CN103950994A - Method for preparing double-shell CoO/Co3O4 hollow nanoparticles - Google Patents

Method for preparing double-shell CoO/Co3O4 hollow nanoparticles Download PDF

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CN103950994A
CN103950994A CN201410200385.6A CN201410200385A CN103950994A CN 103950994 A CN103950994 A CN 103950994A CN 201410200385 A CN201410200385 A CN 201410200385A CN 103950994 A CN103950994 A CN 103950994A
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coo
nano particle
bivalve
hollow nano
preparation
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CN103950994B (en
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刘小鹤
张丹
邱冠周
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Central South University
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Central South University
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Abstract

The invention discloses a method for preparing double-shell CoO/Co3O4 hollow nanoparticles. The method for preparing double-shell CoO/Co3O4 hollow nanoparticles, provided by the invention, comprises the following step of mixing organometallic cobalt salt with an organic solvent, firstly preparing double-shell CoO hollow nanoparticles under high temperature and high pressure conditions, and then preparing double-shell Co3O4 hollow nanoparticles by a high temperature calcining process. The cobalt monoxide and cobalt oxide, prepared by the method disclosed by the invention, have the characteristics of high purity, uniform particle size, strong oxidation resistance, excellent magnetic performance and the like. The double-shell CoO/Co3O4 hollow nanoparticles have the advantages of good quality, simple technological process, wide range of application, and broad application prospects in preparation of lithium batteries, biomedical drug/gene transduction and energy storage.

Description

Bivalve CoO, Co 3o 4the preparation method of hollow Nano particle
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
Because shell hollow nano-material has the larger constructional feature such as internal space and heterogeneous Inhomogeneous Interphase, be therefore with a wide range of applications at aspects such as lithium cell preparation, catalysis, sensing, pharmaceutical carrier and bio-imagings.Well-known transition metals cobalt and oxide compound thereof have good magnetic property and chemical property, therefore about the preparation method of cobaltous oxide and cobaltosic oxide nanoparticles and property research one of are current hot subject.Bond material itself and constructional feature, developed multiple synthetic CoO and Co in recent years 3o 4the method of nanoparticle, the while is also prepared CoO and the Co of different-shape feature 3o 4nanoparticle.The people such as K.J.An and N.Y.Lee utilizes CoCl 2.6H 2o is the sub-cobalt of the synthetic oleic acid of raw material, then adopts the method for high temperature thermolysis 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 the ratio of the sub-cobalt of regulation and control 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 have reported and have utilized 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 synthetic cobalt type oxide is still comparatively complicated at present, the research preparation of the hollow cobalt type oxide of shell nano material is very few.Therefore, exploitation is a kind of simple to operate and product structure feature is obvious, and size homogeneous has CoO and the 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 concentrates, and has bivalve CoO and the 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 stirring 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.
Two kinds of protective material oleic acid 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 1mol:20～25mL.
In aforesaid method, be warming up to and at 260-280 DEG C, react at least 1h; Further preferably be warming up at 260 DEG C and react 1-12h.
Bivalve Co 3o 4the preparation method of hollow Nano particle, the bivalve CoO nano particle that aforesaid method is prepared 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; Further preferably 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. to adopt organo-metallic cobalt salt be raw material in the present invention, using organic solvent as reaction solvent; The long-chain oleic acid adding and oleyl amine play tensio-active agent and protectant effect in the forming process of CoO nanoparticle.
2. adopt pyroreaction still as reactor, can effectively get rid of the interference of external environment; Utilize octadecylene for reaction solvent, avoided 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 mechanism that bivalve CoO hollow structure forms.Adopt high-temperature high-voltage reaction condition, control well the reaction times, make synthetic CoO nano particle along with the prolongation in reaction times by solid change into hollow, be grown to bivalve 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 successful synthetic bivalve CoO hollow Nano particle 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, operational safety, and the quality product obtaining is high, and in the preparation of lithium cell, the aspects such as the conduction of biomedical medicine/gene have broad application prospects.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction figure of the prepared bivalve CoO hollow Nano particle of embodiment 1;
Fig. 2 is the TEM Electronic Speculum detection figure of the prepared bivalve CoO hollow Nano particle of embodiment 1;
Fig. 3 is the SEM Electronic Speculum detection figure of the prepared bivalve CoO hollow Nano particle of embodiment 1;
Fig. 4 is the TEM Electronic Speculum detection figure of the prepared CoO nano particle of embodiment 2;
Fig. 5 is the TEM Electronic Speculum detection figure of the prepared CoO nano particle of embodiment 3;
Fig. 6 is the TEM Electronic Speculum detection figure of the prepared CoO nano particle of embodiment 4;
Fig. 7 is the TEM Electronic Speculum detection figure of the prepared CoO nano particle of embodiment 5;
Fig. 8 is the prepared bivalve Co of embodiment 6 3o 4the X-ray powder diffraction figure of hollow Nano particle;
Fig. 9 is the prepared bivalve Co of embodiment 6 3o 4the TEM Electronic Speculum of hollow Nano particle detects figure;
Figure 10 is the prepared bivalve Co of embodiment 6 3o 4the SEM Electronic Speculum of hollow Nano particle detects figure;
Figure 11 is the prepared Co of embodiment 7 3o 4hollow Nano particle TEM Electronic Speculum detects figure;
Figure 12 is the prepared Co of embodiment 8 3o 4hollow Nano particle TEM Electronic Speculum detects figure;
Figure 13 is the prepared Co of 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 the sub-cobalt 1mmol of methyl ethyl diketone (0.2571g) is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (account for whole reaction system 20%), 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 that reaction is obtained obtains chocolate brown powder through centrifugation, washing, after dry.Product is accredited as cobaltous oxide through X-ray powder diffraction as shown in Figure 1; Cobaltous oxide is carried out to morphology analysis with transmission electron microscope (TEM), as can be seen from Figure 2 its pattern is double-layer hollow nano particle; By scanning electron microscope (SEM), cobaltous oxide is carried out to morphology analysis, as can be seen from Figure 3 its pattern is hollow Nano particle.
Embodiment 2
Taking the sub-cobalt 1mmol of methyl ethyl diketone (0.2571g) is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (account for whole reaction system 20%), 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 that reaction is obtained obtains chocolate brown powder through centrifugation, washing, after dry.Cobaltous oxide is carried out to morphology analysis with transmission electron microscope (TEM), as can be seen from Figure 4 its pattern is the solid nano particle of cobaltous oxide.
Embodiment 3
Taking the sub-cobalt 1mmol of methyl ethyl diketone (0.2571g) is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (account for whole reaction system 20%), 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 that reaction is obtained obtains chocolate brown powder through centrifugation, washing, after dry.Cobaltous oxide is carried out to morphology analysis with transmission electron microscope (TEM), as can be seen from Figure 5 product is the solid nano particle of cobaltous oxide and the sub-cobalt hollow Nano of partial oxidation particle.
Embodiment 4
Taking the sub-cobalt 1mmol of methyl ethyl diketone (0.2571g) is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (account for whole reaction system 20%), 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 that reaction is obtained obtains chocolate brown powder through centrifugation, washing, after dry.Cobaltous oxide is carried out to morphology analysis with transmission electron microscope (TEM), as can be seen from Figure 6 product is cobaltous oxide hollow Nano particle.
Embodiment 5
Taking the sub-cobalt 1mmol of methyl ethyl diketone (0.2571g) is dissolved in 20ml octadecylene, measure oleic acid and oleyl amine (account for whole reaction system 20%), 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 that reaction is obtained obtains chocolate brown powder through centrifugation, washing, after dry.Cobaltous oxide is carried out to morphology analysis with transmission electron microscope (TEM), as can be seen from Figure 7 product is bivalve cobaltous oxide hollow Nano particle, compares compared with embodiment 1, and it is good that nanoparticle structure keeps, and size slightly increases.
Embodiment 6
Take the reaction prepared bivalve of 8h CoO hollow Nano particle 0.1g and proceed in magnetic boat, 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; Tricobalt tetroxide is carried out to morphology analysis with transmission electron microscope (TEM), as can be seen from Figure 9 its pattern is double-layer hollow nano particle; By scanning electron microscope (SEM), tricobalt tetroxide is carried out to morphology analysis, as can be seen from Figure 10 its pattern is hollow Nano particle.
Embodiment 7
Take the hollow CoO nano particle of the reaction prepared part of 2h 0.1g and proceed in magnetic boat, 600 DEG C of high-temperature calcination 2h obtain black powder.Tricobalt tetroxide is carried out to morphology analysis with transmission electron microscope (TEM), as can be seen from Figure 11 its pattern is porous hollow nano particle.
Embodiment 8
Take the prepared CoO hollow Nano of reaction 4h particle 0.1g and proceed in magnetic boat, 600 DEG C of high-temperature calcination 2h obtain black powder.Tricobalt tetroxide is carried out to morphology analysis with transmission electron microscope (TEM), as can be seen from Figure 12 its pattern is porous hollow nano particle, compares compared with Figure 11, and porous area increases.
Embodiment 9
Take the reaction prepared part of 6h bivalve CoO hollow Nano particle 0.1g and proceed in magnetic boat, 600 DEG C of high-temperature calcination 2h obtain black powder.Tricobalt tetroxide is carried out to morphology analysis with transmission electron microscope (TEM), as can be seen from Figure 13 product is still porous hollow nano particle, and the area of its hole is compared further increase compared with Figure 12.

Claims (8)

1. the preparation method of bivalve CoO hollow Nano particle, is characterized in that, 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 stirring in step 2 is heated until generate bivalve CoO hollow Nano particle at 200～280 DEG C.
2. the preparation method of bivalve according to claim 1 CoO hollow Nano particle, is characterized in that, the 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.
3. the preparation method of bivalve according to claim 2 CoO hollow Nano particle, is characterized in that, two kinds of protective material oleic acid 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 1mol:20～25mL.
4. the preparation method of bivalve according to claim 1 CoO hollow Nano particle, is characterized in that, is warming up to and at 260-280 DEG C, reacts at least 6h.
5. the preparation method of bivalve according to claim 4 CoO hollow Nano particle, is characterized in that, is warming up at 260 DEG C and reacts 6-12h.
6. bivalve Co 3o 4the preparation method of hollow Nano particle, is characterized in that, the bivalve CoO nano particle that the preparation method described in claim 1-5 any one is prepared proceeds in magnetic boat, and 400～800 DEG C of calcinings are until generate bivalve Co 3o 4hollow Nano particle.
7. bivalve Co according to claim 6 3o 4the preparation method of hollow Nano particle, is characterized in that, under 600-800 DEG C of high temperature, calcines at least 2h.
8. bivalve Co according to claim 7 3o 4the preparation method of hollow Nano particle, is characterized in that, under 600 DEG C of high temperature, calcines 2-4h.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106082357A (en) * 2016-06-08 2016-11-09 淮阴师范学院 A kind of preparation method of Cobalto-cobaltic oxide Multi-layer hollow microsphere
CN108975415A (en) * 2018-08-31 2018-12-11 肇庆市华师大光电产业研究院 A kind of preparation method that cobalt protoxide is nanocrystalline and its cobalt protoxide of preparation are nanocrystalline
CN109650449A (en) * 2019-01-24 2019-04-19 浙江大学 The preparation method and product of a kind of molybdenum oxide nano material and application

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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

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106082357A (en) * 2016-06-08 2016-11-09 淮阴师范学院 A kind of preparation method of Cobalto-cobaltic oxide Multi-layer hollow microsphere
CN108975415A (en) * 2018-08-31 2018-12-11 肇庆市华师大光电产业研究院 A kind of preparation method that cobalt protoxide is nanocrystalline and its cobalt protoxide of preparation are nanocrystalline
CN109650449A (en) * 2019-01-24 2019-04-19 浙江大学 The preparation method and product of a kind of molybdenum oxide nano material and application
CN109650449B (en) * 2019-01-24 2019-12-31 浙江大学 Preparation method of molybdenum oxide nano material, product and application

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