CN108640214A - One kind having photocatalysis performance seperation film and preparation method thereof - Google Patents
One kind having photocatalysis performance seperation film and preparation method thereof Download PDFInfo
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- CN108640214A CN108640214A CN201810552359.8A CN201810552359A CN108640214A CN 108640214 A CN108640214 A CN 108640214A CN 201810552359 A CN201810552359 A CN 201810552359A CN 108640214 A CN108640214 A CN 108640214A
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- 238000007146 photocatalysis Methods 0.000 title claims abstract description 39
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 238000001338 self-assembly Methods 0.000 claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 12
- 210000004379 membrane Anatomy 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002356 single layer Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 8
- 210000002469 basement membrane Anatomy 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- -1 oxygen Graphite alkene Chemical class 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 229920002301 cellulose acetate Polymers 0.000 claims 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000001476 gene delivery Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- B01J21/18—Carbon
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
Photocatalysis performance seperation film and its manufacturing method being prepared using LBL self-assembly the invention discloses a kind of, this method prepares photocatalysis separation film using ultraviolet-aided LBL self-assembly method, prepares TiO first2Colloidal sol, graphene oxide (GO) aqueous solution, using LBL self-assembly method according to TiO2The sequence of GO is by TiO2Organic ultrafiltration membranes surface is loaded to layer by layer with GO, then again to the TiO of load2Ultraviolet light processing is carried out in ethanol solution with GO layers, forms it into GO TiO2Assembly.
Description
Technical field
The invention belongs to catalysis material technical field and technical field of membrane separation, and in particular to a kind of using layer by layer from group
The method that dress prepares photocatalysis performance seperation film.
Background technology
LBL self-assembly is simple, the multi-functional surface modification method of one kind that the nineties in last century, fast development was got up.
It is using substrate from a kind of technology complementary between alternating sorbent in two or more polymer solutions and other multivalence substances,
There is functional film because it can be generated in the surface of solids, in bio-sensing, drug, gene delivery, regenerative medicine, group weaver
Application in journey and Bionic medicine it has been recognised that, layer-by-layer is in the past few decades, because it is at grouping
At concern that is controllable, simple, receiving with Modulatory character researcher.
Since finding that semi-conducting material has photocatalysis performance, photocatalysis is widely used in having in degradation air and water
Machine pollutant.Catalyst generates electron transition under ultraviolet or visible light photon excitation, and being formed has very high redox
The hole of current potential.The electronics on the substance of absorption is captured in hole, and generating has very strongly active free radical, to organic pollutant
It degrades.Photocatalysis can normal temperature and pressure, do not consume other materials under conditions of, using solar energy degradation of contaminant, to
Efficiently solve problem of environmental pollution.Although photochemical catalytic oxidation process organic pollution achieves certain effect, simultaneously
There is also some shortcomings, the popularization and application of the technique in production are constrained.During concrete application, due to suspension light transmission
Property is poor, light efficiency is low, complex process, cost are excessively high, powder TiO2Catalyst is easily poisoned, and is not easy as traditional separation method institute
Recycling (such as flocculates, precipitates), and recycling rate of waterused is low, and discharge liquor is also easy to produce secondary pollution problems.In addition, most catalyst are only
It can be excited by the shorter ultraviolet light of wavelength, and ultraviolet source then has the defects of high energy consumption, short life；Photo-generate electron-hole simultaneously
The easy compound quantum efficiency for causing light-catalyzed reaction is generally relatively low.
Recent study finds that the recombination energies such as photochemical catalyst and activated carbon, fullerene and graphene increase substantially catalyst
Photocatalysis performance, and it is compound particularly noticeable with graphene.Graphene (Graphene) is one be made of carbon atom
Class new material is the single layer two-dimension plane structure by carbon atom by regular hexagon close-packed arrays at honeycomb crystal lattice, is had very big
Specific surface area and excellent electronic conductivity.Graphene is constituted NEW TYPE OF COMPOSITE photochemical catalyst with semiconductors coupling obviously to carry
High photocatalysis reaction efficiency.Movement velocity of the movement velocity of the electronics of graphene considerably beyond electronics in general conductor, because
It can be improved the mobility of semiconductor light induced electron by this with semiconductors coupling, make photo-generate electron-hole to being easily isolated, from
And improve photocatalysis efficiency.In addition, the larger specific surface area of graphene can improve suction of the degradation of contaminant in catalyst surface
Attached ability promotes the photocatalytic degradation of pollutant to react.TiO2With graphene and its oxide (GO) compound system cheap and easy to get
The absorption region of light can be extended to visible region by the composite material obtained, and effectively improve TiO2Photocatalysis efficiency.
Photocatalysis composite separating film is that occur based on support type photocatalytic membrane reactor, is to bear photochemical catalyst
It carries or is embedded in seperation film, to realize the modification to film, realized using the highlight catalytic active and high-hydrophilic of catalyst
The raising of the processing and film surface antifouling property of Organic substance in water.When with photon irradiation semiconductor catalyst, in semiconductor
It is right that inside forms the hole electronics (e) (hv+)；With molecular oxygen and water serial reaction can occur for electronics respectively with hole, generate strong
Oxidation operation can be H by the hydroxyl radical free radical (OH) of oxidisability, OH2O、CO2.Load TiO2Afterwards, the electronics of formation will
Ti4+It is reduced to Ti3+, Hole oxidation O2-For O2, such film surface will produce a series of Lacking oxygens, and hydrone occupies vacancy, and shape
At hydroxyl so that film surface has Superhydrophilic；TiO simultaneously2The physical properties such as the hydrophily of itself, and its to organic near film
The photocatalytic degradation of object is but also film contamination resistance enhances.On the other hand, which preferably solves TiO2Recycling ask
Topic, and reaction substrate, intermediate product and final product are carried out by online separation in real time by UF membrane effect, in retention pollutant
While matter, the specific aim and water process outlet effect that photocatalysis degrades to specific pollutants are also enhanced；The coupling of two kinds of technologies
Conjunction can also generate a series of synergistic effects so that treatment effect is more obvious.
Invention content
Aiming at the deficiencies in the prior art, present invention offer is a kind of to prepare photocatalysis to the present invention using LBL self-assembly
The method of performance seperation film, the composite photocatalysis membrane with photocatalysis and membrane separating property that preparation structure is simple, practical and convenient
Method.
The present invention, which provides one kind, having photocatalysis performance seperation film, and the seperation film is by TiO2Colloidal sol, graphene oxide GO water
Solution and organic ultrafiltration membranes composition.
Preferred organic ultrafiltration membranes of the present invention are polysulfones, polyether sulfone, polytetrafluoroethylene (PTFE), Kynoar acetic acid fibre
Dimension plain any one of class or polyvinyl chloride.
Preparation method the present invention also provides the seperation film is：
(1) TiO is prepared2Colloidal sol：Configure A liquid：42mL absolute ethyl alcohols are measured, in the most slow mixing speed stirring of magnetic stirring apparatus
Lower addition 24mL butyl titanates and 4.5mL acetic acid keep the mixing speed to stir 10 minutes at room temperature；Configure B liquid：With graduated cylinder amount
It takes 42mL absolute ethyl alcohols to take 4.5mL distilled water to be placed in the beaker with pipette again, a drop concentrated hydrochloric acid, stirring is added while stirring
Uniformly, keep that A liquid mixing speeds are constant that B liquid is slowly added in A liquid, then stirring has just obtained uniform, transparent for 20 minutes
Faint yellow TiO2Colloidal sol；
(2) graphene oxide solution is configured：Graphene oxide is made using Hummers methods using graphite as raw material；Claim
Graphene oxide powder is taken, is added in deionized water, sonic oscillation 30 minutes is allowed to fully dispersed, obtains graphene oxide water
Solution；
(3) organic ultrafiltration membranes are first immersed TiO prepared by step (1) by the method for using LBL self-assembly2In colloidal sol
0.5-3 minutes, take out it is 3-6 hours dry in 30-100 DEG C, repeat this step it is primary more than；Above-mentioned complex sol will be soaked with
Basement membrane is placed at 170-190 DEG C hydro-thermal reaction 1-3 hours, and the TiO of single layer self assembly is made2Laminated film；
(4) step (3) is made to the TiO of single layer self assembly2It is molten that laminated film immerses graphene oxide prepared by step (2)
In liquid, impregnate 30-60 minutes, it is 3-6 hours dry in 30-100 DEG C after taking-up, GO-TiO is made2Photocatalysis performance composite membrane；
(5) GO-TiO is made in step (4)2Photocatalysis performance composite membrane is immersed in 70% alcoholic solution, and in purple
It is irradiated 15 minutes, partial reduction GO under outside line, to establish TiO2Strong combination between GO finally dries it at 100 DEG C
It is 2 hours dry, the seperation film with photocatalysis performance is made by LBL self-assembly method.
Step (3) described in preferred the method for the present invention is first immersed organic ultrafiltration membranes using the method for LBL self-assembly
TiO prepared by step (1)21 minute in colloidal sol, take out it is 5 hours dry in 60 DEG C, repeat this step it is primary more than；It will be soaked with
The basement membrane of above-mentioned complex sol is placed in hydro-thermal reaction 2 hours at 180 DEG C, and the TiO of single layer self assembly is made2Laminated film.
The TiO that step (3) is made to single layer self assembly described in preferred the method for the present invention step (4)2Laminated film soaks
In the graphene oxide solution for entering step (2) preparation, impregnate 30 minutes, it is 5 hours dry at 60 DEG C after taking-up, GO- is made
TiO2 photocatalysis performance composite membranes.
Preferred the method for the present invention step (5) described ultraviolet light is prepared by 120W ultraviolet lamps.
A concentration of 1-2g/L of graphene oxide solution described in preferred the method for the present invention step (5).
Beneficial effects of the present invention：
1.GO-TiO2LBL self-assembly is carried on the composite separating film constituted on basement membrane, makes photocatalysis and UF membrane coupling
It closes, the composite membrane made can carry out photocatalytic degradation to organic matter under visible light, while can be carried out again to the suspended matter in waste water
It efficiently separates, the purification efficiency of waste water can be greatly improved, while reducing operating cost.
2. having many advantages, such as that simple for process, of low cost, reaction condition is mild using layer-by-layer.
3. the composite separating film of LBL self-assembly is immersed into alcoholic solution and is irradiated under ultraviolet light, partial reduction GO, from
And make GO-TiO2It is properer, closely compound between laminated film.
4.TiO2The absorption region of light can be extended to visible light with composite membrane made from graphene oxide layer by layer self assembly
Area effectively improves TiO2Photocatalysis efficiency.
5.GO-TiO2Load, substantially increase the hydrophily of ultrafiltration membranes so that membrane flux is significantly improved.
Description of the drawings
Fig. 1：GO-TiO is obtained for the embodiment of the present invention 12The scanning electron of photocatalysis separation film after LBL self-assembly is aobvious
Micro mirror figure；
Fig. 2：For GO-TiO in the embodiment of the present invention 12Film is respectively to methylene blue (MB) at dark, UV and solar radiation
Degradation rate.
Specific implementation mode
With reference to example is applied, the present invention will be further described in detail, but the present invention is not restricted to following embodiment.
Embodiment 1：The seperation film with photocatalysis performance is prepared, is included the following steps：
(1) TiO is prepared2Colloidal sol：Configure A liquid：42mL absolute ethyl alcohols are measured, in the most slow mixing speed stirring of magnetic stirring apparatus
Lower addition 24mL butyl titanates and 4.5mL acetic acid keep the mixing speed to stir 10 minutes at room temperature；Configure B liquid：With graduated cylinder amount
It takes 42mL absolute ethyl alcohols to take 4.5mL distilled water to be placed in the beaker with pipette again, a drop concentrated hydrochloric acid, stirring is added while stirring
Uniformly, keep that A liquid mixing speeds are constant that B liquid is slowly added in A liquid, then stirring has just obtained uniform, transparent for 20 minutes
Faint yellow TiO2Colloidal sol；
(2) configuration graphene oxide solution graphene oxide is made using Hummers methods using graphite as raw material；Claim
0.1g graphene oxide powders are taken, are added in 100ml deionized waters, sonic oscillation 30 minutes is allowed to fully dispersed, obtains
The graphene oxide water solution of 1g/L；
(3) organic ultrafiltration membranes are first immersed TiO prepared by step (1) by the method for using LBL self-assembly21 point in colloidal sol
Clock, take out it is 5 hours dry in 60 DEG C, repeat this step it is primary more than；The basement membrane for being soaked with above-mentioned complex sol is placed in 180 DEG C
The TiO of single layer self assembly is made in lower hydro-thermal reaction 2 hours2Laminated film；
(4) step (3) is made to the TiO of single layer self assembly2It is molten that laminated film immerses graphene oxide prepared by step (2)
In liquid, impregnate 30 minutes, it is 5 hours dry in 60 DEG C after taking-up, GO-TiO is made2Photocatalysis performance composite membrane；
(5) GO-TiO is made in step (4)2Photocatalysis performance composite membrane is immersed in 70% alcoholic solution, and
It is irradiated 15 minutes, partial reduction GO under 120W ultraviolet lamps, to establish TiO2Strong combination between GO, finally by it in 100
It is dried 2 hours at DEG C, the seperation film with photocatalysis performance is made by LBL self-assembly method.
Embodiment 2：The seperation film with photocatalysis performance is prepared, is included the following steps：
(1) TiO is prepared2Colloidal sol：Configure A liquid：42mL absolute ethyl alcohols are measured, in the most slow mixing speed stirring of magnetic stirring apparatus
Lower addition 24mL butyl titanates and 4.5mL acetic acid keep the mixing speed to stir 10 minutes at room temperature；Configure B liquid：With graduated cylinder amount
It takes 42mL absolute ethyl alcohols to take 4.5mL distilled water to be placed in the beaker with pipette again, a drop concentrated hydrochloric acid, stirring is added while stirring
Uniformly, keep that A liquid mixing speeds are constant that B liquid is slowly added in A liquid, then stirring has just obtained uniform, transparent for 20 minutes
Faint yellow TiO2Colloidal sol；
(2) configuration graphene oxide solution graphene oxide is made using Hummers methods using graphite as raw material；Claim
0.2g graphene oxide powders are taken, are added in 100ml deionized waters, sonic oscillation 30 minutes is allowed to fully dispersed, obtains
The graphene oxide water solution of 2g/L；
(3) organic ultrafiltration membranes are first immersed TiO prepared by step (1) by the method for using LBL self-assembly21 point in colloidal sol
Clock, take out it is 5 hours dry in 100 DEG C, repeat this step it is primary more than；The basement membrane for being soaked with above-mentioned complex sol is placed in 180
The TiO of single layer self assembly is made in hydro-thermal reaction 2 hours at DEG C2Laminated film；
(4) step (3) is made to the TiO of single layer self assembly2It is molten that laminated film immerses graphene oxide prepared by step (2)
In liquid, impregnate 30 minutes, it is 5 hours dry in 100 DEG C after taking-up, GO-TiO is made2Photocatalysis performance composite membrane；
(5) GO-TiO is made in step (4)2Photocatalysis performance composite membrane is immersed in 70% alcoholic solution, and
It is irradiated 15 minutes, partial reduction GO under 120W ultraviolet lamps, to establish TiO2Strong combination between GO, finally by it in 100
It is dried 2 hours at DEG C, the seperation film with photocatalysis performance is made by LBL self-assembly method.
Those skilled in the art can carry out seperation film with photocatalysis performance of the present invention and preparation method thereof
Various modification and variations, the protection content that can be considered as the equivalent present invention without departing from the spirit and scope of the present invention, i.e., originally
Including the modification and variations of invention also comprising these routines.
Claims (7)
1. one kind having photocatalysis performance seperation film, which is characterized in that the seperation film is by TiO2Colloidal sol, graphene oxide GO are water-soluble
Liquid and organic ultrafiltration membranes composition.
2. seperation film according to claim 1, which is characterized in that organic ultrafiltration membranes are polysulfones, polyether sulfone, poly- four
Any one of vinyl fluoride, Kynoar cellulose acetate class or polyvinyl chloride.
3. the preparation method of seperation film according to claim 1, which is characterized in that this method is：
(1) TiO is prepared2Colloidal sol：Configure A liquid：42mL absolute ethyl alcohols are measured, are added under the most slow mixing speed stirring of magnetic stirring apparatus
Enter 24mL butyl titanates and 4.5mL acetic acid, the mixing speed is kept to stir at room temperature 10 minutes；Configure B liquid：It is measured with graduated cylinder
42mL absolute ethyl alcohols take 4.5mL distilled water to be placed in the beaker with pipette again, and a drop concentrated hydrochloric acid is added while stirring, and stirring is equal
It is even, keep that A liquid mixing speeds are constant that B liquid is slowly added in A liquid, then stirring has just obtained uniform, transparent light for 20 minutes
Yellow Ti02 colloidal sols；
(2) graphene oxide solution is configured：Graphene oxide is made using Hummers methods using graphite as raw material；Weigh oxygen
Graphite alkene powder, adds in deionized water, and sonic oscillation 30 minutes is allowed to fully dispersed, obtains graphene oxide water solution；
(3) organic ultrafiltration membranes are first immersed TiO prepared by step (1) by the method for using LBL self-assembly20.5-3 points in colloidal sol
Clock, take out it is 3-6 hours dry in 30-100 DEG C, repeat this step it is primary more than；The basement membrane for being soaked with above-mentioned complex sol is set
Hydro-thermal reaction 1-3 hours at 170-190 DEG C, the TiO of single layer self assembly is made2Laminated film；
(4) step (3) is made to the TiO of single layer self assembly2Laminated film immerses in graphene oxide solution prepared by step (2),
It impregnates 30-60 minutes, it is 3-6 hours dry in 30-100 DEG C after taking-up, GO-TiO is made2Photocatalysis performance composite membrane；
(5) GO-TiO is made in step (4)2Photocatalysis performance composite membrane is immersed in 70% alcoholic solution, and under ultraviolet light
Irradiation 15 minutes, partial reduction GO, to establish TiO2It is small finally to be dried 2 by the strong combination between GO at 100 DEG C for it
When, the seperation film with photocatalysis performance is made by LBL self-assembly method.
4. the preparation method of seperation film according to claim 3, which is characterized in that the step (3) described in this method uses
Organic ultrafiltration membranes are first immersed TiO prepared by step (1) by the method for LBL self-assembly21 minute in colloidal sol, take out dry in 60 DEG C
Dry 5 hours, repeat this step it is primary more than；It is small that the basement membrane for being soaked with above-mentioned complex sol is placed in hydro-thermal reaction 2 at 180 DEG C
When, the TiO of single layer self assembly is made2Laminated film.
5. the preparation method of seperation film according to claim 3, which is characterized in that will walk described in this method step (4)
Suddenly the TiO of single layer self assembly is made in (3)2Laminated film immerses in graphene oxide solution prepared by step (2), impregnates 30 points
Clock, it is 5 hours dry at 60 DEG C after taking-up, GO-TiO is made2Photocatalysis performance composite membrane.
6. the preparation method of seperation film according to claim 3, which is characterized in that this method step (5) described ultraviolet light
It is to be prepared by 120W ultraviolet lamps.
7. the preparation method of seperation film according to claim 3, which is characterized in that the oxidation described in this method step (5)
A concentration of 1-2g/L of graphene solution.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772454A (en) * | 2019-02-28 | 2019-05-21 | 清华大学深圳研究生院 | Photocatalysis membrana and preparation method thereof and degradation application to disinfection by-products formation potential |
| CN110302683A (en) * | 2019-07-09 | 2019-10-08 | 浙江海纳环保科技有限公司 | The preparation method of new anti-pollution reverse osmosis membrane based on molecular channel structural adjustment |
| CN112495361A (en) * | 2020-12-22 | 2021-03-16 | 深圳笨鸟冰虫环保科技有限公司 | Environment-friendly efficient composite photocatalyst |
| CN112604678A (en) * | 2020-12-17 | 2021-04-06 | 中国科学院过程工程研究所 | Photocatalytic composite particle and preparation method and application thereof |
| CN113694915A (en) * | 2021-08-25 | 2021-11-26 | 特灵空调***(中国)有限公司 | Preparation method of titanium dioxide/graphene composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947441A (en) * | 2010-09-07 | 2011-01-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene composite photocatalyst, preparation method and application thereof |
| KR20130113770A (en) * | 2012-04-06 | 2013-10-16 | 한국과학기술원 | Hydrid photocatalyst nanoparticle with improved photoactivity and method for preparing the same |
| CN106732504A (en) * | 2016-12-26 | 2017-05-31 | 成都理工大学 | The preparation method and application of Graphene optically catalytic TiO 2 composite |
-
2018
- 2018-05-31 CN CN201810552359.8A patent/CN108640214A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947441A (en) * | 2010-09-07 | 2011-01-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene composite photocatalyst, preparation method and application thereof |
| KR20130113770A (en) * | 2012-04-06 | 2013-10-16 | 한국과학기술원 | Hydrid photocatalyst nanoparticle with improved photoactivity and method for preparing the same |
| CN106732504A (en) * | 2016-12-26 | 2017-05-31 | 成都理工大学 | The preparation method and application of Graphene optically catalytic TiO 2 composite |
Non-Patent Citations (1)
| Title |
|---|
| 段文慧: "光催化复合分离膜降解持久性有机污染物", 《江苏理工学院学报; 2016年2期》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772454A (en) * | 2019-02-28 | 2019-05-21 | 清华大学深圳研究生院 | Photocatalysis membrana and preparation method thereof and degradation application to disinfection by-products formation potential |
| CN109772454B (en) * | 2019-02-28 | 2021-07-27 | 清华大学深圳研究生院 | Photocatalytic film, preparation method thereof and application of photocatalytic film in degradation of disinfection byproduct precursor |
| CN110302683A (en) * | 2019-07-09 | 2019-10-08 | 浙江海纳环保科技有限公司 | The preparation method of new anti-pollution reverse osmosis membrane based on molecular channel structural adjustment |
| CN112604678A (en) * | 2020-12-17 | 2021-04-06 | 中国科学院过程工程研究所 | Photocatalytic composite particle and preparation method and application thereof |
| CN112495361A (en) * | 2020-12-22 | 2021-03-16 | 深圳笨鸟冰虫环保科技有限公司 | Environment-friendly efficient composite photocatalyst |
| CN113694915A (en) * | 2021-08-25 | 2021-11-26 | 特灵空调***(中国)有限公司 | Preparation method of titanium dioxide/graphene composite material |
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