CN107715699A - A kind of preparation method of the PEI photocatalysis milipore filter of area load titanium dioxide nano thread - Google Patents
A kind of preparation method of the PEI photocatalysis milipore filter of area load titanium dioxide nano thread Download PDFInfo
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- CN107715699A CN107715699A CN201711157984.4A CN201711157984A CN107715699A CN 107715699 A CN107715699 A CN 107715699A CN 201711157984 A CN201711157984 A CN 201711157984A CN 107715699 A CN107715699 A CN 107715699A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 title abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002070 nanowire Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000007788 roughening Methods 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 229920002120 photoresistant polymer Polymers 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000005357 flat glass Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 13
- 230000004907 flux Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- 230000010148 water-pollination Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 239000004697 Polyetherimide Substances 0.000 description 53
- 229920001601 polyetherimide Polymers 0.000 description 53
- 239000003344 environmental pollutant Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 4
- 229940098773 bovine serum albumin Drugs 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
- Physical Water Treatments (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of area load TiO2The preparation method of the PEI photocatalysis milipore filters of nano wire.Method is as follows：1) PEI preparation liquids are prepared：PEI, P25 are solved homogeneously in nmp solution；2) Tu whirl coating is revolved, PEI/P25 composite membranes are made in preparation liquid, and soak in deionized water；3) PEI/P25 films are subjected to surface roughening treatment；4) hydrogen peroxide reaction solution is configured；5) PEI/P25 films are immersed in hydrogen peroxide reaction solution, growth covering hydrogen metatitanic acid nano wire；6) the PEI/P25 films that surface is covered to hydrogen metatitanic acid nano wire submerge in the hot water, and the conversion of hydrogen metatitanic acid nano wire crystallizes into titanium dioxide, and taking-up is rinsed with water.The present invention in PEI film superficial growth titanium dioxide nano threads, improves the hydrophily of film by low temperature crystallization technology, and so as to the flux of raising film while high stage cut is kept, the film can be applied to the fields such as photocatalysis pollution control.
Description
Technical field
The invention belongs to UF membrane and photocatalysis field, is related to a kind of modification technology of polymeric membrane, more particularly to a kind of
Area load titanium dioxide (TiO2) nano wire PEI (PEI) photocatalysis milipore filter preparation method.
Background technology
It is net to be widely used in water body because separative efficiency is good, equipment size is small, the advantage such as easy to maintenance for membrane separation technique
The fields such as change, seawater separation, material concentration and heavy metal filtering.Preferable membrane material should have following characteristic：Good machinery is strong
Degree and pliability；There is excellent stability under the harsh conditions such as soda acid；Pollution resistance；High selectivity；Only need less driving
Power is with regard to that can maintain high flux etc..In practical application, due to the organic pollutions such as protein in waste water often be present, filter for a long time
Afterwards, pollutant can be adsorbed on the surface of film, so as to cause the flux of film to reduce, influence the separating effect of film；Remove these film tables
Face pollutant generally requires periodically to be backwashed, such as physical cleaning or Chemical cleaning, so as to increase running cost, reduces
Production efficiency.
PEI (PEI) is a kind of common engineering plastics, has superior heat endurance, excellent mechanical performance
And anti-wear performance, can be long-term use of under -160~180 DEG C of operating temperature, it is a kind of excellent coating and filmogen.
But common PEI film hydrophilies are poor, the pure water flux of film is influenceed, while hydrophobic PEI films are easily by organic pollution institute
The materials such as pollution, protein are readily adsorbed in the surface of film or block fenestra, reduce membrane separation efficiency.
Optically catalytic TiO 2 technology can under ultraviolet or radiation of visible light decomposing organic pollutant, be carried on film surface
It is favorably improved its antifouling property；The hydrophily of titanium dioxide is also beneficial to the raising of membrane flux simultaneously.With the seperation film of routine
Compare, photocatalysis membrana has the advantages that hydrophily, resistance tocrocking, the degraded of antimicrobial and organic pollutant.Common light is urged
Changing organic film has two kinds of preparation methods：1) by TiO2Nano particle and organic film material are blended, formed preparation liquid prepare it is inorganic-have
Machine composite membrane；2) on the premise of membrane body structure is not changed, using film surface grafting method of modifying, in the surface grafting of film
TiO2Nano particle, so as to improve the antifouling property of film and light cleaning capacity.
The ingenious combination above two method of the present invention, is closely tied by low temperature growth techniques in PEI films surface uniform fold
Unify layer titanium dioxide nano thread film, not only increase water flux, while the pollutant that efficient degradation is adsorbed under uviol lamp,
With preferable pollution-proof performance.
The content of the invention
The purpose of the present invention is low for PEI film surface energies, and hydrophobicity is strong, and resistance tocrocking is poor, can not realize that light cleans work(
A kind of present situation of energy, there is provided area load TiO2The preparation method of the PEI photocatalysis milipore filters of nano wire, passes through low-temperature epitaxy skill
Art is in TiO of the surface of the PEI films coating with photo-catalysis function and good hydrophilic property2Nano wire, realize that PEI films antipollution and light are clear
Clean function.
A kind of preparation of the PEI photocatalysis milipore filter of area load titanium dioxide nano thread disclosed by the invention
Method, including following key step：
Step 1: prepare PEI preparation liquids：P25, PEI and solvent N-methyl pyrilidone (NMP) are mixed, oil bath heating,
And it is stirred with mechanical agitator, more than mixing time 8h so that PEI is substantially dissolved in NMP, and is well mixed；
Step 2: PEI/P25 films are made in molding liquid by revolving Tu whirl coating：The preparation liquid prepared is poured on glass plate
On, be then attached to photoresist spinner internal rotation whirl coating shaping, at room temperature by the glass plate be immersed in deionized water stand 12h with
On, take out stand-by；
Step 3: PEI/P25 films are subjected to surface roughening treatment：PEI/P25 films prepared by step 2 are immersed in NMP
In solvent after 8~10s, taking-up deionized water rinsing, exposed surface P25 titania nanoparticles；
Step 4: match somebody with somebody producing hydrogen peroxide reaction solution；
Step 5: the PEI/P25 films that step 3 obtains are immersed in the hydrogen peroxide reaction solution of step 4 preparation, 60~
80 DEG C of 12~72h of baking oven inside holding covers hydrogen metatitanic acid nano wire in its superficial growth, and taking-up is cleaned stand-by with water；
Step 6: the film for handling to obtain by step 5 is immersed in deionized water, it is incubated 72 at 70~80 DEG C~
120h, you can obtain surface and firmly load TiO2The high performance ultra filtration film of film.
In above-mentioned technical proposal, it is preferred that the mass percent of PEI polymer is 24~34% in described preparation liquid,
P25 mass percent is 1.2~3.2%.Described oil bath heating temperature is 70 DEG C.
Preferably, the hydrogen peroxide reaction solution described in step 4, including following component：Hydrogen peroxide mass percent be 20~
30%th, melamine concentration is 1.3~2.0g/L, nitric acid mass concentration is 0.9~1.4%, titanium sponge is 4~5g/L.
Preferably, the rotary speed of the whirl coating shaping described in step 2 is 4000rpm.The present invention has below beneficial to effect
Fruit：
The a small amount of P25TiO being embedded in PEI is utilized in the present invention2Heterogeneous nucleating center of the nano particle as nano wire,
Under cryogenic conditions one layer of TiO is covered on PEI films surface2Nano wire functional layer, adhesion is good, while improves the performance of film,
Obtain surface modified polyetherimide (PEI) film for having photocatalysis and UF membrane function concurrently.By the composite hyperfiltration membrane of gained and not
Film through processing is compared in pure water flux, resistance tocrocking and rejection etc., and test result shows, and undressed
Film is compared, and the film hydrophily prepared by this method increases substantially, the increase of filtration of demineralized water amount, while to bovine serum albumin (BSA)
Rejection increase significantly, flux decline coefficient reduce.
Brief description of the drawings
Fig. 1 is the load TiO prepared in embodiment one2The SEM characterization result top of the PEI films of nano wire
View；
Fig. 2 is the load TiO prepared in embodiment one2Scanning electricity after the ultrasonic cleaning 30 minutes of the PEI films of nano wire
Sub- microscope characterization result top view；
Fig. 3 is the load TiO prepared in embodiment one2The SEM characterization result of the PEI films of nano wire is cut
Face figure；
Fig. 4 is the load TiO prepared in embodiment one2The X ray diffracting spectrum of the PEI films of nano wire；
Fig. 5 is the load TiO prepared in embodiment one2The pure water contact angle of the PEI films of nano wire；
Fig. 6 is the load TiO prepared in embodiment one2The cutting for BSA (1.0g/L) solution of the PEI films of nano wire
Except rate and the antifouling property test result figure of film；
Fig. 7 is the load TiO prepared in embodiment two2The SEM characterization result top of the PEI films of nano wire
View.
Embodiment：
The present invention is expanded on further with reference to embodiments, but the present invention is not limited solely to following embodiments.
Embodiment 1
Step 1, configuration PEI preparation liquids：By NMP, PEI and commercial Degussa P25 titania nanoparticles in mass ratio
60:20:1 mixing, is placed in being incubated in 70 DEG C of oil bath pans, stirs 8 h using mechanical force agitator, PEI preparation liquids are prepared；
Step 2, the PEI preparation liquids that step 1 obtains are poured on clean glass plate, glass plate are fixed on photoresist spinner,
30s is rotated by 4000rpm rotary speed, the glass plate for being coated with preparation liquid afterwards is immersed in deionized water, makes NMP
Solvent is gradually dissolved in deionized water, forms a tunic after preparation liquid solidification, gained film is immersed in deionized water and stood
12h, you can obtain uniform PEI/P25 films；
Step 3, the PEI/P25 films that step 2 is prepared are placed in 8s in 50 DEG C of nmp solution, deionization is used after taking-up
Water is stand-by after rinsing；
Step 4, with producing hydrogen peroxide reaction solution；Hydrogen peroxide mass concentration is 30% in reaction solution, and melamine concentration is
2.0g/L, nitric acid mass concentration are 1.36%, and the concentration of titanium sponge is 5g/L, and the usage amount of solution is directly proportional to the area of film,
For 2ml/cm2；
Step 5, the PEI/P25 films that step 3 obtains are placed in the hydrogen peroxide reaction solution that step 4 is prepared, in 80 DEG C of baking
Case inside holding 72h, taking-up are cleaned stand-by with water；
Step 6, step 5 is obtained into film be placed in deionized water, in 80 DEG C of baking oven inside holding 120h, you can obtain surface
Firmly load TiO2The high performance ultra filtration film of film.
Surface topography observation result surface, film surface uniform fold nano wire (Fig. 1), is firmly combined with.Through being cleaned by ultrasonic 30
Minute, nano wire layer keeps complete nothing to come off (Fig. 2).Fig. 3 shows the section loose structure of film, and nano surface cable architecture.X
Ray result shows, surface functional layer is by the anatase and rutile structure TiO that crystallize2Composition, and it is unconverted containing some
Hydrogen metatitanic acid (Fig. 4).Fig. 5 shows that gained film has good hydrophily.UF membrane test result (Fig. 6)：Tried by being repeated several times
Test, the property retention of film is stable, and the pure water flux of film is 595L m-2h-1, BSA stage cut is 93.3%, by ultraviolet lighting
After penetrating, the response rate of film is 88.3%.
From the above results, the milipore filter top layer titanium dioxide of preparation is firmly combined with, and hydrophily is high, and stain resistance is strong,
Permeation flux is high, and stage cut is outstanding, and method is simple, and cost is low, has industrial applications prospect well.Simultaneously because titanium dioxide
The photocatalysis characteristic of titanium, when pollutant adsorbs or deposits, titanium dioxide nano thread under uviol lamp light radiation, urged by pollutant
Change degraded so as to reach the purpose that film automatically cleaning improves pollution resistance.Gained polymeric membrane also can be separately as photocatalysis film application
In fields such as photocatalysis pollution controls.
Embodiment 2
Step 1, configuration PEI preparation liquids：By NMP, PEI and P25 particle in mass ratio 40:20:1 mixing, is placed in 70 DEG C
It is incubated in oil bath pan, is stirred 8 hours using mechanical force agitator, PEI preparation liquids are prepared；
Step 2, with embodiment 1；
Step 3, with embodiment 1；
Step 4, with producing hydrogen peroxide reaction solution；Hydrogen peroxide concentration is 20%, melamine concentration 1.3g/L, concentration of nitric acid
For 0.9%, the concentration of titanium sponge is 4g/L, and the usage amount of solution is directly proportional to the area of film, is 2ml/cm2；
Step 5, the PEI/P25 films that step 3 obtains are placed in the hydrogen peroxide reaction solution that step 4 is prepared, in 60 DEG C of baking
Case inside holding 24h, taking-up are cleaned stand-by with water；
Step 6, with embodiment 1.
Embodiment 3
Step 1, configuration PEI preparation liquids：By NMP, PEI and P25 particle in mass ratio 40:20:1 mixing, is placed in 70 DEG C
It is incubated in oil bath pan, 8h is stirred using mechanical force agitator, PEI preparation liquids are prepared；
Step 2, with embodiment 1；
Step 3, the PEI/P25 films that step 2 is prepared are placed in 10s in 50 DEG C of nmp solution, deionization is used after taking-up
Water is stand-by after rinsing；
Step 4, with producing hydrogen peroxide reaction solution；Hydrogen peroxide concentration is 30%, melamine concentration 2g/L, and concentration of nitric acid is
1.4%, the concentration of titanium sponge is 5g/L, and the usage amount of solution is directly proportional to the area of film, is 2ml/cm2；
Step 5, the PEI/P25 films that step 3 obtains are placed in the hydrogen peroxide reaction solution that step 4 is prepared, in 60 DEG C of baking
Case inside holding 72h, taking-up are cleaned stand-by with water；
Step 6, with embodiment 1.
Embodiment 4
Step 1, with embodiment 3；
Step 2, with embodiment 1；
Step 3, with embodiment 1；
Step 4, with embodiment 3；
Step 5, the PEI/P25 films that step 3 obtains are placed in the hydrogen peroxide reaction solution that step 4 is prepared, in 80 DEG C of baking
Case inside holding 12h, taking-up are cleaned stand-by with water；
Step 6, step 5 is obtained into film be placed in deionized water, in 80 DEG C of baking oven inside holding 72h, you can obtain surface
Firmly load TiO2The high performance ultra filtration film of film.
Embodiment 5
Step 1, configuration PEI preparation liquids：By NMP, PEI and P25 particle in mass ratio 50:20:1 mixing, is placed in 70 DEG C
It is incubated in oil bath pan, 8h is stirred using mechanical force agitator, PEI preparation liquids are prepared；
Step 2, with embodiment 1；
Step 3, with embodiment 1；
Step 4, with embodiment 3；
Step 5, the PEI/P25 films that step 3 obtains are placed in the hydrogen peroxide reaction solution that step 4 is prepared, in 70 DEG C of baking
Case inside holding 48h, taking-up are cleaned stand-by with water；
Step 6, step 5 is obtained into film be placed in deionized water, in 70 DEG C of baking oven inside holding 96h, you can obtain surface
Firmly load TiO2The high performance ultra filtration film of film.
Claims (6)
- A kind of 1. area load TiO2The preparation method of the PEI photocatalysis milipore filters of nano wire, it is characterised in that preparation process bag Include following key step：Step 1: prepare PEI preparation liquids：P25, PEI and solvent NMP are mixed, oil bath heating, and 8h is stirred with mechanical agitator More than so that PEI is substantially dissolved in NMP, and is well mixed；Step 2: PEI/P25 films are made in molding liquid by revolving Tu whirl coating：The preparation liquid prepared is poured on cleaning plate glass On, it is then attached in photoresist spinner, rotation whirl coating shaping, the glass plate is immersed in deionized water at room temperature stood afterwards More than 12h, take out stand-by；Step 3: PEI/P25 films are subjected to surface roughening treatment：PEI/P25 films prepared by step 2 are immersed in nmp solvent In after 8~10s, taking-up deionized water rinsing；Step 4: match somebody with somebody producing hydrogen peroxide reaction solution；Step 5: the PEI/P25 films that step 3 obtains are immersed in the hydrogen peroxide reaction solution of step 4 preparation, at 60~80 DEG C 12~72h of baking oven inside holding, taking-up cleaned with deionized water it is stand-by；Step 6: the film after step 5 is handled is immersed in deionized water, 72-120h is incubated at 80 DEG C, you can To area load TiO2The PEI photocatalysis milipore filters of nano wire.
- A kind of 2. area load TiO according to claim 12The preparation method of the PEI photocatalysis milipore filters of nano wire, its It is characterised by, the mass percent of PEI polymer is 24~34% in the preparation liquid described in step 1.
- A kind of 3. area load TiO according to claim 12The preparation method of the PEI photocatalysis milipore filters of nano wire, its It is characterised by, P25 mass percent is 1.2~3.2% in the preparation liquid described in step 1.
- A kind of 4. area load TiO according to claim 12The preparation method of the PEI photocatalysis milipore filters of nano wire, its It is characterised by, the hydrogen peroxide reaction solution described in step 4, including following component：Hydrogen peroxide mass percent be 20~30%, Melamine concentration is 1.3~2.0g/L, nitric acid mass concentration is 0.9~1.4%, titanium sponge is 4~5g/L.
- A kind of 5. area load TiO according to claim 12The preparation method of the PEI photocatalysis milipore filters of nano wire, its It is characterised by, the oil bath heating temperature described in step 1 is 70 DEG C.
- A kind of 6. area load TiO according to claim 12The preparation method of the PEI photocatalysis milipore filters of nano wire, its It is characterised by, the rotary speed of the whirl coating shaping described in step 2 is 4000rpm.
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| CN103566914A (en) * | 2013-11-06 | 2014-02-12 | 浙江大学 | Method for loading titanium dioxide nanowire on glass fiber |
| US20140144834A1 (en) * | 2012-11-29 | 2014-05-29 | Seok Won Hong | Membrane with titanium dioxide nanostructure and method for fabricating the same |
| CN106660839A (en) * | 2014-06-06 | 2017-05-10 | 休斯敦大学体系 | Porous nanocomposite polymers for water treatment |
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| US20140144834A1 (en) * | 2012-11-29 | 2014-05-29 | Seok Won Hong | Membrane with titanium dioxide nanostructure and method for fabricating the same |
| CN103566914A (en) * | 2013-11-06 | 2014-02-12 | 浙江大学 | Method for loading titanium dioxide nanowire on glass fiber |
| CN106660839A (en) * | 2014-06-06 | 2017-05-10 | 休斯敦大学体系 | Porous nanocomposite polymers for water treatment |
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