CN105129865B - It is micro-nano and preparation method and application magnetic - Google Patents
It is micro-nano and preparation method and application magnetic Download PDFInfo
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- CN105129865B CN105129865B CN201510519389.5A CN201510519389A CN105129865B CN 105129865 B CN105129865 B CN 105129865B CN 201510519389 A CN201510519389 A CN 201510519389A CN 105129865 B CN105129865 B CN 105129865B
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 28
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 18
- 230000001788 irregular Effects 0.000 claims abstract description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 230000005389 magnetism Effects 0.000 claims abstract description 9
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 15
- 229910000859 α-Fe Inorganic materials 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 230000005415 magnetization Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000005307 ferromagnetism Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 51
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 239000011449 brick Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 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
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor 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
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a kind of magnetism micro-nano and preparation method and application, micro-nano of the magnetism is that a kind of dispersiveness and homogeneity are good, the α Fe of size adjustable2O3Or Fe3O4Micro-nano.α Fe are prepared for using the hot method of mixed solvent2O3Micro-nano, by varying the ratio between amount of the volume of water, reactant concentration, alkali and metal salt material, the controllable size of micro-nano of the type of alkali and pattern (nanometer sheet of hexagon or subcircular, its a diameter of 60~510nm, 8~30nm of thickness；Irregular micron film, its a diameter of 2~16 μm, 0.35~1 μm of thickness).α‑Fe2O3The Fe of ferromagnetism and excellent microwave absorbing property is further transformed to by carbo-thermal process3O4Micro-nano.The present invention is without surfactant, preparation flow is simple, raw material is cheap and easy to get, cost is low, yield is high, is easy to commercial Application popularization.Micro-nano provided has application prospect in fields such as photocatalysis, microwave absorption, electrode material, magnetic recording material, sensor and biomedical engineerings.
Description
Technical field
The present invention relates to magnetic Nano technical field, and in particular to a kind of to prepare the simple, controllable of micro-nano of magnetism
Method.
Background technology
α-Fe2O3And Fe3O4Due to the characteristic such as its stabilization, low toxicity, rich reserves, cheap, and as most important two
The oxide of class iron.α-Fe2O3It is a kind of n-type semiconductor, its energy gap is 2.1V, in inorganic pigment, catalyst, electricity
The fields such as pole material, sensor have extensive potential application.Fe3O4It is a kind of traditional magnetic material, nanoscale
Fe3O4With size and the relevant electricity of pattern and magnetic performance, such as single magnetic domain characteristic, coercivity change in size, relatively low residence
In temperature and superparamagnetism, make its magnetic recording, microwave absorption, sensor, bio-separation, biological diagnosis, target administration etc. lead
Domain has a wide range of applications and potential using value.Thus, α-Fe2O3And Fe3O4Controllable preparation and application study have it is important
Science and practical significance, enjoy the concern of domestic and international researcher.
Two-dimensional nano piece has the light, electricity, magnetic property of novelty because of its unique shape anisotropy.Thus develop green
Color, simple, efficiently, inexpensive method prepare good dispersion, size, adjustable micro-nano of composition as current chemistry and material
The research hotspot in material field.
The method for synthesizing the oxide nano-slice of iron mainly has high temperature pyrolytic cracking (HTP), ball-milling method, coprecipitation and microwave method.Specially
Sharp document (CN101560695A) discloses a kind of high temperature pyrolytic cracking (HTP) and prepares binary magnetic oxide single crystal nanoplate, and this method is
By dissolving metal salts in diethylene glycol, reacted in 140~190 DEG C of oil bath pans by controlling the method for reflux to control, then pass through
500 degree of annealing obtain single crystal nanoplate, the higher organic solvent of this method use cost, the nanometer sheet homogeneity of preparation is poor,
Reaction is not easy to control, and the saturation magnetization of products therefrom is relatively low.Patent document (CN104174855A) discloses a kind of table
Face activating agent, organic matter auxiliary ball milling method prepare magnetic Nano piece, and this method is easily achieved a large amount of productions, but the ball milling cycle it is long,
Use that such as oleic acid, oleyl amine cost is higher, surfactant and organic solvent of not environment friendly, and the post-processing of product
It is more complicated, it is difficult to obtain clean product.Patent document (CN104341010A) discloses a kind of coprecipitation and prepares superparamagnetism
Ferroferric oxide nano-piece, this method is simple, easy to operate, and gained particle dispersiveness and homogeneity are preferable, but the crystallinity of product
Relatively low with saturation magnetization, the size adjustable scope of particle is small.Patent document (CN101717122A) discloses a kind of microwave
Method prepares ferroferric oxide nano-piece, and this method is simple, efficient, but has used surfactant, and prepared product is to receive
The flower of rice piece composition, rather than single dispersing ferroferric oxide nano-piece.
In the present invention, without surfactant, only with cheap water and ethanol as solvent, pass through the hot legal system of mixed solvent
For dispersiveness and the good α-Fe of homogeneity2O3Micro-nano, and change the amount of water, reactant concentration, alkali and metal salt material
The ratio between amount, the type of alkali can have preferable photocatalysis performance in the size of a wide range of interior micro-nano of regulation and control, gained nanometer sheet.
α-Fe2O3Micro-nano can be changed into ferromagnetism and microwave absorbing property is excellent by inert gas shielding carbo-thermal process
Fe3O4Micro-nano.Prepared micro-nano will be in electrode material, magnetic recording material, sensor and biomedical engineering
Also there is wide potential application foreground Deng field.
The content of the invention
The technical problems to be solved by the invention are：It is a kind of dispersed good with homogeneity to provide, and size, pattern and composition can
The preparation method of magnetic micro-nano of tune.Preparation flow of the present invention is simple, cost is low, yield is high, is easy to commercial Application popularization；
Micro-nano of gained has stronger magnetic responsiveness.
The present invention solves its technical problem and uses following technical solution：
Micro-nano provided by the invention, it is α-Fe2O3Or Fe3O4Micro-nano.
Above-mentioned α-Fe provided by the invention2O3Micro-nano, it uses the hot method of mixed solvent to prepare, and is specifically：By certain
Molysite, water and absolute ethyl alcohol are first added in polytetrafluoroethyllining lining by stoichiometric ratio, stir 5~10min；Alkali is added again
30min is mixed into liner, then liner is put into stainless steel kettle and reacts 6~12h at 150~200 DEG C, is used after cooling
Water and absolute ethyl alcohol centrifuge washing, most afterwards through being dried to obtain micro-nano of the good dispersion；It is the molysite, water, anhydrous
Ethanol and alkali are with magnitude relation：Molysite is 2~8mmol；The ratio between amount of alkali and metal salt material is 5~20；Water for 1.0~
The cumulative volume of 25.0mL, water and absolute ethyl alcohol is 40.0mL.
The molysite is Iron trichloride hexahydrate, the one or more in anhydrous ferric chloride, nine water ferric nitrates.
The alkali is sodium acetate, one kind in sodium carbonate, sodium hydroxide.
α-the Fe2O3Micro-nano, it is characterised in that when using sodium acetate as alkali, the α-Fe of gained2O3For single dispersing
Property and the nanometer sheet of the good hexagon of homogeneity or quasi-circular, its a diameter of 60~510nm, thickness is 8~30nm；When with carbonic acid
When sodium is alkali, the α-Fe of gained2O3For irregular nanometer sheet, its a diameter of 180~210nm, thickness is 18~21nm；When with
When sodium hydroxide is alkali, the α-Fe of gained2O3For the irregular micron film of good dispersion, its a diameter of 2~16 μm, thickness is
0.35~1 μm.
Above-mentioned α-the Fe prepared using the hot method of mixed solvent2O3Micro-nano, it is in catalyst, electrode material, inorganic pigment
Or the application in sensor.
The preparation method of magnetic micro-nano, with above-mentioned α-Fe2O3Micro-nano is used as predecessor, and use is lazy
Property gas shield carbo-thermal process prepares scattered Fe3O4Micro-nano, it is specifically：By 0.2g above-mentioned micro-nano and
1.0~3.0mL benzene or acetone are heat-treated 2h under 400~500 DEG C, nitrogen or argon gas atmosphere, and heating-up time 1h, obtains magnetism
Stronger Fe3O4Micro-nano.
The Fe3O4Micro-nano saturation magnetization is 82.51~89.50emu/g.
The above-mentioned Fe prepared using inert gas shielding carbo-thermal process3O4Micro-nano, it is in catalyst, electrode material
Application in material, microwave absorption, high density magnetic recording material or sensor.
The present invention is allowed to compared with prior art, have the following advantages that and accumulate as a result of above-mentioned technical solution
Pole effect：
(1) α-Fe that this method provides2O3And Fe3O4Micro-nano good with dispersiveness and homogeneity, and size range is wide
(hexagonal nanosheet grows 60~510nm, thickness about 8~30nm；It is irregular 2~16 μm of micron film, about 0.35~1 μm thick) etc. spy
Property.
(2) this method is without surfactant, green high-efficient.Raw materials used cheap and easy to get, manufacturing cost is low.
(3) this method preparation process is simple and practicable, reproducible.
(4) application is wide：Magnetic micro-nano of offer has excellent photocatalysis performance, strong magnetic response and microwave absorption
Performance, will have in fields such as catalyst, electrode material, microwave absorption, magnetic recording material, sensor and biomedical engineerings
Wide application prospect.
Brief description of the drawings
Fig. 1~Fig. 2 is respectively the thing phase of 1 products therefrom of embodiment and the pattern observed under scanning electron microscope.
Fig. 3~Figure 14 is respectively the pattern that 2~embodiment of embodiment, 13 products therefrom observes under scanning electron microscope.
That Figure 15~Figure 16 is respectively rhodamine B solution under embodiment 1 and the effect of 4 products therefrom of embodiment is ultraviolet-and can
See collection of illustrative plates.
Figure 17~Figure 19 is respectively the thing phase of 14 products therefrom of embodiment, the pattern observed under scanning electron microscope and magnetostatic
Performance map.
Figure 20~Figure 21 is respectively the thing phase of 15 products therefrom of embodiment and the pattern observed under scanning electron microscope.
Figure 22~Figure 27 is respectively the pattern that 16~embodiment of embodiment, 21 products therefrom observes under scanning electron microscope.
It is Figure 28~Figure 31 is respectively the thing phase of 22 products therefrom of embodiment, is observed under scanning electron microscope pattern, magnetostatic
Performance map and reflection loss curve.
Embodiment
The present invention uses the hot method of mixed solvent, by varying the volume of water and absolute ethyl alcohol, reactant concentration, alkali and metal
The ratio between amount of salt material, the type of alkali regulate and control α-Fe2O3The size of micro-nano.And α-Fe2O3Piece passes through inert gas shielding
Carbo-thermal process can be further transformed to ferromagnetic Fe3O4Micro-nano.Micro-nano of gained has dispersed and homogeneous
Property the characteristic such as good and size adjustable.
With reference to embodiment and attached drawing, the invention will be further described, but is not limited solely to the following examples.
Embodiment 1：
By 4mmol FeCl3·6H2O, 3.0mL distilled water, 37.0mL absolute ethyl alcohols are added in polytetrafluoroethyllining lining, magnetic
Power stirs 5min, obtains clear solution.40mmol sodium acetates (the ratio between amount of alkali and metal salt material is 10) are added to liner
Middle mixing 30min.Finally liner is put into stainless steel kettle and reacts 12h, centrifuge washing after cooling at 180 DEG C.60 DEG C dry
Dry 6h obtains required dispersed nano piece.Products therefrom is brick-red, the thing phase of product, the pattern observed under scanning electron microscope
Respectively as shown in Figs. 1-2.As it can be seen that product is hexagon α-Fe2O3Nanometer sheet, its diameter are (for the external diameter of a circle of hexagon)
121~173nm, thickness are about 10nm.
10mg samples are weighed in 100 milliliters of small beakers, 50mL 0.02mmol/L rhodamine B solution is measured, pours into above-mentioned
In small beaker, 30min is stirred under dark condition, 0.255mL 30%H are then added into small beaker2O2Solution, then by small beaker
Be placed under 300W xenon lamps illumination magnetic agitation and react 120min, and different time (0min, 10min, 20min, 40min,
70min, 120min) take 4mL reaction solutions to centrifuge, supernatant is taken, finally surveys solution using ultraviolet-visible spectrophotometer
Ultraviolet-visible spectrum is as shown in figure 15.
Embodiment 2：
It is identical with 1 step of embodiment, but distilled water is 1.0mL, absolute ethyl alcohol 39.0mL.Products therefrom to be brick-red,
The pattern observed under scanning electron microscope is as shown in Figure 3, it is seen then that the reduction of water causes α-Fe2O3The diameter of hexagonal nanosheet
It is about 30nm to increase as 355~868nm, thickness.
Embodiment 3：
It is identical with 1 step of embodiment, but distilled water is 4.0mL, absolute ethyl alcohol 36.0mL.Products therefrom to be brick-red,
The pattern observed under scanning electron microscope is as shown in Figure 4, it is seen then that the increase of water causes α-Fe2O3The diameter of hexagonal nanosheet
It is decreased to 83~120nm, thickness is about 15nm.
Embodiment 4：
It is identical with 1 step of embodiment, but distilled water is 8.0mL, absolute ethyl alcohol 32.0mL.Products therefrom to be brick-red,
The pattern observed under scanning electron microscope is as shown in Figure 5, it is seen then that the further increase of water causes α-Fe2O3Hexagonal nanosheet
Diameter be decreased to 48~68nm.The UV-visible spectrum of rhodamine B solution different exposure times under catalyst action is such as
Shown in Figure 16.
Embodiment 5：
It is identical with 1 step of embodiment, but sodium acetate is 20mmol (the ratio between amount of alkali and metal salt material is 5).Gained produces
Thing is brick-red, and the pattern observed under scanning electron microscope is as shown in Figure 6, it is seen then that alkali subtracts with the ratio between the amount of metal salt material
It is small to cause α-Fe2O3The diameter of hexagonal nanosheet is decreased to 58~96nm.
Embodiment 6：
It is identical with 1 step of embodiment, but sodium acetate is 80mmol (the ratio between amount of alkali and metal salt material is 20).Gained produces
Thing is brick-red, and the pattern observed under scanning electron microscope is as shown in Figure 7, it is seen then that alkali and the increasing of the ratio between the amount of metal salt material
Adding causes α-Fe2O3The diameter of hexagonal nanosheet is increased to 250~350nm, and thickness is about 8nm.
Embodiment 7：
It is identical with 1 step of embodiment, but alkali is natrium carbonicum calcinatum.Products therefrom is brick-red, is observed under scanning electron microscope
The pattern arrived is as shown in Figure 8, it is seen then that product is irregular α-Fe2O3Nanometer sheet, nanometer sheet length about 180~210nm, thickness
For 18~21nm.
Embodiment 8：
It is identical with 1 step of embodiment, but FeCl3·6H2O is 2mmol, and sodium acetate 20mmol, products therefrom is brick red
Color, the pattern observed under scanning electron microscope are as shown in Figure 9, it is seen then that the reduction of iron salt concentration causes hexagon α-Fe2O3Nanometer
The diameter of piece is reduced to 103~141nm.
Embodiment 9：
It is identical with 1 step of embodiment, but FeCl3·6H2O is 8mmol, and sodium acetate 80mmol, products therefrom is brick red
Color, the pattern observed under scanning electron microscope are as shown in Figure 10, it is seen then that the increase of iron salt concentration causes hexagon α-Fe2O3Nanometer
The diameter of piece is increased to 220~281nm.
Embodiment 10：
It is identical with 1 step of embodiment, but molysite is Fe (NO3)3·9H2O.Products therefrom is brick-red, under scanning electron microscope
The pattern observed is as shown in figure 11, it is seen then that product is the α-Fe of hexagon2O3Nanometer sheet, nanometer sheet a diameter of 126~
171nm, thickness are about 20nm.
Embodiment 11：
It is identical with 1 step of embodiment, but molysite is anhydrous FeCl3.Products therefrom is brick-red, is observed under scanning electron microscope
The pattern arrived is as shown in figure 12, it is seen then that product is the α-Fe of hexagon2O3Nanometer sheet, a diameter of 174~225nm of nanometer sheet are thick
Degree is about 20nm.
Embodiment 12：
It is identical with 1 step of embodiment, but reaction temperature is 150 DEG C.Products therefrom is brick-red, is observed under scanning electron microscope
The pattern arrived is as shown in figure 13, it is seen then that product is the α-Fe of subcircular2O3Nanometer sheet, nanometer sheet adsorption a large amount of unreacteds
Complete is nanocrystalline, and a diameter of 139~160nm of nanometer sheet, thickness is about 25nm.
Embodiment 13：
It is identical with 12 step of embodiment, but reaction temperature is 200 DEG C.Products therefrom is brick-red, is seen under scanning electron microscope
The pattern measured is as shown in figure 14, it is seen then that product is the α-Fe of subcircular2O3Nanometer sheet, a diameter of 124~165nm of nanometer sheet,
Thickness is about 20nm.
Embodiment 14：
By gained sample in 0.2 gram of embodiment 1, loaded with the ceramic Noah's ark of 6cm × 3cm × 1.5cm, added into Noah's ark
3 milliliters of acetone, Noah's ark is placed in single warm tube furnace, and (heating-up time is small for 1 when 400 DEG C of reactions 1 are small under argon gas protection
When).After reaction under argon gas protection furnace cooling to room temperature.The thing phase of products therefrom, observe under scanning electron microscope
Pattern is respectively as shown in Figure 17~Figure 18, it is seen then that product is hexagon Fe after calcining3O4Nanometer sheet.Using U.S. LakeShore
The electrostatic theory that 7404 type vibrating specimen magnetometers of company's production measure product is as shown in figure 19, its saturation magnetization is
82.51emu/g, coercivity 256.56Oe, remanent magnetism 26.00emu/g.
Embodiment 15：
It is identical with 1 step of embodiment, but alkali is sodium hydroxide.Products therefrom is bright atropurpureus, the thing phase of product,
The pattern observed under scanning electron microscope is respectively as shown in Figure 20~Figure 21, it is seen then that product is irregular α-Fe2O3Micron film, piece
A diameter of 5~17 μm, thickness is about 0.75 μm.
Embodiment 16：
It is identical with 15 step of embodiment, but distilled water is 15.0mL, absolute ethyl alcohol 25.0mL.Products therefrom is bright
Atropurpureus, the pattern observed under scanning electron microscope such as Figure 22, it is seen then that product is irregular α-Fe2O3Micron film, piece diameter
For 3~12 μm, thickness is about 0.75 μm.
Embodiment 17：
It is identical with 15 step of embodiment, but distilled water is 25.0mL, absolute ethyl alcohol 15.0mL.Products therefrom is bright
Atropurpureus, the pattern observed under scanning electron microscope such as Figure 23, it is seen then that product is irregular α-Fe2O3Micron film, piece surface have
More little particle, a diameter of 0.79~3.1 μm, thickness is about 0.35 μm.
Embodiment 18：
It is identical with 15 step of embodiment, but reaction temperature is 150 DEG C.Products therefrom is bright atropurpureus, in scanning electricity
The pattern observed under mirror such as Figure 24, it is seen then that product is irregular α-Fe2O3There is more floccule on micron film, piece surface, directly
Footpath is 7~20 μm, and thickness is about 1 μm.
Embodiment 19：
It is identical with 15 step of embodiment, but reaction temperature is 200 DEG C.Products therefrom is bright atropurpureus, in scanning electricity
The pattern observed under mirror such as Figure 25, it is seen then that product is irregular α-Fe2O3Micron film, a diameter of 10~24 μm of piece, thickness
About 1 μm.
Embodiment 20：
It is identical with 8 step of embodiment, but alkali is sodium hydroxide.Products therefrom is bright atropurpureus, under scanning electron microscope
The pattern difference observed is as shown in figure 26, it is seen then that product is irregular α-Fe2O3The flower of micron film or micron film composition, piece
A diameter of 9~16 μm, thickness is about 0.8 μm.
Embodiment 21：
It is identical with 15 step of embodiment, but the reaction time for 6 it is small when.Products therefrom is bright black, in scanning electron microscope
Under the pattern that observes it is as shown in figure 27, it is seen then that product is irregular α-Fe2O3Micron film, a diameter of 11~22 μm of piece are thick
About 0.8 μm of degree.
Embodiment 22：
By gained sample in 0.2 gram of embodiment 15, loaded with the ceramic Noah's ark of 6cm × 3cm × 1.5cm, added into Noah's ark
Enter 1 milliliter of benzene, Noah's ark is placed in single warm tube furnace, reacts 2h (heating-up time 1h) in 500 DEG C under nitrogen protection.Reaction
After under nitrogen protection furnace cooling to room temperature.The thing phase of products therefrom, the pattern observed under scanning electron microscope difference
As shown in Figure 28~Figure 29, it is seen then that product morphology does not change after calcining, is irregular Fe3O4Micron film.Product
Electrostatic theory figure is as shown in figure 30, its saturation magnetization is 89.50emu/g, coercivity 238.54Oe, and remanent magnetism is
22.50emu/g.By the Fe that mass fraction is 60%3O4Nanometer sheet/paraffin composite material is pressed into internal diameter 3mm, outside diameter 7mm, height
The coaxial sample of about 3.5mm, its Micro-wave low-noise transistor is tested in Agilent 5230A network vector analyzers, then is usedFormula calculates microwave reflection rate, and reflection loss curve is as shown in figure 31.6.0-
16.8GHz frequency range internal reflection rates are less than -20dB, and maximum reflection loss is -32.5dB.
Claims (5)
- A kind of a kind of 1. preparation method of micro-nano of magnetism, it is characterized in that α-Fe to be prepared using the hot method of mixed solvent2O3It is micro- Nanometer sheet is predecessor, and Fe is prepared using inert gas shielding carbo-thermal process3O4The method of micro-nano, the α-Fe2O3 The preparation method of micro-nano is：Molysite, water and absolute ethyl alcohol are first added to polytetrafluoroethylene (PTFE) by certain stoichiometric ratio In liner, 5~10min is stirred；Alkali is added in liner again 30min is mixed, the molysite, water, absolute ethyl alcohol and alkali Be with magnitude relation：Molysite is 2~8mmol；The ratio between amount of alkali and metal salt material is 5~20；Water is 1.0~25.0mL, water Cumulative volume with absolute ethyl alcohol is 40.0mL；Then liner is put into stainless steel kettle and reacts 6~12h at 150~200 DEG C, it is cold But 40mL water centrifuge washing 2 times after, with 20mL absolute ethyl alcohols centrifuge washing 1 time, with water and absolute ethyl alcohol centrifuge washing, most passes through afterwards It is dried to obtain the α-Fe2O3Micro-nano；The alkali is sodium acetate, one kind in sodium carbonate, sodium hydroxide.
- 2. the preparation method of micro-nano as claimed in claim 1 magnetic, it is characterised in that molysite is Iron trichloride hexahydrate, anhydrous One or more in iron chloride, nine water ferric nitrates.
- 3. preparation method micro-nano magnetic as claimed in claim 1, it is characterised in that when using sodium acetate as alkali, gained α-Fe2O3It is for monodispersity and the nanometer sheet of the good hexagon of homogeneity or quasi-circular, its a diameter of 60~510nm, thickness 8~30nm；When using sodium carbonate as alkali, the α-Fe of gained2O3For irregular nanometer sheet, its a diameter of 180~210nm, thickness For 18~21nm；When using sodium hydroxide as alkali, the α-Fe of gained2O3For the irregular micron film of good dispersion, its is a diameter of 2~16 μm, thickness is 0.35~1 μm.
- 4. a kind of preparation method of micro-nano of magnetism, it is characterised in that with the α-Fe obtained by claims 1 to 32O3Micro-nano As predecessor, Fe is prepared using inert gas shielding carbo-thermal process3O4Micro-nano, it is specifically：By the α of 0.2g- Fe2O3Micro-nano, 1.0~3.0mL benzene or acetone are heat-treated 2h, heating-up time under 400~500 DEG C, nitrogen or argon gas atmosphere For 1h, the Fe of relatively high magnetism is obtained3O4Micro-nano.
- 5. preparation method micro-nano magnetic as claimed in claim 4, it is characterised in that the Fe3O4Micro-nano, its Saturation magnetization range is 82.51~89.50emu/g.
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| CN106735300B (en) * | 2016-12-22 | 2018-09-21 | 东南大学 | A kind of synthetic method of ultra-thin silver nanoparticle plate |
| CN107324397A (en) * | 2017-06-12 | 2017-11-07 | 衢州学院 | A kind of α Fe2O3The preparation method of nano-stack material and the method that benzaldehyde is prepared using the material |
| CN107324398A (en) * | 2017-06-19 | 2017-11-07 | 华南理工大学 | A kind of flake nano iron oxide and preparation method thereof |
| CN107265509A (en) * | 2017-06-19 | 2017-10-20 | 华南理工大学 | A kind of cubic nano-sized iron oxide and preparation method thereof |
| CN107381650B (en) * | 2017-08-11 | 2022-05-06 | 浙江师范大学 | Monodisperse ferrite micro-nanosheet and preparation method thereof |
| CN107720831B (en) * | 2017-10-09 | 2019-11-12 | 福州大学 | Ferric oxide nano-material and its application based on solvent-thermal method controlledly synthesis |
| CN110038572A (en) * | 2019-04-30 | 2019-07-23 | 南开大学 | A kind of α-Fe for degradable organic pollutant2O3/ Fe photochemical catalyst and preparation method thereof |
| CN110104692A (en) * | 2019-05-16 | 2019-08-09 | 南京航空航天大学 | One kind having anisotropic magnetic iron ore electromagnetic-wave absorbent and preparation method thereof |
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| CN110697790B (en) * | 2019-10-18 | 2023-03-28 | 临沂大学 | Chapped sheet iron oxide nano material and preparation method thereof |
| CN111704115A (en) * | 2020-05-29 | 2020-09-25 | 南昌航空大学 | A granular α -Fe2O3Preparation of Fe having microwave absorbing Properties4Method of N |
| CN111978721A (en) * | 2020-06-06 | 2020-11-24 | 南昌航空大学 | alpha-Fe2O3Preparation method of conductive polyaniline composite material |
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| CN112897592B (en) * | 2021-01-25 | 2022-12-02 | 中国科学院广州地球化学研究所 | Micro-nano iron oxide mineral color developing agent and preparation method and application thereof |
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