5mL spinning liquid storage devices, nozzle internal diameter
From 0.2-1.0mm, spinning distance 10-20cm, spinning voltage 8-25kV, the speed of injecting of solution is 1.5-3.5mL/h.Spinning
After 30min, you can obtain polylactic acid nano fiber film of the fibre diameter in the range of 150-400nm, be placed on vacuum drying
Drying at room temperature is for 24 hours in case.
6 Electrospun of nylon：Under magnetic stirring, the hexafluoroisopropanol spinning solution of 7-12wt.% nylon 6 is prepared.In spinning
Under conditions of 10-60 DEG C of temperature, spinning humidity 20-60%, 3mL spinning solutions is taken to be added in 5mL spinning liquid storage devices, nozzle internal diameter
From 0.2-1.0mm, spinning distance 10-20cm, spinning voltage 8-25kV, the speed of injecting of solution is 1-3mL/h.Spinning 40min
Afterwards, you can obtain nylon 6/nanometer tunica fibrosa of the fibre diameter in the range of 200-500nm, be placed on room in vacuum drying chamber
Temperature is dry for 24 hours.
Polystyrene Electrospun：Under magnetic stirring, the n,N-Dimethylformamide of 16-24wt.% polystyrene is prepared
Spinning solution.Under conditions of 10-60 DEG C of spinning temperature, spinning humidity 20-60%, 3mL spinning solutions is taken to be added to 5mL spinning liquid storages
In device, nozzle internal diameter is from 0.2-1.0mm, and spinning distance 10-20cm, spinning voltage 8-25kV, the speed of injecting of solution is 1-
3mL/h.After spinning 40min, you can polystyrene nano fiber film of the fibre diameter in the range of 250-500nm is obtained,
It is placed in vacuum drying chamber drying at room temperature for 24 hours.
(2) using polymer nanofiber as template, titanium deoxid film is prepared：Using titanium tetrachloride as presoma,
Strong stirring under ice-water bath instills the titanium tetrachloride of certain mass in deionized water, will be dissolved with the water of ammonium sulfate and concentrated hydrochloric acid
Solution is added drop-wise in the titanium tetrachloride aqueous solution of gained.In mixed process temperature control at 15 DEG C hereinafter, tetrachloro wherein in solution
Change the control of titanium concentration in 0.2-2mol/L, molar ratio Ti4+：H+：60-100 is warming up to 3 DEG C/min
DEG C, polymer nanofibre film is added in mixed solution, the pH value of whole system is adjusted as 7 using ammonium hydroxide.It naturally cools to
Room temperature, ageing is for 24 hours.After taking out film and being washed respectively using distilled water and ethyl alcohol, 60 DEG C of dry 12h in vacuum drying chamber, you can
Obtain polymer/titanium dioxide nanofiber film.
(3) using the dopamine solution of Tris-HCl buffer solutions configuration pH=8.5, the polymer/dioxy that will be prepared
Change titanium nano fibrous membrane to be immersed in dopamine solution, be taken out after the completion of impregnating and cleaned 3-4 times with deionized water, be placed in vacuum
60 DEG C of dryings are for 24 hours in drying box, you can obtain the amine-modified polymer/titanium deoxid film of DOPA.Wherein dopamine concentration control
System is controlled in 1-6g/L, soaking time in 12-24h.
(4) aqueous solution of silver nitrate is prepared, silver nitrate will be immersed in through the amine-modified polymer/titanium deoxid film of DOPA
Aqueous solution in, and be sealed with sealed membrane, after the completion of immersion, take out and simultaneously cleaned 3-4 times with deionized water, be placed in vacuum and do
60 DEG C of dryings are for 24 hours in dry case, you can obtaining deposition has polymer/nano titania laminated film of silver nano-grain.Wherein
The concentration control of silver nitrate is controlled in 0.5h-24h, soaking temperature at 0-60 DEG C in 0.5-20g/L, soaking time control.Entirely
Process should be protected from light operation, and silver nitrate is avoided to be decomposed under ultraviolet light or visible ray.
Description of the drawings
The digital photograph of Fig. 1 nano titania laminated films
Fig. 2 is the stereoscan photograph of polyacrylonitrile nanofiber film.
Fig. 3 a, b, c are the scanning of polyacrylonitrile, polylactic acid, polystyrene electro spinning nano fiber carried titanium dioxide respectively
Electronic Speculum compares photo
Fig. 3 d, e are after shell thickness distinguishes 185nm and 68nm polyacrylonitrile nanofiber carried titanium dioxide particles respectively
Fiber surface and section stereoscan photograph
Fig. 4 is the transmission electron microscope photo after polyacrylonitrile nanofiber film carried titanium dioxide nano particle
Fig. 5 is the XRD diagram of polyacrylonitrile nanofiber film load anatase titanium dioxide nano particle
Fig. 6 is the scanning electricity of the fiber surface for polymer/nano titania laminated film that deposition has silver nano-grain
Mirror and transmission electron microscope photo
Fig. 7 is polymer/titanium dioxide, polymer/titanium dioxide/poly-dopamine, polymer/titanium dioxide/poly- DOPA
The ultraviolet-visible absorption spectroscopy of amine/silver nano-grain
Fig. 8 is the song for polymer/nano titania composite membrane catalytic degradation methylene blue that deposition has silver nano-grain
Line chart
Specific embodiment
Below by specific implementation embodiment the invention will be further described, following embodiment be it is descriptive, no
It is limited, it is impossible to which protection scope of the present invention is limited with this.
Embodiment 1：9wt.% polyacrylonitrile solutions are prepared, wherein n,N-Dimethylformamide is as solvent, in 15kV electricity
Pressure receives distance 15cm, and 30 DEG C of spinning temperature, spinning humidity 30%, solution flow rate 2.0mL/h, nozzle internal diameter 0.5mm are received
Time 40min prepares the polyacrylonitrile nanofiber film that average fibre diameter is 300nm.Using polyacrylonitrile nanofiber film as
Template using titanium tetrachloride as presoma, prepares the titanium tetrachloride aqueous solution of a concentration of 0.2mol/L, according to molar ratio Ti4+/
H+=1/5,It will be added drop-wise in above-mentioned solution dissolved with the aqueous solution of ammonium sulfate and hydrochloric acid, it is molten in mixed process
Liquid temperature is controlled below 15 DEG C.60 DEG C are warming up to 3 DEG C/min, polyacrylonitrile nanofiber film is added to mixed solution
In, keep the temperature 1h.Then ammonium hydroxide is added in, the pH value for adjusting whole system is 7.Cooled to room temperature later is aged 12h.It takes out
Film and after being washed respectively with distilled water and ethyl alcohol, 60 DEG C of dry 12h in vacuum drying chamber, you can obtain polyacrylonitrile/titanium dioxide
Titanium nano thin-film.Wherein nanofiber diameter is 320nm, shell thickness 10nm.By polyacrylonitrile/titanium dioxide nanofiber
It impregnates for 24 hours in the dopamine solution that film is 8.5, a concentration of 1g/L in pH, is cleaned 3-4 times with deionized water after taking-up, is placed in true
60 DEG C of dryings for 24 hours, obtain the amine-modified polyacrylonitrile/titanium deoxid film of DOPA in empty drying box.Prepare the nitric acid of 0.5g/L
Silver-colored aqueous solution will be immersed in through the amine-modified polyacrylonitrile/titanium deoxid film of DOPA in the aqueous solution of silver nitrate, and with sealing
Film is sealed at 0 DEG C and is kept in dark place for 24 hours, after the completion of immersion, takes out and is cleaned 3-4 times with deionized water, be placed in vacuum drying chamber
Interior 60 DEG C of dryings are for 24 hours, you can obtaining deposition has polymer/nano titania laminated film of silver nano-grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 1
Polyacrylonitrile/nano titania laminated film that the 10mg depositions of preparation have silver nano-grain is Photodegradation catalyst, it is seen that
120min is irradiated under light, methylene blue ultimate density reaches the 2% of initial concentration.
Embodiment 2：The polyacrylonitrile nanofiber film prepared using embodiment 1 is template, using titanium tetrachloride as forerunner
Body prepares the titanium tetrachloride aqueous solution of a concentration of 1.0mol/L, according to molar ratio Ti4+/H+=1/5,It will
It is added drop-wise in above-mentioned solution dissolved with the aqueous solution of ammonium sulfate and hydrochloric acid, solution temperature control is below 15 DEG C in mixed process.With 3
DEG C/min is warming up to 80 DEG C, and polyacrylonitrile nanofiber film is added in mixed solution, keep the temperature 1h.Then ammonium hydroxide is added in, is adjusted
The pH value for saving whole system is 7.Cooled to room temperature later is aged 12h.It takes out film and is washed respectively with distilled water and ethyl alcohol
Afterwards, 60 DEG C of dry 12h in vacuum drying chamber, you can obtain titanium dioxide nano-film.Polyacrylonitrile/titanium dioxide in nano thin-film
Titanium nanofiber diameter is 550nm, shell thickness 125nm.By polyacrylonitrile/titanium dioxide nanofiber film pH for 8.5,
It impregnates in the dopamine solution of a concentration of 1g/L for 24 hours, is cleaned 3-4 times with deionized water after taking-up, is placed in 60 in vacuum drying chamber
It is DEG C dry for 24 hours, obtain the amine-modified polyacrylonitrile/titanium deoxid film of DOPA.The silver nitrate aqueous solution of 1g/L is prepared, it will be through more
Bar amine-modified polyacrylonitrile/titanium deoxid film is immersed in the aqueous solution of silver nitrate, and be sealed at 0 DEG C and kept away with sealed membrane
Light preserves for 24 hours, after the completion of immersion, takes out and is simultaneously cleaned 3-4 times with deionized water, is placed in vacuum drying chamber 60 DEG C of dryings for 24 hours, i.e.,
Can obtain deposition has polyacrylonitrile/nano titania laminated film of silver nano-grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 2
Polyacrylonitrile/nano titania laminated film that the 10mg depositions of preparation have silver nano-grain is Photodegradation catalyst, it is seen that
120min is irradiated under light, methylene blue ultimate density reaches the 5% of initial concentration.
Embodiment 3：The polyacrylonitrile nanofiber film prepared using embodiment 1 is template, using titanium tetrachloride as forerunner
Body prepares the titanium tetrachloride aqueous solution of a concentration of 2.0mol/L, according to molar ratio Ti4+/H+=1/5,It will
It is added drop-wise in above-mentioned solution dissolved with the aqueous solution of ammonium sulfate and hydrochloric acid, solution temperature control is below 15 DEG C in mixed process.With 3
DEG C/min is warming up to 100 DEG C, and polyacrylonitrile nanofiber film is added in mixed solution, keep the temperature 1h.Then ammonium hydroxide is added in, is adjusted
The pH value for saving whole system is 7.Cooled to room temperature later is aged 12h.It takes out film and is washed respectively with distilled water and ethyl alcohol
Afterwards, 60 DEG C of dry 12h in vacuum drying chamber, you can obtain titanium dioxide nano-film.Polyacrylonitrile/titanium dioxide in nano thin-film
Titanium nanofiber diameter is 800nm, shell thickness 250nm.By polyacrylonitrile/titanium dioxide nanofiber film pH for 8.5,
It impregnates in the dopamine solution of a concentration of 1g/L for 24 hours, is cleaned 3-4 times with deionized water after taking-up, is placed in 60 in vacuum drying chamber
It is DEG C dry for 24 hours, obtain the amine-modified polyacrylonitrile/titanium deoxid film of DOPA.The silver nitrate aqueous solution of 5g/L is prepared, it will be through more
Bar amine-modified polymer/titanium deoxid film is immersed in the aqueous solution of silver nitrate, and be sealed at 0 DEG C and be protected from light with sealed membrane
18h is preserved, after the completion of immersion, takes out and is simultaneously cleaned 3-4 times with deionized water, be placed in vacuum drying chamber 60 DEG C of dryings for 24 hours, you can
Obtaining deposition has polyacrylonitrile/nano titania laminated film of silver nano-grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 3
Polyacrylonitrile/nano titania laminated film that the deposition of preparation has silver nano-grain is Photodegradation catalyst, it is seen that under light
120min is irradiated, methylene blue ultimate density reaches the 3% of initial concentration.
Embodiment 4：Prepare 10wt.% PLA solutions, wherein trifluoroacetic acid is as solvent, in 16kV voltages, receive away from
From 15cm, 30 DEG C of spinning temperature, spinning humidity 30%, solution flow rate 2.6mL/h, nozzle internal diameter 0.5mm, receiving time 40min,
Prepare the polylactic acid nano fiber film that average fibre diameter is 250nm.Using polylactic acid nano fiber film as template, using four chlorinations
Titanium prepares the titanium tetrachloride aqueous solution of a concentration of 0.3mol/L, according to molar ratio Ti as presoma4+/H+=1/5,It will be added drop-wise in above-mentioned solution dissolved with the aqueous solution of ammonium sulfate and hydrochloric acid, solution temperature control in mixed process
System is below 15 DEG C.70 DEG C are warming up to 3 DEG C/min, polylactic acid nano fiber film is added in mixed solution, keeps the temperature 1h.So
After add in ammonium hydroxide, adjust whole system pH value be 7.Cooled to room temperature later is aged 12h.It takes out film and uses distilled water
After being washed respectively with ethyl alcohol, 60 DEG C of dry 12h in vacuum drying chamber, you can obtain titanium dioxide nano-film.In nano thin-film
Polylactic acid/titanium dioxide nanofiber a diameter of 266nm, shell thickness 8nm.By polylactic acid/titanium dioxide nanofiber film
It is impregnated for 24 hours in the dopamine solution for being 8.5, a concentration of 2g/L in pH, is cleaned 3-4 times with deionized water after taking-up, be placed in vacuum
60 DEG C of dryings for 24 hours, obtain the amine-modified polylactic acid/titanium deoxid film of DOPA in drying box.The silver nitrate for preparing 5g/L is water-soluble
Liquid will be immersed in the aqueous solution of silver nitrate, and be sealed in sealed membrane through the amine-modified polylactic acid/titanium deoxid film of DOPA
It is kept in dark place at 25 DEG C for 24 hours, after the completion of immersion, takes out and cleaned 3-4 times with deionized water, be placed in vacuum drying chamber and do for 60 DEG C
It is dry for 24 hours, you can obtaining deposition has polylactic acid/nano titania laminated film of silver nano-grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 4
Polylactic acid/nano titania laminated film that the 10mg depositions of preparation have silver nano-grain is Photodegradation catalyst, it is seen that light
Lower irradiation 120min, methylene blue ultimate density reach the 8% of initial concentration.
Embodiment 5：The polylactic acid nano fiber film prepared using embodiment 4 is template, using titanium tetrachloride as presoma,
The titanium tetrachloride aqueous solution of a concentration of 1.2mol/L is prepared, according to molar ratio Ti4+/H+=1/5,It will be dissolved with
The aqueous solution of ammonium sulfate and hydrochloric acid is added drop-wise in above-mentioned solution, and solution temperature control is below 15 DEG C in mixed process.With 3 DEG C/
Min is warming up to 75 DEG C, and polylactic acid nano fiber film is added in mixed solution, keeps the temperature 1h.Then ammonium hydroxide is added in, is adjusted entire
The pH value of system is 7.Cooled to room temperature later is aged 12h.After taking out film and being washed respectively with distilled water and ethyl alcohol, very
60 DEG C of dry 12h in empty drying box, you can obtain titanium dioxide nano-film.Polylactic acid/nano titania in nano thin-film
Fibre diameter is 350nm, shell thickness 75nm.By polylactic acid/titanium dioxide nanofiber film pH for 8.5, a concentration of 2g/
It impregnates in the dopamine solution of L for 24 hours, is cleaned 3-4 times with deionized water after taking-up, be placed in vacuum drying chamber 60 DEG C of dryings for 24 hours,
Obtain the amine-modified polylactic acid/titanium deoxid film of DOPA.The silver nitrate aqueous solution of 5g/L is prepared, will be gathered through DOPA is amine-modified
Lactic acid/titanium deoxid film is immersed in the aqueous solution of silver nitrate, and is sealed at 25 DEG C with sealed membrane and 18h is kept in dark place, leaching
It after the completion of bubble, takes out and simultaneously clean 3-4 times with deionized water, be placed in vacuum drying chamber 60 DEG C of dryings for 24 hours, you can obtaining depositing has
The polylactic acid of silver nano-grain/nano titania laminated film.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 5
10mg polylactic acid/nano titania laminated film of preparation is Photodegradation catalyst, it is seen that 120min, methylene are irradiated under light
Blue ultimate density reaches the 5% of initial concentration.
Embodiment 6：The polylactic acid nano fiber film prepared using embodiment 4 is template, using titanium tetrachloride as presoma,
The titanium tetrachloride aqueous solution of a concentration of 1.8mol/L is prepared, according to molar ratio Ti4+/H+=1/5,It will be dissolved with
The aqueous solution of ammonium sulfate and hydrochloric acid is added drop-wise in above-mentioned solution, and solution temperature control is below 15 DEG C in mixed process.With 3 DEG C/
Min is warming up to 100 DEG C, and polylactic acid nano fiber film is added in mixed solution, keeps the temperature 1h.Then ammonium hydroxide is added in, is adjusted whole
The pH value of a system is 7.Cooled to room temperature later is aged 12h.After taking out film and being washed respectively with distilled water and ethyl alcohol,
60 DEG C of dry 12h in vacuum drying chamber, you can obtain titanium dioxide nano-film.Polylactic acid/titanium dioxide is received in nano thin-film
Rice fibre diameter is 500nm, shell thickness 125nm.By polylactic acid/titanium dioxide nanofiber film pH for 8.5, it is a concentration of
It impregnates in the dopamine solution of 2g/L for 24 hours, is cleaned 3-4 times with deionized water after taking-up, be placed in 60 DEG C of dryings in vacuum drying chamber
For 24 hours, the amine-modified polylactic acid/titanium deoxid film of DOPA is obtained.The silver nitrate aqueous solution of 5g/L is prepared, it will be amine-modified through DOPA
Polylactic acid/titanium deoxid film be immersed in the aqueous solution of silver nitrate, and be sealed at 0 DEG C with sealed membrane and 12h is kept in dark place,
It after the completion of immersion, takes out and is simultaneously cleaned 3-4 times with deionized water, be placed in vacuum drying chamber 60 DEG C of dryings for 24 hours, you can deposited
There is polylactic acid/nano titania laminated film of silver nano-grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 6
Polylactic acid/nano titania laminated film that the 10mg depositions of preparation have silver nano-grain is Photodegradation catalyst, it is seen that light
Lower irradiation 120min, methylene blue ultimate density reach the 8% of initial concentration.
Embodiment 7：Prepare 6 solution of 8wt.% nylon, wherein hexafluoroisopropanol is as solvent, in 18kV voltages, receive away from
From 20cm, 30 DEG C of spinning temperature, spinning humidity 40%, solution flow rate 2.8mL/h, nozzle internal diameter 0.5mm, receiving time 40min,
Prepare the nylon 6/nanometer tunica fibrosa that average fibre diameter is 155nm.Using nylon 6/nanometer tunica fibrosa as template, using titanium tetrachloride
As presoma, the titanium tetrachloride aqueous solution of a concentration of 0.3mol/L is prepared, according to molar ratio Ti4+/H+=1/5,It will be added drop-wise in above-mentioned solution dissolved with the aqueous solution of ammonium sulfate and hydrochloric acid, solution temperature control in mixed process
System is below 15 DEG C.90 DEG C are warming up to 3 DEG C/min, PAN nanofiber membrane is added in mixed solution, keeps the temperature 1.5h.So
After add in ammonium hydroxide, adjust whole system pH value be 7.Cooled to room temperature later is aged 12h.It takes out film and uses distilled water
After being washed respectively with ethyl alcohol, 60 DEG C of dry 12h in vacuum drying chamber, you can obtain titanium dioxide nano-film.In nano thin-film
6/ titanium dioxide nanofiber of nylon a diameter of 171nm, shell thickness 8nm.6/ titanium dioxide nanofiber film of nylon is existed
PH is to be impregnated for 24 hours in the dopamine solution of 8.5, a concentration of 4g/L, is cleaned 3-4 times with deionized water after taking-up, is placed in vacuum and does
60 DEG C of dryings for 24 hours, obtain amine-modified 6/ titanium deoxid film of nylon of DOPA in dry case.The silver nitrate aqueous solution of 15g/L is prepared,
It will be immersed in the aqueous solution of silver nitrate, and 30 DEG C are sealed in sealed membrane through amine-modified 6/ titanium deoxid film of nylon of DOPA
Under 6h is kept in dark place, after the completion of immersion, take out simultaneously cleaned 3-4 times with deionized water, be placed in 60 DEG C of dryings in vacuum drying chamber
For 24 hours, you can obtaining deposition has the 6/ nano titania laminated film of nylon of silver nano-grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 7
The 6/ nano titania laminated film of nylon that the 10mg depositions of preparation have silver nano-grain is Photodegradation catalyst, it is seen that under light
120min is irradiated, methylene blue ultimate density reaches the 4% of initial concentration.
Embodiment 8：The nylon 6/nanometer tunica fibrosa prepared using embodiment 7 is template, using titanium tetrachloride as presoma,
The titanium tetrachloride aqueous solution of a concentration of 0.8mol/L is prepared, according to molar ratio Ti4+/H+=1/5,It will be dissolved with
The aqueous solution of ammonium sulfate and hydrochloric acid is added drop-wise in above-mentioned solution, and solution temperature control is below 15 DEG C in mixed process.With 3 DEG C/
Min is warming up to 95 DEG C, and PAN nanofiber membrane is added in mixed solution, keeps the temperature 1h.Then ammonium hydroxide is added in, adjusts entire body
The pH value of system is 7.Cooled to room temperature later is aged 12h.After taking out film and being washed respectively with distilled water and ethyl alcohol, vacuum
60 DEG C of dry 12h in drying box, you can obtain titanium dioxide nano-film.PAN/ titanium dioxide nanofibers are straight in nano thin-film
Diameter is 295nm, shell thickness 70nm.By 6/ titanium dioxide nanofiber film of nylon in the DOPA that pH is 8.5, a concentration of 4g/L
18h is impregnated in amine aqueous solution, is cleaned 3-4 times with deionized water after taking-up, 60 DEG C of dryings in vacuum drying chamber is placed in and for 24 hours, obtains more
Bar 6/ titanium deoxid film of amine-modified nylon.The silver nitrate aqueous solution of 15g/L is prepared, it will be through the amine-modified nylon 6/ 2 of DOPA
Thin film of titanium oxide is immersed in the aqueous solution of silver nitrate, and is sealed at 45 DEG C with sealed membrane and 3h is kept in dark place, after the completion of immersion,
It takes out and simultaneously clean 3-4 times with deionized water, be placed in vacuum drying chamber 60 DEG C of dryings for 24 hours, you can obtaining depositing has silver nanoparticle
The 6/ nano titania laminated film of nylon of grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 8
The 6/ nano titania laminated film of nylon that the 10mg depositions of preparation have silver nano-grain is Photodegradation catalyst, it is seen that under light
120min is irradiated, methylene blue ultimate density reaches the 8% of initial concentration.
Embodiment 9：The nylon 6/nanometer tunica fibrosa prepared using embodiment 7 is template, using titanium tetrachloride as presoma,
The titanium tetrachloride aqueous solution of a concentration of 1.6mol/L is prepared, according to molar ratio Ti4+/H+=1/5,It will be dissolved with
The aqueous solution of ammonium sulfate and hydrochloric acid is added drop-wise in above-mentioned solution, and solution temperature control is below 15 DEG C in mixed process.With 3 DEG C/
Min is warming up to 100 DEG C, and nylon 6/nanometer tunica fibrosa is added in mixed solution, keeps the temperature 1h.Then ammonium hydroxide is added in, is adjusted entire
The pH value of system is 7.Cooled to room temperature later is aged 12h.After taking out film and being washed respectively with distilled water and ethyl alcohol, very
60 DEG C of dry 12h in empty drying box, you can obtain titanium dioxide nano-film.6/ nano titania of nylon is fine in nano thin-film
Tie up a diameter of 455nm, shell thickness 150nm.By 6/ titanium dioxide nanofiber film of nylon pH for 8.5, a concentration of 4g/L
Dopamine solution in impregnate 12h, cleaned 3-4 times with deionized water after taking-up, be placed in vacuum drying chamber 60 DEG C of dryings for 24 hours,
Obtain amine-modified 6/ titanium deoxid film of nylon of DOPA.The silver nitrate aqueous solution of 15g/L is prepared, it will be through the amine-modified Buddhist nun of DOPA
Imperial 6/ titanium deoxid film is immersed in the aqueous solution of silver nitrate, and be sealed at 30 DEG C with sealed membrane and 2h is kept in dark place, and is impregnated
After the completion, it takes out and clean 3-4 times with deionized water, be placed in vacuum drying chamber 60 DEG C of dryings for 24 hours, you can obtaining depositing has silver
The 6/ nano titania laminated film of nylon of nano particle.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 9
The 6/ nano titania laminated film of nylon that the deposition of preparation has silver nano-grain is Photodegradation catalyst, it is seen that is irradiated under light
120min, methylene blue ultimate density reach the 6% of initial concentration.
Embodiment 10：20wt.% polystyrene solutions are prepared, wherein n,N-Dimethylformamide is as solvent, in 15kV
Voltage receives distance 15cm, and 30 DEG C of spinning temperature, spinning humidity 40%, solution flow rate 2.5mL/h, nozzle internal diameter 0.5mm connect
40min between time receiving prepares the nylon 6/nanometer tunica fibrosa that average fibre diameter is 250nm.Using nylon 6/nanometer tunica fibrosa as template,
Using titanium tetrachloride as presoma, the titanium tetrachloride aqueous solution of a concentration of 0.3mol/L is prepared, according to molar ratio Ti4+/H+=
1/5,It will be added drop-wise in above-mentioned solution dissolved with the aqueous solution of ammonium sulfate and hydrochloric acid, solution temperature in mixed process
Degree control is below 15 DEG C.90 DEG C are warming up to 3 DEG C/min, polystyrene nano fiber film is added in mixed solution, is protected
Warm 1.5h.Then ammonium hydroxide is added in, the pH value for adjusting whole system is 7.Cooled to room temperature later is aged 12h.Take out film simultaneously
After being washed respectively with distilled water and ethyl alcohol, 60 DEG C of dry 12h in vacuum drying chamber, you can obtain titanium dioxide nano-film.It receives
6/ titanium dioxide nanofiber of nylon a diameter of 260nm, shell thickness 5nm in rice film.Polystyrene/titanium dioxide is received
12h is impregnated in the dopamine solution that rice tunica fibrosa is 8.5, a concentration of 6g/L in pH, is cleaned 3-4 times with deionized water after taking-up,
It is placed in 60 DEG C of dryings in vacuum drying chamber and for 24 hours, obtains the amine-modified polystyrene/titanium deoxid film of DOPA.Prepare 20g/L's
Silver nitrate aqueous solution will be immersed in the aqueous solution of silver nitrate through the amine-modified polystyrene/titanium deoxid film of DOPA, be used in combination
Sealed membrane is sealed at 60 DEG C and 0.5h is kept in dark place, and after the completion of immersion, takes out and is cleaned 3-4 times with deionized water, be placed in vacuum
60 DEG C of dryings are for 24 hours in drying box, you can obtaining deposition has polystyrene/nano titania laminated film of silver nano-grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 10
Polystyrene/nano titania laminated film that the 10mg depositions of preparation have silver nano-grain is Photodegradation catalyst, it is seen that
120min is irradiated under light, methylene blue ultimate density reaches the 6% of initial concentration.
Embodiment 11：The nylon 6/nanometer tunica fibrosa prepared using embodiment 10 is template, using titanium tetrachloride as forerunner
Body prepares the titanium tetrachloride aqueous solution of a concentration of 0.8mol/L, according to molar ratio Ti4+/H+=1/5,It will
It is added drop-wise in above-mentioned solution dissolved with the aqueous solution of ammonium sulfate and hydrochloric acid, solution temperature control is below 15 DEG C in mixed process.With 3
DEG C/min is warming up to 95 DEG C, and PAN nanofiber membrane is added in mixed solution, keep the temperature 1h.Then ammonium hydroxide is added in, is adjusted entire
The pH value of system is 7.Cooled to room temperature later is aged 12h.After taking out film and being washed respectively with distilled water and ethyl alcohol, very
60 DEG C of dry 12h in empty drying box, you can obtain titanium dioxide nano-film.Polystyrene/titanium dioxide is received in nano thin-film
Rice fibre diameter is 290nm, shell thickness 20nm.By polystyrene/titanium dioxide nanofiber film pH for 8.5, concentration
To impregnate 12h in the dopamine solution of 6g/L, cleaned 3-4 times with deionized water after taking-up, be placed in vacuum drying chamber and do for 60 DEG C
It is dry for 24 hours, obtain the amine-modified polystyrene/titanium deoxid film of DOPA.The silver nitrate aqueous solution of 20g/L is prepared, it will be through DOPA
Amine-modified polystyrene/titanium deoxid film is immersed in the aqueous solution of silver nitrate, and is sealed at 20 DEG C and kept away with sealed membrane
Light preserves 1h, after the completion of immersion, takes out and is simultaneously cleaned 3-4 times with deionized water, is placed in vacuum drying chamber 60 DEG C of dryings for 24 hours, i.e.,
Can obtain deposition has polystyrene/nano titania laminated film of silver nano-grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 11
Polystyrene/nano titania laminated film that the 10mg depositions of preparation have silver nano-grain is Photodegradation catalyst, it is seen that
120min is irradiated under light, methylene blue ultimate density reaches the 4% of initial concentration.
Embodiment 12：The nylon 6/nanometer tunica fibrosa prepared using embodiment 10 is template, using titanium tetrachloride as forerunner
Body prepares the titanium tetrachloride aqueous solution of a concentration of 1.6mol/L, according to molar ratio Ti4+/H+=1/5,It will
It is added drop-wise in above-mentioned solution dissolved with the aqueous solution of ammonium sulfate and hydrochloric acid, solution temperature control is below 15 DEG C in mixed process.With 3
DEG C/min is warming up to 100 DEG C, and nylon 6/nanometer tunica fibrosa is added in mixed solution, keep the temperature 1h.Then ammonium hydroxide is added in, is adjusted
The pH value of whole system is 7.Cooled to room temperature later is aged 12h.It takes out film and is washed respectively with distilled water and ethyl alcohol
Afterwards, 60 DEG C of dry 12h in vacuum drying chamber, you can obtain titanium dioxide nano-film.6/ titanium dioxide of nylon in nano thin-film
Nanofiber diameter is 350nm, shell thickness 50nm.By polystyrene/titanium dioxide nanofiber film pH for 8.5, it is dense
It spends in the dopamine solution for 6g/L and impregnates 12h, cleaned 3-4 times with deionized water after taking-up, be placed in vacuum drying chamber 60 DEG C
Drying for 24 hours, obtains the amine-modified polystyrene/titanium deoxid film of DOPA.The silver nitrate aqueous solution of 20g/L is prepared, it will be through more
Bar amine-modified polystyrene/titanium deoxid film is immersed in the aqueous solution of silver nitrate, and be sealed at 15 DEG C with sealed membrane
2h is kept in dark place, after the completion of immersion, takes out and is simultaneously cleaned 3-4 times with deionized water, be placed in vacuum drying chamber 60 DEG C of dryings for 24 hours,
Deposition, which can be obtained, polystyrene/nano titania laminated film of silver nano-grain.
Photocatalytic degradation methylene blue is tested：For the 20mL methylene blue solutions of a concentration of 10mg/mL, with embodiment 12
Polystyrene/nano titania laminated film that the 10mg depositions of preparation have silver nano-grain is Photodegradation catalyst, it is seen that
120min is irradiated under light, methylene blue ultimate density reaches the 8% of initial concentration.
Claims (3)
1. a kind of nano titania preparation method of composite film, which is characterized in that include the following steps：In ice-water bath, companion
With stirring, titanium tetrachloride is instilled in deionized water, then will be added drop-wise to gained dissolved with the aqueous solution of ammonium sulfate and hydrochloric acid
In titanium tetrachloride aqueous solution, the addition of ammonium sulfate and hydrochloric acid is controlled according to molar ratio Ti4+：H+：It carries out；
Temperature control is below 15 DEG C in mixed process；Solution is warming up to 60-100 DEG C with the rate of 3 DEG C/min, by polymer nanocomposite
Tunica fibrosa is added in solution, and after keeping the temperature 1h, the pH value that whole system is adjusted using ammonium hydroxide is 7；Cooled to room temperature later,
It is aged 12h；After taking out film and being washed respectively using distilled water and ethyl alcohol, 60 DEG C of dry 12h, are polymerize in vacuum drying chamber
Object/titanium dioxide nano-film；12-24h is impregnated in the aqueous dopamine solution of a concentration of 1-6g/L, is obtained amine-modified through DOPA
Polymer/titanium dioxide nano-film；By this membranes submerged in the silver nitrate solution of a concentration of 0.5-20g/L, temperature is
0.5-24h is kept in dark place at 0-60 DEG C, obtaining deposition has polymer/nano titania composite membrane of silver nano-grain.
2. a kind of nano titania preparation method of composite film according to claim 1, it is characterised in that：Polymer nanocomposite
Material used in tunica fibrosa is polyacrylonitrile, cellulose, polyvinyl alcohol, polyurethane, makrolon, polyester, polyimides, polyamides
Amine, polyvinyl chloride, polystyrene, polyethylene, polypropylene or polytetrafluoroethylene (PTFE).
A kind of 3. nano titania preparation method of composite film according to claim 1, which is characterized in that polymer nanocomposite
The preparation process of tunica fibrosa is as follows：
Under magnetic stirring, the organic solvent spinning solution of 7-24wt.% polymer is prepared；It is wet in 10-60 DEG C of spinning temperature, spinning
It spends under conditions of 20-60%, spinning solution is added in spinning liquid storage device, and nozzle internal diameter is from 0.2-1.0mm, spinning distance 10-
20cm, spinning voltage 8-25kV, solution inject speed as 1-4mL/h；After spinning 30-40min, obtain a fibre diameter and exist
Polymer nanofibre film in the range of 100-500nm is placed on drying at room temperature 20-24h in vacuum drying chamber.
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| CN201510519203.6A CN105057003B (en) | 2015-08-22 | 2015-08-22 | A kind of nano titania preparation method of composite film |
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