CN104163456B - A kind of monodisperse water soluble ferroferric oxide nano granules - Google Patents
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- CN104163456B CN104163456B CN201410339561.4A CN201410339561A CN104163456B CN 104163456 B CN104163456 B CN 104163456B CN 201410339561 A CN201410339561 A CN 201410339561A CN 104163456 B CN104163456 B CN 104163456B
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000008187 granular material Substances 0.000 title claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000002105 nanoparticle Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000005291 magnetic effect Effects 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 230000005415 magnetization Effects 0.000 claims description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000013590 bulk material Substances 0.000 claims description 9
- 230000005308 ferrimagnetism Effects 0.000 claims description 9
- 230000005294 ferromagnetic effect Effects 0.000 claims description 9
- 239000011553 magnetic fluid Substances 0.000 claims description 9
- 230000005389 magnetism Effects 0.000 claims description 9
- 239000013110 organic ligand Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000703 high-speed centrifugation Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 abstract description 10
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 95
- 150000002500 ions Chemical class 0.000 description 4
- 239000002122 magnetic nanoparticle Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Abstract
The invention discloses a kind of monodisperse water soluble four and be oxidized three body nano particles, adopt the method for fractional precipitation, again in conjunction with n-hexyl alcohol as co-precipitation solvent, under stirring velocity condition comparatively fast, prepare good dispersity and undersized water miscible ferroferric oxide nano granules.Preparation process of the present invention is simple, and preparation condition is gentle; Preparation process technique is controlled, reproducible, can carry out technology production; The ferroferric oxide nano granules obtained has homogeneous pattern and extra small size, and has excellent magnetic performance; The n-hexyl alcohol used can recycle, can be cost-saving.
Description
Technical field
The invention belongs to ferroferric oxide nano granules Material Field, particularly a kind of monodisperse water soluble ferroferric oxide nano granules.
Background technology
In recent years, relevant magnetic nanoparticle Quality Research comes into one's own, and this is not only because magnetic nano-particle has special meaning in basic physical properties research, and has purposes widely in actual applications.In all kinds of magnetic nanoparticle, relevant Z 250 (Fe
3o
4) applied research of nano particle especially receives publicity.By controlling suitable reaction conditions, people can prepare diameter from several to the Fe of tens nanometers
3o
4nano particle, shows due to it all character of being different from block materials and is applied to multiple fields.
Fe
3o
4having inverse spinel structure spacer is Fd3m, lattice constant
oxonium ion forms cubic close and piles up, half Fe
3+occupy tetrahedron space (A case), Fe
2+with second half Fe
3+occupy octahedral interstices (B case), as Fig. 1-2.Each structure cell has 32 O
2-, 16 Fe
3+with 8 Fe
2+, structural formula can write Fe
3+ 8[Fe
2+ 8fe
3+ 8] O
32, in [], represent that B case ion is at Fe
3o
4in crystal, the ion magnetic moment between A case positively charged ion and B case positively charged ion is 4 μ
b, the magnetic moment of each molecule is M=M
b-M
a=4 μ
b.Specific saturation magnetization ó under room temperature
s=82emu/g, Curie temperature is T
c=575 DEG C, easy magnetization axis is [111], and magnetocrystalline anisotropy constant is K
1=-1.1 × 10
5erg/cm
3.
Preparation Fe
3o
4the method of magnetic nano-particle is a lot, has coprecipitation method, microemulsion method, thermal decomposition method, biological auxiliary synthesis method etc., and wherein best with the size of particles topography uniformity of high temperature thermal decomposition method synthesis, coprecipitation method is simple, the most most economical synthetic method.
The Fe that Co deposited synthesis obtains
3o
4the dispersiveness of nanoparticle not as high temperature pyrolytic cracking (HTP), but makes it be subject to extensive research without other parts and water miscible feature due to surface.
Its reaction mechanism is as follows:
2Fe
3++Fe
2++8OH
-1→Fe
3O
4↓+4H
2O
The Fe synthesized
3o
4the common agglomeration of nanoparticle.
Now a lot of investigators also adopts the method adding tensio-active agent particularly some macromolecular compounds to prepare ferroferric oxide nano granules to carry out coprecipitation method, the nano particle adopting the method to prepare is better water-soluble, but owing to introducing macromolecular compound, limit the application of the type ferroferric oxide nano granules, macromolecular compound is as the thick coat of one deck, affect the magnetic response of ferroferric oxide nano granules, and carrying out, in Z 250 surface treatment process, also there is certain complicacy.How to adopt easy method to prepare the emphasis that high-quality good dispersity water-soluble ferroferric oxide nano particle remains everybody research now.
Summary of the invention
The object of the invention is for the problems referred to above, develop a kind of monodisperse water soluble ferroferric oxide nano granules, by using the method for twice precipitation, in the solution taking n-hexyl alcohol as solvent, prepare the ferroferric oxide nano granules that diameter is 5-10 nanometer, prepared ferroferric oxide nano granules size monodisperse is good, and highly stable in aqueous, at 300K, nanoparticle display superparamagnetism, saturation magnetization is 55-65emu/g, without remanent magnetism.Compared with bulk material, its saturation magnetization is very high, and the crystal formation of interpret sample is better, and surface organic ligands is less.When temperature reduces to 10K, nanoparticle has obvious magnetic trapping phenomena, and be ferrimagnetism, saturation magnetization increases to 65-75emu/g, has ferromagnetic nanoparticle like this and will have important application in biology or magnetic fluid etc.
A kind of monodisperse water soluble ferroferric oxide nano granules, its preparation method is as follows:
1) first, by analytically pure iron(ic) chloride and iron protochloride, add respectively in deionized water, magnetic stirring apparatus stirs and makes it dissolve, the clear solution B of obtained Fe3+ concentration to be the clear solution A of 0.1mol/L and Fe2+ concentration be 0.1mol/L;
2) get solution A and the solution B of same volume, mix, then continue to add a small amount of ammoniacal liquor, after adding ammoniacal liquor, stir half an hour, the solution formed is the orange solution C of transparent and homogeneous;
3) getting 50ml n-hexyl alcohol joins in 100ml round-bottomed flask, in whipping process, slowly adds the solution C of 5-20ml, add complete after, continue to stir 0.5-2 hour, form the solution D of transparent and homogeneous;
4) round-bottomed flask is used heating in water bath, until temperature is 60-100 DEG C, and then in solution D, add the sodium hydroxide of appropriate amount, magnetic agitation speed is regulated to be 1000-2000rpm/min, under rapid stirring, reaction 2-3 hour, and to control atmosphere be argon gas, after reaction terminates, naturally cool to room temperature;
5) by step 4) react the solution left standstill 1-3 hour obtained, can see that solution is obviously divided into two-layer, upper strata is organic solvent n-hexyl alcohol, lower floor is ferroferric oxide nano granules solution layer, conventional separate mode is used to be separated by n-hexyl alcohol, and dewater by adding siccative, the n-hexyl alcohol obtained can recycle; The ferroferric oxide nano granules solution of lower floor is by washing with alcohol, and high speed centrifugation is separated, dry, can obtain ferroferric oxide nano granules powder;
The diameter of prepared ferroferric oxide nano granules is 5-10 nanometer, has higher monodispersity, and has good solvability in aqueous, and at 300K, nanoparticle display superparamagnetism, saturation magnetization is 55-65emu/g, without remanent magnetism.Compared with bulk material, its saturation magnetization is very high, and the crystal formation of interpret sample is better, and surface organic ligands is less.When temperature reduces to 10K, nanoparticle has obvious magnetic trapping phenomena, and be ferrimagnetism, saturation magnetization increases to 65-75emu/g, has ferromagnetic nanoparticle like this and will have important application in biology or magnetic fluid etc.
As preferably, step 4) in temperature of reaction be 80 DEG C.
As preferably, step 4) in stirring velocity be 1500rpm/min.
Preparation process of the present invention is comparatively simple, by first carrying out ammoniacal liquor co-precipitation, re-use sodium hydroxide and carry out co-precipitation, secondary co-precipitation has material impact for the size of nano material and monodispersity, first time carries out weak precipitation agent and carries out co-precipitation, but the homogeneous crystal seed that can't reunite will be formed, and when sodium hydroxide carries out secondary sedimentation, precipitation process will be accelerated, again on existing crystal seed basis, carry out heterogeneous nucleation, particle diameter and the monodispersity of ferroferric oxide nano granules can be controlled preferably, stop nanoparticles solution in primary sedimentation process to reunite, and do not need to need to add tensio-active agent to control the monodispersity of nano particle in homogeneous nucleation yet,
Simultaneously, adopt n-hexyl alcohol as co-precipitation solvent in process of the present invention, compared to pure water solution and the aqueous solution/alcohol mixed solution, n-hexyl alcohol solution is on the one hand by having certain polarity, the ferroferric oxide nano granules that can be formed for coprecipitation method plays certain stabilization, although this effect is faint, also can prevent ferroferric oxide nano granules from reuniting; Meanwhile, the polarity of n-hexyl alcohol and the aqueous solution also has certain difference, therefore, needs to select stirring velocity to react under condition comparatively fast, thus just can make better to react between reactant; Meanwhile, after the completion of reaction, also can be good at being separated, namely be can be recycled by simple process.
Beneficial effect of the present invention:
(1) preparation process of the present invention is simple, and preparation condition is gentle;
(2) preparation process technique of the present invention is controlled, reproducible, can carry out technology production;
(3) ferroferric oxide nano granules that the present invention prepares has homogeneous pattern and extra small size;
(4) n-hexyl alcohol used in the present invention can recycle, can be cost-saving;
(5) ferroferric oxide nano granules prepared by has very strong and excellent magnetic performance.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
The ferroferric oxide nano granules of Fig. 1 prepared by the embodiment of the present invention 1;
The ferroferric oxide nano granules of Fig. 2 prepared by comparative example 1 of the present invention.
Embodiment
Below in conjunction with specific embodiment, and comparable data describes in further detail the present invention.Should be understood that these embodiments just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1:
A kind of monodisperse water soluble ferroferric oxide nano granules, its preparation method is as follows:
1) first, by analytically pure iron(ic) chloride and iron protochloride, add respectively in deionized water, magnetic stirring apparatus stirs and makes it dissolve, the clear solution B of obtained Fe3+ concentration to be the clear solution A of 0.1mol/L and Fe2+ concentration be 0.1mol/L;
2) get solution A and the solution B of same volume, mix, then continue to add a small amount of ammoniacal liquor, after adding ammoniacal liquor, stir half an hour, the solution formed is the orange solution C of transparent and homogeneous;
3) getting 50ml n-hexyl alcohol joins in 100ml round-bottomed flask, in whipping process, slowly adds the solution C of 5ml, add complete after, continue stirring 0.5 hour, form the solution D of transparent and homogeneous;
4) round-bottomed flask is used heating in water bath, until temperature is 60 DEG C, and then in solution D, add the sodium hydroxide of appropriate amount, magnetic agitation speed is regulated to be 1000pm/min, under rapid stirring, react 2 hours, and to control atmosphere be argon gas, after reaction terminates, naturally cool to room temperature;
5) by step 4) react the solution left standstill that obtains 1 hour, can see that solution is obviously divided into two-layer, upper strata is organic solvent n-hexyl alcohol, lower floor is ferroferric oxide nano granules solution layer, conventional separate mode is used to be separated by n-hexyl alcohol, and dewater by adding siccative, the n-hexyl alcohol obtained can recycle; The ferroferric oxide nano granules solution of lower floor is by washing with alcohol, and high speed centrifugation is separated, dry, can obtain ferroferric oxide nano granules powder;
The diameter of prepared ferroferric oxide nano granules is 5 nanometers, has higher monodispersity, and has good solvability in aqueous, and at 300K, nanoparticle display superparamagnetism, saturation magnetization is 55emu/g, without remanent magnetism.Compared with bulk material, its saturation magnetization is very high, and the crystal formation of interpret sample is better, and surface organic ligands is less.When temperature reduces to 10K, nanoparticle has obvious magnetic trapping phenomena, and be ferrimagnetism, saturation magnetization increases to 65emu/g, has ferromagnetic nanoparticle like this and will have important application in biology or magnetic fluid etc.
Embodiment 2:
A kind of monodisperse water soluble ferroferric oxide nano granules, its preparation method is as follows:
1) first, by analytically pure iron(ic) chloride and iron protochloride, add respectively in deionized water, magnetic stirring apparatus stirs and makes it dissolve, the clear solution B of obtained Fe3+ concentration to be the clear solution A of 0.1mol/L and Fe2+ concentration be 0.1mol/L;
2) get solution A and the solution B of same volume, mix, then continue to add a small amount of ammoniacal liquor, after adding ammoniacal liquor, stir half an hour, the solution formed is the orange solution C of transparent and homogeneous;
3) getting 50ml n-hexyl alcohol joins in 100ml round-bottomed flask, in whipping process, slowly adds the solution C of 20ml, add complete after, continue stirring 2 hours, form the solution D of transparent and homogeneous;
4) round-bottomed flask is used heating in water bath, until temperature is 100 DEG C, and then in solution D, add the sodium hydroxide of appropriate amount, magnetic agitation speed is regulated to be 2000rpm/min, under rapid stirring, react 3 hours, and to control atmosphere be argon gas, after reaction terminates, naturally cool to room temperature;
5) by step 4) react the solution left standstill that obtains 3 hours, can see that solution is obviously divided into two-layer, upper strata is organic solvent n-hexyl alcohol, lower floor is ferroferric oxide nano granules solution layer, conventional separate mode is used to be separated by n-hexyl alcohol, and dewater by adding siccative, the n-hexyl alcohol obtained can recycle; The ferroferric oxide nano granules solution of lower floor is by washing with alcohol, and high speed centrifugation is separated, dry, can obtain ferroferric oxide nano granules powder;
The diameter of prepared ferroferric oxide nano granules is 10 nanometers, has higher monodispersity, and has good solvability in aqueous, and at 300K, nanoparticle display superparamagnetism, saturation magnetization is 65emu/g, without remanent magnetism.Compared with bulk material, its saturation magnetization is very high, and the crystal formation of interpret sample is better, and surface organic ligands is less.When temperature reduces to 10K, nanoparticle has obvious magnetic trapping phenomena, and be ferrimagnetism, saturation magnetization increases to 75emu/g, has ferromagnetic nanoparticle like this and will have important application in biology or magnetic fluid etc.
Embodiment 3:
A kind of monodisperse water soluble ferroferric oxide nano granules, its preparation method is as follows:
1) first, by analytically pure iron(ic) chloride and iron protochloride, add respectively in deionized water, magnetic stirring apparatus stirs and makes it dissolve, the clear solution B of obtained Fe3+ concentration to be the clear solution A of 0.1mol/L and Fe2+ concentration be 0.1mol/L;
2) get solution A and the solution B of same volume, mix, then continue to add a small amount of ammoniacal liquor, after adding ammoniacal liquor, stir half an hour, the solution formed is the orange solution C of transparent and homogeneous;
3) getting 50ml n-hexyl alcohol joins in 100ml round-bottomed flask, in whipping process, slowly adds the solution C of 20ml, add complete after, continue stirring 2 hours, form the solution D of transparent and homogeneous;
4) round-bottomed flask is used heating in water bath, until temperature is 70 DEG C, and then in solution D, add the sodium hydroxide of appropriate amount, magnetic agitation speed is regulated to be 2000rpm/min, under rapid stirring, react 3 hours, and to control atmosphere be argon gas, after reaction terminates, naturally cool to room temperature;
5) by step 4) react the solution left standstill that obtains 3 hours, can see that solution is obviously divided into two-layer, upper strata is organic solvent n-hexyl alcohol, lower floor is ferroferric oxide nano granules solution layer, conventional separate mode is used to be separated by n-hexyl alcohol, and dewater by adding siccative, the n-hexyl alcohol obtained can recycle; The ferroferric oxide nano granules solution of lower floor is by washing with alcohol, and high speed centrifugation is separated, dry, can obtain ferroferric oxide nano granules powder;
The diameter of prepared ferroferric oxide nano granules is 10 nanometers, has higher monodispersity, and has good solvability in aqueous, and at 300K, nanoparticle display superparamagnetism, saturation magnetization is 60emu/g, without remanent magnetism.Compared with bulk material, its saturation magnetization is very high, and the crystal formation of interpret sample is better, and surface organic ligands is less.When temperature reduces to 10K, nanoparticle has obvious magnetic trapping phenomena, and be ferrimagnetism, saturation magnetization increases to 70emu/g, has ferromagnetic nanoparticle like this and will have important application in biology or magnetic fluid etc.
Embodiment 4:
A kind of monodisperse water soluble ferroferric oxide nano granules, its preparation method is as follows:
1) first, by analytically pure iron(ic) chloride and iron protochloride, add respectively in deionized water, magnetic stirring apparatus stirs and makes it dissolve, the clear solution B of obtained Fe3+ concentration to be the clear solution A of 0.1mol/L and Fe2+ concentration be 0.1mol/L;
2) get solution A and the solution B of same volume, mix, then continue to add a small amount of ammoniacal liquor, after adding ammoniacal liquor, stir half an hour, the solution formed is the orange solution C of transparent and homogeneous;
3) getting 50ml n-hexyl alcohol joins in 100ml round-bottomed flask, in whipping process, slowly adds the solution C of 20ml, add complete after, continue stirring 2 hours, form the solution D of transparent and homogeneous;
4) round-bottomed flask is used heating in water bath, until temperature is 80 DEG C, and then in solution D, add the sodium hydroxide of appropriate amount, magnetic agitation speed is regulated to be 1500rpm/min, under rapid stirring, react 3 hours, and to control atmosphere be argon gas, after reaction terminates, naturally cool to room temperature;
5) by step 4) react the solution left standstill that obtains 3 hours, can see that solution is obviously divided into two-layer, upper strata is organic solvent n-hexyl alcohol, lower floor is ferroferric oxide nano granules solution layer, conventional separate mode is used to be separated by n-hexyl alcohol, and dewater by adding siccative, the n-hexyl alcohol obtained can recycle; The ferroferric oxide nano granules solution of lower floor is by washing with alcohol, and high speed centrifugation is separated, dry, can obtain ferroferric oxide nano granules powder;
The diameter of prepared ferroferric oxide nano granules is 10 nanometers, has higher monodispersity, and has good solvability in aqueous, and at 300K, nanoparticle display superparamagnetism, saturation magnetization is 57emu/g, without remanent magnetism.Compared with bulk material, its saturation magnetization is very high, and the crystal formation of interpret sample is better, and surface organic ligands is less.When temperature reduces to 10K, nanoparticle has obvious magnetic trapping phenomena, and be ferrimagnetism, saturation magnetization increases to 65emu/g, has ferromagnetic nanoparticle like this and will have important application in biology or magnetic fluid etc.
Embodiment 5:
A kind of monodisperse water soluble ferroferric oxide nano granules, its preparation method is as follows:
1) first, by analytically pure iron(ic) chloride and iron protochloride, add respectively in deionized water, magnetic stirring apparatus stirs and makes it dissolve, the clear solution B of obtained Fe3+ concentration to be the clear solution A of 0.1mol/L and Fe2+ concentration be 0.1mol/L;
2) get solution A and the solution B of same volume, mix, then continue to add a small amount of ammoniacal liquor, after adding ammoniacal liquor, stir half an hour, the solution formed is the orange solution C of transparent and homogeneous;
3) getting 50ml n-hexyl alcohol joins in 100ml round-bottomed flask, in whipping process, slowly adds the solution C of 20ml, add complete after, continue stirring 2 hours, form the solution D of transparent and homogeneous;
4) round-bottomed flask is used heating in water bath, until temperature is 90 DEG C, and then in solution D, add the sodium hydroxide of appropriate amount, magnetic agitation speed is regulated to be 1700rpm/min, under rapid stirring, react 3 hours, and to control atmosphere be argon gas, after reaction terminates, naturally cool to room temperature;
5) by step 4) react the solution left standstill that obtains 3 hours, can see that solution is obviously divided into two-layer, upper strata is organic solvent n-hexyl alcohol, lower floor is ferroferric oxide nano granules solution layer, conventional separate mode is used to be separated by n-hexyl alcohol, and dewater by adding siccative, the n-hexyl alcohol obtained can recycle; The ferroferric oxide nano granules solution of lower floor is by washing with alcohol, and high speed centrifugation is separated, dry, can obtain ferroferric oxide nano granules powder; The diameter of prepared ferroferric oxide nano granules is 6 nanometers, has higher monodispersity, and has good solvability in aqueous, and at 300K, nanoparticle display superparamagnetism, saturation magnetization is 57emu/g, without remanent magnetism.Compared with bulk material, its saturation magnetization is very high, and the crystal formation of interpret sample is better, and surface organic ligands is less.When temperature reduces to 10K, nanoparticle has obvious magnetic trapping phenomena, and be ferrimagnetism, saturation magnetization increases to 68emu/g, has ferromagnetic nanoparticle like this and will have important application in biology or magnetic fluid etc.
Comparative example 1:
A kind of monodisperse water soluble ferroferric oxide nano granules, its preparation method is as follows:
1) first, by analytically pure iron(ic) chloride and iron protochloride, add respectively in deionized water, magnetic stirring apparatus stirs and makes it dissolve, the clear solution B of obtained Fe3+ concentration to be the clear solution A of 0.1mol/L and Fe2+ concentration be 0.1mol/L;
2) get solution A and the solution B of same volume, mix, then continue to add a small amount of ammoniacal liquor, after adding ammoniacal liquor, stir half an hour, the solution formed is the orange solution C of transparent and homogeneous;
3) getting 50ml ethanol joins in 100ml round-bottomed flask, in whipping process, slowly adds the solution C of 5ml, add complete after, continue stirring 0.5 hour, form the solution D of transparent and homogeneous;
4) round-bottomed flask is used heating in water bath, until temperature is 60 DEG C, and then in solution D, add the sodium hydroxide of appropriate amount, magnetic agitation speed is regulated to be 1000pm/min, under rapid stirring, react 2 hours, and to control atmosphere be argon gas, after reaction terminates, naturally cool to room temperature;
5) by step 4) react the solution left standstill that obtains 1 hour, can see that solution is obviously divided into two-layer, upper strata is organic solvent n-hexyl alcohol, lower floor is ferroferric oxide nano granules solution layer, conventional separate mode is used to be separated by n-hexyl alcohol, and dewater by adding siccative, the n-hexyl alcohol obtained can recycle; The ferroferric oxide nano granules solution of lower floor is by washing with alcohol, and high speed centrifugation is separated, dry, can obtain ferroferric oxide nano granules powder; The diameter of prepared ferroferric oxide nano granules is 5 nanometers, has higher monodispersity, and has good solvability in aqueous, and at 300K, nanoparticle display superparamagnetism, saturation magnetization is 45emu/g, without remanent magnetism.Compared with bulk material, its saturation magnetization is very high, and the crystal formation of interpret sample is better, and surface organic ligands is less.When temperature reduces to 10K, nanoparticle has obvious magnetic trapping phenomena, and be ferrimagnetism, saturation magnetization increases to 55emu/g, has ferromagnetic nanoparticle like this and will have important application in biology or magnetic fluid etc.
Claims (3)
1. a monodisperse water soluble ferroferric oxide nano granules, is characterized in that:
Its preparation method is as follows:
1) first, by analytically pure iron(ic) chloride and iron protochloride, add respectively in deionized water, magnetic stirring apparatus stirs and makes it dissolve, obtained Fe
3+concentration is clear solution A and Fe of 0.1mol/L
2+concentration is the clear solution B of 0.1mol/L;
2) get solution A and the solution B of same volume, mix, then continue to add a small amount of ammoniacal liquor, after adding ammoniacal liquor, stir half an hour, the solution formed is the orange solution C of transparent and homogeneous;
3) getting 50ml n-hexyl alcohol joins in 100ml round-bottomed flask, in whipping process, slowly adds the solution C of 5-20ml, add complete after, continue to stir 0.5-2 hour, form the solution D of transparent and homogeneous;
4) round-bottomed flask is used heating in water bath, until temperature is 60-100 DEG C, and then in solution D, add the sodium hydroxide of appropriate amount, magnetic agitation speed is regulated to be 1000-2000rpm/min, under rapid stirring, reaction 2-3 hour, and to control atmosphere be argon gas, after reaction terminates, naturally cool to room temperature;
5) by step 4) react the solution left standstill 1-3 hour obtained, can see that solution is obviously divided into two-layer, upper strata is organic solvent n-hexyl alcohol, lower floor is ferroferric oxide nano granules solution layer, conventional separate mode is used to be separated by n-hexyl alcohol, and dewater by adding siccative, the n-hexyl alcohol obtained recycles; The ferroferric oxide nano granules solution of lower floor is by washing with alcohol, and high speed centrifugation is separated, dry, can obtain ferroferric oxide nano granules powder;
The diameter of prepared ferroferric oxide nano granules is 5-10 nanometer, has higher monodispersity, and has good solvability in aqueous, at 300K, and nanoparticle display superparamagnetism, saturation magnetization is 55-65emu/g, without remanent magnetism; Compared with bulk material, its saturation magnetization is very high, and the crystal formation of interpret sample is better, and surface organic ligands is less; When temperature reduces to 10K, nanoparticle has obvious magnetic trapping phenomena, and be ferrimagnetism, saturation magnetization increases to 65-75emu/g, has ferromagnetic nanoparticle like this and will have important application in biology or magnetic fluid.
2. a monodisperse water soluble ferroferric oxide nano granules as claimed in claim 1, is characterized in that step 4) in temperature of reaction be 80 DEG C.
3. a monodisperse water soluble ferroferric oxide nano granules as claimed in claim 1 or 2, is characterized in that step 4) in stirring velocity be 1500rpm/min.
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