CN107029798A - A kind of preparation method and application of hollow magnetic nanoparticle - Google Patents
A kind of preparation method and application of hollow magnetic nanoparticle Download PDFInfo
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- CN107029798A CN107029798A CN201710236366.2A CN201710236366A CN107029798A CN 107029798 A CN107029798 A CN 107029798A CN 201710236366 A CN201710236366 A CN 201710236366A CN 107029798 A CN107029798 A CN 107029798A
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- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004793 Polystyrene Substances 0.000 claims abstract description 71
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920002223 polystyrene Polymers 0.000 claims abstract description 28
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 150000003233 pyrroles Chemical class 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 241001062009 Indigofera Species 0.000 claims 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229940097275 indigo Drugs 0.000 claims 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 239000010908 plant waste Substances 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 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 abstract description 13
- 239000002082 metal nanoparticle Substances 0.000 abstract description 13
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 13
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000004005 microsphere Substances 0.000 abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 229920000128 polypyrrole Polymers 0.000 description 29
- 239000000243 solution Substances 0.000 description 14
- 235000013339 cereals Nutrition 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011806 microball Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- 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
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention belongs to the preparation method and application technical field of magnetic Nano material, and in particular to a kind of preparation method and application of hollow magnetic nanoparticle, mainly solve existing noble metal nano particles and there is easy in inactivation and the technical problem for being difficult to reclaim.Hollow magnetic nanoparticle is used as metal nanoparticles loaded catalytic carrier by the present invention.The polystyrene microsphere of carboxylated has been synthesized by emulsion polymerization first, sodium borohydride effect under by Electrostatic Absorption its surface Ag+In-situ reducing is Nano silver grain, then further constructs Fe3O4@PPy support shell, dissolve polystyrene microsphere in tetrahydrofuran solution, have obtained hollow magnetic Nano microsphere (Ag Fe3O4@PPy)。Ag@Fe3O4@PPy can be catalyzed sodium borohydride reduction methylene blue with efficient and sensible, and magnetic field has good magnetic response to external world, and being reclaimed still has higher catalytic performance after being recycled for multiple times, there is potential application value in environmental area.
Description
Technical field
The invention belongs to the preparation method and application technical field of magnetic Nano material, and in particular to a kind of hollow magnetic is received
Meter Wei Qiu preparation method and application.
Background technology
Metal nanoparticle is due to its special physics and chemical property, in catalysis, optics, biological medicine and biological biography
The fields such as sensor are all with a wide range of applications.Especially in catalytic field, the noble metal such as Au, Ag shows higher catalysis
Performance, but directly make the drawbacks of catalyst has very big using its nano-particle, the higher specific surface energy of such as nano-particle causes
They easily reunite, and reaction terminates rear catalyst and is not easily recycled.Therefore, these metal nanoparticles are fixed on active
On the carrier material in site, to widen its application.
New material of the hollow microsphere as Size Distribution in nanometer to micrometer range, due to its low-density, high surface
The advantages of long-pending, larger volume space and excellent optical property, it is used as metal nanoparticles loaded preferred catalytic and carries
One of body.Hollow microsphere generally has three positions for metal nanoparticles loaded：Cavity inside, shell layer surface, embedded housing.
Metal nanoparticle is loaded in inside hollow microsphere, can still be reunited by long period particle；If metal nanoparticle is consolidated
It is scheduled on the support surface of hollow ball, can be directly exposed in reaction solution, them may be caused to be come off simultaneously from supporter
Inactivated by solution corrosion, it is difficult to reclaim.
The content of the invention
There is easy in inactivation and the technical problem for being difficult to reclaim present invention aim to address existing noble metal nano particles, carry
For a kind of preparation method and application of hollow magnetic nanoparticle.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of hollow magnetic nanoparticle, comprises the following steps：
1) by styrene (polymerized monomer), acrylic acid (branched monomer), lauryl sodium sulfate (emulsifying agent), potassium peroxydisulfate
(initiator), sodium acid carbonate are with 3636：400-500：15-17：24-27：24-27 mass ratio is well mixed, and adjusts mixture
The pH of system is 8-10, and 5-8h is reacted at a temperature of 75-80 DEG C, Properties of Polystyrene Nano Particles is obtained；
2) 11 are pressed：Properties of Polystyrene Nano Particles is scattered in the NaOH solution that concentration is 8% by 10000-11000 mass ratio
In, the Properties of Polystyrene Nano Particles of carboxylated is made in mechanical agitation 30-50min, and to the Properties of Polystyrene Nano Particles of carboxylated
Middle addition AgNO3, control Properties of Polystyrene Nano Particles and AgNO3Mass ratio be 11：250-280, by Electrostatic Absorption by Ag+
Adsorb on the surface of the Properties of Polystyrene Nano Particles of carboxylated, NaBH is then added into reaction system4Successive reaction, control is poly-
Styrene nanoparticle and NaBH4Mass ratio be 11：2-3, by Ag+PS/Ag is made into silver nanoparticle in in-situ reducing, then will
PS/Ag, which is dispersed in secondary water, is made PS/Ag dispersion liquids；
3) pyrroles is added in PS/Ag dispersion liquids, the mass ratio for controlling PS/Ag and pyrroles is 1000:1-2, at room temperature
Stir, and in N2The FeCl that mass percent is 5wt% is slowly added dropwise under environment into reaction system3Solution, controls PS/
The Ag and FeCl that mass percent is 5wt%3The mass ratio of solution is 1:By FeCl after 50-60, mechanical agitation 4-5h2·4H2O
And NH3·4H2O is sequentially added in above-mentioned reaction system, controls PS/Ag and FeCl2·4H2O and NH3·4H2O mass ratio difference
For 1：1-2 and 1：15-20, is made PS/Ag@Fe3O4@PPy；
4) according to 1：50-60 mass ratio is by PS/Ag@Fe3O4@PPy are scattered in THF, stir 20-24h, are removed PS and are received
Rice layer, reactant is separated with magnet, and is washed with ethanol, that is, hollow magnetic nanoparticle Ag@Fe are made3O4@PPy.(synthesis
Route map is shown in Fig. 1) in the present invention as stated above we select to be fixed on Nano silver grain into mode in the shell of hollow microsphere, simultaneously
Fe is embedded in hollow shell3O4Magnetic Nano material, so not only overcomes its defect for being difficult to reclaim, and reach
The purpose of metal nanoparticle is recycled under additional magnetic fields.
The hollow magnetic nanoparticle can be used for the processing of wastewater containing methylene blue.Hollow magnetic produced by the present invention is received
Meter Wei Qiu can be used for the processing of wastewater containing methylene blue.The present invention introduces silver nano-grain in hollow nanoshells, and Ag receives
After rice grain shows higher catalytic performance to sodium borohydride reduction methylene blue, but they easily reunite, and reaction terminates
Catalyst is not easily recycled.Therefore these metal nanoparticles are fixed on the carrier material in active site, in combination with
Hollow layer has higher specific surface area and larger volume space, substantially increases its catalytic performance.
The present invention uses above technical scheme, because Nano silver grain has higher specific surface energy, if directly using silver
Nano-particle makees catalyst can be so that they easily reunite, and reaction terminates rear catalyst and is not easily recycled.The present invention is with modified poly-
Phenylethylene micro ball is template, by Nano silver grain and Fe3O4Magnetic nano-particle combines, will be poly- in tetrahydrofuran solution
Phenylethylene micro ball dissolves, and has obtained hollow magnetic silver nanoparticle microballoon (Ag@Fe3O4@PPy).Using magnetic Nano material additional
Good magnetic response under magnetic field, is realized to Cu in system2+Removal, overcome the defect that Nano silver grain is difficult to reclaim, reach
Recycle in the presence of externally-applied magnetic field the purpose of metal nanoparticle.
Brief description of the drawings
Fig. 1 is synthetic route chart of the present invention；
Fig. 2 is 1PS@of embodiment of the present invention Ag, Fe3O4With Ag@Fe3O4@PPy FTIR spectrum；
Fig. 3 is 1Ag@of embodiment of the present invention Fe3O4@PPy thermogravimetric curve；
Fig. 4 is the 25mg FeCl of the embodiment of the present invention 12·4H2O and 50mg FeCl2·4H2O VSM spectrograms；
Fig. 5 is 1Fe of the embodiment of the present invention3O4, PS@Ag and Ag@Fe3O4@PPy x-ray diffraction pattern；
Fig. 6 is 1Ag@of embodiment of the present invention Fe3O4@PPy are catalyzed the ultraviolet-ray visible absorbing of sodium borohydride reduction methylene blue
Spectrum change figure.(a) the absorption spectrogram (c) of absorption spectrum (b) the mixing methylene blue and sodium borohydride 1.0h of methylene blue is mixed
Close methylene blue and add 2.0mg into methylene blue and sodium borohydride mixed solution with sodium borohydride 25h absorption spectrogram (d)
Ag@Fe3O4Absorption spectrogram after@PPy 25min；
Fig. 7 is the embodiment of the present invention 1 by Ag@Fe3O4@PPy circulate the speed constant comparison diagram of five times.
Embodiment
Embodiment 1
A kind of preparation method of hollow magnetic nanoparticle in the present embodiment, comprises the following steps：
1) by styrene 18.18g, acrylic acid 2.0g, lauryl sodium sulfate 75mg, potassium peroxydisulfate 120mg, sodium acid carbonate
120mg is well mixed, and the pH of regulation mixed system is 8, reacts 5h at a temperature of 75 DEG C, obtains Properties of Polystyrene Nano Particles；
2) Properties of Polystyrene Nano Particles 55mg is scattered in the NaOH solution 50g that concentration is 8%, mechanical agitation 30min
The Properties of Polystyrene Nano Particles of carboxylated is made, and AgNO is added into the Properties of Polystyrene Nano Particles of carboxylated31.25g, lead to
Electrostatic Absorption is crossed by Ag+Adsorb on the surface of the Properties of Polystyrene Nano Particles of carboxylated, then added into reaction system
NaBH410mg successive reactions, by Ag+In-situ reducing is made PS/Ag, 50mg PS/Ag then is dispersed in into 30mL bis- into silver nanoparticle
PS/Ag dispersion liquids are made in secondary water；
3) the μ g of pyrroles 50 are added in PS/Ag dispersion liquids, be stirred at room temperature uniformly, and in N2To reaction system under environment
In be slowly added dropwise mass percent be 5wt% FeCl3By FeCl after solution 2.5g, mechanical agitation 4h2·4H2O 50mg and
NH3·4H2O 725mg are sequentially added in above-mentioned reaction system, and PS/Ag@Fe are made3O4@PPy；
4) by PS/Ag@Fe3O4@PPy 500mg are scattered in THF25g, stir 20h, PS nanometer layers are removed, by reactant
Separated, and washed with ethanol with magnet, that is, hollow magnetic nanoparticle Ag@Fe are made3O4@PPy。
To Ag@Fe3O4@PPy carry out structural characterization, such as Fig. 2,3,4,5.Ag@Fe in Fig. 2 FT-IR spectrum3O4@PPy curves
In 1576,1190,1036,925cm-1Peak be pyrroles characteristic absorption peak, 579cm-1Characteristic absorption peak being stretched for Fe-O keys
Contracting vibration peak, it was demonstrated that magnetic nano-particle has successfully been coated in pyrroles's shell with Nano silver grain.Fig. 3 thermogravimetric curve
The middle 30-200 DEG C quality lost is mainly by Ag@Fe3O4Caused by the losing of the crystallization water in@PPy；200-450 DEG C loses
Quality is mainly what is caused by the degraded of polypyrrole, and last remaining quality is about 86%.Ag@Fe in Fig. 43O4@PPy X- is penetrated
2 θ=30.14 ° in line diffraction curve, 35.7 °, 43.33 °, 53.6 °, 57.1 °, 62.8 ° of diffraction maximum correspond to Emission in Cubic respectively
Fe3O4(220), (311), (400), (422), (511) and (440) crystal plane, and 2 θ=38.14 °, 44.09 °,
64.36 °, 77.29 °, 81.31 ° of diffraction maximum respectively correspond to Nano silver grain (111), (200), (220), (311) and
(222) crystal plane, illustrates Ag@Fe3O4Nano silver grain and Fe are successfully combined in@PPy hollow nanospheres3O4
Magnetic nano-particle.
The hollow magnetic nanoparticle can be used for the processing of wastewater containing methylene blue：
By 2.0mg Ag@Fe3O4@PPy are dispersed in 2.5mL, 24mgL-1In methylene blue solution, 1.0mL is then added,
15mg·L-1NaBH4, the color of mixed solution gradually becomes colourless by blueness, determines the change of its ultraviolet-visible absorption spectroscopy
Figure, such as Fig. 6.The result illustrates Ag@Fe3O4@PPy have higher catalytic performance to sodium borohydride reduction methylene blue, greatly
Shorten its catalysis time.
Ag@Fe3O4@PPy catalytic performance loop test
By external magnetic field by 2.0mg Ag@Fe3O4@PPy concentration and separations come out, and are cleaned with secondary water twice, according to above-mentioned
Step continues to be catalyzed sodium borohydride reduction methylene blue, calculates its speed constant, carries out after five parallel laboratory tests, obtains its circulation
Utilize figure, such as Fig. 7.Due to Ag@Fe3O4Fe is embedded in@PPy hollow shell3O4Magnetic Nano material, so not only overcomes
It is difficult to the defect reclaimed, and has reached the purpose that metal nanoparticle is recycled in the presence of externally-applied magnetic field, Fig. 7
Prove Ag@Fe3O4@PPy are recycled after five times, still possess higher catalytic performance.
Embodiment 2
A kind of preparation method of hollow magnetic nanoparticle in the present embodiment, comprises the following steps：
1) by styrene 18.18g, acrylic acid 2.3g, lauryl sodium sulfate 80mg, potassium peroxydisulfate 125mg, sodium acid carbonate
125mg is well mixed, and the pH of regulation mixed system is 10, reacts 8h at a temperature of 80 DEG C, obtains Properties of Polystyrene Nano Particles；
2) Properties of Polystyrene Nano Particles 55mg is scattered in the NaOH solution 53g that concentration is 8%, mechanical agitation 50min
The Properties of Polystyrene Nano Particles of carboxylated is made, and AgNO is added into the Properties of Polystyrene Nano Particles of carboxylated31.4g, passes through
Electrostatic Absorption is by Ag+Adsorb on the surface of the Properties of Polystyrene Nano Particles of carboxylated, then added into reaction system
NaBH413mg successive reactions, by Ag+In-situ reducing is made PS/Ag, 50mg PS/Ag then is dispersed in into 30mL bis- into silver nanoparticle
PS/Ag dispersion liquids are made in secondary water；
3) the μ g of pyrroles 80 are added in PS/Ag dispersion liquids, be stirred at room temperature uniformly, and in N2To reaction system under environment
In be slowly added dropwise mass percent be 5wt% FeCl3By FeCl after solution 2.8g, mechanical agitation 5h2·4H2O80mg and
NH3·4H2O800mg is sequentially added in above-mentioned reaction system, and PS/Ag@Fe are made3O4@PPy；
4) by PS/Ag@Fe3O4@PPy500mg are scattered in THF27g, stir 24h, remove PS nanometer layers, reactant is used
Magnet is separated, and is washed with ethanol, that is, hollow magnetic nanoparticle Ag@Fe are made3O4@PPy。
Embodiment 3
A kind of preparation method of hollow magnetic nanoparticle in the present embodiment, comprises the following steps：
1) by styrene 18.18mg, acrylic acid 2.5g, lauryl sodium sulfate 85mg, potassium peroxydisulfate 135mg, bicarbonate
Sodium 135mg is well mixed, and the pH of regulation mixed system is 9, reacts 6h at a temperature of 78 DEG C, obtains pipe/polyhenylethylene nano micro-
Ball；
2) Properties of Polystyrene Nano Particles 55mg is scattered in the NaOH solution 55g that concentration is 8%, mechanical agitation 40min
The Properties of Polystyrene Nano Particles of carboxylated is made, and AgNO is added into the Properties of Polystyrene Nano Particles of carboxylated31.4g, leads to
Electrostatic Absorption is crossed by Ag+Adsorb on the surface of the Properties of Polystyrene Nano Particles of carboxylated, then added into reaction system
NaBH415mg successive reactions, by Ag+In-situ reducing is made PS/Ag, 50mg PS/Ag then is dispersed in into 30mL bis- into silver nanoparticle
PS/Ag dispersion liquids are made in secondary water；
3) the μ g of pyrroles 100 are added in PS/Ag dispersion liquids, be stirred at room temperature uniformly, and in N2To reactant under environment
The FeCl that mass percent is 5wt% is slowly added dropwise in system3By FeCl after solution 3.0g, mechanical agitation 4.5h2·4H2O100mg
And NH3·4H2O1.0g is sequentially added in above-mentioned reaction system, and PS/Ag@Fe are made3O4@PPy；
4) by PS/Ag@Fe3O4@PPy500mg are scattered in THF30g, stir 22h, remove PS nanometer layers, reactant is used
Magnet is separated, and is washed with ethanol, that is, hollow magnetic nanoparticle Ag@Fe are made3O4@PPy。
Protection scope of the present invention is not limited by above example.
Claims (2)
1. a kind of preparation method of hollow magnetic nanoparticle, it is characterised in that：Comprise the following steps：
1) by styrene, acrylic acid, lauryl sodium sulfate, potassium peroxydisulfate, sodium acid carbonate with 3636：400-500：15-17：
24-27：24-27 mass ratio is well mixed, and the pH of regulation mixed system is 8-10, and 5-8h is reacted at a temperature of 75-80 DEG C,
Obtain Properties of Polystyrene Nano Particles；
2) 11 are pressed：Properties of Polystyrene Nano Particles is scattered in the NaOH solution that concentration is 8% by 10000-11000 mass ratio,
The Properties of Polystyrene Nano Particles of carboxylated is made in mechanical agitation 30-50min, and adds into the Properties of Polystyrene Nano Particles of carboxylated
Enter AgNO3, control Properties of Polystyrene Nano Particles and AgNO3Mass ratio be 11：250-280, by Electrostatic Absorption by Ag+Absorption
On the surface of the Properties of Polystyrene Nano Particles of carboxylated, NaBH is then added into reaction system4Successive reaction, controls polyphenyl second
Alkene nanoparticle and NaBH4Mass ratio be 11：2-3, by Ag+Into silver nanoparticle PS/Ag is made, then by PS/Ag in in-situ reducing
It is dispersed in secondary water and PS/Ag dispersion liquids is made；
3) pyrroles is added in PS/Ag dispersion liquids, the mass ratio for controlling PS/Ag and pyrroles is 1000:1-2, is stirred at room temperature
Uniformly, and in N2The FeCl that mass percent is 5wt% is slowly added dropwise under environment into reaction system3Solution, control PS/Ag with
Mass percent is 5wt% FeCl3The mass ratio of solution is 1:By FeCl after 50-60, mechanical agitation 4-5h2·4H2O and
NH3·4H2O is sequentially added in above-mentioned reaction system, controls PS/Ag and FeCl2·4H2O and NH3·4H2O mass ratio is respectively
1：1-2 and 1：15-20, is made PS/Ag@Fe3O4@PPy；
4) according to 1：50-60 mass ratio is by PS/Ag@Fe3O4@PPy are scattered in THF, stir 20-24h, remove PS nanometer layers,
Reactant is separated with magnet, and washed with ethanol, that is, hollow magnetic nanoparticle Ag@Fe are made3O4@PPy。
2. a kind of application of hollow magnetic nanoparticle, it is characterised in that：The hollow magnetic nanoparticle can be used for containing methylene
The processing of base indigo plant waste water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108714420A (en) * | 2018-05-08 | 2018-10-30 | 宁波工程学院 | The preparation method of optomagnetic response hollow microsphere |
| CN115739062A (en) * | 2022-11-11 | 2023-03-07 | 中触媒新材料股份有限公司 | TiO with controllable particle size 2 Catalyst, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773638A (en) * | 2005-11-10 | 2006-05-17 | 北京科技大学 | Method for producing magnetic powder by form method |
| KR100816128B1 (en) * | 2006-10-24 | 2008-03-21 | 전북대학교산학협력단 | Tio2-capsulated metallic nanoparticles for photocatalyst and its preparation method |
| CN104193862A (en) * | 2014-09-10 | 2014-12-10 | 齐鲁工业大学 | Preparation method of polystyrene/silver/titanium dioxide composite material |
| US20160082418A1 (en) * | 2014-09-19 | 2016-03-24 | Georgia Tech Research Corporation | Silver nanowires, methods of making silver nanowires, core-shell nanostructures, methods of making core-shell nanostructures, core-frame nanostructures, methods of making core-frame nanostructures |
| CN106268958A (en) * | 2016-07-18 | 2017-01-04 | 浙江大学 | The preparation of a kind of nanometer silver magnetic polystyrene microsphere and application thereof |
-
2017
- 2017-04-12 CN CN201710236366.2A patent/CN107029798A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773638A (en) * | 2005-11-10 | 2006-05-17 | 北京科技大学 | Method for producing magnetic powder by form method |
| KR100816128B1 (en) * | 2006-10-24 | 2008-03-21 | 전북대학교산학협력단 | Tio2-capsulated metallic nanoparticles for photocatalyst and its preparation method |
| CN104193862A (en) * | 2014-09-10 | 2014-12-10 | 齐鲁工业大学 | Preparation method of polystyrene/silver/titanium dioxide composite material |
| US20160082418A1 (en) * | 2014-09-19 | 2016-03-24 | Georgia Tech Research Corporation | Silver nanowires, methods of making silver nanowires, core-shell nanostructures, methods of making core-shell nanostructures, core-frame nanostructures, methods of making core-frame nanostructures |
| CN106268958A (en) * | 2016-07-18 | 2017-01-04 | 浙江大学 | The preparation of a kind of nanometer silver magnetic polystyrene microsphere and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| BINGQI MAO ET AL: "Multifunctional hollow polydopamine-based composites(Fe3O4/PDA@Ag) for efficient degradation of organic dyes", 《RSC ADVANCES》 * |
| JU-MEI L ET AL: "Poly(styrene-co-acrylic acid) core and silver nanoparticle/silica shell composite microspheres as high performance surface-enhanced Raman spectroscopy (SERS) substrate and molecular barcode label", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| MINCHEOL CHANG ET AL: "mparting Chemical Stability in Nanoparticulate Silver via a Conjugated Polymer Casing Approach", 《ACS APPLIED MATERIAL INTERFACES》 * |
| 张树永等: "《综合化学实验》", 31 August 2006, 化学工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108714420A (en) * | 2018-05-08 | 2018-10-30 | 宁波工程学院 | The preparation method of optomagnetic response hollow microsphere |
| CN115739062A (en) * | 2022-11-11 | 2023-03-07 | 中触媒新材料股份有限公司 | TiO with controllable particle size 2 Catalyst, preparation method and application thereof |
| CN115739062B (en) * | 2022-11-11 | 2024-05-28 | 中触媒新材料股份有限公司 | Particle size controllable TiO2Catalyst, preparation method and application thereof |
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