CN107442178A - A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres - Google Patents
A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres Download PDFInfo
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- CN107442178A CN107442178A CN201710651092.3A CN201710651092A CN107442178A CN 107442178 A CN107442178 A CN 107442178A CN 201710651092 A CN201710651092 A CN 201710651092A CN 107442178 A CN107442178 A CN 107442178A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 133
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000243 solution Substances 0.000 claims abstract description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011259 mixed solution Substances 0.000 claims abstract description 45
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 38
- 229940056319 ferrosoferric oxide Drugs 0.000 claims abstract description 31
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 24
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 21
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 19
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 18
- 239000001632 sodium acetate Substances 0.000 claims abstract description 17
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 17
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 12
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 238000012805 post-processing Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000002572 peristaltic effect Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 239000011941 photocatalyst Substances 0.000 abstract description 7
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 6
- 229940012189 methyl orange Drugs 0.000 abstract description 6
- 229920001690 polydopamine Polymers 0.000 description 79
- 239000000463 material Substances 0.000 description 19
- 150000001336 alkenes Chemical class 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 229960003638 dopamine Drugs 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000009514 concussion Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 235000011091 sodium acetates Nutrition 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005426 magnetic field effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- 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
-
- 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
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/393—
-
- B01J35/397—
-
- B01J35/51—
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to photocatalyst technology field, and in particular to a kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, including：Step 1, Iron(III) chloride hexahydrate and sodium acetate are dissolved into the ethylene glycol of equivalent respectively, two kinds of solution are mixed evenly afterwards, 10 30wt% polyacrylic acid solutions are added to continue to stir 6 12h, it is placed in reactor, 180~210 DEG C and 4~12h of reaction is kept, obtain black product ferroso-ferric oxide；Step 2, ferroso-ferric oxide is distributed in the ethanol solution of polyvinylpyrrolidone, the rear aqueous solution for adding Dopamine hydrochloride, water-bath, abundant ultrasonic disperse, forms mixed solution b；Step 3, ammoniacal liquor is added drop-wise in above-mentioned mixed solution b, continues ultrasonic reaction 25 hours, obtain Fe3O4@PDA complex microspheres；Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, are put into shaking table and shake 8 16 hours, Magneto separate, post processing, produce Fe3O4@PDA@Ag complex microspheres.Degraded degraded methyl orange significant effect, it is reusable.
Description
Technical field
The invention belongs to photocatalyst technology field, and in particular to a kind of visible light catalyst Fe3O4@PDA@Ag are compound micro-
The preparation method of ball.
Background technology
In recent years, developed rapidly with scientific and technical and industrial technology, the living standard of people is greatly improved.
But the problems such as economy of rapid development and the environmental pollution that brings of industry and shortage of resources also getting worse.Photocatalysis technology
It is a kind of effective means curbed environmental pollution developed rapidly in recent years.IUPAC is so fixed
Justice is light-catalysed：Under the effect of ultraviolet, visible or Infrared irradiation, light is absorbed by photochemical catalyst and participates in the change of reactant
The change for learning change to cause chemical reaction rate or cause chemical reaction.The essence of photocatalysis technology is entered using solar energy
Row chemical catalysis reacts, and is a kind of inexpensive, efficient green science and technology.At present, due to TiO2With nontoxic, oxidability
By force, the advantages that cheap is the catalysis material for being mainly used in Environment control.However, due to TiO2Greater band gap (about
3.2eV), the ultraviolet light that absorbing wavelength is less than 380nm is only capable of, and in sunshine, ultraviolet light only accounts for 4% of sunshine or so,
Visible ray but accounts for 45% or so, TiO2The property of itself limits its practical application as photochemical catalyst.In addition, examine
Consider catalysis material presence be difficult to reclaim, cause the shortcomings of wasting of resources, therefore, exploration is efficient, it is visible light-responded to have,
The photochemical catalyst that can be recycled is the emphasis of current photocatalysis field research.
There are some complicated materials in nature, existing photocatalytic activity, itself has superparamagnetism again, such as some calcium titaniums
Ore deposit and spinelle etc., but due to the limits throughput of natural resources, and performance is not sufficiently stable.In order that material has magnetic, grind
The person of studying carefully is by photocatalytic activity material load to magnetic carrier, thus the composite can keep the catalysis of photochemical catalyst
Activity, can cause again material again externally-applied magnetic field effect under quick Magneto separate, effectively increase the repetition of nano-photocatalyst material
Utilization rate, cost is saved.The ferriferrous oxide material of superparamagnetic meets this requirement well.Noble metal is due to very
Strong visible plasma resonance effects, the visible absorbance of photochemical catalyst can be strengthened, wherein possessing d10 electronics knot with Ag+
Structure, full up or complete empty electronic structure comparatively facilitate lifting photocatalytic activity, therefore the micro-nano material based on precious metals ag
Material turns into the important materials of photocatalysis degradation organic contaminant research.Magnetic material ferroso-ferric oxide and photochemical catalyst are had
Imitate compound so that material can photocatalysis performance, again have quick separation of solid and liquid and recycling advantage, avoid making environment
Into secondary pollution.
And ferriferrous oxide material has very high surface energy, tending to reunite increases the size of particle, influences certainly
The magnetic property of body.Simultaneously because the influence of skin effect, in atmosphere easily oxidation, cause the reduction of its magnetic, therefore, explore one
The emphasis that kind is efficient, there is photochemical catalyst that is visible light-responded, can recycling to be current photocatalysis field research.
The content of the invention
It is an object of the invention to provide a kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres.Need
Illustrate, in the present invention, PDA is poly-dopamine.
To achieve the above object, the technical solution adopted by the present invention is a kind of visible light catalyst Fe3O4@PDA@Ag are compound
The preparation method of microballoon, it is characterised in that comprise the following steps：
Step 1, Iron(III) chloride hexahydrate and sodium acetate are dissolved into the ethylene glycol of equivalent respectively, after by two kinds of solution
It is mixed evenly, adds 10-30wt% polyacrylic acid solutions and continue to stir 6-12h, form mixed solution a, and will mix molten
Liquid a is placed in reactor, 180~210 DEG C and keeps 4~12h of reaction, obtains black product ferroso-ferric oxide；
Step 2, ferroso-ferric oxide is distributed in the ethanol solution of polyvinylpyrrolidone, adds Dopamine hydrochloride afterwards
The aqueous solution, water-bath, abundant ultrasonic disperse, form mixed solution b；
Step 3, ammoniacal liquor is added drop-wise in above-mentioned mixed solution b, continues ultrasonic reaction 2-5 hours, rear Magneto separate simultaneously washs
For several times, Fe is obtained3O4@PDA complex microspheres；
Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, put
Enter concussion 8-16 hours in shaking table, Magneto separate, post processing, produce Fe3O4@PDA@Ag complex microspheres.
Preferably, the mol ratio of Iron(III) chloride hexahydrate and ethylene glycol is 1: 300~500 in the step 1, acetic acid
The mol ratio of sodium and ethylene glycol is 1: 100~300, ethylene glycol and the body of 10-30wt% polyacrylic acid solutions in mixed solution a
Product is than being 40~80: 1.
Preferably, the mass ratio of ferroso-ferric oxide and polyvinylpyrrolidone is 1: 2~3 in the step 2, poly- second
The mol ratio of alkene pyrrolidone and ethanol is 1: 30~150.
Further, the mass ratio of the Dopamine hydrochloride of the step 2 and water is 1~3, and the volume ratio of second alcohol and water is 1
: 3~2.
Preferably, the concentration of ammoniacal liquor is 3~14.5mol/L in the step 3.
Specifically, the dropwise addition of the step 3 is added dropwise using peristaltic pump.
Preferably, the step 4 Fe3O4The mass ratio of@PDA complex microspheres and silver nitrate is 1~6, the concentration of ammoniacal liquor
For 0.2~3mol/L.
Preferably, the bath temperature of the step 2 is 25 DEG C.
Specifically, the post processing of the step 4 is to be cleaned 2~6 times with ethanol, the drying process in 60-80 DEG C of baking oven.
Present invention additionally comprises a kind of Fe3O4@PDA@Ag complex microspheres, it is characterised in that by above-mentioned any one preparation side
Method is prepared.
The beneficial effect comprise that：
(1) present invention is by by photocatalytic activity material load to magnetic carrier, the photochemical catalyst Fe of preparation3O4@
The existing photocatalysis effect of PDA@Ag complex microspheres, simultaneously because introduce ferroso-ferric oxide magnetic core, can quick Magneto separate, have
The repeat usage of nano-photocatalyst material is improved to effect, has saved cost, while avoid and secondary pollution is caused to environment.
(2) present invention is by the use of poly-dopamine (PDA) as dressing agent, in Fe3O4Surface forms decorative layer, poly-dopamine tool
There is extremely strong adhesiveness, can be in Fe3O4Autohemagglutination film forming in matrix, Fe can be improved3O4Surface hydrophilicity and biocompatibility；
Meanwhile poly-dopamine has certain reproducibility, the electroless metallising of material surface can be realized, is easy to the cladding of Ag particles.
(3) photochemical catalyst Fe prepared by the present invention3O4@PDA@Ag complex microspheres have degraded well to degraded methyl orange
Effect, there is very big application value in terms of organic sewage processing, and the raw material that the preparation method uses is easy to get, technique letter
It is single, it is the nano-photocatalyst material of great potential.
Brief description of the drawings
, below will be in embodiment in order to illustrate more clearly of the technical scheme in the specific embodiment of the invention
The required accompanying drawing used does simple introduction, it should be apparent that, drawings in the following description are some embodiment party of the present invention
Formula, for those of ordinary skill in the art, on the premise of not paying creative work, it can also be obtained according to these accompanying drawings
To other accompanying drawings.
Fig. 1 is the electron scanning micrograph of super-paramagnetic ferriferrous oxide nano microballoon prepared by embodiment 1；
Fig. 2 is the transmission electron microscope photo of super-paramagnetic ferriferrous oxide microballoon prepared by embodiment 1；
Fig. 3 is Fe prepared by embodiment 13O4The electron scanning micrograph of@PDA complex microspheres；
Fig. 4 is Fe prepared by embodiment 13O4The transmission electron microscope photo of@PDA complex microspheres；
Fig. 5 is Fe prepared by embodiment 13O4The electron scanning micrograph of@PDA@Ag complex microspheres；
Fig. 6 is Fe prepared by embodiment 13O4The EDS collection of illustrative plates of@PDA@Ag complex microspheres；
Fig. 7 is Fe prepared by embodiment 13O4The MH collection of illustrative plates of@PDA@Ag complex microspheres；
Fig. 8 is Fe prepared by embodiment 23O4The electron scanning micrograph of@PDA@Ag complex microspheres；
Fig. 9 is Fe prepared by embodiment 33O4The electron scanning micrograph of@PDA@Ag complex microspheres；
Figure 10 is visible light catalyst Fe made from embodiment 1-33O4The photocatalytic degradation methyl of@PDA@Ag complex microspheres
Orange catalytic performance collection of illustrative plates.
Embodiment
Clear, complete description is carried out to present disclosure below in conjunction with the accompanying drawings, it is clear that described embodiment is this
The part of the embodiment of invention, rather than whole embodiments.Occupy the embodiment in the present invention, those of ordinary skill in the art
The other embodiment obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.
Embodiment 1
A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that including following step
Suddenly：
Step 1, Iron(III) chloride hexahydrate and sodium acetate are dissolved into the ethylene glycol of equivalent respectively, after by two kinds of solution
It is mixed evenly, adds 10-30wt% polyacrylic acid solutions and continue to stir 6-12h, form mixed solution a, and will mix molten
Liquid a is placed in reactor, 180~210 DEG C and keeps 4~12h of reaction, obtains black product ferroso-ferric oxide；
Step 2, ferroso-ferric oxide is distributed in the ethanol solution of polyvinylpyrrolidone, adds Dopamine hydrochloride afterwards
The aqueous solution, water-bath, abundant ultrasonic disperse, form mixed solution b；
Step 3, ammoniacal liquor is added drop-wise in above-mentioned mixed solution b, continues ultrasonic reaction 2-5 hours, rear Magneto separate simultaneously washs
For several times, Fe is obtained3O4@PDA complex microspheres；
Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, put
Enter concussion 8-16 hours in shaking table, Magneto separate, post processing, produce Fe3O4@PDA@Ag complex microspheres.
It is above the core content of the present invention, crosses and photocatalytic activity materials A g is loaded into Fe on magnetic carrier3O4,
The photochemical catalyst Fe of preparation3O4The existing photocatalysis effect of@PDA@Ag complex microspheres, simultaneously because introducing ferroso-ferric oxide magnetic core, make
It can quick Magneto separate, be effectively improved the repeat usage of nano-photocatalyst material, saved cost, avoided simultaneously
Secondary pollution is caused to environment.In addition, photochemical catalyst Fe prepared by the invention3O4@PDA@Ag complex microspheres are to degraded methyl orange tool
There is good degradation effect, there is very big application value, and the raw material that the preparation method uses in terms of organic sewage processing
Be easy to get, technique it is simple, be the nano-photocatalyst material of great potential.
Specifically, step 1, equivalent is dissolved into by Iron(III) chloride hexahydrate and sodium acetate respectively according to mol ratio for 1: 350
Ethylene glycol in, the mol ratio of sodium acetate and ethylene glycol is 1: 200, after two kinds of solution are mixed evenly, add 10-
30wt% polyacrylic acid solutions continue to stir 8h, form mixed solution a, ethylene glycol total amount and 10- in wherein mixed solution a
The volume ratio of 30wt% polyacrylic acid solutions is 40: 1, and mixed solution is injected into reactor 203 DEG C and keeps reaction 8 hours
To black product ferroso-ferric oxide；
Step 2, ferroso-ferric oxide is taken to be distributed in the ethanol solution of polyvinylpyrrolidone, ferroso-ferric oxide and poly- second
The mass ratio of alkene pyrrolidone is 1: 1, and the mol ratio of polyvinylpyrrolidone and ethanol is 1: 80, rear addition Dopamine hydrochloride
The mass ratio of the aqueous solution, Dopamine hydrochloride and water is 2: 1, and the volume ratio of second alcohol and water is 1: 2 in system, abundant in 25 DEG C of water-bath
Ultrasonic disperse, form mixed solution b；
Step 3, the ammoniacal liquor for taking 5ml concentration to be 5mol/L are added drop-wise in above-mentioned mixed solution with peristaltic pump, and it is anti-to continue ultrasound
Answer 3 hours, rear Magneto separate and wash obtain Fe for several times3O4@PDA complex microspheres；
Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, put
Enter in shaking table and shake 12 hours；Wherein Fe3O4The mass ratio of@PDA complex microspheres and silver nitrate is 2: 1, and the concentration of ammoniacal liquor is
2mol/L。
The mixture that step reacts to obtain is cleaned 2~6 times after Magneto separate with ethanol, then done in 70 DEG C of baking ovens
It is dry, produce Fe3O4@PDA@Ag complex microspheres.
The ESEM and transmission electron microscope photo such as Fig. 1 and 2 of the super-paramagnetic ferriferrous oxide microballoon prepared in the present embodiment
Shown, as can be seen from Figure 2 synthetic product is highly uniform, favorable dispersibility, average grain diameter 200nm.It is manufactured in the present embodiment
Fe3O4The ESEM and transmission electron microscope photo of@PDA complex microspheres as shown in Figures 3 and 4, from Fig. 3 scanning it can be seen from the figure that its
After coating a strata dopamine, good dispersiveness is still kept, obvious poly-dopamine shell is can see in Fig. 4 transmission pictures
Layer, thickness 20nm or so.Final product Fe manufactured in the present embodiment3O4Stereoscan photograph such as Fig. 5 of@PDA@Ag complex microspheres
It is shown, it can be seen that one layer of Ag nanometer sheet is coated on Fe in figure3O4@PDA complex microspheres surface, whole complex microsphere remains good
Good dispersiveness.To the Fe prepared in the present embodiment3O4@PDA@Ag complex microspheres carry out EDS collection of illustrative plates sign as shown in fig. 6, collection of illustrative plates
The middle peak for obvious Fe, Ag and O element occur, and occur without other miscellaneous peaks.To the superparamagnetic Fe prepared in the present embodiment3O4With
Fe3O4@PDA@Ag complex microspheres carry out magnetic characterization as shown in fig. 7, saturation magnetization point ratio be 53 and 33emu/g, finally produce
Thing Fe3O4Although the more original Fe of@PDA@Ag complex microspheres3O4Microballoon saturation magnetization decreases, but remains to meet soon
The demand of fast Magneto separate.
Embodiment 2
A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that including following step
Suddenly：
Step 1, according to mol ratio it is 1: 500 second two for being dissolved into equivalent respectively by Iron(III) chloride hexahydrate and sodium acetate
In alcohol, the mol ratio of sodium acetate and ethylene glycol is 1: 200, after two kinds of solution are mixed evenly, add 10-30wt% poly- third
Olefin(e) acid solution continues to stir 8h, and the volume ratio of wherein ethylene glycol total amount and 10-30wt% polyacrylic acid solutions is 40: 1, and mixing is molten
Liquid is injected into reactor 203 DEG C and keeps reaction to obtain black product ferroso-ferric oxide in 12 hours；
Step 2: take ferroso-ferric oxide to be distributed in the ethanol solution of polyvinylpyrrolidone, ferroso-ferric oxide and poly- second
The mass ratio of alkene pyrrolidone is 1: 1, and the mol ratio of polyvinylpyrrolidone and ethanol is 1: 100, adds Dopamine hydrochloride afterwards
The aqueous solution, the mass ratio of Dopamine hydrochloride and water is 3: 1, and the volume ratio of second alcohol and water is 1: 2 in system, and in water-bath, 25 DEG C are filled
Divide ultrasonic disperse；
Step 3, the ammoniacal liquor for taking 5ml concentration to be 6mol/L are added drop-wise in the mixed solution of step 2 with peristaltic pump, continue to surpass
Phonoresponse 3 hours, rear Magneto separate and washing obtain Fe for several times3O4@PDA complex microspheres；
Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, put
Enter in shaking table and shake 8 hours, wherein Fe3O4The mass ratio of@PDA complex microspheres and silver nitrate is 4: 1, and the concentration of ammoniacal liquor is 2mol/
L；
The mixture that step reaction is obtained is cleaned 2~6 times after Magneto separate with ethanol, is then done in 70 DEG C of baking ovens
It is dry, produce Fe3O4@PDA@Ag complex microspheres.
Final product Fe manufactured in the present embodiment3O4The stereoscan photograph of@PDA@Ag complex microspheres is as shown in figure 8, in figure
It can be seen that one layer of comparatively dense Ag nano particle is coated on Fe3O4@PDA complex microspheres surface, Ag nanoparticle sizes are about
8nm。
Embodiment 3
A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that including following step
Suddenly：
Step 1, according to mol ratio it is 1: 350 second two for being dissolved into equivalent respectively by Iron(III) chloride hexahydrate and sodium acetate
In alcohol, the mol ratio of sodium acetate and ethylene glycol is 1: 200, after two kinds of solution are mixed evenly, add 10-30wt% poly- third
Olefin(e) acid solution continues to stir 8h, wherein the volume ratio of total ethylene glycol and 10-30wt% polyacrylic acid solutions is 40: 1, mixed solution
It is injected into reactor 203 DEG C and keeps reaction to obtain black product ferroso-ferric oxide in 8 hours；
Step 2, ferroso-ferric oxide is taken to be distributed in the ethanol solution of polyvinylpyrrolidone, ferroso-ferric oxide and poly- second
The mass ratio of alkene pyrrolidone is 1: 1, and the mol ratio of polyvinylpyrrolidone and ethanol is 1: 80, rear addition Dopamine hydrochloride
The mass ratio of the aqueous solution, Dopamine hydrochloride and water is 2: 1, and the volume ratio of second alcohol and water is 1: 2 in system, abundant in 25 DEG C of water-bath
Ultrasonic disperse；
Step 3, the ammoniacal liquor for taking 5ml concentration to be 5mol/L are added drop-wise in above-mentioned mixed solution with peristaltic pump, and it is anti-to continue ultrasound
Answer 3 hours, rear Magneto separate and wash obtain Fe for several times3O4@PDA complex microspheres；
Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, put
Enter in shaking table and shake 12 hours；Wherein Fe3O4The mass ratio of@PDA complex microspheres and silver nitrate is 1: 1, and the concentration of ammoniacal liquor is
1mol/L。
Obtained mixture will be reacted to be cleaned 2~6 times with ethanol after Magneto separate, then dried in 70 DEG C of baking ovens,
Produce Fe3O4@PDA@Ag complex microspheres.
Final product Fe manufactured in the present embodiment3O4The stereoscan photograph of@PDA@Ag complex microspheres is as shown in figure 9, in figure
It can be seen that one layer of more sparse Ag nano particle is coated on Fe3O4@PDA complex microspheres surface.
Embodiment 4
Degrading experiment
10mg/mL methyl orange aqueous solution 180mL is taken respectively, adds in embodiment 1,2,3 visible light catalyst prepared
Fe3O4@PDA@Ag complex microsphere complex microsphere 30mg, then by three groups of methyl orange aqueous solutions in the optical filter xenon lamp plus 400nm
80min is irradiated under (500W) light source, the degradation results of gained are as shown in Figure 10.As shown in fig. 6, the degraded in embodiment 1,2,3
As a result respectively with ▲, ●, ■ represent.As seen from the figure, all have to degraded methyl orange using photochemical catalyst prepared by embodiment 1-3
Good degradation effect.The Ag of wherein sheet shows more superior degradation effect, and comparative particle's shape Ag can be seen that intensive Ag
The sparse Ag arrangements of ratio of particle arrangement show more preferable degradation effect.
Embodiment 5
A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, comprises the following steps：
Step 1, according to mol ratio it is 1: 300 second two for being dissolved into equivalent respectively by Iron(III) chloride hexahydrate and sodium acetate
In alcohol, the mol ratio of sodium acetate and ethylene glycol is 1: 100, after two kinds of solution are mixed evenly, add 10-30wt% poly- third
Olefin(e) acid solution continues to stir 6h, forms mixed solution a, the ethylene glycol total amount in wherein mixed solution a and 10-30wt% polypropylene
The volume ratio of acid solution is 40: 1, and mixed solution is injected into reactor 180 DEG C and keeps reaction to obtain black product four in 4 hours
Fe 3 O；
Step 2, ferroso-ferric oxide is taken to be distributed in the ethanol solution of polyvinylpyrrolidone, ferroso-ferric oxide and poly- second
The mass ratio of alkene pyrrolidone is 1: 1, and the mol ratio of polyvinylpyrrolidone and ethanol is 1: 30, rear addition Dopamine hydrochloride
The mass ratio of the aqueous solution, Dopamine hydrochloride and water is 1: 1, and the volume ratio of second alcohol and water is 1: 2 in system, abundant in 25 DEG C of water-bath
Ultrasonic disperse, form mixed solution b；
Step 3, the ammoniacal liquor for taking 5ml concentration to be 3mol/L are added drop-wise in above-mentioned mixed solution with peristaltic pump, and it is anti-to continue ultrasound
Answer 2 hours, rear Magneto separate and wash obtain Fe for several times3O4@PDA complex microspheres；
Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, put
Enter in shaking table and shake 8 hours；Wherein Fe3O4The mass ratio of@PDA complex microspheres and silver nitrate is 1: 1, and the concentration of ammoniacal liquor is
0.2mol/L。
The mixture that step reacts to obtain is cleaned 2~6 times after Magneto separate with ethanol, then done in 60 DEG C of baking ovens
It is dry, produce Fe3O4@PDA@Ag complex microspheres.
Embodiment 6
A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, comprises the following steps：
Step 1, according to mol ratio it is 1: 500 second two for being dissolved into equivalent respectively by Iron(III) chloride hexahydrate and sodium acetate
In alcohol, the mol ratio of sodium acetate and ethylene glycol is 1: 300, after two kinds of solution are mixed evenly, add 10-30wt% poly- third
Olefin(e) acid solution continues to stir 12h, forms mixed solution a, the ethylene glycol total amount in wherein mixed solution a and 10-30wt% poly- third
The volume ratio of olefin(e) acid solution is 80: 1, and mixed solution is injected into reactor 210 DEG C and keeps reaction to obtain within 12 hours black production
Thing ferroso-ferric oxide；
Step 2, ferroso-ferric oxide is taken to be distributed in the ethanol solution of polyvinylpyrrolidone, ferroso-ferric oxide and poly- second
The mass ratio of alkene pyrrolidone is 1: 3, and the mol ratio of polyvinylpyrrolidone and ethanol is 1: 150, adds Dopamine hydrochloride afterwards
The aqueous solution, the mass ratio of Dopamine hydrochloride and water is 3: 1, and the volume ratio of second alcohol and water is 1: 3 in system, and in water-bath, 25 DEG C are filled
Divide ultrasonic disperse, form mixed solution b；
Step 3, the ammoniacal liquor for taking 5ml concentration to be 14.5mol/L are added drop-wise in above-mentioned mixed solution with peristaltic pump, continue to surpass
Phonoresponse 5 hours, rear Magneto separate and washing obtain Fe for several times3O4@PDA complex microspheres；
Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, put
Enter in shaking table and shake 16 hours；Wherein Fe3O4The mass ratio of@PDA complex microspheres and silver nitrate is 6: 1, and the concentration of ammoniacal liquor is
3mol/L。
The mixture that step reacts to obtain is cleaned 2~6 times after Magneto separate with ethanol, then done in 80 DEG C of baking ovens
It is dry, produce Fe3O4@PDA@Ag complex microspheres.
Embodiment 7
A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, comprises the following steps：
Step 1, according to mol ratio it is 1: 400 second two for being dissolved into equivalent respectively by Iron(III) chloride hexahydrate and sodium acetate
In alcohol, the mol ratio of sodium acetate and ethylene glycol is 1: 200, after two kinds of solution are mixed evenly, add 10-30wt% poly- third
Olefin(e) acid solution continues to stir 8h, forms mixed solution a, the ethylene glycol total amount in wherein mixed solution a and 10-30wt% polypropylene
The volume ratio of acid solution is 60: 1, and mixed solution is injected into reactor 190 DEG C and keeps reaction to obtain black product four in 6 hours
Fe 3 O；
Step 2, ferroso-ferric oxide is taken to be distributed in the ethanol solution of polyvinylpyrrolidone, ferroso-ferric oxide and poly- second
The mass ratio of alkene pyrrolidone is 1: 3, and the mol ratio of polyvinylpyrrolidone and ethanol is 1: 120, adds Dopamine hydrochloride afterwards
The aqueous solution, the mass ratio of Dopamine hydrochloride and water is 3: 1, and the volume ratio of second alcohol and water is 1: 2 in system, and in water-bath, 25 DEG C are filled
Divide ultrasonic disperse, form mixed solution b；
Step 3, the ammoniacal liquor for taking 5ml concentration to be 10mol/L are added drop-wise in above-mentioned mixed solution with peristaltic pump, continue ultrasound
Reaction 3 hours, rear Magneto separate and washing obtain Fe for several times3O4@PDA complex microspheres；
Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, put
Enter in shaking table and shake 10 hours；Wherein Fe3O4The mass ratio of@PDA complex microspheres and silver nitrate is 3: 1, and the concentration of ammoniacal liquor is
2mol/L。
The mixture that step reacts to obtain is cleaned 2~6 times after Magneto separate with ethanol, then done in 80 DEG C of baking ovens
It is dry, produce Fe3O4@PDA@Ag complex microspheres.
Embodiment 8
A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, comprises the following steps：
Step 1,2.16g Iron(III) chloride hexahydrates are dissolved in 40ml ethylene glycol, 18g sodium acetates are dissolved in 40ml second
In glycol, after two kinds of solution are mixed evenly, add 2mL 10-wt% polyacrylic acid solutions and continue to stir 6h, formed mixed
Solution a is closed, and mixed solution a is placed in reactor, 180 DEG C and keeps reacting 4h, obtains black product ferroso-ferric oxide；
Step 2,0.02g ferroso-ferric oxides are distributed in the ethanol solution of 0.1-0.5g polyvinylpyrrolidones, will
0.1g Dopamine hydrochlorides are dissolved in 25mL water, will be formed hydrochloric acid aqueous dopamine solution and are added thereto, and by the aqueous solution, 25 DEG C of water
Bath, abundant ultrasonic disperse, form mixed solution b；
Step 3,0.5mL ammoniacal liquor is added drop-wise in above-mentioned mixed solution b with peristaltic pump, continues ultrasonic reaction 2 hours, after
Magneto separate simultaneously washs for several times, obtains Fe3O4@PDA complex microspheres；
Step 4, by the Fe of the above-mentioned preparations of 0.05g3O4@PDA complex microspheres be added to ammoniacal liquor and silver nitrate to be made into silver-colored ammonia molten
Liquid, concussion 8-16 hours in shaking table are put into, Magneto separate, are cleaned 2~6 times with ethanol, the drying process in 60-80 DEG C of baking oven, i.e.,
Obtain Fe3O4@PDA@Ag complex microspheres；The ammoniacal liquor and silver nitrate are made into silver ammino solution, ammoniacal liquor 2mL, silver nitrate 0.4g, water
40mL。
Embodiment 9
A kind of visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, comprises the following steps：
Step 1,2.16g Iron(III) chloride hexahydrates are dissolved in 40ml ethylene glycol, 18g sodium acetates are dissolved in 40ml second
In glycol, after two kinds of solution are mixed evenly, add 2mL 30wt% polyacrylic acid solutions and continue to stir 12h, formed mixed
Solution a is closed, and mixed solution a is placed in reactor, 210 DEG C and keeps reacting 12h, obtains black product ferroso-ferric oxide；
Step 2,0.02g ferroso-ferric oxides are distributed in the ethanol solution of 0.1-0.5g polyvinylpyrrolidones, will
0.1g Dopamine hydrochlorides are dissolved in 25mL water, will be formed hydrochloric acid aqueous dopamine solution and are added thereto, and by the aqueous solution, 25 DEG C of water
Bath, abundant ultrasonic disperse, form mixed solution b；
Step 3,0.5mL ammoniacal liquor is added drop-wise in above-mentioned mixed solution b with peristaltic pump, continues ultrasonic reaction 5 hours, after
Magneto separate simultaneously washs for several times, obtains Fe3O4@PDA complex microspheres；
Step 4, by the Fe of the above-mentioned preparations of 0.05g3O4@PDA complex microspheres be added to ammoniacal liquor and silver nitrate to be made into silver-colored ammonia molten
Liquid, it is put into shaking table and shakes 16 hours, Magneto separate, cleaned 2~6 times, the drying process in 60-80 DEG C of baking oven, produced with ethanol
Fe3O4@PDA@Ag complex microspheres；The ammoniacal liquor and silver nitrate are made into silver ammino solution, ammoniacal liquor 2mL, silver nitrate 0.4g, water 40mL.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
- A kind of 1. visible light catalyst Fe3O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that comprise the following steps：Step 1, Iron(III) chloride hexahydrate and sodium acetate are dissolved into the ethylene glycol of equivalent respectively, after two kinds of solution are mixed Stir, add 10-30wt% polyacrylic acid solutions and continue to stir 6-12h, form mixed solution a, and mixed solution a is put In reactor, 180~210 DEG C and 4~12h of reaction is kept, obtain black product ferroso-ferric oxide；Step 2, ferroso-ferric oxide is distributed in the ethanol solution of polyvinylpyrrolidone, the rear water for adding Dopamine hydrochloride Solution, water-bath, abundant ultrasonic disperse, form mixed solution b；Step 3, ammoniacal liquor is added drop-wise in above-mentioned mixed solution b, continues ultrasonic reaction 2-5 hours, rear Magneto separate simultaneously washs number It is secondary, obtain Fe3O4@PDA complex microspheres；Step 4, by the Fe of above-mentioned preparation3O4@PDA complex microspheres are added to ammoniacal liquor and silver nitrate is made into silver ammino solution, are put into and shake Shaken in bed 8-16 hours, Magneto separate, post processing, produce Fe3O4@PDA@Ag complex microspheres.
- 2. Fe as claimed in claim 13O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that in the step 1 The mol ratio of Iron(III) chloride hexahydrate and ethylene glycol is 1: 300~500, the mol ratio of sodium acetate and ethylene glycol for 1: 100~ The volume ratio of ethylene glycol and 10-30wt% polyacrylic acid solutions in 300, mixed solution a is 40~80: 1.
- 3. Fe as claimed in claim 13O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that in the step 2 The mass ratio of ferroso-ferric oxide and polyvinylpyrrolidone is 1: 1~3, and the mol ratio of polyvinylpyrrolidone and ethanol is 1: 30 ~150.
- 4. the Fe as described in claim 1 or 33O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that the step 2 Dopamine hydrochloride and the mass ratio of water be 1~3: 1, the volume ratio of second alcohol and water is 1: 3~2.
- 5. Fe as claimed in claim 13O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that in the step 3 The concentration of ammoniacal liquor is 3~14.5mol/L.
- 6. the Fe as described in claim 1 or 53O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that the step 3 Dropwise addition using peristaltic pump be added dropwise.
- 7. Fe as claimed in claim 13O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that the step 4 Fe3O4The mass ratio of@PDA complex microspheres and silver nitrate is 1~6: 1, and the concentration of ammoniacal liquor is 0.2~3mol/L.
- 8. Fe as claimed in claim 13O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that the step 2 Bath temperature is 25 DEG C.
- 9. Fe as claimed in claim 13O4The preparation method of@PDA@Ag complex microspheres, it is characterised in that the step 4 Post-process and be, cleaned 2~6 times with ethanol, the drying process in 60-80 DEG C of baking oven.
- A kind of 10. Fe3O4@PDA@Ag complex microspheres, it is characterised in that by the preparation of claim 1-9 any one preparation method .
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