CN108283923A - A kind of TiO2/Fe3O4Adulterate the application of the preparation method and its catalytic degradation polybrominated biphenyls of pvdf membrane - Google Patents
A kind of TiO2/Fe3O4Adulterate the application of the preparation method and its catalytic degradation polybrominated biphenyls of pvdf membrane Download PDFInfo
- Publication number
- CN108283923A CN108283923A CN201711389647.8A CN201711389647A CN108283923A CN 108283923 A CN108283923 A CN 108283923A CN 201711389647 A CN201711389647 A CN 201711389647A CN 108283923 A CN108283923 A CN 108283923A
- Authority
- CN
- China
- Prior art keywords
- tio
- pvdf membrane
- preparation
- time
- adulterate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000012528 membrane Substances 0.000 title claims abstract description 32
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 27
- 230000015556 catabolic process Effects 0.000 title claims abstract description 16
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 6
- 150000004074 biphenyls Chemical class 0.000 title claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 title abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000005266 casting Methods 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 238000007146 photocatalysis Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 230000006698 induction Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 210000000577 adipose tissue Anatomy 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 polybrominated biphenyl compound Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
-
- B01J35/33—
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
The invention belongs to material preparation and the technical fields of environmental pollution improvement, provide a kind of TiO2/Fe3O4The application of the preparation method and its catalytic degradation polybrominated biphenyls of pvdf membrane is adulterated, preparation method is as follows：Step 1 prepares TiO2/Fe3O4Composite photo-catalyst；Step 2, magnetic force induce TiO2/Fe3O4Composite material prepares photocatalysis membrana.The present invention is preparing catalytic membrane using magnetic force induction, while improving traditional blend film degradation efficiency, using the method for pre-freeze casting solution, solves the problems, such as to shrink crumple during pvdf membrane inversion of phases.Film surface made from this method is smooth, and has many advantages, such as higher photocatalytic degradation efficiency, convieniently synthesized.
Description
Technical field
The invention belongs to material preparation and the technical field of environmental pollution improvement, it is related to a kind of to improve traditional blend film
Degradation efficiency and when inversion of phases being overcome to form a film film fold film-forming method, specially a kind of efficient degradation polybrominated biphenyls
TiO2/Fe3O4Adulterate pvdf membrane Preparation method and use.
Background technology
Air, bed mud, soil etc. of the polybrominated biphenyls (PBBs) as widely applied bromide fire retardant in the world
It is detected in environmental sample, becomes the research hotspot in current international environment field.PBBs lipophilicitys are very strong, easily in biological body fat
Middle accumulation and be difficult to decompose, long-term harm can be caused even to have carcinogenic danger to organism.Itself has very steady
The hydrophobicity of fixed chemical constitution and height, the bromine atom on phenyl ring is to lead to high toxicity, high stability and be difficult to be aoxidized
The reason of degradation.Therefore, it establishes and develops effectively and economic and practical processing means are come to remove in environment PBBs residuals be extremely urgent
It cuts.
Photocatalysis membrana system is a kind of processing method of efficient green, it can integrate absorption degradation, and have
It is easily controllable, at low cost, the advantages that being easy to industrial applications.There are mainly three types of the catalytic membranes of currently used structure：Blend film,
Surface modified membrane, self-supported membrane.Wherein due to being to be directly appended to be made in casting solution by catalyst, catalyst is easy blend film
Envelope matrix entrapment, to influence catalytic efficiency.In addition, common Kynoar (PVDF) membrane material is worked as in inversion of phases process
In be easy shrink crumple, influence the planarization of film.
Invention content
In view of the problems of the existing technology, the method that the present invention utilizes induced by magnetic field pre-freeze casting solution sum, in inversion of phases
The preceding casting solution by evenly laid out in culture dish is transferred in magnetic field, and magnetic composite is made to be migrated under the induction in magnetic field
To film surface, then by casting solution pre-freeze, casting solution is made to cure, is then then transferred in deionized water and carries out inversion of phases.It prepares
Composite membrane macrostructure it is smooth, while can efficiently remove decabromodiphenyl.This is the removal of polybrominated biphenyl compound in water
Provide new technological means.The present invention prepares a kind of composite material catalytic membrane for capableing of efficient degradation polybrominated biphenyls.Its is excellent
Point is that this method from a kind of novel angle, provides a kind of new think of for improving tradition and catalytic membrane degradation efficiency being blended
Road is solved the problems, such as that catalyst embeds in blend film, and then catalyst is made effectively to be reached using light source to a certain extent
The effectively purpose of degradation environmental wastewater.In addition the method that pre-freeze is utilized before inversion of phases overcomes film in conversion process to shrink
The shortcomings that crumple.
A kind of TiO2/Fe3O4The preparation method of pvdf membrane is adulterated, steps are as follows：
Step 1 prepares Fe3O4：
By FeCl3·6H2O, NaAc-3H2O is dissolved in certain proportion in ethylene glycol, after supersound process, by buff colloid
It after solution is transferred in the stainless steel autoclave of teflon lining, heats at a certain temperature, then cooled to room temperature；It
Afterwards, black precipitate is washed with ethyl alcohol, is dried to obtain Fe3O4；
Step 2 prepares TiO2/Fe3O4Composite photo-catalyst：
Weigh a certain amount of Fe3O4Then ultrasonic disperse is added ammonium hydroxide and obtains mixed liquor A in ethyl alcohol and acetonitrile mixture,
A certain amount of butyl titanate (TBOT) is added drop-wise in mixed liquor A again and is stirred；Then cetyl trimethylammonium bromide is added
(CTAB), mixture reacts again；Products therefrom is washed with ethyl alcohol, is calcined in Muffle furnace after dry；Obtain TiO2/Fe3O4It is multiple
Closing light catalyst；
Step 3, magnetic force induce TiO2/Fe3O4Composite material prepares photocatalysis membrana：
Take gained TiO in step 22/Fe3O4Composite photo-catalyst is added in dimethyl sulfoxide (DMSO), and ultrasonic disperse obtains
TiO2/Fe3O4Composite photocatalyst agent dispersing liquid B；Kynoar (PVDF) is added into dispersion liquid B, machinery stirs at 40~50 DEG C
It mixes uniformly, obtains casting solution；The bubble in casting solution is removed with the method vacuumized, a clean culture dish is then taken, by one
Quantitative casting solution pours into culture dish, and introduce magnetic field after tiling uniformly is put into ice after magnetic force induces a period of time by culture dish
It case freezing a period of time, is then slowly dipped in deionized water and impregnates, obtain that photocatalysis membrana is blended；By film room temperature storage in
It is spare in deionized water.
In step 1, used FeCl3·6H2O and NaAc3H2O molar ratios are 1:10, ethylene glycol dosage with
FeCl3·6H2The ratio of O dosages is 70ml：5mmol；The autoclave heating temperature is 200 degree, soaking time 16h.
In step 2, the Fe3O4：Ammonium hydroxide：TBOT：The usage ratio of CTAB is 0.1g：1ml：2~8ml：20mg；
In the mixed liquor of the ethyl alcohol and acetonitrile, the volume ratio of ethyl alcohol and acetonitrile is 3：1；
In mixed liquor A, mixing time is 1 hour when butyl titanate is added, and adds cetyl trimethylammonium bromide
After react half an hour；The Muffle furnace calcination temperature is 450 degree, and calcination time is 2~3h.
In step 3, TiO is prepared2/Fe3O4When adulterating pvdf membrane, the TiO2/Fe3O4Composite photo-catalyst and DMSO's
Mass ratio is 0.1~0.4g:17.9~17.6g；The time of the ultrasonic disperse is 30min；In the casting solution, the PVDF
Mass fraction be casting solution 5%~20%, the churned mechanically time be 4h；The bubble removing time that vacuumizes is
1h, the amount for pouring into casting solution in culture dish are 1~5g；The magnetic force induction time is 30min~180min；It is described in refrigerator
Middle cooling time is at least 10min, it is therefore an objective to make the contraction for resisting film when inversion of phases, keep film smooth；It impregnates in deionized water
Time be at least 30min.
The dimethyl sulfoxide in the above technical solution, it acts as solvent, PVDF is to prepare casting solution for dissolving.
The PVDF in the above technical solution, it acts as matrix.
The deionized water in the above technical solution, it acts as non-solvents.
The technological merit of the present invention：
(1)TiO2It is in situ to wrap up to Fe3O4Surface constitutes nucleocapsid, TiO2It can be good at generating light induced electron, and fast
Speed is transferred to Fe3O4On semiconductor, to effectively prevent the compound of electron hole, photocatalysis efficiency can be thus improved, is improved
To the degradation rate of target substance.
(2) magnetic field is introduced before inversion of phases, will have magnetic composite material using the method for induced by magnetic field is attracted to
Film surface, film made from this method solve tradition and the drawbacks of catalyst is easily embedded in catalytic membrane are blended so that catalyst is sudden and violent
Film surface is exposed to without regard to falling off, therefore can effectively realize the degradation to target contaminant, and entire synthetic method
It is simple and convenient.
(3) by using the low melting point of DMSO, the culture dish equipped with uniform casting solution is put into refrigerator before inversion of phases, is made
It obtains casting solution and is frozen into solid, then carry out the contraction crumple that can resist membrane matrix when inversion of phases, this is structure good appearance
Smooth membrane material provide new thinking.
Description of the drawings
Fig. 1 is the TiO prepared2/Fe3O4Composite material transmission electron microscope picture.
Specific implementation mode
With reference to specific implementation example, the present invention will be further described.
The present invention is by taking casting solution gross mass is 20g as an example.
Embodiment 1：
(1)TiO2/Fe3O4The preparation of composite catalyst
By FeCl3·6H2O (5mmol, 1.35g), NaAc-3H2O (0.05mol, 6.8g) is dissolved in ethylene glycol (70mL).
It is ultrasonically treated after five minutes, buff colloidal solution is transferred in the stainless steel autoclave of teflon lining.By it at 200 DEG C
Lower heating 16 hours, then cooled to room temperature.Later, black precipitate is washed 3 times with ethyl alcohol, dry Fe3O4。
Weigh 0.1g Fe3O4Ultrasonic disperse in the mixed liquor that 80ml ethyl alcohol and acetonitrile volume ratio are 3/1, then with 1ml
Ammonium hydroxide is mixed to get mixed liquor A.2ml TBOT are added dropwise into mixed liquor A under agitation, 20mg is added after being kept stirring 1h
CTAB is stirred for 30min.The product being dried to obtain calcines 2h to get to TiO at 450 DEG C2/Fe3O4Composite photo-catalyst.
(2) magnetic force induces TiO2/Fe3O4Composite material prepares catalytic membrane
Take 0.1g TiO2/Fe3O4Composite photo-catalyst is added in 17.9g DMSO, then 2g is added in ultrasonic disperse 1h
PVDF, mechanical agitation 4h obtains uniform casting solution under the conditions of 50 DEG C, sloughs the bubble that stirring generates with the method vacuumized, so
A clean culture dish is taken afterwards, is taken 2.5g casting solutions evenly laid out in wherein introducing magnetic field afterwards, is then put after magnetic force induction 30min
Enter refrigerator freezing 10min, be then dipped in deionized water, is taken out after immersion 30min and be stored in deionization to get catalytic membrane
In water.
Embodiment 2：
In the case of ensureing that other conditions are constant, it is as follows to establish contrast test：(1) TiO processed2/Fe3O4When composite catalyst,
Different amounts of TBOT (1ml, 4ml, 6ml) is added dropwise to Fe3O4In dispersion liquid；(2) magnetic force induction TiO is prepared2/Fe3O4It is multiple
When condensation material photocatalysis membrana, the film not prepared casting solution pre-freeze before inversion of phases is as a comparison.
Embodiment 3：
Prepare magnetic force induction TiO2/Fe3O4When composite material photocatalysis membrana (other conditions are constant), lured by changing magnetic force
(3min, 30min, 60min, 180min) is led the time to investigate influence of the induction time to catalyst migration process, and to light
The influence of catalytic degradation effect；Prepare magnetic force induction TiO2/Fe3O4When composite material photocatalysis membrana (other conditions are constant), pass through
Change the addition (1g, 3g, 4g) of PVDF to investigate influence of the coefficient of viscosity for induced by magnetic field of casting solution, to further
Probe into the optimal proportion of casting solution.The lower catalytic membrane built of magnetic force induction is under ultraviolet light to the degradation effect of decabromodiphenyl
Reach 90% or more.
Claims (9)
1. a kind of TiO2/Fe3O4Adulterate pvdf membrane, which is characterized in that the TiO2/Fe3O4Composite material is by TiO2It is wrapped in
Fe3O4The nucleocapsid that grain crystalline periphery is combined.
2. a kind of TiO2/Fe3O4Adulterate the preparation method of pvdf membrane, which is characterized in that steps are as follows：
Step 1 prepares Fe3O4, spare；
Step 2 prepares TiO2/Fe3O4Composite photo-catalyst：
Weigh a certain amount of Fe3O4Then ultrasonic disperse is added ammonium hydroxide and obtains mixed liquor A, then will in ethyl alcohol and acetonitrile mixture
A certain amount of butyl titanate TBOT, which is added drop-wise in mixed liquor A, to be stirred；Then cetyl trimethylammonium bromide CTAB is added, mixes
Object is closed to react again；Products therefrom is washed with ethyl alcohol, is calcined in Muffle furnace after dry；Obtain TiO2/Fe3O4Composite photocatalyst
Agent；
Step 3, magnetic force induce TiO2/Fe3O4Composite material prepares photocatalysis membrana：
Take gained TiO in step 22/Fe3O4Composite photo-catalyst is added in dimethyl sulfoxide DMSO, and ultrasonic disperse obtains TiO2/
Fe3O4Composite photocatalyst agent dispersing liquid B；Kynoar PVDF is added into dispersion liquid B, mechanical agitation is uniform at 40~50 DEG C,
Obtain casting solution；The bubble in casting solution is removed with the method vacuumized, a clean culture dish is then taken, by a certain amount of casting
Film liquid is poured into culture dish, and introduce magnetic field after tiling uniformly is put into refrigerator freezing one after magnetic force induces a period of time by culture dish
It the section time, is then slowly dipped in deionized water and impregnates, obtain that photocatalysis membrana is blended；By film room temperature storage in deionized water
In, it is spare.
3. a kind of TiO according to claim 22/Fe3O4Adulterate the preparation method of pvdf membrane, which is characterized in that step 1
In, prepare Fe3O4The step of be：By FeCl3·6H2O, NaAc-3H2O is dissolved in certain proportion in ethylene glycol, after supersound process,
After buff colloidal solution is transferred in the stainless steel autoclave of teflon lining, heat at a certain temperature, it is then natural
It is cooled to room temperature；Later, black precipitate is washed with ethyl alcohol, is dried to obtain Fe3O4。
4. a kind of TiO according to claim 32/Fe3O4Adulterate the preparation method of pvdf membrane, which is characterized in that used
FeCl3·6H2O and NaAc3H2O molar ratios are 1:10, ethylene glycol dosage and FeCl3·6H2The ratio of O dosages is 70ml：
5mmol；The autoclave heating temperature is 200 degree, soaking time 16h.
5. a kind of TiO according to claim 22/Fe3O4Adulterate the preparation method of pvdf membrane, which is characterized in that step 2
In, the Fe3O4：Ammonium hydroxide：TBOT：The usage ratio of CTAB is 0.1g：1ml：2~8ml：20mg；The ethyl alcohol and acetonitrile it is mixed
It closes in liquid, the volume ratio of ethyl alcohol and acetonitrile is 3：1.
6. a kind of TiO according to claim 22/Fe3O4Adulterate the preparation method of pvdf membrane, which is characterized in that step 2
In, mixing time is 1 hour when butyl titanate being added in mixed liquor A, is reacted after adding cetyl trimethylammonium bromide
Half an hour；The Muffle furnace calcination temperature is 450 degree, and calcination time is 2~3h.
7. a kind of TiO according to claim 22/Fe3O4Adulterate the preparation method of pvdf membrane, which is characterized in that step 3
In, prepare TiO2/Fe3O4When adulterating pvdf membrane, the TiO2/Fe3O4The mass ratio of composite photo-catalyst and DMSO be 0.1~
0.4g:17.9~17.6g；The time of the ultrasonic disperse is 30min；In the casting solution, the mass fraction of the PVDF is
The 5%~20% of casting solution, the churned mechanically time are 4h.
8. a kind of TiO according to claim 22/Fe3O4Adulterate the preparation method of pvdf membrane, which is characterized in that step 3
In, the bubble removing time that vacuumizes is 1h, and the amount for pouring into casting solution in culture dish is 1~5g；When the magnetic force induces
Between be 30min~180min；The cooling time in refrigerator is at least 10min；The time impregnated in deionized water is at least
For 30min.
9. TiO prepared by the method described in claim 1~8 any one2/Fe3O4The purposes of pvdf membrane is adulterated, feature exists
In by the TiO2/Fe3O4It adulterates pvdf membrane and is used as degradation polybrominated biphenyls.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711389647.8A CN108283923B (en) | 2017-12-21 | 2017-12-21 | Preparation method of TiO2/Fe3O4 sized PVDF file and application of file in catalytic definition of branched biphenyls |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711389647.8A CN108283923B (en) | 2017-12-21 | 2017-12-21 | Preparation method of TiO2/Fe3O4 sized PVDF file and application of file in catalytic definition of branched biphenyls |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108283923A true CN108283923A (en) | 2018-07-17 |
| CN108283923B CN108283923B (en) | 2020-06-09 |
Family
ID=62832052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711389647.8A Active CN108283923B (en) | 2017-12-21 | 2017-12-21 | Preparation method of TiO2/Fe3O4 sized PVDF file and application of file in catalytic definition of branched biphenyls |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108283923B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330091A (en) * | 2019-05-27 | 2019-10-15 | 中南林业科技大学 | Magnetic green material function Carbon fibe and its preparation method and application based on the catalysis of light Fenton |
| CN112371175A (en) * | 2020-10-30 | 2021-02-19 | 江苏大学 | CN/LiNbO3PVDF piezoelectric photocatalytic composite membrane and preparation method and application thereof |
| CN113578366A (en) * | 2021-08-13 | 2021-11-02 | 南京信息工程大学 | OCN-TiO2@Fe3O4Magnetic photocatalytic material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117292A (en) * | 2014-08-01 | 2014-10-29 | 天津工业大学 | Preparation method of polymer/inorganic nano-material composite ultrafiltration membrane |
| CN104383821A (en) * | 2014-09-12 | 2015-03-04 | 天津工业大学 | Preparation method for organic-inorganic composite separation membrane with hydrophilicity and function of photocatalytic degradation of pollutants |
-
2017
- 2017-12-21 CN CN201711389647.8A patent/CN108283923B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117292A (en) * | 2014-08-01 | 2014-10-29 | 天津工业大学 | Preparation method of polymer/inorganic nano-material composite ultrafiltration membrane |
| CN104383821A (en) * | 2014-09-12 | 2015-03-04 | 天津工业大学 | Preparation method for organic-inorganic composite separation membrane with hydrophilicity and function of photocatalytic degradation of pollutants |
Non-Patent Citations (3)
| Title |
|---|
| PARISA DARAEI, ET AL.: "Fouling resistant mixed matrix polyethersulfone membranes blended with magnetic nanoparticles: Study of magnetic field induced casting", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
| ZHIWEI XU, ET AL.: "Manipulating Migration Behavior of Magnetic Graphene Oxide via Magnetic Field Induced Casting and Phase Separation toward High-Performance Hybrid Ultrafiltration Membranes", 《APPLIED MATERIALS & INTERFACES》 * |
| 辛铁军等: "Fe3 O4 @ TiO2核壳磁性纳米材料的制备及表征", 《功能材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330091A (en) * | 2019-05-27 | 2019-10-15 | 中南林业科技大学 | Magnetic green material function Carbon fibe and its preparation method and application based on the catalysis of light Fenton |
| CN110330091B (en) * | 2019-05-27 | 2022-02-15 | 中南林业科技大学 | Magnetic biomass functional carbon fiber based on photo-Fenton catalysis and preparation method and application thereof |
| CN112371175A (en) * | 2020-10-30 | 2021-02-19 | 江苏大学 | CN/LiNbO3PVDF piezoelectric photocatalytic composite membrane and preparation method and application thereof |
| CN113578366A (en) * | 2021-08-13 | 2021-11-02 | 南京信息工程大学 | OCN-TiO2@Fe3O4Magnetic photocatalytic material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108283923B (en) | 2020-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108283923A (en) | A kind of TiO2/Fe3O4Adulterate the application of the preparation method and its catalytic degradation polybrominated biphenyls of pvdf membrane | |
| CN108187715A (en) | A kind of novel magnetic induces C3N4/Fe3O4The preparation method and its usage of composite membrane | |
| CN102718295B (en) | Compound medicament for treating coking wastewater and preparation method thereof | |
| CN106881139B (en) | A kind of CdS/Ag/g-C3N4Heterojunction composite photocatalyst and preparation method | |
| CN106732731A (en) | A kind of ZnO/g C3N4The preparation method of ozone composite catalyst and application | |
| CN107744816A (en) | A kind of carbon point modification type composite material photocatalyst and preparation method and application | |
| CN106076379B (en) | A kind of controllable synthesis method of graphene-manganese compound nanocomposite | |
| CN104399514B (en) | Preparation method for boric-acid-modified microporous molecular sieve shape-selective catalyst | |
| CN102861609A (en) | Gradient composite molecular sieve membrane catalytic material and preparation method and application thereof | |
| CN107555491B (en) | It is co-precipitated the method that a step prepares nitrate anion intercalation cobalt aluminium houghite | |
| CN204602078U (en) | A kind of chemical industry agitator tank | |
| CN107651712B (en) | It is co-precipitated the method that a step prepares nitrate anion intercalation NiAl-HTLcs | |
| CN105753009B (en) | A kind of adjustable Beta molecular sieves of polymorph relative amount and its synthetic method | |
| CN103877952B (en) | Similar soft sweet type polysiloxane adsorption material as well as preparation and application of surface modified sponge | |
| CN107754825A (en) | A kind of spherical silicon substrate multiphase Fenton catalyst of nanofiber and synthetic method and application | |
| CN109569705A (en) | A kind of preparation method of graphene oxide modified micropore molecular sieve shape-selective catalyst | |
| CN105800728B (en) | It is a kind of for the suspension diaphragm plate of sewage treatment, preparation method and applications | |
| CN204656450U (en) | The adjustable magnetic stirring apparatus of a kind of enhancement mode | |
| CN113893855B (en) | Resin fibrous mesoporous SiO 2 Loaded with Fe 2 O 3 Catalyst, preparation method and application thereof | |
| CN109399661A (en) | A kind of preparation method of Fe-SSZ-24 molecular sieve | |
| CN207493695U (en) | A kind of reaction kettle | |
| CN103193244B (en) | Method for increasing hydrothermal stability of mesoporous material | |
| CN109174150A (en) | A kind of CQDs/CdIn2S4The preparation method and application of/N-rGO multidimensional photochemical catalyst | |
| CN107963639A (en) | A kind of Fast back-projection algorithm method of even particle diameter ZSM-5 molecular sieve | |
| CN103769028A (en) | Novel reaction apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |