CN104261482B - Method for preparing ferrite nanospheres by molten salt method - Google Patents
Method for preparing ferrite nanospheres by molten salt method Download PDFInfo
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- CN104261482B CN104261482B CN201410495471.4A CN201410495471A CN104261482B CN 104261482 B CN104261482 B CN 104261482B CN 201410495471 A CN201410495471 A CN 201410495471A CN 104261482 B CN104261482 B CN 104261482B
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- divalent metal
- wustite
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 150000003839 salts Chemical class 0.000 title claims abstract description 28
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 22
- 239000002077 nanosphere Substances 0.000 title abstract 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 24
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 15
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011572 manganese Substances 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 12
- 238000000227 grinding Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011780 sodium chloride Substances 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 235000011164 potassium chloride Nutrition 0.000 abstract 2
- 239000001103 potassium chloride Substances 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 239000002060 nanoflake Substances 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 11
- 206010013786 Dry skin Diseases 0.000 description 8
- 238000010612 desalination reaction Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 229910003321 CoFe Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 229910008452 SnFe Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 206010073071 hepatocellular carcinoma Diseases 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
Abstract
The invention discloses a method for preparing ferrite nanospheres by a molten salt method, which comprises the steps of grinding a divalent metal compound serving as a raw material, a ferric iron compound serving as a raw material, sodium chloride serving as molten salt and potassium chloride serving as molten salt, uniformly mixing, placing the mixture in a crucible, placing the crucible in a tubular furnace, heating to 800-880 ℃, roasting for 4-6 h, and carrying out post-treatment to obtain nano ferrite; the molar ratio of the raw materials to the molten salt is 3: 11y, wherein y is more than or equal to 0.6 and less than 13, and the prepared nano ferrite is ferrite nanospheres; the molar ratio of the divalent metal to the trivalent iron in the raw materials is x: 3-x, wherein x is more than or equal to 0.01 and less than or equal to 1; the molar ratio of sodium chloride to potassium chloride in the molten salt is 10: 1. The method has the advantages of simple equipment, short reaction time, low energy consumption, environmental friendliness, low cost and rich product types, and is suitable for industrial production.
Description
The application is application number is 201210499432.2, and the applying date is on November 29th, 2012, and invention and created name is the divisional application of the application for a patent for invention of " method that molten-salt growth method prepares nano ferrite ".
Technical field
The present invention relates to a kind of preparation method of wustite, be specifically related to a kind of method that molten-salt growth method prepares nano ferrite.
Background technology
Spinel type wustite has been widely used in mutual inductance device, magnetic recording material as a kind of soft magnetic material.At present, along with the development of technology, the practical ranges of spinel type wustite is also increasingly extensive, such as, as catalyzer, can be applied in the oxidation deoxygenation of synthetic ammonia, butylene.It is found that, after the size of material reaches nanometer range, there will be and body phase material different properties, such as, Japan Kobe university uses wustite nanometer ball as the carrier of medicine, and Hepatoma therapy, kidney succeed.This shows that the carrier that wustite can be used as cancer therapy drug has good prospect in medical.Therefore, the synthesis of novel Ferrite Nanocrystalline Materials and character research become study hotspot widely.
A few days ago, the existing research to the synthesis of spinel type wustite is mainly on nano magnetic microballoon both at home and abroad, and its preparation method mainly contains Physical and the large class of chemical method two.
Physical mainly adopt high energy mechanical grind make presoma react generate needed for nanocrystalline, presoma is generally two kinds of corresponding oxide compounds of metal, prepares corresponding wustite.The advantage of Physical is that technique is simple, and chemical constitution easily controls.Shortcoming is then consume energy comparatively greatly, and long reaction time, particularly easily introduces impurity, and dispersiveness is good not.
Chemical method mainly makes the uniform ion of reactant mix by chemical reaction, obtains the granular product of nano-scale at a certain temperature, as hydrothermal method or solvent-thermal method (as Chinese patent literature CN1645530A, CN102583567A etc.).The advantage of chemical method is that particle size is less, and pattern is homogeneous.Shortcoming is then that the crystallinity of product is bad, and needs organic solvent and tensio-active agent, so not only adds cost but also easily causes environmental pollution.
Summary of the invention
The object of the invention is to solve the problem, provide that a kind of equipment is simple, the reaction times is short, energy consumption is low, environmental friendliness, cost are lower, product type is enriched, be suitable for the method that the molten-salt growth method of suitability for industrialized production prepares nano ferrite.
The technical scheme realizing the object of the invention is: a kind of molten-salt growth method prepares the method for nano ferrite, it is ground the bivalent metallic compound as raw material, the ferric iron compound as raw material, the sodium-chlor as fused salt and the Repone K as fused salt, mix, mixture is positioned in crucible, again crucible is put into tube furnace, be warming up to 800 DEG C ~ 880 DEG C roasting 4h ~ 6h, obtain nano ferrite through aftertreatment.
The mol ratio of described raw material and described fused salt is 3: 11y, wherein 0.6≤y≤50; Divalent metal in described raw material and ferric mol ratio are x: 3-x, wherein 0.01≤x≤1; Sodium-chlor in described fused salt and the mol ratio of Repone K are 10: 1.
Described ferric iron compound is ferric oxide, ironic hydroxide, iron nitrate, ironic acetate, ironic oxalate or iron carbonate.
Described bivalent metallic compound is bivalent metal oxide, Divalent metal hydroxide, divalent metal nitrate, divalent metal acetate, divalent metal oxalate or bivalent metal carbonate.
Described divalent metal is one in magnesium, nickel, copper, cadmium, calcium, strontium, barium, zinc, manganese or two kinds.
Or described divalent metal is one in lead, cobalt, tin or two kinds, in preparation process, before intensification roasting, passes into rare gas element in tube furnace.
Aforesaid method can according to the different nano ferrites that obtain different-shape of raw material from the mol ratio of fused salt: as 0.6≤y < 13, obtained nano ferrite is wustite nanometer ball.When 13≤y≤50, obtained nano ferrite is wustite nano flake.
And aforesaid method can obtain the nano ferrite of different composition according to the quantity of divalent metal in raw material and the different of ferric mol ratio and divalent metal.Specific as follows:
(1) when only having a kind of divalent metal and divalent metal and ferric mol ratio are 1: 2, then obtain consisting of MFe
2o
4nano ferrite, wherein M represents divalent metal.
Generate oxide compound because oxyhydroxide, nitrate, acetate, oxalate, carbonate etc. at high temperature decompose, therefore above-mentioned chemical reaction is expressed as follows:
MO
(s)+Fe
2O
3(s)+NaCl+KCl→MFe
2O
4(s)。
(2) when only having a kind of divalent metal and divalent metal and ferric mol ratio are x: 3-x (0.01≤x < 1), then obtain consisting of M
xfe
3-xo
4nano ferrite, wherein M represents divalent metal.
Above-mentioned chemical reaction is expressed as follows:
xMO
(s)+(3-x)/2Fe
2O
3(s)+NaCl+KCl→M
xFe
3-xO
4(s)。
(3) when there being two kinds of divalent metals, mole total amount of divalent metal and ferric mol ratio are 1: 2, and when the mol ratio between two kinds of divalent metals is x: 1-x (0.01≤x < 1), can obtain M
1 xm
2 1-xfe
2o
4nano ferrite, wherein M
1, M
2represent different divalent metals.
Above-mentioned chemical reaction is expressed as follows:
xM
1O
(s)+(1-x)M
2O
(s)+Fe
2O
3(s)+NaCl+KCl→M
1 xM
2 1-xFe
2O
4(s)。
(4) when there being two kinds of divalent metals, mole total amount of divalent metal and ferric mol ratio are x: 3-x(0.01≤x < 1), and the mol ratio between two kinds of divalent metals is when being m: x-m (0.01≤m < x), can obtain M
1 mm
2 x-mfe
3-xo
4nano ferrite, wherein M
1, M
2represent different divalent metals.
Above-mentioned chemical reaction is expressed as follows:
mM
1O
(s)+(x-m)M
2O
(s)+(3-x)/2Fe
2O
3(s)+NaCl+KCl→M
1 mM
2 x-mFe
3-xO
4(s)。
The positively effect that the present invention has: (1) the inventive method adopts sodium-chlor and Repone K (mol ratio is 10: 1) as fused salt, by heating fused salt, raw material is reacted in the environment of melting sodium-chlor and Repone K and can obtain nano ferrite in several hours, have that equipment is simple, easy and simple to handle, the reaction times is short, energy consumption is low, advantages of environment protection.(2) method of the present invention is by controlling the mol ratio of fused salt and raw material, not only can obtain wustite nanometer (magnetic bead) ball, wustite nano flake can also be obtained, thus also have that product type is abundant, excellent performance, steady quality, controllability strong, be suitable for the advantages such as suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the MgFe that embodiment 1 obtains
2o
4the x-ray diffraction pattern of nanometer ball.
Fig. 2 is the MgFe that embodiment 1 obtains
2o
4the field emission scanning electron microscope figure of nanometer ball.
Fig. 3 is Ni prepared by embodiment 3
0.6fe
2.4o
4the scanning electron microscope (SEM) photograph of nanometer ball Flied emission.
Fig. 4 is Mn prepared by embodiment 4
0.4zn
0.6fe
2o
4the scanning electron microscope (SEM) photograph of nanometer ball.
Fig. 5 is ZnFe prepared by embodiment 5
2o
4the scanning electron microscope (SEM) photograph of nano flake.
Fig. 6 is Mg prepared by embodiment 8
0.5ni
0.5fe
2o
4the scanning electron microscope (SEM) photograph of nano flake.
Embodiment
(embodiment 1)
The present embodiment is MgFe
2o
4the preparation method of nanometer ball:
Put 1mmol magnesium oxide, 2mmol iron nitrate, 100mmol sodium-chlor, the grinding of 10mmol Repone K, Homogeneous phase mixing, is positioned over mixture in alumina crucible, then alumina crucible is put into tube furnace, by the ramp to 820 DEG C of 5 DEG C/min, and roasting 4h.
Naturally cool to envrionment temperature (0 ~ 40 DEG C, lower same), distilled water dipping desalination, suction filtration, washing, 70 DEG C of dryings, obtained MgFe
2o
4nanometer ball.
This MgFe
2o
4the x-ray diffraction pattern of nanometer ball is shown in Fig. 1, as shown in Figure 1: the X-ray diffraction peak position of this product is consistent with standard X-ray diffraction card (JCPDS36-0398), proves that the present embodiment products therefrom is the MgFe of pure phase
2o
4powder.
This MgFe
2o
4the field emission scanning electron microscope figure of nanometer ball is shown in Fig. 2, and as shown in Figure 2: this product has spherical morphology, diameter is greatly about 700nm ~ 900nm, MgFe
2o
4the productive rate of nanometer ball is approximately 90wt%.
Control divalent metal and ferric mol ratio are 1: 2, the mol ratio of raw material and fused salt is 3: 11y(0.6≤y < 13), replace above-mentioned Mg with Ni, Cu, Cd, Ca, Sr, Ba, Zn, Mn etc. respectively, adopt identical method can obtain NiFe respectively
2o
4, CuFe
2o
4, CdFe
2o
4, CaFe
2o
4, SrFe
2o
4, BaFe
2o
4, ZnFe
2o
4, MnFe
2o
4deng wustite nanometer ball.
(embodiment 2)
The present embodiment is PbFe
2o
4the preparation method of nanometer ball:
Put 2mmol lead carbonate, 4mmol iron nitrate, 100mmol sodium-chlor, the grinding of 10mmol Repone K; Homogeneous phase mixing; mixture is positioned in alumina crucible; again alumina crucible is put into tube furnace; pass into rare gas element; under protection of inert gas, by the ramp to 840 DEG C of 5 DEG C/min, roasting 4h.
Naturally cool to envrionment temperature, flood desalination with distilled water, suction filtration, washing, 60 DEG C of dryings, obtained particle diameter is the PbFe of 800nm ~ 1000nm
2o
4nanometer ball.
Control divalent metal and ferric mol ratio are 1: 2, and the mol ratio of raw material and fused salt is 3: 11y(0.6≤y < 13), Pb is replaced to Co or Sn, adopts identical method can obtain CoFe respectively
2o
4, SnFe
2o
4nanometer ball.
(embodiment 3)
The present embodiment is Ni
0.6fe
2.4o
4the preparation method of nanometer ball:
Set to 0 .6mmol nickelous nitrate, the iron nitrate of 2.4mmol, 80mmol sodium-chlor, the grinding of 8mmol Repone K, Homogeneous phase mixing, is positioned over mixture in alumina crucible, then alumina crucible is put into tube furnace, by the ramp to 860 DEG C of 5 DEG C/min, roasting 6h.
Naturally cool to envrionment temperature, distilled water dipping desalination, suction filtration, washing, 60 DEG C of dryings, obtained Ni
0.6fe
2.4o
4nanometer ball.
This Ni
0.6fe
2.4o
4the field emission scanning electron microscope figure of nanometer ball is shown in Fig. 3, and as shown in Figure 3: this product has spherical morphology, diameter is greatly about 600nm ~ 1100nm, Ni
0.6fe
2.4o
4the productive rate of nanometer ball is approximately 80wt%.
Control divalent metal and ferric mol ratio are x: 3-x(0.01≤x < 1), the mol ratio of raw material and fused salt is 3: 11y(0.6≤y < 13), replace above-mentioned Ni with Mg, Cu, Cd, Ca, Sr, Ba, Zn, Mn etc. respectively, adopt identical method can obtain Mg respectively
xfe
3-xo
4, Cu
xfe
3-xo
4, Cd
xfe
3-xo
4, Ca
xfe
3-xo
4, Sr
xfe
3-xo
4, Ba
xfe
3-xo
4, Zn
xfe
3-xo
4, Mn
xfe
3-xo
4deng wustite nanometer ball.
(embodiment 4)
The present embodiment is Mn
0.4zn
0.6fe
2o
4the preparation method of nanometer ball:
Set to 0 .6mmol zinc nitrate, 0.4mmol manganous oxalate, 2mmol iron nitrate, 90mmol sodium-chlor, the grinding of 9mmol Repone K, Homogeneous phase mixing, is positioned over mixture in alumina crucible, then alumina crucible is put into tube furnace, by the ramp to 820 DEG C of 5 DEG C/min, roasting 6h.
Naturally cool to envrionment temperature, distilled water dipping desalination, suction filtration, washing, 80 DEG C of dryings, obtained Mn
0.4zn
0.6fe
2o
4nanometer ball.
This Mn
0.4zn
0.6fe
2o
4the scanning electron microscope (SEM) photograph of nanometer ball is shown in Fig. 4, and as shown in Figure 4: this product has spherical morphology, diameter is greatly about 500nm ~ 800nm, Mn
0.4zn
0.6fe
2o
4the productive rate of nanometer ball is approximately 80wt%.
Mole total amount and the ferric mol ratio that control divalent metal equal 1: 2, the mol ratio of raw material and fused salt is 3: 11y(0.6≤y < 13), adopt any two kinds of above-mentioned Zn and Mn of replacement in Mg, Ni, Cu, Cd, Ca, Sr, Ba, Zn, Mn, adopt same procedure can obtain corresponding acid ferric complex salt nanometer ball.
(embodiment 5)
The present embodiment is ZnFe
2o
4the preparation method of nano flake:
Put 1mmol zinc nitrate, 2mmol iron nitrate, 150mmol sodium-chlor, the grinding of 15mmol Repone K, Homogeneous phase mixing, is positioned over mixture in alumina crucible, then alumina crucible is put into tube furnace, by the ramp to 820 DEG C of 5 DEG C/min, and roasting 6h.
Naturally cool to envrionment temperature, distilled water dipping desalination, suction filtration, washing, 60 DEG C of dryings, obtained ZnFe
2o
4nano flake.
This ZnFe
2o
4the scanning electron microscope (SEM) photograph of nano flake is shown in Fig. 5, as shown in Figure 5: this ZnFe
2o
4have sheet structure, the Thickness Ratio of nano flake is more homogeneous, and productive rate is approximately 85wt%.
Control divalent metal and ferric mol ratio are 1: 2, and the mol ratio of raw material and fused salt is 3: 11y(13≤y≤50), replace above-mentioned Zn with Mg, Ni, Cu, Cd, Ca, Sr, Ba, Mn etc. respectively, adopt identical method can obtain MgFe respectively
2o
4, NiFe
2o
4, CuFe
2o
4, CdFe
2o
4, CaFe
2o
4, SrFe
2o
4, BaFe
2o
4, MnFe
2o
4deng wustite nano flake.
(embodiment 6)
The present embodiment is CoFe
2o
4the preparation method of nano flake:
Put 1mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 2mmol iron nitrate, 0.2mol sodium-chlor, the grinding of 0.02mol Repone K; Homogeneous phase mixing; mixture is positioned in alumina crucible; again alumina crucible is put into tube furnace; pass into rare gas element; under protection of inert gas, by the ramp to 840 DEG C of 5 DEG C/min, roasting 4h.
Naturally cool to envrionment temperature, distilled water dipping desalination, suction filtration, washing, 50 DEG C of dryings, obtained CoFe
2o
4nano flake.
Control divalent metal and ferric mol ratio are 1: 2, and the mol ratio of raw material and fused salt is 3: 11y(13≤y≤50), Co is replaced to Pb or Sn, adopts identical method can obtain PbFe respectively
2o
4, SnFe
2o
4nano flake.
(embodiment 7)
The present embodiment is Mn
0.4fe
2.6o
4the preparation method of nano flake:
Set to 0 .4mmol manganous oxalate, 2.6mmol iron nitrate, 0.2mol sodium-chlor, the grinding of 0.02mol Repone K, Homogeneous phase mixing, is positioned over mixture in alumina crucible, then alumina crucible is put into tube furnace, by the ramp to 840 DEG C of 5 DEG C/min, roasting 6h.
Naturally cool to envrionment temperature, distilled water dipping desalination, suction filtration, washing, 60 DEG C of dryings, obtained Mn
0.4fe
2.6o
4nano flake.
Control divalent metal and ferric mol ratio are x: 3-x(0.01≤x < 1), the mol ratio of raw material and fused salt is 3: 11y(13≤y≤50), replace above-mentioned Mn with Mg, Ni, Cu, Cd, Ca, Sr, Ba, Zn etc. respectively, adopt identical method can obtain Mg respectively
xfe
3-xo
4, Ni
xfe
3-xo
4, Cu
xfe
3-xo
4, Cd
xfe
3-xo
4, Ca
xfe
3-xo
4, Sr
xfe
3-xo
4, Ba
xfe
3-xo
4, Zn
xfe
3-xo
4deng wustite nano flake.
(embodiment 8)
The present embodiment is Mg
0.5ni
0.5fe
2o
4the preparation method of nano flake:
Set to 0 .5mmol magnesium nitrate, 0.5mmol nickelous nitrate, 2mmol iron nitrate, 180mmol sodium-chlor, the grinding of 18mmol Repone K, Homogeneous phase mixing, is positioned over mixture in alumina crucible, then alumina crucible is put into tube furnace, by the ramp to 820 DEG C of 5 DEG C/min, roasting 6h.
Naturally cool to envrionment temperature, distilled water dipping desalination, suction filtration, washing, 70 DEG C of dryings, obtained Mg
0.5ni
0.5fe
2o
4nano flake.
This Mg
0.5ni
0.5fe
2o
4the scanning electron microscope (SEM) photograph of nano flake is shown in Fig. 6, as shown in Figure 6: this Mg
0.5ni
0.5fe
2o
4have sheet structure, the thickness of nano flake is homogeneous, and productive rate is approximately 80wt%.
Mole total amount and the ferric mol ratio that control divalent metal equal 1: 2, the mol ratio of raw material and fused salt is 3: 11y(13≤y≤50), adopt any two kinds of above-mentioned Mg and Ni of replacement in Mg, Ni, Cu, Cd, Ca, Sr, Ba, Zn, Mn, adopt same procedure can obtain corresponding acid ferric complex salt nano flake.
Claims (8)
1. a molten-salt growth method prepares the method for wustite nanometer ball, it is characterized in that: the bivalent metallic compound as raw material, the ferric iron compound as raw material, the sodium-chlor as fused salt and the Repone K as fused salt are ground, mix, mixture is positioned in crucible, again crucible is put into tube furnace, be warming up to 800 DEG C ~ 880 DEG C roasting 4h ~ 6h, obtain nano ferrite through aftertreatment;
The mol ratio of described raw material and described fused salt is 3: 11y, wherein 0.6≤y < 13, and obtained nano ferrite is wustite nanometer ball;
Divalent metal in described raw material and ferric mol ratio are x: 3-x, wherein 0.01≤x≤1;
Sodium-chlor in described fused salt and the mol ratio of Repone K are 10: 1.
2. molten-salt growth method according to claim 1 prepares the method for wustite nanometer ball, it is characterized in that: described divalent metal is one in magnesium, nickel, copper, cadmium, calcium, strontium, barium, zinc, manganese or two kinds.
3. molten-salt growth method according to claim 2 prepares the method for wustite nanometer ball, it is characterized in that: described divalent metal is one in magnesium, zinc, manganese or two kinds.
4. molten-salt growth method according to claim 3 prepares the method for wustite nanometer ball, it is characterized in that: described divalent metal is magnesium or is zinc and manganese.
5. molten-salt growth method according to claim 1 prepares the method for wustite nanometer ball, it is characterized in that: described divalent metal is one in lead, cobalt, tin or two kinds; Before intensification roasting, in tube furnace, pass into rare gas element.
6. prepare the method for wustite nanometer ball according to the molten-salt growth method one of claim 1 to 5 Suo Shu, it is characterized in that: described ferric iron compound is ferric oxide, ironic hydroxide, iron nitrate, ironic acetate, ironic oxalate or iron carbonate.
7. prepare the method for wustite nanometer ball according to the molten-salt growth method one of claim 1 to 5 Suo Shu, it is characterized in that: described bivalent metallic compound is bivalent metal oxide, Divalent metal hydroxide, divalent metal nitrate, divalent metal acetate, divalent metal oxalate or bivalent metal carbonate.
8. molten-salt growth method according to claim 6 prepares the method for wustite nanometer ball, it is characterized in that: described bivalent metallic compound is bivalent metal oxide, Divalent metal hydroxide, divalent metal nitrate, divalent metal acetate, divalent metal oxalate or bivalent metal carbonate.
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| CN106865621B (en) * | 2017-02-27 | 2018-08-07 | 陕西科技大学 | A kind of coralloid ferrous acid powder for lithium and preparation method thereof |
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| WO2019198304A1 (en) * | 2018-04-10 | 2019-10-17 | パウダーテック株式会社 | Ferrite particles, carrier core material for electrophotographic developers, ferrite carrier for electrophotographic developers, and electrophotographic developer |
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| CN108793231B (en) * | 2018-08-13 | 2020-02-14 | 江苏理工学院 | Method for synthesizing spindle-shaped zinc germanate nanoparticles by molten salt method |
| CN110510676A (en) * | 2019-08-12 | 2019-11-29 | 江苏理工学院 | A kind of LiFeO2Nano particle and preparation method thereof |
| JP7312401B2 (en) * | 2019-09-24 | 2023-07-21 | 独立行政法人国立高等専門学校機構 | Gas sensor and manufacturing method of alkaline earth ferrite |
| CN111029563B (en) * | 2019-12-10 | 2022-11-29 | 河南创力新能源科技股份有限公司 | Preparation method of alkaline secondary battery iron negative electrode material |
| CN111977696B (en) * | 2020-08-13 | 2022-06-07 | 吉林化工学院 | Preparation method and application of pomegranate-shaped magnetic visible light heterogeneous Fenton catalyst material |
| CN113060766A (en) * | 2021-04-08 | 2021-07-02 | 成都理工大学 | Dispersed flaky magnesium ferrite spinel magnetic nano material and preparation method thereof |
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| CN104276607B (en) | 2016-03-30 |
| CN102923786B (en) | 2014-11-12 |
| CN104229899A (en) | 2014-12-24 |
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| CN102923786A (en) | 2013-02-13 |
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| CN104261482A (en) | 2015-01-07 |
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