CN106582331A - Preparation method of photocatalytic ultrafilter membrane material with visible light activity - Google Patents
Preparation method of photocatalytic ultrafilter membrane material with visible light activity Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 26
- 230000000694 effects Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000007146 photocatalysis Methods 0.000 claims description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000000108 ultra-filtration Methods 0.000 claims description 16
- 229920002492 poly(sulfone) Polymers 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 235000013877 carbamide Nutrition 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229950000845 politef Drugs 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- -1 urine Element Substances 0.000 claims description 2
- 210000002700 urine Anatomy 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 238000005086 pumping Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 5
- 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 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 229910011210 Ti—O—N Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a photocatalytic ultrafilter membrane material with visible light activity. The method comprises the following steps: 1, preparing N-TiO2 powder; 2, preparing N-TiO2/GO particles; 3, preparing an ultrafilter membrane; and 4, producing an ultrafilter membrane with the surface loaded with N-TiO2/GO: processing the N-TiO2/GO particles to prepare an N-TiO2/GO dispersion, tiling the ultrafilter membrane on a suction filtration device, pouring the N-TiO2/GO dispersion, carrying out vacuum pumping, and airing the obtained membrane to obtain the ultrafilter membrane with the surface loaded with N-TiO2/GO. The photocatalytic material with the advantages of visible light activity, hydrophilic property and difficulty in loss of nano-particles is obtained through the preparation method of the photocatalytic ultrafilter membrane material with visible light activity.
Description
Technical field
The present invention relates to a kind of preparation method of the photocatalysis ultrafiltration membrane material with visible light activity, belongs to photocatalysis material
Material technical field.
Background technology
Photocatalyst with titanium dioxide as representative has that photocatalytic activity is high, stability is good, fast light corrosivity strong, into
The advantages of this cheap, harmless, light-catalyzed reaction can be carried out at normal temperatures and pressures, optically catalytic TiO 2 technology is to ring
Border pollution control has good effect, therefore more and more concerned.But due to the limitation of this body structure of titanium dioxide, such as
Titanium dioxide forbidden energy gap is big, and the ultraviolet excitation of 387.5nm can only be less than by wavelength, and ultraviolet light is only accounted in sunlight
4%；And compound and surface recombination the probability of the body phase of titanium dioxide photoproduction electron-hole is very high, causes photo-generate electron-hole
Cannot effectively participate in redox reaction, its quantum efficiency at most not higher than 20%, therefore to the utilization ratio of sunlight only
For 1%.These shortcomings significantly limit optically catalytic TiO 2 application in practice.
At present, TiO2Preparation often nanorize, nano-TiO2Due to quantum effect, small-size effect, skin effect
And interfacial effect, and good photocatalysis performance is shown, but the TiO of nano-scale2Also easily flow in water treatment procedure
Lose, its recoverys is more difficult, and nano-particle is likely to invade human body and the natural system of defense of other species, into cell and break
The function of bad cell, with nanometer toxicity.
The content of the invention
The technical problem to be solved is to provide a kind of with visible light activity, hydrophilic, nanometer small toxicity
The preparation method of photocatalysis ultrafiltration membrane material.
To solve above-mentioned technical problem, the technical solution used in the present invention is：
A kind of preparation method of the photocatalysis ultrafiltration membrane material with visible light activity, comprises the following steps：
S01, prepares N-TiO2Powder：Butyl titanate is dissolved in dehydrated alcohol and forms solution A；By dehydrated alcohol, pure
Water, carbamide, glacial acetic acid uniformly mix and adjust pH formation solution Bs；It is stirred vigorously down, solution B is added dropwise in solution A,
And persistently stir；Standing gel post-drying, grinding, calcining form N-TiO2Powder；
S02, prepares N-TiO2/ GO granules：Weigh graphene oxide GO to pour in appropriate pure water, ultrasonic vibration disperses it
It is uniform to obtain GO dispersion liquids, then weigh appropriate N-TiO2Powder is poured in GO dispersion liquids, is continued GO and N-TiO after ultrasonic disperse2's
Mixed solution is transferred in autoclave, is reacted in hot environment, is taken out after natural cooling, and N- is obtained after lyophilization
TiO2/ GO granules；
S03, prepares ultrafilter membrane；
S04, prepares area load N-TiO2The ultrafilter membrane of/GO：By N-TiO2/ GO granules make N-TiO2/ GO dispersion liquids,
Ultrafilter membrane is laid in Suction filtration device again, pours N-TiO into2/ GO dispersion liquids, evacuation obtains area load N- after drying
TiO2The ultrafilter membrane of/GO.
The preparation method of the ultrafilter membrane is comprised the following steps：Weigh the polysulfones after drying and be added to N-Methyl pyrrolidone
In solution, the concussion in 50 DEG C of environment makes polysulfones fully dissolve, and adds polyvinylpyrrolidone, continues to shake, and is being dried atmosphere
Middle standing and defoaming is enclosed into casting solution；The thickness of coating device is adjusted, it is on clean glass plate that the casting solution for having configured is uniform
Spread to thin film, by be loaded with coat casting solution glass plate immersion pure water in, ultrafilter membrane slowly comes off from glass plate, will be obtained
Ultrafilter membrane soaks at least 24h in pure water, and midway at least changes a water, after taking-up is dried, obtains polysulfone membrane.
Butyl titanate and the volume ratio of dehydrated alcohol are 1 in solution A in S01:(4～6), in solution B dehydrated alcohol with it is molten
The volume ratio of butyl titanate is 1 in liquid A：(0.5～1), pure water is 1 with the volume ratio of butyl titanate:(2～3), glacial acetic acid and titanium
The volume ratio of acid butyl ester is 1:(4～6), carbamide is 1 with the mass ratio of butyl titanate:(8～20), adjust pH used by solution be
The hydrochloric acid of 6mol/L, the pH after regulation is 1.5～2.2.
The time that S01 is persistently stirred is at least 30min, temperature during drying be 60～150 DEG C, during calcining with 1～3 DEG C/
The speed of min is warming up to 500 DEG C of calcining at least 2h.
GO and N-TiO in S022The mass ratio of powder is 1:19, the hot environment is 150～200 DEG C, and the response time is
12～20h.
The inner lining material of the autoclave is politef, and volume is 150mL.
The mass percent of the polysulfones, N-Methyl pyrrolidone and polyvinylpyrrolidone is (15.6～20%)：(78
～84%)：(0.4～2%).
The thickness adjustable extent of the coating device is 100～200 μm.
The N-TiO2The concentration of/GO dispersion liquids is 0.5g/L, N-TiO2/ GO dispersion liquid volumes are 10～40mL.
The present invention prepares N-TiO with carbamide, butyl titanate, graphene oxide GO etc. as raw material2/ GO granules, and then by N-
TiO2/ GO particulate loads are on polysulphones hyperfiltration membrane.By the modified TiO of N and GO2, TiO2Energy gap reduce, light induced electron is empty
The recombination rate in cave is reduced, and its photocatalysis performance lifts and have under visible light photocatalytic activity.By being supported on ultrafilter membrane,
Photocatalyst losing issue is preferably solved, and the hydrophilic and photocatalysis performance of photocatalyst can lift the parent of ultrafilter membrane
Aqueouss and resistance tocrocking.
The beneficial effects of the present invention is：The doping of nonmetalloid nitrogen may replace TiO2Lacking oxygen in lattice, forms
Ti-N keys or Ti-O-N keys, reduce forbidden energy gap energy, and excitation wavelength is extended to visible region, significantly increases by ultraviolet region
Its responsiveness and photocatalysis effect under visible light.Graphene is one kind by sp2The carbon atom of hydridization is with hexagon row
The periodic cellular shape two dimension carbonaceous new material that row are formed, its specific surface area is up to 2600m2/ g, can improve photocatalyst to having
The absorbability of machine thing；Transmission and transfer of the electron mobility of its superelevation to electronics in light-catalyzed reaction plays a driving role, and subtracts
Less photo-generate electron-hole is compound；Oxygen element in the doping energy replacement of titanium dioxide lattice of carbon, reduces energy gap band, opens up
Wide photoresponse scope；And its outstanding chemistry, calorifics, optics and electrochemical stability can improve the use longevity of photocatalyst
Life, graphene oxide is that oxygen-containing functional group is increased on the architecture basics of Graphene so as to lift its hydrophilic.With ultrafilter membrane
Support type photocatalysis membrana for carrier can be significantly reduced the loss of photocatalyst, nanometer small toxicity, meanwhile, possess hydrophilic and
The photocatalyst of photocatalysis performance can lift the antifouling property of film, extend the service life of film.Therefore the present invention is obtained one kind
Photocatalytic activity is high, with the catalysis material that visible light activity, hydrophilic and nano-particle are not easily runed off.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure of ultrafiltration membrane material prepared by the present invention；
Fig. 2 be the present invention prepare ultrafiltration membrane material under different light sources to the removal effect figure of methylene blue.
Specific embodiment
The present invention is further described below.
Embodiment 1：
As shown in Fig. 1～Fig. 2, a kind of preparation method of the photocatalysis ultrafiltration membrane material with visible light activity, including with
Lower step：
(1) N-TiO is prepared2Powder：Measure 10ml butyl titanates and be mixed to form solution A with 40ml dehydrated alcohol, will
0.486g carbamide, 10ml dehydrated alcohol, 4ml pure water mix with 2ml glacial acetic acid, and adjust pH=2 formation solution Bs, in stirring bar
Solution B is added dropwise in solution A under part, stirring 30min is continued after being added dropwise to complete and is allowed to mixing completely, stand about 3h into gel
Shape, is put in air dry oven 100 DEG C and is dried 24h, grinds after cooling, is put in resistance furnace and is heated to the speed of 2 DEG C/min
500 DEG C of calcining 2h, take out after natural cooling and obtain N-TiO2Powder.
(2) N-TiO is prepared2/ GO granules：Measure 0.025g GO to pour in 100mL pure water, ultrasonic vibration makes its dispersion equal
It is even, then measure 0.475g N-TiO2In pouring GO dispersion liquids into, continue GO and N-TiO after ultrasound 1h2Mixed solution be transferred to
In the autoclave of inner liner polytetrafluoroethylene, 18h is reacted in 180 DEG C of environment, taken out after natural cooling, after lyophilization
To N-TiO2/ GO granules.
(3) area load N-TiO is prepared2The ultrafilter membrane of/GO：18g is weighed after polysulfones is dried and is added to 80g N- methyl
In pyrrolidone solution, shaking 5h in 50 DEG C of environment makes polysulfones fully dissolve, and adds 2g polyvinylpyrrolidones, continues to shake
0.5h is swung, 24h deaerations are stood in atmosphere is dried into casting solution.The thickness of coating device is adjusted to into 100 μm, in clean glass plate
On the casting solution for having configured uniformly is spread to into thin film, by be loaded with coat casting solution glass plate immersion pure water in, ultrafilter membrane meeting
Slowly come off from glass plate, obtained ultrafilter membrane is soaked into 24h in pure water, midway through changing a water.After taking-up is dried,
Obtain polysulfone membrane.Polysulfone membrane is laid in Suction filtration device, the N-TiO that 20mL concentration is 0.5mg/L is poured into2/ GO dispersion liquids, lead to
Cross evacuation and it is uniformly supported on film surface, area load N-TiO is obtained after drying2The ultrafilter membrane of/GO.
Area load N-TiO2The scanning electron microscope (SEM) of the ultrafilter membrane of/GO is as shown in Figure 1.
Light-catalysed concrete test procedure is as follows：The methylene blue of configuration 1mg/L, 3mg/L, 5mg/L, 7mg/L, 9mg/L
Solution, using wavelength the absorbance of above-mentioned solution is measured respectively for the ultraviolet-spectrophotometer of 665nm, and fitting forms methylene
Base indigo plant concentration-absorbance standard curve.
Take area load N-TiO manufactured in the present embodiment2The ultrafilter membrane of/GO, adds the methylene blue of the 50mg/L of 50mL
Solution, under different light sources (dark, ultraviolet light, sunlight), every 30min a sample is taken, after diluting 10 times per sub-sampling 1mL
Its absorbance is measured, so as to obtain the clearance of each time period methylene blue, as shown in Figure 2.
Embodiment 2：
The present embodiment is differed only in embodiment 1：
Butyl titanate and the volume ratio of dehydrated alcohol are 1 in solution A in S01:6, in solution B in dehydrated alcohol and solution A
The volume ratio of butyl titanate is 1：0.5, pure water is 1 with the volume ratio of butyl titanate:2, the volume ratio of glacial acetic acid and butyl titanate
For 1:4, carbamide is 1 with the mass ratio of butyl titanate:8, hydrochloric acid of the solution used by pH for 6mol/L is adjusted, the pH after regulation is
1.5。
Temperature when drying in S01 is 60 DEG C, and 500 DEG C of calcining 2h are warming up to the speed of 1 DEG C/min during calcining.
GO and N-TiO in S022The mass ratio of powder is 1:19, the hot environment is 150 DEG C, and the response time is 12h.
The mass percent of the polysulfones, N-Methyl pyrrolidone and polyvinylpyrrolidone is 15.6：84：0.4.
The thickness of the coating device is 200 μm.
The N-TiO2The concentration of/GO dispersion liquids is 0.5g/L, N-TiO2/ GO dispersion liquid volumes are 10mL.
Embodiment 3：
The present embodiment is differed only in embodiment 1：
Butyl titanate and the volume ratio of dehydrated alcohol are 1 in solution A in S01:5, in solution B in dehydrated alcohol and solution A
The volume ratio of butyl titanate is 1：0.8, pure water is 1 with the volume ratio of butyl titanate:3, the volume ratio of glacial acetic acid and butyl titanate
For 1:6, carbamide is 1 with the mass ratio of butyl titanate:15, hydrochloric acid of the solution used by pH for 6mol/L is adjusted, the pH after regulation is
2.2。
Temperature when drying in S01 is 150 DEG C, and 500 DEG C of calcining 2h are warming up to the speed of 3 DEG C/min during calcining.
GO and N-TiO in S022The mass ratio of powder is 1:19, the hot environment is 200 DEG C, and the response time is 20h.
The mass percent of the polysulfones, N-Methyl pyrrolidone and polyvinylpyrrolidone is 20：78：2.
The thickness of the coating device is 150 μm.
The N-TiO2The concentration of/GO dispersion liquids is 0.5g/L, N-TiO2/ GO dispersion liquid volumes are 40mL.
The above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of the photocatalysis ultrafiltration membrane material with visible light activity, it is characterised in that：Comprise the following steps：
S01, prepares N-TiO2Powder：Butyl titanate is dissolved in dehydrated alcohol and forms solution A；By dehydrated alcohol, pure water, urine
Element, glacial acetic acid uniformly mix and adjust pH formation solution Bs；It is stirred vigorously down, solution B is added dropwise in solution A, and continues
Stirring；Standing gel post-drying, grinding, calcining form N-TiO2Powder；
S02, prepares N-TiO2/ GO granules：Weigh graphene oxide GO to pour in appropriate pure water, ultrasonic vibration makes it be uniformly dispersed
GO dispersion liquids are obtained, then weighs appropriate N-TiO2Powder is poured in GO dispersion liquids, is continued GO and N-TiO after ultrasonic disperse2Mixing
Solution is transferred in autoclave, is reacted in hot environment, is taken out after natural cooling, and N-TiO is obtained after lyophilization2/
GO granules；
S03, prepares ultrafilter membrane；
S04, prepares area load N-TiO2The ultrafilter membrane of/GO：By N-TiO2/ GO granules make N-TiO2/ GO dispersion liquids, then will
Ultrafilter membrane is laid in Suction filtration device, pours N-TiO into2/ GO dispersion liquids, evacuation obtains area load N-TiO after drying2/GO
Ultrafilter membrane.
2. the preparation method of a kind of photocatalysis ultrafiltration membrane material with visible light activity according to claim 1, it is special
Levy and be：The preparation method of the ultrafilter membrane is comprised the following steps：Weigh the polysulfones after drying and be added to N-Methyl pyrrolidone
In solution, the concussion in 50 DEG C of environment makes polysulfones fully dissolve, and adds polyvinylpyrrolidone, continues to shake, and is being dried atmosphere
Middle standing and defoaming is enclosed into casting solution；The thickness of coating device is adjusted, it is on clean glass plate that the casting solution for having configured is uniform
Spread to thin film, by be loaded with coat casting solution glass plate immersion pure water in, ultrafilter membrane slowly comes off from glass plate, will be obtained
Ultrafilter membrane soaks at least 24h in pure water, and midway at least changes a water, after taking-up is dried, obtains polysulfone membrane.
3. the preparation method of a kind of photocatalysis ultrafiltration membrane material with visible light activity according to claim 1, it is special
Levy and be：Butyl titanate and the volume ratio of dehydrated alcohol are 1 in solution A in S01:(4～6), dehydrated alcohol and solution in solution B
The volume ratio of butyl titanate is 1 in A：(0.5～1), pure water is 1 with the volume ratio of butyl titanate:(2～3), glacial acetic acid and metatitanic acid
The volume ratio of butyl ester is 1:(4～6), carbamide is 1 with the mass ratio of butyl titanate:(8～20), adjust pH used by solution be
The hydrochloric acid of 6mol/L, the pH after regulation is 1.5～2.2.
4. the preparation method of a kind of photocatalysis ultrafiltration membrane material with visible light activity according to claim 1, it is special
Levy and be：The time that S01 is persistently stirred is at least 30min, temperature during drying be 60～150 DEG C, during calcining with 1～3 DEG C/
The speed of min is warming up to 500 DEG C of calcining at least 2h.
5. the preparation method of a kind of photocatalysis ultrafiltration membrane material with visible light activity according to claim 1, it is special
Levy and be：GO and N-TiO in S022The mass ratio of powder is 1:19, the hot environment is 150～200 DEG C, and the response time is
12～20h.
6. the preparation method of a kind of photocatalysis ultrafiltration membrane material with visible light activity according to claim 1, it is special
Levy and be：The inner lining material of the autoclave is politef.
7. the preparation method of a kind of photocatalysis ultrafiltration membrane material with visible light activity according to claim 2, it is special
Levy and be：The mass percent of the polysulfones, N-Methyl pyrrolidone and polyvinylpyrrolidone is (15.6～20%)：(78
～84%)：(0.4～2%).
8. the preparation method of a kind of photocatalysis ultrafiltration membrane material with visible light activity according to claim 2, it is special
Levy and be：The thickness adjustable extent of the coating device is 100～200 μm.
9. the preparation method of a kind of photocatalysis ultrafiltration membrane material with visible light activity according to claim 1, it is special
Levy and be：The N-TiO2The concentration of/GO dispersion liquids is 0.5g/L, N-TiO2/ GO dispersion liquid volumes are 10～40mL.
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