CN107029802A - A kind of method for preparing magnetic porous material - Google Patents
A kind of method for preparing magnetic porous material Download PDFInfo
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- CN107029802A CN107029802A CN201610962169.4A CN201610962169A CN107029802A CN 107029802 A CN107029802 A CN 107029802A CN 201610962169 A CN201610962169 A CN 201610962169A CN 107029802 A CN107029802 A CN 107029802A
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000011148 porous material Substances 0.000 title claims abstract description 37
- 239000000839 emulsion Substances 0.000 claims abstract description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910003264 NiFe2O4 Inorganic materials 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 6
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- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 239000003990 capacitor Substances 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims abstract description 3
- 230000003287 optical effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 210000003022 colostrum Anatomy 0.000 claims description 19
- 235000021277 colostrum Nutrition 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
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- 210000000481 breast Anatomy 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
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- 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention discloses a kind of method for preparing magnetic porous material, using have it is magnetic, by modified hydrophobic NiFe2O4With hydrophilic TiO2As stabilizer, NiFe is prepared using solvent-thermal method2O4, sol-gal process prepare TiO2After prepare the multiple Pickering emulsions of W/O/W types；Multiple Pickering emulsion polymerizations prepare TiO2/PS/NiFe2O4Composite magnetic catalyst.The internal outer layer colloidal particle of polystyrene of the present invention is fixed, internal layer NiFe2O4As magnetic medium, outer layer TiO2Serve catalytic action；TiO2Outer layer is coated on, the influence to its catalytic performance due to polystyrene is farthest alleviated.And wherein its excellent electrical property of polystyrene basis, high frequency characteristics and the linear energy of anti-radiation, have a wide range of applications in terms of optical chemical instrument part, transparent membrane and capacitor dielectric layer.
Description
Technical field
The invention belongs to technical field of macromolecules, more particularly to a kind of method for preparing magnetic porous material.
Background technology
Raising with people to material structure performance requirement, researchers are increased to material preparation method, microcosmic knot
The research of structure and performance, and attempt to carry out by the microstructure that changes material, to inorganic-organic material compound etc. to improve material
The performance of material.Wherein porous material is because with pore passage structure is regularly arranged, size is adjustable, specific surface area is high, and adsorption capacity is big
The features such as, have evolved into and enjoy one of research field of concern.According to the rule of IUPAC
Fixed, pore size can be divided into micropore（Less than 2nm）, mesopore（2~50nm）And macropore（More than 50nm）Three classes.Prepare porous
The method of material mainly includes：Template, gas foaming method, phase separation method, solvent pore method etc..Emulsion template in template
Method, can realize the pre-control to porous material structure by changing species, the size of emulsion template, thus as the heat of research
Point, and achieve certain achievement.But the template used at present is generally substance emulsion template, the method using substance emulsion droplet as
Template, at a certain temperature, polymerisation is carried out in droplet surface, polymerization is dried through washing after terminating and obtains loose structure and gather
Compound material.This method, which prepares porous material, mainly to be included：Water-In-Oil (W/O) emulsion system method, oil-in-water (O/W) emulsion body
It is method and supercritical CO2（C/W）Method etc..Because substance emulsion only has one interface of oil-water, it is impossible to realize to two kinds not
The inorganic particulate of congenerous carries out controllable compound.Accordingly, it is considered to prepare porous material using multiple emulsion polymerization.
Multiple emulsion is by a kind of emulsion（That is colostrum）The multilayer emulsion formed in another continuous phase is dispersed in, it is common
Have W/O/W and O/W/O two types, be usually using with amphipathic emulsifying agent as stabilizer, using one-step method or two
Prepared by footwork, one-step method is to emulsify to form multiple emulsion by aqueous phase, oil phase, lipophile and hydrophilic emulsifier mixed once, and two
Footwork is first to prepare W/O（Or O/W）Colostrum, is then added to aqueous phase（Or oil phase）In be made W/O/W（Or O/W/O）Multiple emulsion,
One-step method is easier, and power consumption is few, but the ratio of inside and outside aqueous phase and the distribution of active material are difficult to control to, so two-step method is
Relatively common preparation method.
Conventional emulsifying agent has surfactant（Such as SDS, CTAB, SPAN-80）With the polymer with surface-active
（Such as protein and polysaccharide）, but there is the multiple solution for using both emulsifying agents to prepare less stable, emulsifying agent to use
The shortcomings of amount is big, toxicity is larger.In recent years, traditional emulsifying agent is replaced to prepare by different particle-stabilised using colloidal particle
Emulsion（It is called Pickering emulsions）Cause and widely pay close attention to.Pickering emulsions compared with conventional emulsion, with
Lower advantage：
（l）Emulsifying effectiveness is good, and consumption is few, cost is low；（2）Toxicity is much smaller than organic surface active agent；（3）Stability of emulsion is strong,
It is difficult to be influenceed by environment temperature；（4）Convenient separation or without separation, be easy to industrialized production.Multiple Pickering emulsions
Multiple emulsion has unique " two film three-phases " multi-compartment structure in structure, if it is possible to will be different particle-stabilised in difference
Film layer on, just can prepare portal inside and outside with difference in functionality porous material.
But the research of current this aspect is actually rare, inorganic particulate oleophylic, the hydrophilicity of distinct methods preparation are different, parent
The easily prepared Water-In-Oil of oil type particle (W/O) emulsion system, the easily prepared oil-in-water of hydrophilic particle (O/W) emulsion system is more
Weight Pickering emulsions are W/O/W（Or O/W/O）, accordingly, it would be desirable to the hydrophily or lipophilic of two kinds of particles are on the contrary, otherwise,
Hydrophilic, the oleophylic performance of two kinds of inorganic particulates will be unable to matching；The inorganic particulate prepared simultaneously possibly can not form stable
Colostrum is modified with multiple emulsion, it is necessary to carry out appropriate hydrophobic or oleophobic to it.Influence prepares multiple Pickering breasts in addition
Liquid factor is more, including particle diameter size, oil-water ratio, pH value etc..
In summary, two kinds of inorganic particulates of lipophilic particle and hydrophilic particle in the preparation method of current porous material
Hydrophilic, oleophylic performance difficulty of matching is big, and the inorganic particulate prepared can not form stable colostrum and multiple emulsion；And mesh
Before prepare after multiple emulsion and there is no progress to have polymerization, the porous material function of preparation is single.
The content of the invention
It is an object of the invention to provide a kind of method for preparing magnetic porous material, it is intended to solves current porous material
Hydrophilic, oleophylic performance the difficulty of matching of two kinds of inorganic particulates of lipophilic particle and hydrophilic particle is big in preparation method, prepares
The inorganic particulate gone out can not form stable colostrum and multiple emulsion；And prepare does not have progress to have poly- at present after multiple emulsion
Close, the problem of porous material function of preparation is single.
The present invention is achieved in that a kind of method for preparing magnetic porous material, including：
Using have it is magnetic, by modified hydrophobic NiFe2O4With hydrophilic TiO2As stabilizer, prepared using solvent-thermal method
NiFe2O4, sol-gal process prepare TiO2After prepare the multiple Pickering emulsions of W/O/W types；
Multiple Pickering emulsion polymerizations prepare TiO2/PS/NiFe2O4Composite magnetic catalyst.
Further, solvent-thermal method prepares NiFe2O4Including：
By 0.5g ~ 1g Ni (NO3)2·6H2O and 1.5 g ~ 2.5g Fe (NO3)3·9H2O is dissolved in about 50 mL absolute ethyl alcohols,
Stirring, which is transferred at polytetrafluoroethylene (PTFE) autoclave, 200 DEG C, reacts 8 hours ~ 10 hours, generates reddish-brown precipitation, centrifuges,
Obtain NiFe2O4Solid powder；
Weigh 1.5 g ~ 2.5g NiFe2O4It is scattered in suitable quantity of water, the sodium pyrophosphate of addition 50% is in scattered at 75 DEG C
30min, regulation pH is 7 ~ 8, and the CTAB for adding 6% continues to stir 1.5h, centrifuges, deionized water is washed three times, drying,
Obtain surface and be modified NiFe2O4。
Further, sol-gal process prepares TiO2Including：
By 18ml ~ 25ml absolute ethyl alcohols and a certain amount of butyl titanate, ultrasonic disperse 30min, then in the feelings of thermostatic ultrasonic
Under condition, 2 ~ 3mlH is added dropwise2O, 0.1 ~ 05ml dense HCl and 18 ~ 25mL absolute ethyl alcohol mixed solution, until forming colloidal sol, are aged
Wet gel, is dried, finely ground rear roasting, produces TiO2。
Further, the preparation method of the multiple Pickering emulsions of W/O/W includes：
Weigh the NiFe that 50 mg ~ 100mg is modified2O4Ultrasonic disperse added in 5mL ~ 10mL toluene, after 10min 3 mL ~
6mL distilled water fully vibrates to obtain W/O colostrums；
Weigh 100 ~ 150mg TiO2It is scattered in 8 ~ 10mL water, ultrasonic disperse 10min, to the TiO after ultrasonic disperse2Solution
Middle addition 6 ~ 9mL W/O colostrums, vibrate to obtain W/O/W type Pickering emulsions.
Further, multiple Pickering emulsion polymerizations prepare TiO2/PS/NiFe2O4The method bag of composite magnetic catalyst
Include：
Weigh 280 mg ~ 320mg TiO2Ultrasonic disperse 5min in 10 mL ~ 15mL water is scattered in, labeled as dispersed phase；
Pipette 3mL ~ 5mLW/O colostrums and 0.5mL ~ 1mL styrene is added into colostrum, shake up and be added in above-mentioned dispersed phase, shake
Swing oil phase be the W/O/W type Pickering emulsions containing styrene monomer, polymerized at room temperature 12h, centrifuge, deionized water, nothing
Water-ethanol respectively washing three times, drying obtains TiO2/PS/NiFe2O4Compound porous magnetic catalyst；I.e. magnetic porous material.
Another object of the present invention is to provide a kind of receiving using the above-mentioned method for preparing magnetic porous material preparation
Meter level hydridization superstructure micro-sphere material.
Another object of the present invention is to provide a kind of the micro- of the above-mentioned method for the preparing magnetic porous material preparation of utilization
Meter level hydridization superstructure micro-sphere material.
NiFe is mixed in a kind of method for preparing magnetic porous material that the present invention is provided2O4It can be very good in additional magnetic
Carry out high efficiente callback under field condition to it, the rate of recovery is up to 98%.The internal outer layer colloidal particle of polystyrene of the present invention is consolidated
It is fixed, internal layer NiFe2O4It is used as magnetic medium, outer layer TiO2Catalytic action is served, using methylene blue as substrate, under uviol lamp
Its degradation efficiency can reach 93.8% after 160min；Magnetic porous material prepared by the present invention is very cleverly by magnetic and catalytic
It has been melted into all over the body, internal layer NiFe2O4As magnetic medium, facilitate recovery of the catalyst under external magnetic field, outer layer TiO2Play
Catalytic action.The TiO of the present invention2Outer layer is coated on as catalytic active center, polystyrene is farthest reduced to work
The covering at property center, alleviates the influence to its catalytic performance.And wherein its excellent electrical property, high frequency of polystyrene basis
Characteristic and the linear energy of anti-radiation, there is extensive in terms of optical chemical instrument part, transparent membrane and capacitor dielectric layer
Application prospect.
Brief description of the drawings
Fig. 1 is the method flow diagram provided in an embodiment of the present invention for preparing magnetic porous material.
Fig. 2 is NiFe provided in an embodiment of the present invention2O4Hysteresis curve figure.
Fig. 3 is that the embodiment of the present invention is provided（A）0.8mL、（B）0.6mL、（C）0.4mL、（D）0.2mL styrene consumption with
Photocatalytic activity curve map.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Polymerization technique of the present invention based on Pickering emulsions prepares the polymer microballoon material of hydridization superstructure, this
The microballoon prepared is invented with the superparticle structure using inorganic particulate as shell, can assign microballoon unique function.Colloid
Particle forms orderly sphere colloid shell in emulsion droplet surface self-organization, fixes the colloidal particle on emulsion droplet surface to prepare core shell structure
Microcapsules.Self assembly plays protection emulsion in polymerization process in the colloidal particle of oil-water interfaces instead of surfactant
Stable effect, and the surface of resulting polymer microballoon is stayed in after the completion of reaction, it is used as and builds inorganic/organic composite
Raw material.The polymerization technique of Pickering emulsions is applied in dispersin polymerization, micro-emulsion polymerization and suspension polymerisation, can be effectively
Prepare from nanometer to micron-sized hydridization superstructure microballoon.
The application principle of the present invention is elaborated below in conjunction with the accompanying drawings.
As shown in figure 1, the method provided in an embodiment of the present invention for preparing magnetic porous material, including：
S101：Using have it is magnetic, by modified hydrophobic NiFe2O4With hydrophilic TiO2As stabilizer, using solvent-thermal method
Prepare NiFe2O4, sol-gal process prepare TiO2After prepare the multiple Pickering emulsions of W/O/W types；
S102：Multiple Pickering emulsion polymerizations prepare TiO2/PS/NiFe2O4Composite magnetic catalyst.
The application principle of the present invention is further described with reference to experiment.
1. experimental section
1.1 solvent-thermal method prepares NiFe2O4And it is modified
By 0.5863g Ni (NO3)2·6H2O and 1.6289g Fe (NO3)3·9H2O is dissolved in about 48mL absolute ethyl alcohols, and stirring turns
Enter and reacted 10 hours at polytetrafluoroethylene (PTFE) autoclave, 200 DEG C, generate reddish-brown precipitation, centrifuge, obtain NiFe2O4Solid
Powder；
Weigh 2g NiFe2O4It is scattered in suitable quantity of water, the sodium pyrophosphate for adding 50% is in scattered 30min at 75 DEG C, regulation pH
Between 7 ~ 8, the CTAB for adding 6% continues to stir 1.5h, centrifuges, deionized water is washed three times, drying, obtains surface modification
NiFe2O4。
1.2 sol-gal processes prepare TiO2
By 20ml absolute ethyl alcohols and a certain amount of butyl titanate, ultrasonic disperse 30min, then in the case of thermostatic ultrasonic,
1.5mlH is added dropwise2The dense HCl and 20mL absolute ethyl alcohols mixed solution of O, 0.1ml, until forming colloidal sol, is aged to obtain wet gel, dries,
It is calcined after finely ground, produces TiO2。
The preparation of the multiple Pickering emulsions of 1.3 W/O/W
Weigh the NiFe of 60mg modifications2O4Ultrasonic disperse adds 3mL distilled water in 4mL toluene, after 10min and fully vibrated
W/O colostrums.Weigh 120mg TiO2It is scattered in 6mL water, ultrasonic disperse 10min, 4mL colostrums is added thereto, are vibrated
W/O/W type Pickering emulsions.
The polymerization of 1.4 multiple emulsions prepares TiO2/PS/NiFe2O4Composite magnetic catalyst
Weigh 300mg TiO2It is scattered in 12mL water and adds 4mL concentration for 1mol/mL HCl ultrasonic disperse 5min, pipettes
3mL colostrums add 0.6mL styrene thereto, shake up and are added to dispersed phase, vibrate oil phase be the W/O/W containing styrene monomer
Type Pickering emulsions, polymerized at room temperature 12h is centrifuged, and deionized water, absolute ethyl alcohol are respectively washed three times, is dried, is obtained
TiO2/PS/NiFe2O4Compound porous magnetic catalyst.
1.5 photocatalytic degradation methylene blues
Light-catalyzed reaction is carried out in homemade photo catalysis reactor, and reactor is wooden dark box device, and light source is high-pressure sodium lamp
And sodium vapor lamp.Light source is placed in directly over reactor, the centre of luminescence and liquid layer center about 10cm.It is accurate to prepare methylene blue solution, move
250mL is taken in beaker, catalyst fines is added（Catalyst amount 1:10）, beaker is placed on mechanical agitator, under dark-state
Stir after 30min, take this small amount of liquid to centrifuge 10min on centrifuge, the absorbance and record data for surveying resulting solution are C0；
Open uviol lamp and start simultaneously at stirring, survey an absorbance every 20min and record data is Ct；Under uviol lamp, in repetition
Operation is stated to be tested.
2. result is with discussing
The structure determination of 2.1 target stable particles
Pass through made sample NiFe2O4XRD spectrums, sample more completely keeps NiFe2O4Type spinel structure, passes through institute's sample preparation
Product TiO2XRD spectrum, can obtain, prepared TiO2For duplex grain structure, XRD test results show, prepared solid grain
Son is target product.
In addition, Fig. 2 NiFe2O4Magnetism testing shows the NiFe prepared2O4Particle has good paramagnetism, and it is satisfied
It is 10.8 emug with the intensity of magnetization-1, coercivity is 105.82 Oe, is magnetic conductivity the characteristics of be soft magnetic materials, this material
Higher, the emulsion that the higher intensity of magnetization ensure that particle and subsequently prepare has strong magnetic responsiveness.
The microscopic appearance of 2.2 stable particles
Pass through NiFe2O4SEM photograph, it can be seen that NiFe2O4Pattern it is more regular, even particle distribution is size
In 140nm or so particles.Pass through TiO2SEM photograph, it can be seen that TiO2Pattern it is more regular, even particle distribution,
It is size in the similar spheric granules of 75nm or so.Prepared two kinds of sample particles distribution is all than more uniform, to prepare stable, grain
The uniform Pickering emulsions in footpath provide reliable condition.
2.3NiFe2O4Hydrophobically modified
The NiFe directly prepared due to the precipitation method2O4Particulate prepares stable w/o type Pickering emulsions, present invention CTAB
Its surface is modified；
Before modified in 1047cm-1And 595cm-1There are 2 absworption peaks at place, and this is due in spinel-type ferrite molecule, each
O2-Shared by 1 tetrahedron cation and 3 octahedral cations, so O2-All vibrations all simultaneously with tetrahedron and eight
Face body is relevant.In 1047cm-1The absworption peak at place is Ni in the position of four sides2+-O2-The vibration of key, 595cm-1The absworption peak at place is eight
Fe in the position of face3+ - O2-The vibration of key.
Through the modified NiFe of CTAB2O4In 2915cm-1And 2843cm-1Place occurs in that methyl-CH respectively3With methine-
CH2Symmetrical stretching vibration peak, this explanation NiFe2O4Surface have been incorporated with organic group, realize NiFe2O4Organise
It is modified.
Meanwhile, the present invention again determine before modified after Zeta potential, unmodified NiFe2O4Surface potential value in zero point
Left and right.
After being modified using CTAB to it, NiFe2O4Surface is introduced into organic group, and surface potential is increased to about
12.5mV, the potential value of particle is smaller, illustrates that the particle is relatively hydrophobic, it is adaptable to do water-in-oil emulsion, consistent with experimental phenomena,
It is able to demonstrate that and is modified successfully.
The preparation of 2.4 multiple Pickering emulsions
The colostrums of different water-oil factors is emulsified again can obtain preferable multiple emulsion, and these multiple emulsion drops are wrapped in many
Droplet.Double emulsion is substantially maintained by hand preparation, thus the structure of colostrum, the drop of parcel inside multiple emulsion
Size and density are consistent with colostrum substantially.
2.5 porous material patterns and photocatalysis performance
When the multiple Pickering emulsions prepared to two-step method polymerize, keep other conditions constant, change styrene list
Body consumption, determines its photocatalysis performance.
Fig. 3 is that the embodiment of the present invention is provided（A）0.8mL、（B）0.6mL、（C）0.4mL、（D）0.2mL styrene polymers
Photocatalytic degradation curve map；As can be seen from Figure 3 when styrene monomer consumption increase, its photocatalysis performance is reduced, main former
Cause is styrene polymerization in TiO2Surface, cause its photochemical reaction site reduce.But when styrene monomer consumption is reduced,
The structure of composite can not be supported well.Learn when styrene consumption is 0.8mL there is good light by analysis
Catalytic performance, can guarantee that its structure again.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of method for preparing magnetic porous material, it is characterised in that the method for preparing magnetic porous material includes：
Using have it is magnetic, by modified hydrophobic NiFe2O4With hydrophilic TiO2As stabilizer, prepared using solvent-thermal method
NiFe2O4, sol-gal process prepare TiO2After prepare the multiple Pickering emulsions of W/O/W types；
Multiple Pickering emulsion polymerizations prepare TiO2/PS/NiFe2O4Composite magnetic catalyst.
2. the method for magnetic porous material is prepared as claimed in claim 1, it is characterised in that solvent-thermal method prepares NiFe2O4Bag
Include：
By 0.5g ~ 1g Ni (NO3)2·6H2O and 1.5 g ~ 2.5g Fe (NO3)3·9H2O is dissolved in about 50 mL absolute ethyl alcohols,
Stirring, which is transferred at polytetrafluoroethylene (PTFE) autoclave, 200 DEG C, reacts 8 hours ~ 10 hours, generates reddish-brown precipitation, centrifuges,
Obtain NiFe2O4Solid powder；
Weigh the g NiFe of 1.5 g ~ 2.52O4It is scattered in suitable quantity of water, the sodium pyrophosphate of addition 50% is in scattered at 75 DEG C
30min, regulation pH is 7 ~ 8, and the CTAB for adding 6% continues to stir 1.5h, centrifuges, deionized water is washed three times, drying,
Obtain surface and be modified NiFe2O4。
3. the method for magnetic porous material is prepared as claimed in claim 1, it is characterised in that sol-gal process prepares TiO2Bag
Include：
By 18ml ~ 25ml absolute ethyl alcohols and a certain amount of butyl titanate, ultrasonic disperse 30min, then in the feelings of thermostatic ultrasonic
Under condition, 2 ~ 3ml H are added dropwise2O, 0.1 ~ 05ml dense HCl and 18 ~ 25mL absolute ethyl alcohol mixed solution, until forming colloidal sol, are aged
Wet gel, is dried, finely ground rear roasting, produces TiO2。
4. the method for magnetic porous material is prepared as claimed in claim 1, it is characterised in that the multiple Pickering breasts of W/O/W
The preparation method of liquid includes：
Weigh the NiFe that the mg of 50 mg ~ 100 is modified2O4Ultrasonic disperse adds 3 mL ~ 6 in 5mL ~ 10mL toluene, after 10min
ML distilled water fully vibrates to obtain W/O colostrums；
Weigh 100 ~ 150mg TiO2It is scattered in 8 ~ 10mL water, ultrasonic disperse 10min, to the TiO after ultrasonic disperse2Solution
Middle addition 6 ~ 9mL W/O colostrums, vibrate to obtain W/O/W type Pickering emulsions.
5. the method for magnetic porous material is prepared as claimed in claim 1, it is characterised in that multiple Pickering emulsions are gathered
Close and prepare TiO2/PS/NiFe2O4The method of composite magnetic catalyst includes：
Weigh 280 mg ~ 320mg TiO2Ultrasonic disperse 5min in 10 mL ~ 15mL water is scattered in, labeled as dispersed phase；
Pipette 3mL ~ 5mLW/O colostrums and 0.5mL ~ 1mL styrene is added into colostrum, shake up and be added in above-mentioned dispersed phase, shake
Swing oil phase be the W/O/W type Pickering emulsions containing styrene monomer, polymerized at room temperature 12h, centrifuge, deionized water, nothing
Water-ethanol respectively washing three times, drying obtains TiO2/PS/NiFe2O4Compound porous magnetic catalyst.
6. one kind prepares nanoscale hydridization superjunction prepared by the method for magnetic porous material as described in claim 1 ~ 5 any one
Structure micro-sphere material.
7. one kind prepares micron order hydridization superjunction prepared by the method for magnetic porous material as described in claim 1 ~ 5 any one
Structure micro-sphere material.
8. one kind prepares optical chemical instrument zero prepared by the method for magnetic porous material as described in claim 1 ~ 5 any one
Part.
9. one kind prepares transparent membrane prepared by the method for magnetic porous material as described in claim 1 ~ 5 any one.
10. one kind prepares capacitor dielectric layer prepared by the method for magnetic porous material as described in claim 1 ~ 5 any one.
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