CN103950994B - Bivalve CoO, Co 3o 4the preparation method of hollow Nano particle - Google Patents
Bivalve CoO, Co 3o 4the preparation method of hollow Nano particle Download PDFInfo
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- CN103950994B CN103950994B CN201410200385.6A CN201410200385A CN103950994B CN 103950994 B CN103950994 B CN 103950994B CN 201410200385 A CN201410200385 A CN 201410200385A CN 103950994 B CN103950994 B CN 103950994B
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Abstract
The invention discloses a kind of bivalve CoO, Co
3o
4the preparation method of hollow Nano particle.Preparation bivalve CoO and Co provided by the present invention
3o
4the step of hollow Nano particle comprises: mixed with organic solvent by organo-metallic cobalt salt, it is characterized in that first adopting high temperature, high pressure prepares bivalve CoO hollow Nano particle, then obtain bivalve Co by high-temperature calcination
3o
4hollow Nano particle.The cobaltous oxide prepared by the inventive method and tricobalt tetroxide have the features such as the magnetic property that purity is high, grain diameter is homogeneous, oxidation-resistance is strong and good.Quality product of the present invention is good, and technical process is simple, and scope on probation is wide, and in the preparation of lithium cell, biomedical medicine/gene conduction and energy storage aspect have broad application prospects.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to a kind of bivalve CoO, Co
3o
4the preparation method of hollow Nano particle.
Background technology
There is due to shell hollow nano-material the constructional features such as larger internal space and heterogeneous Inhomogeneous Interphase, be therefore with a wide range of applications in lithium cell preparation, catalysis, sensing, pharmaceutical carrier and bio-imaging etc.Well-known transition metals cobalt and oxide compound thereof have excellent magnetic property and chemical property, therefore about the preparation method of cobaltous oxide and cobaltosic oxide nanoparticles and character research are one of current hot subject.Bond material itself and constructional feature, developed multiple synthesis CoO and Co in recent years
3o
4the method of nanoparticle, also prepares CoO and Co of different-shape feature simultaneously
3o
4nanoparticle.The people such as K.J.An and N.Y.Lee utilize CoCl
2.6H
2o is the sub-cobalt of Material synthesis oleic acid, then adopts the method for high temperature thermal decomposition to reprocess the sub-cobalt of oleic acid, finally prepares CoO nanometer rod (J.Am.Chem.Soc.2006,128,9753-9760); The people such as Y.L.Zhang, by regulating and controlling the ratio of the sub-cobalt of oleic acid and activator or inhibitor, have prepared petal-like CoO nanoparticle (J.Phys.Chem.C, 2008,112,5322-5327); The people such as H.T.Wang report and utilize CoCl
2.6H
2o and Co (NO
3)
2.6H
2o is raw material, finally obtains tabular and flower-shaped Co by hydrothermal method and high-temperature calcination
3o
4(J.Phys.Chem.C, 2011,115,17599 – 17605).But the method for synthesis cobalt type oxide is still comparatively complicated at present, the research preparation of shell hollow cobalt type oxide nano material is very few.Therefore, exploitation one is simple to operate and product structure feature obvious, and size uniformity, has CoO and Co of good magnetic property and chemical property
3o
4preparation method be still a vital task of field of material preparation.
Summary of the invention
The object of this invention is to provide and prepared that shape characteristic is obvious, size-grade distribution is concentrated, there is bivalve CoO and Co of good magnetic and chemical property
3o
4the method of hollow Nano particle.
The preparation method of bivalve CoO hollow Nano particle, comprises the following steps:
Step 1: organo-metallic cobalt salt is mixed with two kinds of protective materials and organic solvent;
Step 2: the mixed solution of step 1 is stirred and is sealed in reactor;
Step 3: the mixed solution stirred in step 2 is heated until generate bivalve CoO hollow Nano particle (particle diameter is 250-300nm) at 200 ~ 280 DEG C.
Organic solvent described in step 1 comprises octadecylene; Described organo-metallic cobalt salt comprises the sub-cobalt of methyl ethyl diketone; Two kinds of described protective materials comprise oleic acid and oleyl amine.
Described in step 1 two kind of protective material oleic acid and oleyl amine mol ratio are 4:10, account for 20% of whole reaction system; The amount of substance of organo-metallic cobalt salt and the volume ratio of organic solvent are 1mol:20 ~ 25mL.
At least 1h is reacted at being warming up to 260-280 DEG C in aforesaid method; 1-12h is reacted at being preferably warming up to 260 DEG C further.
Bivalve Co
3o
4the preparation method of hollow Nano particle, the bivalve CoO nano particle prepared by aforesaid method proceeds in magnetic boat, and 400 ~ 800 DEG C of calcinings are until generate bivalve Co
3o
4hollow Nano particle (particle diameter is 300nm-400nm).Preferably under 600-800 DEG C of high temperature, calcine at least 2h; Preferably further under 600 DEG C of high temperature, calcine 2-4h.
The present invention compared with prior art, has the following advantages and high-lighting effect:
1. the present invention adopts organo-metallic cobalt salt to be raw material, using organic solvent as reaction solvent; The long-chain oleic acid added and oleyl amine play tensio-active agent and protectant effect in the forming process of CoO nanoparticle.
2. adopt pyroreaction still as reactor, effectively can get rid of the interference of external environment; Utilize octadecylene for reaction solvent, avoid the problem such as environmental pollution and human injury that in existing synthetic route, ether solvent hypertoxicity is brought.
3. the present invention proposes the Ostwald ripening mechanisms that bivalve CoO hollow structure is formed.Adopt high-temperature high-voltage reaction condition, control the reaction times well, make the CoO nano particle of synthesis along with the reaction times prolongation by solid change into hollow, bivalve is grown to from monoshell, finally be grown to bivalve hollow Nano particle, it it should be noted that CoO outer shell and inner layer case are cobaltous oxide pure phase.
4. the present invention is using the bivalve CoO hollow Nano particle of success synthesis as presoma, and in magnetic boat, bivalve Co is prepared in high-temperature calcination
3o
4hollow Nano particle, wherein outer shell and inner layer case are Co
3o
4.
5. the inventive method technique is simple, and operational safety, the quality product obtained is high, and in the preparation of lithium cell, the aspects such as the conduction of biomedical medicine/gene have broad application prospects.
Accompanying drawing explanation
The X-ray powder diffraction figure of the bivalve CoO hollow Nano particle of Fig. 1 prepared by embodiment 1;
The TEM Electronic Speculum detection figure of the bivalve CoO hollow Nano particle of Fig. 2 prepared by embodiment 1;
The SEM Electronic Speculum detection figure of the bivalve CoO hollow Nano particle of Fig. 3 prepared by embodiment 1;
The TEM Electronic Speculum detection figure of the CoO nano particle of Fig. 4 prepared by embodiment 2;
The TEM Electronic Speculum detection figure of the CoO nano particle of Fig. 5 prepared by embodiment 3;
The TEM Electronic Speculum detection figure of the CoO nano particle of Fig. 6 prepared by embodiment 4;
The TEM Electronic Speculum detection figure of the CoO nano particle of Fig. 7 prepared by embodiment 5;
The bivalve Co of Fig. 8 prepared by embodiment 6
3o
4the X-ray powder diffraction figure of hollow Nano particle;
The bivalve Co of Fig. 9 prepared by embodiment 6
3o
4the TEM Electronic Speculum of hollow Nano particle detects figure;
The bivalve Co of Figure 10 prepared by embodiment 6
3o
4the SEM Electronic Speculum of hollow Nano particle detects figure;
The Co of Figure 11 prepared by embodiment 7
3o
4hollow Nano particle TEM Electronic Speculum detects figure;
The Co of Figure 12 prepared by embodiment 8
3o
4hollow Nano particle TEM Electronic Speculum detects figure;
The Co of Figure 13 prepared by embodiment 9
3o
4hollow Nano particle TEM Electronic Speculum detects figure.
Embodiment
Following examples are intended to further illustrate the present invention, and unrestricted the present invention.
Embodiment 1
Taking sub-cobalt 1mmol (0.2571g) of methyl ethyl diketone is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (accounting for 20% of whole reaction system), mol ratio is that 4:10 joins in above-mentioned solution, be moved in 40ml reactor, sealed reactor after uniform stirring 10min, be warming up to 260 DEG C, be incubated 8 hours.The product be obtained by reacting is obtained chocolate brown powder after centrifugation, washing, drying.Product is accredited as cobaltous oxide through X-ray powder diffraction as shown in Figure 1; Carry out morphology analysis with transmission electron microscope (TEM) to cobaltous oxide, as can be seen from Figure 2 its pattern is double-layer hollow nano particle; Carry out morphology analysis by scanning electron microscope (SEM) to cobaltous oxide, as can be seen from Figure 3 its pattern is hollow Nano particle.
Embodiment 2
Taking sub-cobalt 1mmol (0.2571g) of methyl ethyl diketone is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (accounting for 20% of whole reaction system), mol ratio is that 4:10 joins in above-mentioned solution, be moved in 40ml reactor, sealed reactor after uniform stirring 10min, be warming up to 260 DEG C, insulation 1h.The product be obtained by reacting is obtained chocolate brown powder after centrifugation, washing, drying.Carry out morphology analysis with transmission electron microscope (TEM) to cobaltous oxide, as can be seen from Figure 4 its pattern is cobaltous oxide solid nanoparticles.
Embodiment 3
Taking sub-cobalt 1mmol (0.2571g) of methyl ethyl diketone is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (accounting for 20% of whole reaction system), mol ratio is that 4:10 joins in above-mentioned solution, be moved in 40ml reactor, sealed reactor after uniform stirring 10min, be warming up to 260 DEG C, insulation 2h.The product be obtained by reacting is obtained chocolate brown powder after centrifugation, washing, drying.Carry out morphology analysis with transmission electron microscope (TEM) to cobaltous oxide, as can be seen from Figure 5 product is cobaltous oxide solid nanoparticles and partial oxidation sub-cobalt hollow Nano particle.
Embodiment 4
Taking sub-cobalt 1mmol (0.2571g) of methyl ethyl diketone is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (accounting for 20% of whole reaction system), mol ratio is that 4:10 joins in above-mentioned solution, be moved in 40ml reactor, sealed reactor after uniform stirring 10min, be warming up to 260 DEG C, insulation 4h.The product be obtained by reacting is obtained chocolate brown powder after centrifugation, washing, drying.Carry out morphology analysis with transmission electron microscope (TEM) to cobaltous oxide, as can be seen from Figure 6 product is cobaltous oxide hollow Nano particle.
Embodiment 5
Taking sub-cobalt 1mmol (0.2571g) of methyl ethyl diketone is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (accounting for 20% of whole reaction system), mol ratio is that 4:10 joins in above-mentioned solution, be moved in 40ml reactor, sealed reactor after uniform stirring 10min, be warming up to 260 DEG C, insulation 12h.The product be obtained by reacting is obtained chocolate brown powder after centrifugation, washing, drying.Carry out morphology analysis with transmission electron microscope (TEM) to cobaltous oxide, as can be seen from Figure 7 product is bivalve cobaltous oxide hollow Nano particle, and comparatively embodiment 1 is compared, and nanoparticle structure keeps good, and size slightly increases.
Embodiment 6
Taking the bivalve CoO hollow Nano particle 0.1g of reaction obtained by 8h proceeds in magnetic boat, and 600 DEG C of high-temperature calcination 2h obtain black powder.Product is accredited as tricobalt tetroxide through X-ray powder diffraction as shown in Figure 8; Carry out morphology analysis with transmission electron microscope (TEM) to tricobalt tetroxide, as can be seen from Figure 9 its pattern is double-layer hollow nano particle; Carry out morphology analysis by scanning electron microscope (SEM) to tricobalt tetroxide, as can be seen from Figure 10 its pattern is hollow Nano particle.
Embodiment 7
Taking the part hollow CoO nano particle 0.1g of reaction obtained by 2h proceeds in magnetic boat, and 600 DEG C of high-temperature calcination 2h obtain black powder.Carry out morphology analysis with transmission electron microscope (TEM) to tricobalt tetroxide, as can be seen from Figure 11 its pattern is porous hollow nano particle.
Embodiment 8
Taking the CoO hollow Nano particle 0.1g of reaction obtained by 4h proceeds in magnetic boat, and 600 DEG C of high-temperature calcination 2h obtain black powder.Carry out morphology analysis with transmission electron microscope (TEM) to tricobalt tetroxide, as can be seen from Figure 12 its pattern is porous hollow nano particle, and comparatively Figure 11 compares, and porous area increases.
Embodiment 9
Taking the part bivalve CoO hollow Nano particle 0.1g of reaction obtained by 6h proceeds in magnetic boat, and 600 DEG C of high-temperature calcination 2h obtain black powder.Carry out morphology analysis with transmission electron microscope (TEM) to tricobalt tetroxide, as can be seen from Figure 13 product is still porous hollow nano particle, and the area of its hole comparatively Figure 12 compares further increase.
Claims (6)
1. the preparation method of bivalve CoO hollow Nano particle, is characterized in that, comprise the following steps:
Step 1: organo-metallic cobalt salt is mixed with two kinds of protective materials and organic solvent;
Step 2: the mixed solution of step 1 is stirred and is sealed in reactor;
Step 3: by the mixed solution that stirs in step 2 at 260 ~ 280 DEG C of reacting by heating at least 6h, until generate bivalve CoO hollow Nano particle;
Organic solvent described in step 1 is octadecylene; Described organo-metallic cobalt salt is the sub-cobalt of methyl ethyl diketone; Two kinds of described protective materials are oleic acid and oleyl amine.
2. the preparation method of bivalve according to claim 1 CoO hollow Nano particle, is characterized in that, kind of the protective material oleic acid of two described in step 1 and oleyl amine mol ratio are 4:10, account for 20% of whole reaction system; The amount of substance of organo-metallic cobalt salt and the volume ratio of organic solvent are 1mmol:20 ~ 25mL.
3. the preparation method of bivalve according to claim 1 CoO hollow Nano particle, is characterized in that, react 6-12h at being warming up to 260 DEG C.
4. bivalve Co
3o
4the preparation method of hollow Nano particle, is characterized in that, the bivalve CoO nano particle preparation method described in any one of claim 1-3 prepared proceeds in magnetic boat, and 400 ~ 800 DEG C of calcinings are until generate bivalve Co
3o
4hollow Nano particle.
5. bivalve Co according to claim 4
3o
4the preparation method of hollow Nano particle, is characterized in that, calcines at least 2h under 600-800 DEG C of high temperature.
6. bivalve Co according to claim 5
3o
4the preparation method of hollow Nano particle, is characterized in that, under 600 DEG C of high temperature, calcine 2-4h.
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| CN106082357B (en) * | 2016-06-08 | 2017-07-11 | 淮阴师范学院 | A kind of preparation method of cobaltosic oxide Multi-layer hollow microballoon |
| CN108975415B (en) * | 2018-08-31 | 2020-07-10 | 肇庆市华师大光电产业研究院 | Cobalt protoxide nano-crystal preparation method and cobalt protoxide nano-crystal prepared by using same |
| CN109650449B (en) * | 2019-01-24 | 2019-12-31 | 浙江大学 | Preparation method of molybdenum oxide nano material, product and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101958411A (en) * | 2009-07-13 | 2011-01-26 | 北京工业大学 | CoO-Co composite material with core-shell structure and preparation method thereof |
| CN102464304A (en) * | 2010-11-12 | 2012-05-23 | 中国科学院过程工程研究所 | Multi-shell-layer metal oxide hollow ball and preparation method thereof |
| CN103771544A (en) * | 2014-02-22 | 2014-05-07 | 吉林大学 | Preparation method of hollow cobaltosic oxide microsphere |
-
2014
- 2014-05-13 CN CN201410200385.6A patent/CN103950994B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101958411A (en) * | 2009-07-13 | 2011-01-26 | 北京工业大学 | CoO-Co composite material with core-shell structure and preparation method thereof |
| CN102464304A (en) * | 2010-11-12 | 2012-05-23 | 中国科学院过程工程研究所 | Multi-shell-layer metal oxide hollow ball and preparation method thereof |
| CN103771544A (en) * | 2014-02-22 | 2014-05-07 | 吉林大学 | Preparation method of hollow cobaltosic oxide microsphere |
Non-Patent Citations (3)
| Title |
|---|
| Controlling the synthesis of CoO nanocrystals with various morphologies;Zhang, Yuliang等;《JOURNAL OF PHYSICAL CHEMISTRY C》;20080318;第112卷(第14期);5322-5327页 * |
| Phase- and size-controlled synthesis of hexagonal and cubic CoO nanocrystals;Seo, WS等;《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》;20050504;第127卷(第17期);6188-6189页 * |
| TEMPO-mediated, room temperature synthesis of pure CoO nanoparticles;Lagunas, A等;《CHEMICAL COMMUNICATIONS》;20060213;1307-1309页 * |
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