CN109453679A - A kind of preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane - Google Patents
A kind of preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane Download PDFInfo
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- CN109453679A CN109453679A CN201811275923.2A CN201811275923A CN109453679A CN 109453679 A CN109453679 A CN 109453679A CN 201811275923 A CN201811275923 A CN 201811275923A CN 109453679 A CN109453679 A CN 109453679A
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- graphene oxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 title claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- 230000000802 nitrating effect Effects 0.000 title claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 235000019441 ethanol Nutrition 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000006228 supernatant Substances 0.000 claims 1
- 210000002700 urine Anatomy 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 12
- 230000010148 water-pollination Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000003618 dip coating Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 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 9
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000004907 flux Effects 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
Abstract
The invention belongs to catalysis material technical fields, and in particular to a kind of preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane, this method prepare TiO first2Then colloidal sol, graphene oxide prepare nitrating graphene oxide titanium dioxide blending dispersion liquid by nitrogen source of urea.Ultrafiltration membrane surface is modified using dip-coating method, the novel photocatalysis film of nitrating graphene oxide composite titania material is made in conjunction with hydro-thermal method, finally film is handled with ethyl alcohol and ultraviolet light, make stable bond between catalyst and film, nitrating graphene oxide titanium dioxide composite hyperfiltration membrane is made.Composite hyperfiltration membrane prepared by the present invention can all be increased using longer wavelengths of visible light come degradable organic pollutant, hydrophily and resistance tocrocking.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of nitrating graphene oxide titanium dioxide is compound super
The preparation method of filter membrane.
Background technique
Membrane separation technique is a kind of separated from contaminants with development potential, purification techniques, it is efficiently convenient, and without secondary
Pollution.But during water process, ultrafiltration membrane there are water fluxes it is low, rejection is low, anti-pollution is poor the problems such as.Therefore, it seeks
The method for looking for degradation of contaminant is very important, and the pollutant that can be effectively reduced in water in this way and will not reduce infiltration
Rate.Photocatalysis technology as oxidation technology is considered as that a kind of low cost and sustainable method carry out decomposing organic pollutant,
Luminous energy is converted into chemical energy by it, and photochemical catalyst can generate oneself of strong oxidizing property under conditions of ultraviolet or visible light shines
By base, major part can be decomposed to human body and the harmful organic substance of environment and part inorganic substances, and ultimately generate H2O、CO2
Equal inorganic molecules, are avoided that the formation of the wasting of resources and secondary pollution.In this case, UF membrane and light-catalysed coupling
It is the ideal method for reducing fouling membrane and improving film properties.
Photochemical catalyst can be fixed in film, and method is to embed them into film or coat on the surface.By the way that light is urged
Agent, which is added in curtain coating coating solution, realizes insertion.During film is formed, photochemical catalyst is distributed in film.Such light
Catalytic membrane improves the performance (water penetration, hydrophily, pollution resistance) of film.However, it is difficult to stimulate internal photochemical catalyst, and this
Photocatalysis membrana shows weak photocatalysis performance.It is this by physically or chemically combining photochemical catalyst grafting on the surface of the film
Photocatalysis membrana shows excellent photocatalysis performance.Due to the raising of photocatalysis performance, film surface organic matter is reduced, fouling membrane
It decreases.
TiO2Photochemical catalyst is due to having many advantages, such as that inexpensive, non-toxic, photochemical stability is strong and does not bring secondary pollution
It is widely used in water treatment field.TiO2Organic pollutant (such as organic dyestuff, toxic micropollutants, oil) can be divided completely
Solution is at H2O、CO2.It has been found that by TiO2Nano particle, which is integrated in water filter membrane, can enhance its flux, pollutant removal and anti-pollution
Metachromia.However, TiO is used alone2The photocatalytic activity of manufactured photocatalysis membrana in the sunlight is very low.This is because TiO2Tool
Have higher band-gap energy (3.2eV), therefore the electron hole of photocatalysis can only be less than 387nm by wavelength and energy is higher than
The ultraviolet photoactivation of 3.2eV, so the visible light with longer wavelength cannot excite TiO2Photocatalytic activity.In addition, photoproduction
The recombination rate of electron-hole pair is higher, and then the activity that will lead to photochemical catalyst reduces.These problems seriously hinder TiO2Make
For the extensive use of photochemical catalyst.
Additive of the graphene oxide usually as enhancing polymer composites mechanical property.Correlative study shows oxygen
Graphite alkene contains a large amount of functional group, huge specific surface area makes graphene oxide become a kind of ideal adsorbent material,
Perforated membrane based on graphene oxide shows good separative efficiency and adsorption capacity, as dye molecule can by hydrogen bond,
Electrostatic attraction effect is adsorbed on graphene oxide.The functional groups such as carboxyl and hydroxyl in graphene oxide make it as addition
When agent, the hydrophily of film can be improved.The outstanding electronics transfer performance of graphene oxide (GO) is considered as expanding TiO2Light is rung
Answer the ideal nano material of range.GO can be used as TiO2The electron transport body of nano particle, therefore electronics-can be significantly improved
The service life in hole pair.Therefore, TiO2/ GO nanocomposite has broader optical response range, and photocatalysis is imitated under visible light
Rate improves.Nitrating graphene oxide has good electric conductivity, hydrophily, thermal stability and machine as the derivative of graphene
The properties such as tool intensity can greatly improve the dispersibility and hydrophily of titanium dioxide as carrier.
Summary of the invention
Invention broadly provides a kind of preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane,.Its skill
Art scheme is as follows:
A kind of preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane, comprising the following steps:
(1) by graphite in KMnO4、H2SO4And NaNO3Mixture in aoxidize, filter mixture to collect solid particle,
The solid in deionized water is washed to removing chemical residue by settling flux and centrifuge cycle, using ultrasonic cleaner by GO
Particle suspension liquid ultrasonication is, at GO nanometer sheet, to remove any unpeeled stone finally by centrifugation for graphite oxide removing
The suspension is freeze-dried to obtain pure GO nanometer sheet suspension and obtains GO powder by black residue；
(2) using urea as nitrogen source, by ultrasonic treatment in deionized water, then weighed urea and GO powder are dispersed
Dispersion liquid is blended with GO in urea and is slowly added to TiO2In colloidal sol, continue to stir after adding, it is still aging, obtain nitrogen oxidation graphite
Alkene titanium dioxide blending dispersion liquid；
(3) commercially available ultrafiltration membrane is used, ultrafiltration membrane is immersed in nitrogen oxidation graphene titanium dioxide with the mode of Best-Effort request
Titanium is blended in dispersion liquid, obtains modified ultrafiltration membrane, then dries in an oven, then obtained film is put into equipped with ethanol solution
Autoclave in, autoclave is put in vacuum oven, finally film is handled with ethyl alcohol and ultraviolet light, makes dispersion liquid and film
Between stable bond, be made nitrating graphene oxide titanium dioxide composite hyperfiltration membrane.
Preferably, the mass ratio of GO powder and urea is 10:1 in step (2).
Preferably, dispersion liquid and TiO are blended in step (2)2The volume ratio of colloidal sol is 1:1-2.
Preferably, TiO described in step (2)2Colloidal sol is made by sol-gal process, it is specific the preparation method is as follows:
Configuration A liquid: it measures dehydrated alcohol and is added to the container, butyl titanate and acetic acid are added while stirring, keeps at room temperature
Stirring 5-15 minutes；
Configuration B liquid: it measures dehydrated alcohol and is placed in container, then remove ionized water and be placed in the container, be added while stirring
Concentrated hydrochloric acid makes PH=2~3, stirs evenly；
It keeps A liquid mixing speed is constant B liquid is added in A liquid, then stirs to get uniform, transparent faint yellow colloidal sol,
For TiO2Colloidal sol.
Preferably, the heating condition of step (3) mesohigh kettle is 115-125 DEG C, and autoclave is in a vacuum drying oven
Time is 18h.
Preferably, the material of ultrafiltration membrane described in step (3) is polysulfones, polyether sulfone, polytetrafluoroethylene (PTFE), Kynoar vinegar
Any one of acid cellulose class and polyvinyl chloride.
Preferably, the built-in ballasts ultraviolet lamp that ultraviolet light described in step (3) is 120 watts.
Using the above scheme, the invention has the following advantages that
The present invention makes the catalysis of film surface by the way that nitrogen oxidation graphene titanium dioxide optical catalyst to be grafted on to the surface of film
Dosage is more, and specific surface area of catalyst is big, which shows excellent photocatalysis performance, and carries out using visible light
Photocatalytic degradation.Due to the raising of photocatalysis performance, film surface organic matter is reduced, so that the water contact angle of ultrafiltration membrane obviously drops
It is low, improve the resistance tocrocking of film.
Detailed description of the invention
Fig. 1 is that embodiment 1 obtains the scanning electron microscope diagram of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane；
Fig. 2 is nitrating graphene oxide titanium dioxide composite hyperfiltration membrane in embodiment 1 respectively in dark, ultraviolet and day illumination
Penetrate the lower degradation efficiency figure to methylene blue (MB).
Specific embodiment
Experimental method in following embodiment is conventional method unless otherwise required, related experiment reagent and material
Material is conventional biochemical reagent and material unless otherwise required.
Embodiment 1
The nitrating graphene oxide titanium dioxide composite hyperfiltration membrane of the present embodiment the preparation method is as follows:
(1) GO nanometer sheet is synthesized by graphite modified Hummers method.Synthesis process includes by graphite in KMnO4, H2SO4With
NaNO3Mixture in aoxidize, filter mixture to collect solid particle (i.e. graphite oxide), pass through settling flux three times and centrifugation
Solid in circulation washing deionized water is to removing chemical residue, using ultrasonic cleaner by GO particle suspension liquid ultrasonic wave
Processing is, at GO nanometer sheet, it is pure to obtain to remove any unpeeled graphite residue finally by centrifugation for graphite oxide removing
The suspension is freeze-dried and obtains GO powder by GO nanometer sheet suspension.
(2) it configures A liquid: measuring 14mL dehydrated alcohol with graduated cylinder and be added in beaker, in the most slow mixing speed of magnetic stirring apparatus
It is added with stirring 8mL butyl titanate and 1.5mL acetic acid, the mixing speed is kept to stir at room temperature 10 minutes.Configure B liquid: dosage
Cylinder measures 14mL dehydrated alcohol and is placed in a beaker, then takes 1.5mL deionized water to be placed in the beaker with pipette, while stirring plus
Enter concentrated hydrochloric acid, make PH=2~3, stirs evenly.It keeps that A liquid mixing speed is constant that B liquid is slowly added in A liquid, then stirs 30
Minute has just obtained uniform, transparent faint yellow colloidal sol.
(3) using urea as nitrogen source, 5mg urea and 0.05gGO powder are dispersed in 50mL deionized water by being ultrasonically treated
Middle 1h.Then dispersion liquid is blended with GO in urea and is slowly added to 50mLTiO2In colloidal sol, continues to stir 30min after adding, stand
2h ageing, obtains nitrating graphene oxide titanium dioxide blending dispersion liquid.
(4) commercially available PVDF ultrafiltration (UF) film is used, with the mode modified PVDF membrane of Best-Effort request, dries 30 in an oven
Minute.Then obtained film is put into 100mL equipped in the Teflon stainless steel autoclave of ethanol solution, reaction kettle is put into
18h in 120 ° of vacuum ovens, autoclave are cooled to room temperature, and are finally handled with ethyl alcohol and ultraviolet light film, make to change
Property agent and film between stable bond, be made NGT/PVDF film.
(5) calculated in the cross-flow devices of laboratory using ultraviolet specrophotometer NGT/PVDF film dark, ultraviolet and
To the degradation efficiency of methylene blue (MB) under solar radiation, as shown in Figure 2.As shown in Figure 2, under dark surrounds, Compound Ultrafiltration
Film is 17% or so to the degradation rate of methylene blue；Under solar radiation, composite hyperfiltration membrane is to the degradation rate of methylene blue
73% or so；Under ultraviolet light, composite hyperfiltration membrane is 80% or so to the degradation rate of methylene blue.
Embodiment 2
(1) GO nanometer sheet is synthesized by graphite modified Hummers method.Synthesis process includes by graphite in KMnO4, H2SO4With
NaNO3Mixture in aoxidize, filter mixture to collect solid particle (i.e. graphite oxide), pass through settling flux three times and centrifugation
Solid in circulation washing deionized water is to removing chemical residue, using ultrasonic cleaner by GO particle suspension liquid ultrasonic wave
Processing is, at GO nanometer sheet, it is pure to obtain to remove any unpeeled graphite residue finally by centrifugation for graphite oxide removing
The suspension is freeze-dried and obtains GO powder by GO nanometer sheet suspension.
(2) it configures A liquid: measuring 14mL dehydrated alcohol with graduated cylinder and be added in beaker, in the most slow mixing speed of magnetic stirring apparatus
It is added with stirring 8mL butyl titanate and 1.5mL acetic acid, the mixing speed is kept to stir at room temperature 10 minutes.Configure B liquid: dosage
Cylinder measures 14mL dehydrated alcohol and is placed in a beaker, then takes 1.5mL deionized water to be placed in the beaker with pipette, while stirring plus
Enter concentrated hydrochloric acid, make PH=2~3, stirs evenly.It keeps that A liquid mixing speed is constant that B liquid is slowly added in A liquid, then stirs 30
Minute has just obtained uniform, transparent faint yellow colloidal sol.
(3) using urea as nitrogen source, 5mg urea and 0.05gGO powder are dispersed in 50mL deionized water by being ultrasonically treated
Middle 1h.Then dispersion liquid is blended with GO in urea and is slowly added to 100mLTiO2In colloidal sol, continues to stir 30min after adding, stand
2h ageing, obtains nitrating graphene oxide titanium dioxide blending dispersion liquid.
(4) commercially available polysulfones ultrafiltration (UF) film is used, with the mode modified polysulfone film of Best-Effort request, dries 30 in an oven
Minute.Then obtained film is put into 100mL equipped in the Teflon stainless steel autoclave of ethanol solution, reaction kettle is put into
18h in 120 ° of vacuum ovens, autoclave are cooled to room temperature, and are finally handled with ethyl alcohol and ultraviolet light film, make to change
Property agent and film between stable bond, be made NGT/ PS membrane.
Wherein, the material of ultrafiltration membrane can also be polyether sulfone, polytetrafluoroethylene (PTFE), Kynoar cellulose acetate class or poly-
Vinyl chloride.
Comparative example 1
(1) 350mg graphene oxide is placed in a beaker, 90mL deionized water is added, ultrasonic vibration 1h is obtained uniform
Graphene oxide solution.1.2g urea is added into graphene oxide solution, and continues stirring 1h and obtains uniform mixed solution.
Mixed solution is put into 150mL reaction kettle and is heated for 24 hours at 180 DEG C.After reaction kettle naturally cools to room temperature, by what is obtained
Black solid obtains nitrating graphene oxide with deionized water repeated flushing 3 times after freeze-drying；
(2) it solution A: will be uniformly mixed in 10mL butyl titanate and 40mL dehydrated alcohol beaker.B solution: by anhydrous second
Alcohol, pure water, glacial acetic acid take 10mL, 4mL, 2mL to be uniformly mixed respectively, and adjust PH=2 with dilute hydrochloric acid.B solution is added dropwise dropwise
Into solution A, and continue to stir 30min.After stirred, by the static 3h gelled of mixed solution.By above-mentioned spawn
It is placed in air dry oven the drying at 100 DEG C and for 24 hours, is ground into powdery after cooling, then be placed in resistance furnace with the speed of 2 DEG C/min
Degree is heated to 500 DEG C of calcining 2h, takes out after natural cooling and obtains TiO2Particle；
(3) 350mg nitrating graphene oxide and 210mg TiO are taken2It is placed in a beaker, 100mL water is added in ultrasound condition
Under be uniformly mixed liquid.Mixed solution is put into 150mL reaction kettle and is heated for 24 hours at 180 DEG C.To reaction kettle natural cooling
To after room temperature, by obtained gray solid with deionized water repeated flushing 3 times, obtained after freeze-drying nitrating graphene oxide/
TiO2Composite particles；
(4) by 100mg nitrating graphene oxide/TiO2Composite particles are scattered in 78.9gN- methyl pyrrole under ultrasound condition
In pyrrolidone (NMP), after ultrasonic 2h, polyvinylpyrrolidone 3g, polysulfones 18g are added to the solution under stirring, 50 DEG C
Lower stirring 6h, forms uniform casting solution；
(5) by the static deaeration for 24 hours of casting solution.After deaeration, at room temperature, on a glass by casting solution, utilize
Knifing machine (its scraper be 100 μm) is uniformly scraped film on a glass, and is immediately moved into visible thin after coagulation bath (water) 1~2min
Film automatically disengages glass plate；It impregnates in deionized water for 24 hours, it is ensured that complete phase transfer；Film is placed between two layers of filter paper, greenhouse
It air-dries, preparation is completed.
PS membrane obtained is calculated in the cross-flow devices of laboratory using ultraviolet specrophotometer under ultraviolet light
To the degradation efficiency of methylene blue (MB), result 34% illustrates this kind of film to the degradation effect of organic dyestuff not as good as this case system
Standby composite hyperfiltration membrane.This is because using the method for cladding inside film, to have composite catalyst particles coat in comparative example 1
Effect catalytic amount is far smaller than the composite membrane of this case preparation, thus poor to the light degradation effect of organic dyestuff.
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas
Corresponding change and deformation, and all these changes and deformation all should belong to the protection scope of the claims in the present invention
Within.
Claims (7)
1. a kind of preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane, it is characterised in that: the following steps are included:
(1) by graphite in KMnO4、H2SO4And NaNO3Mixture in aoxidize, filter mixture to collect solid particle, by again
It suspends with the solid in centrifuge cycle washing deionized water to chemical residue is removed, is hanged GO particle using ultrasonic cleaner
Supernatant liquid ultrasonication is, at GO nanometer sheet, it is remaining to remove any unpeeled graphite finally by centrifugation for graphite oxide removing
The suspension is freeze-dried to obtain pure GO nanometer sheet suspension and obtains GO powder by object；
(2) using urea as nitrogen source, weighed urea and GO powder are dispersed in deionized water by ultrasonic treatment, it then will urine
Element is blended dispersion liquid with GO and is slowly added to TiO2In colloidal sol, continue to stir after adding, it is still aging, obtain nitrogen oxidation graphene two
Dispersion liquid is blended in titanium oxide；
(3) commercially available ultrafiltration membrane is used, ultrafiltration membrane is immersed in nitrogen oxidation graphene titanium dioxide with the mode of Best-Effort request and is total to
In mixed dispersion liquid, modified ultrafiltration membrane is obtained, is then dried in an oven, obtained film is then put into the height equipped with ethanol solution
It presses in kettle, autoclave is put in vacuum oven, finally film is handled with ethyl alcohol and ultraviolet light, is made between dispersion liquid and film
Nitrating graphene oxide titanium dioxide composite hyperfiltration membrane is made in stable bond.
2. the preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane according to claim 1, feature exist
In: the mass ratio of GO powder and urea is 10:1 in step (2).
3. the preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane according to claim 1, feature exist
In: dispersion liquid and TiO are blended in step (2)2The volume ratio of colloidal sol is 1:1-2.
4. the preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane according to claim 1, feature exist
In: TiO described in step (2)2Colloidal sol is made by sol-gal process, it is specific the preparation method is as follows:
Configuration A liquid: it measures dehydrated alcohol and is added to the container, butyl titanate and acetic acid are added while stirring, is kept stirring at room temperature
5-15 minutes；
Configuration B liquid: it measures dehydrated alcohol and is placed in container, then remove ionized water and be placed in the container, dense salt is added while stirring
Acid makes PH=2~3, stirs evenly；
It keeps A liquid mixing speed is constant B liquid is added in A liquid, then stirs to get uniform, transparent faint yellow colloidal sol, be TiO2
Colloidal sol.
5. the preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane according to claim 1, feature exist
In: the heating condition of step (3) mesohigh kettle is 115-125 DEG C, and autoclave to time in a vacuum drying oven is 18h.
6. the preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane according to claim 1, feature exist
In: the material of ultrafiltration membrane described in step (3) be polysulfones, polyether sulfone, polytetrafluoroethylene (PTFE), Kynoar cellulose acetate class and
Any one of polyvinyl chloride.
7. the preparation method of nitrating graphene oxide titanium dioxide composite hyperfiltration membrane according to claim 1, feature exist
In: the built-in ballasts ultraviolet lamp that ultraviolet light described in step (3) is 120 watts.
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Application publication date: 20190312 |