CN101234751B - Method for preparing nano material by flame combustion - Google Patents
Method for preparing nano material by flame combustion Download PDFInfo
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- CN101234751B CN101234751B CN200810101361XA CN200810101361A CN101234751B CN 101234751 B CN101234751 B CN 101234751B CN 200810101361X A CN200810101361X A CN 200810101361XA CN 200810101361 A CN200810101361 A CN 200810101361A CN 101234751 B CN101234751 B CN 101234751B
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Abstract
The invention relates to a direct burning method for preparing high crystallinity metal and oxide nano-particles thereof, metal with carbon shell structure and oxide nano-particles thereof, hollow nano ball of metal oxide, nano-particles with inorganic/inorganic heterogeneous structure and nano carbon pipe of water dispersion. Organic solvent is taken as comburent and carbon providing body; soluble metal compound is taken as metal precursor of nano material; through burning directly the organic solvent of the soluble metal compound precursor in the air, the nano material can be obtained in different positions of flame. The main technical characteristics of the method of the invention are that different kinds and different appearances of nano material can be collected in different positions of the flame; the appearances comprise medicine balls, hollow spheres, polyhedron and one dimensional nano-tube; the structure consists of a catamaran heterogeneous structure and a shell-core structure.
Description
Technical field
The present invention relates to preparation of nanomaterials, particularly the preparation of nanomaterials of metal, metal oxide and complex construction thereof.
Background technology
The distinctive small-size effect of nano particle, surface and interfacial effect, quantum size effect and macro quanta tunnel effect make it have many physics-chem characteristics different with body phase material.Therefore, nano particle shows great application prospect in fields such as materials chemistry, catalytic chemistry and biomedicines.
The synthetic method of nano material can be divided into physical method and chemical process roughly.Typical case's representative of chemical process is solution (a wetting) chemical process; Typical case's representative of physical method is a comminuting method.In addition, adopt extreme condition (as: high temperature, high pressure and high vacuum etc.) the preparation special construction and the nano material of pattern to become a very important method.Yet from bibliographical information, in above-mentioned extreme condition reaction method for preparing, the preparation of nanomaterials that has flame to participate in is actually rare, and conclusion gets up can roughly be divided into following several: gel combustion method, Production by Catalytic Combustion Process and flame atomizing pyrolysis method etc.
Gel combustion method: Chinese patent application number: 200510018263.6,200510068007.8 and 200610109215.2 introduced the method for preparing nano material by incendiary gel.This method needs to prepare earlier the gel that contains metallic compound, again this gel combustion is obtained containing the ashes of nano material, and grinding, calcining by to this ashes finally obtain nano material.At first, this method is to need to form earlier the gel that contains metal ion, therefore, has very large limitation; Secondly, material preparation process complexity belongs to intermittently preparation process, is not suitable for continuous production.
Production by Catalytic Combustion Process: Chinese patent application number: 200510119084.1 and 200510016849.9 have introduced the combustion preparation method of carbon pipe.The raw material that is adopted in preparation process is a polyolefine, needs to add metal catalyst and polynite in the preparation process.By the burning said polyolefins, obtain CNT (carbon nano-tube) at ashes.Owing to contain polynite in the product, therefore, product also needs through special purge process.This method only is fit to preparation CNT (carbon nano-tube) material except the defective with above-mentioned gel combustion method.
Flame atomizing pyrolysis method: Chinese patent application number: 03815626.1 and 00129582.9 has introduced the flame atomizing pyrolysis method.Its principle is the presoma wiring solution-forming with nano material, then its mode with droplet is ejected in the high-temperature furnace body, by metal precursor burning or the thermolysis preparation that realizes nano material at high temperature, finally collect and obtain nano material in the bottom of Reaktionsofen.Recently, Wang Zhonglin (science, 2006,312,1504～1508) utilizes this method to prepare titanium doped cerium dioxide nano material.The shortcoming of spray pyrolysis is to need a cover complex apparatus, and because the restriction of roasting kiln makes can handlingly reducing greatly of reaction process.In addition, the precursor solution of this method need could atomize by spraying into of gas, has so also strengthened the complicacy and the uncontrollability of reaction process.
In a word, also do not have a kind of suitable utilization burning to prepare the method for nano material at present, such method is applicable to the preparation of multiple inorganic nano material and CNT (carbon nano-tube) and amorphous nano-carbon material, and can adopt simple equipment to realize continuous production.
Summary of the invention
At the problems referred to above, the invention provides a kind of method of preparing nano material by flame combustion, organic solution by the dissimilar metals compound that directly burns in air prepares the nano material of different sorts and pattern, and the nano material by the preparation of flame method is provided.
Particularly, the present invention includes following aspect.
The present invention is to be that combustionmaterial and carbon provide body with the organic solvent, with the metallic compound that dissolves in organic solvent is the metal precursor of nano material, by the organic solution of the soluble metal compound presoma that in air, directly burns, on the different positions of flame, collect and obtain nano material; Wherein, soluble metal compound is originated as the metallic element in the nano material; Organic solvent also is used to provide carbon source except being used for the dissolution of metals compound.
Acetylacetonate, acetate, oxalate, Citrate trianion, gluconate, carbonyl-complexes, muriate that metallic compound presoma of the present invention is chosen from Fe, cobalt, nickel, manganese, the acetylacetonate of yttrium or lanthanide rare metal, muriate, perhaps at least a in the titanic acid ester.Wherein, because the character of subgroup metallic iron, cobalt, nickel, manganese is quite similar, therefore the same metalloid presoma by them can both obtain similar product.
Organic solvent of the present invention is the inflammable organic solvent of using always, comprise alcohols, aldehydes, ketone, ester class, alkanes, pyrrolidone and derivative, polyacrylic, benzene and derivative thereof, polyoxyethylene glycol, tetrahydrofuran (THF), dimethyl formamide, type siloxane etc., these organic solvents can be used alone or in combination.
Adopt method of the present invention, collect the nano material that obtains at the flame internal flame and comprise the metal nanoparticle material, have the metal nano material of carbon shell, the metal oxide nano-material that has the carbon shell, metallic oxide hollow nano-sphere or CNT (carbon nano-tube), collect the nano-particle material that the nano material that obtains comprises described metal oxide nanoparticles material or has inorganic/inorganic heterogeneous structure at the flame flame envelope.
Method major technique characteristics of the present invention are to collect the nano material of different sorts and different-shape on the different positions of flame, and its pattern comprises: solid sphere, hollow ball, polyhedron, 1-dimention nano pipe; Its structure comprises: binary heterojunction structure and core-shell structure.Compare with the disclosed the whole bag of tricks of background technology, the present invention has more obvious advantage.At first, method of the present invention is applicable to the preparation of more inorganic nano materials, comprises the preparation of nearly all nano material that contains transition metal and rare earth metal, also is applicable to the preparation of CNT (carbon nano-tube) and amorphous nano-carbon material simultaneously.In addition, also be applicable to the preparation of nano material with carbon shell structure; Secondly, the present invention selects for use the organic solution that is dissolved with the metallic compound presoma as stock liquid, and it can be joined in the reaction unit continuously, realizes continuous production.Once more, the present invention is the preparation that realizes nano material by the aerial direct burning of reaction raw materials, without any need for complex apparatus.The most important thing is, adopt the inventive method in reaction process, on the different position of flame, to obtain having the nano material of different compositions and structure.
The inventive method is widely used in elemental metals nano particle, metal oxide nanoparticles, has the preparation of materials such as the metal nano material of carbon shell, the metal oxide nano-material that has the carbon shell, metallic oxide hollow nano-sphere, the nano particle with inorganic/inorganic heterogeneous structure or CNT (carbon nano-tube).
Description of drawings
Fig. 1. the transmission electron microscope photo of the embodiment of the invention 1 gained sample.
Fig. 2. the electron diffraction photo of the embodiment of the invention 1 gained sample.
Fig. 3. the high resolution transmission electron microscopy photo of the embodiment of the invention 1 gained sample.
Fig. 4. the magnetic hysteresis loop figure of the embodiment of the invention 1 gained sample.
Fig. 5. the electron scanning micrograph of the embodiment of the invention 1 gained sample.
Fig. 6. the transmission electron microscope photo of the embodiment of the invention 10 gained samples.
Fig. 7. the transmission electron microscope photo of the embodiment of the invention 11 gained samples.
Fig. 8. the transmission electron microscope photo of the embodiment of the invention 14 gained samples.
Fig. 9. the transmission electron microscope photo of the embodiment of the invention 16 gained samples.
Figure 10. the transmission electron microscope photo of the embodiment of the invention 17 gained samples.
Figure 11. the transmission electron microscope photo of the embodiment of the invention 18 gained samples.
Figure 12. the transmission electron microscope photo of the embodiment of the invention 19 gained samples.
Figure 13. the transmission electron microscope photo of the embodiment of the invention 20 gained samples.
Figure 14. the transmission electron microscope photo of the embodiment of the invention 21 gained samples.
Figure 15. the transmission electron microscope photo of the embodiment of the invention 23 gained samples.
Figure 16. the transmission electron microscope photo of the embodiment of the invention 24 gained samples.
Figure 17. the transmission electron microscope photo of the embodiment of the invention 25 gained samples.
Figure 18. the transmission electron microscope photo of the embodiment of the invention 26 gained samples.
Embodiment
The concrete grammar of preparing nano material by flame combustion of the present invention may further comprise the steps:
(1) will dissolve in organic solvent the metallic compound presoma (hereinafter referred to as: the soluble metal compound presoma) be dissolved in the selected organic solvent, obtaining concentration is the organic solution of the soluble metal compound presoma of 0.005～0.5mol/L;
(2) organic solution of the resulting soluble metal compound presoma of step (1) is transferred in the open container, after lighting the organic solution of soluble metal compound presoma, on the different positions of flame, collect the different types of nano material that obtains.
The standard of the metallic compound presoma that the present invention is selected is: certain solubleness is arranged in great majority or specific organic solvent.Described metallic compound presoma is a chosen from Fe, cobalt, nickel, the acetylacetonate of manganese, acetate, oxalate, Citrate trianion, gluconate, carbonyl-complexes, muriate, the acetylacetonate of yttrium or lanthanide rare metal, muriate, perhaps at least a in the titanic acid ester, include, but are not limited to: praseodynium iron, diacetyl acetone iron, iron pentacarbonyl, iron acetate, ironic oxalate, ironic citrate, ferrous gluconate, ferrocene, FERRIC CHLORIDE ANHYDROUS, anhydrous ferrous chloride, four iron chloride hexahydrate, Iron(III) chloride hexahydrate, ironic oxalate, praseodynium nickel, diacetyl acetone nickel, four carbon back nickel, anhydrous chlorides of rase nickel, Nickel dichloride hexahydrate, nickelous oxalate, citric acid nickel, nickel acetate, the praseodynium cobalt, diacetyl acetone cobalt, eight carbon backs, two cobalts, cobalt chloride, Cobaltous diacetate, cobalt chloride hexahydrate, cobalt oxalate, the citric acid cobalt, the capric acid cobalt, praseodynium manganese, diacetyl acetone manganese, cyclopentadiene tricarbonyl manganese, Manganous chloride tetrahydrate, manganese acetate, manganous oxalate, manganese citrate, manganese gluconate, butyl (tetra) titanate, titanium isopropylate, the metatitanic acid n-propyl, titanium ethanolate, the metatitanic acid methyl esters, titanium tetrachloride, the methyl ethyl diketone yttrium, the acetylacetonate of lanthanide rare metal, the muriate of Yttrium trichloride or lanthanide rare metal.
The standard of the organic solvent that the present invention is selected is: for the metallic compound presoma certain solubleness is arranged, and be easy to burning.Described organic solvent comprises alcohols, aldehydes, ketone, the ester class, alkanes, pyrrolidone and derivative thereof, polyacrylic, benzene and derivative thereof, polyoxyethylene glycol, tetrahydrofuran (THF), dimethyl formamide, type siloxane etc., its specific examples comprises, but be not limited to: methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, acetone, formaldehyde, acetaldehyde, alpha-pyrrolidone, N-vinyl-2-Pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, dimethyl formamide, tetrahydrofuran (THF), Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyacrylic acid, polymethyl acrylic acid, benzene, toluene, normal hexane, hexanaphthene, tetraethyl-silica alkane, ethyl acetate, these organic solvents can be used alone or in combination.
Of the present invention to collect the nano material obtain on different flame locations be metal nanoparticle, metal oxide nanoparticles, have the metal nano material of carbon shell, the metal oxide nano-material that has the carbon shell, metallic oxide hollow nano-sphere, the nano particle with inorganic/inorganic heterogeneous structure or CNT (carbon nano-tube).
Described metal nanoparticle material, the metal nano material that has the carbon shell, the metal oxide nano-material that has the carbon shell, metallic oxide hollow nano-sphere or CNT (carbon nano-tube) concentrate on the flame internal flame; Described metal oxide nanoparticles, the nano particle with inorganic/inorganic heterogeneous structure concentrate on the flame flame envelope.
Metal nanoparticle of the present invention is Co or Ni nano particle, and as shown in figure 13, the particle diameter of nano particle is 5 nanometers～20 nanometers.
Metal oxide nanoparticles of the present invention is γ-Fe
2O
3, Fe
3O
4, CoO, NiO, MnO
2, CoFe
2O
4, NiFe
2O
4, MnFe
2O
4, TiO
2, FeTiO
3, CoTiO
3, NiTiO
3, MnTiO
3, Y
2O
3Or the lanthanide rare metal oxide nanoparticles, shown in Fig. 1,5,7,8,9,10,11,12, the particle diameter of nano particle is 10 nanometers～300 nanometers.
The metal nano material that has the carbon shell of the present invention is the Ni nano particle that has the Co of carbon shell or have the carbon shell; Above-mentioned particle diameter with nano particle of nucleocapsid structure is 5 nanometers～20 nanometers, and the carbon thickness of the shell is 2 nanometers～10 nanometers.
The metal oxide nano-material that has the carbon shell of the present invention is the Fe that has the carbon shell
3O
4, have the carbon shell CoO, have the carbon shell NiO, have the Y of carbon shell
2O
3Or have a lanthanide rare metal oxide nanoparticles of carbon shell; Shown in Figure 14,15, above-mentioned particle diameter with nano particle of nucleocapsid structure is 10 nanometers～100 nanometers, and the carbon thickness of the shell is 2 nanometers～20 nanometers.
Metallic oxide hollow nano-sphere of the present invention is Fe
3O
4, CoO or NiO hollow nano-sphere, as shown in figure 16, the particle diameter of hollow nano-sphere is 10 nanometers～400 nanometers.
Global shape with nano particle of inorganic/inorganic heterogeneous structure of the present invention is circle or oval, and is made up of two different pieces, and wherein, a part is a metal oxide, as γ-Fe
2O
3, CoO, NiO or MnO
2Another part is SiO
2As shown in figure 18, the particle overall dimensions is 20 nanometers～200 nanometers.
CNT (carbon nano-tube) length of the present invention is 10 nanometers～10 micron, as shown in figure 17.
The product that adopts the inventive method to prepare has rich diversity, and metal oxide especially is not only of a great variety but also pattern is different.Its concrete pattern comprises: have the polyhedron or the solid sphere of high symmetry, erose particle is also arranged; Grain pattern is monocrystalline, polycrystalline or non-crystal structure; Its magnetic property shows as superparamagnetism, paramagnetism, ferromegnetism, ferrimagnetism or antiferromagnetism.The present invention is applicable to the preparation of following metal oxide nanoparticles, comprising: Fe
3O
4, γ-Fe
2O
3, CoO, NiO, MnO
2, CoFe
2O
4, NiFe
2O
4, MnFe
2O
4, TiO
2, FeTiO
3, CoTiO
3, NiTiO
3, MnTiO
3, Y
2O
3Or lanthanide rare metal oxide.Fe
3O
4, γ-Fe
2O
3, CoO, NiO, MnO
2, CoFe
2O
4, NiFe
2O
4, MnFe
2O
4, TiO
2, FeTiO
3, CoTiO
3, NiTiO
3Or MnTiO
3Be shaped as polyhedron or solid sphere, Y
2O
3Or the lanthanide rare metal oxide particle is irregularly shaped.The metal oxide nanoparticles particle diameter is 10 nanometers～300 nanometers.
The present invention is applicable to the preparation of following metal simple-substance nanoparticle simultaneously, comprises Co and Ni nano particle, and its particle diameter is 5 nanometers～20 nanometers.
The present invention is applicable to the following preparation that has the metal and the metal oxide nano-material of carbon shell simultaneously, and the metal nano material that wherein has the carbon shell comprises: Co, Ni; The metal oxide nano-material that has the carbon shell comprises: Fe
3O
4, CoO, NiO and rare-earth oxide.Above-mentioned particle diameter with nano particle of nucleocapsid structure is 5 nanometers～100 nanometers, and the carbon thickness of the shell is 2 nanometers～20 nanometers.
The present invention is applicable to following preparation with metal oxide nano-material of hollow ball structure simultaneously, and the metal oxide that wherein constitutes hollow ball structure comprises: Fe
3O
4, CoO or NiO, the diameter of hollow ball is 10 nanometers～400 nanometers.
The present invention is applicable to following preparation with nano particle of inorganic/inorganic heterogeneous structure simultaneously.Particulate global shape with inorganic/inorganic heterogeneous structure is circle or oval, and is made up of two different pieces.Wherein, a part is a metal oxide, as γ-Fe
2O
3, CoO, NiO or MnO
2Another part is SiO
2The particle overall dimensions is 20 nanometers～200 nanometers.
The present invention is applicable to the preparation of water-soluble nano carbon pipe simultaneously, and wherein, the length of gained carbon pipe is 10 nanometers～10 micron.Usually be surrounded by metal oxide particle in the head of above-mentioned carbon pipe or the pipe, but through after the concentrated hydrochloric acid processing, metal oxide particle can be removed, and then obtains being scattered in the CNT (carbon nano-tube) of water.CNT (carbon nano-tube) is scattered in the colloidal stability that formed solution has excellence in the water, and carbon-free pipe precipitation is separated out in half a year.
Starting raw material of the present invention is cheap and easy to get, but the nano material preparation process is simple and the nano material continuous production, easy and simple to handle, do not need complicated plant and instrument, organic solution by the soluble metal compound presoma that in air, directly burns, reach on the different positions that adopts different soluble metal compound presomas or be chosen at flame product is collected, can obtain having the nano material of different sorts (composition) and different structure (pattern).The inventive method has been enriched the preparation means of nano material on the one hand as an extreme condition technology of preparing; On the other hand, adopt method of the present invention can prepare the special nano material of unavailable pattern under the normal condition, the special nano particle that the pattern that adopts the technology of the present invention to prepare does not appear in the newspapers not only has many special propertys, and will show wide application prospect, as: γ-Fe
2O
3Have dozens of rule and symmetric crystal face simultaneously, the saturation magnetization height, near the numerical value of body phase material, and the surface do not coat any material, therefore showing great application prospect aspect catalytic field, gas sensor, bioseparation and the purifying.Metal nanoparticle, metal oxide nanoparticles, the metal that has the carbon shell or metal oxide nano-material can be used to the magnetic recording aspect; The water dispersible CNT (carbon nano-tube) can be used for aspects such as biological diagnosis and disease treatment; Metallic oxide hollow nano-sphere, the nano particle with inorganic/inorganic heterogeneous structure can be used as the magnetic parting material, are used for biomedical sector.
In a word, the inventive method is as a kind of brand new technical of preparation nano material, be not only the important supplement of traditional preparation method of nano material, and, have broad application prospects owing to its product structure and the singularity of pattern and universality, the simplicity of the inventive method.
Embodiment
Embodiment 1
Take by weighing 0.88g praseodynium iron, be dissolved in the 50mL dehydrated alcohol.This solution is transferred in the open container, and after lighting, flame status reached stable in about 1 minute.After treating that flame status is stable, at a most advanced and sophisticated sheet glass collection that has moisture film, the sustainable flour that obtains of using of flame flame envelope.When liquid level decline caused flame location to descend, the relative position that can suitably adjust receiving trap made it still to receive in above-mentioned position.After treating that solution combustion fully, with the red-brown flour of collecting 20mL deionized water ultra-sonic dispersion, adopt the method collection of centrifugation (4000 rev/mins) to obtain throw out, and with washed with de-ionized water 3 times of this throw out, should precipitate at last with deionized water and mix and ultra-sonic dispersion, promptly obtain the aqueous dispersion liquid of product.X-ray diffraction is the result show, this product is γ-Fe
2O
3Nano particle.Accompanying drawing 1 is this γ-Fe
2O
3The transmission electron microscope photo of nano particle, photo show that its projection of shape is a Polygons, and its particle diameter is 10～300 nanometers.Accompanying drawing 2 is this γ-Fe
2O
3The electron diffraction photo of nano particle, this photo show the degree of crystallinity height of this magnetic nanoparticle.Accompanying drawing 3 is this γ-Fe
2O
3The high resolution transmission electron microscopy photo of nano particle, as seen from the figure, this nano particle overwhelming majority is monocrystalline or twin.This γ-Fe
2O
3The magnetic hysteresis loop of nano particle (accompanying drawing 4) shows that its saturation magnetization is 69.5 magnetostatic ampere/grams, has ferromegnetism.Accompanying drawing 5 is this γ-Fe
2O
3The electron scanning micrograph of nano particle, by photo as can be seen, its three-dimensional profile is a polyhedral structure, and each crystal face of nano particle is regular and symmetrical.
Embodiment 2
Take by weighing 8.83g praseodynium iron, be dissolved in the mixed solvent of 30mL methyl alcohol and 20mL N-vinyl-2-Pyrrolidone.Except that collection time was after lighting 5～60 minutes, all the other were operated all with embodiment 1.γ-the Fe that obtains
2O
3Nano particle has ferromegnetism, and its saturation magnetization is 70.4 magnetostatic ampere/grams, near the saturation magnetization value of body phase material; Particle diameter is 20～300 nanometers.
Embodiment 3
Take by weighing 0.088g praseodynium iron, be dissolved in the mixed solvent of 25mL formaldehyde and 25mL tetrahydrofuran (THF).All the other operations are all with embodiment 1.Resulting product is the high γ-Fe of degree of crystallinity through electron diffraction and transmission electron microscope detection
2O
3Nano particle, particle diameter are 10～50 nanometers.
Embodiment 4
Take by weighing the 1.35g Iron(III) chloride hexahydrate, be dissolved in the 50mL ethanol.All the other operations are all with embodiment 1.Resulting product is degree of crystallinity γ-Fe high, polyhedral structure through electron diffraction and transmission electron microscope detection
2O
3Nano particle, particle diameter is 10～200 nanometers, has ferromegnetism.
Embodiment 5
Take by weighing the 0.49g pentacarbonyl iron, be dissolved in the mixed solvent of 25mL ethanol and 25mL acetone.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are degree of crystallinity γ-Fe high, polyhedral structure
2O
3Nano particle, particle diameter is 10～200 nanometers, has ferromegnetism.
Embodiment 6
Take by weighing the 0.44g iron acetate, be dissolved in the mixed solvent of 40mL methyl alcohol and 10mL dimethyl formamide.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are degree of crystallinity γ-Fe high, polyhedral structure
2O
3Nano particle, particle diameter is 10～200 nanometers, has ferromegnetism.
Embodiment 7
Take by weighing the 0.072g ironic oxalate, be dissolved in the mixed solvent of 40mL methyl alcohol and 10mL alpha-pyrrolidone.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are degree of crystallinity γ-Fe high, polyhedral structure
2O
3Nano particle, particle diameter is 10～50 nanometers, has ferromegnetism.
Embodiment 8
Take by weighing the 0.84g ironic citrate, be dissolved in the mixed solvent of 40mL methyl alcohol and 10mL alpha-pyrrolidone.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are degree of crystallinity γ-Fe high, polyhedral structure
2O
3Nano particle, particle diameter is 10～200 nanometers, has ferromegnetism.
Embodiment 9
Take by weighing the 0.48g ferrous gluconate, be dissolved in 50mL methyl alcohol.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are degree of crystallinity γ-Fe high, polyhedral structure
2O
3Nano particle, particle diameter is 10～200 nanometers, has ferromegnetism.
Take by weighing 0.65g diacetyl acetone cobalt, be dissolved in the methyl alcohol of 50mL.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the high CoO nano particle of degree of crystallinity, and particle diameter is 10～100 nanometers.Accompanying drawing 6 is the transmission electron microscope photo of this CoO nano particle.
Embodiment 11
Take by weighing 0.43g diacetyl acetone cobalt and 1.17g praseodynium iron, be dissolved in the lump in the 50mL methyl alcohol.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the high CoFe of degree of crystallinity
2O
4Nano particle, particle diameter are 10～200 nanometers.Accompanying drawing 7 is this CoFe
2O
4The transmission electron microscope photo of nano particle.
Embodiment 12
Take by weighing 0.64g diacetyl acetone nickel, be dissolved in the methyl alcohol of 50mL.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the high NiO nano particle of degree of crystallinity, and particle diameter is 10～100 nanometers.
Embodiment 13
Take by weighing 3.53g praseodynium manganese, be dissolved in the 50mL methyl alcohol.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the high MnO of degree of crystallinity
2Nano particle, particle diameter are 10～200 nanometers.
Embodiment 14
Take by weighing 0.95g praseodynium yttrium, be dissolved in the 50mL ethanol.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the high Y of degree of crystallinity
2O
3Nano particle, particle diameter are 10～100 nanometers.Accompanying drawing 8 is this Y
2O
3The transmission electron microscope photo of nano particle.
Embodiment 15
Take by weighing 0.77g seven hydration yttrium trichlorides, be dissolved in the 50mL methyl alcohol.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the high Y of degree of crystallinity
2O
3Nano particle, particle diameter are 10～100 nanometers.
Embodiment 16
Take by weighing 1.10g praseodynium lanthanum, be dissolved in the 50mL ethanol.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the high La of degree of crystallinity
2O
3Nano particle, particle diameter are 10～100 nanometers.Accompanying drawing 9 is this La
2O
3The transmission electron microscope photo of nano particle.
Embodiment 17
Take by weighing the 2.72mL butyl (tetra) titanate, be dissolved in the 18mL Virahol.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the high TiO of degree of crystallinity
2Nano particle, particle diameter are 10～200 nanometers.Accompanying drawing 10 is this TiO
2The transmission electron microscope photo of nano particle.
Embodiment 18
Take by weighing 1.36mL butyl (tetra) titanate and 1.41g praseodynium iron, be dissolved in the lump in the 19mL ethyl acetate.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the high FeTiO of degree of crystallinity
3Nano particle, particle diameter are 10～200 nanometers.Accompanying drawing 11 is this FeTiO
3The transmission electron microscope photo of nano particle.
Embodiment 19
Take by weighing 0.88g praseodynium iron, be dissolved in the 50mL dehydrated alcohol.This solution is transferred in the open container, and after lighting, flame status reached stable in about 1 minute.After treating that flame status is stable, use a sheet glass that has moisture film to collect the sustainable flour that obtains near the internal flame place at flame envelope.When liquid level decline caused flame location to descend, the relative position that can suitably adjust receiving trap made it still to receive in above-mentioned position.After treating that solution combustion fully, with the black flour of collecting 20mL deionized water ultra-sonic dispersion, adopt the method collection of centrifugation (4000 rev/mins) to obtain throw out, and with washed with de-ionized water 3 times of this throw out, should precipitate at last with deionized water and mix and ultra-sonic dispersion, promptly obtain the colloid aqueous solution of product.Resulting product electron diffraction and transmission electron microscope are Fe
3O
4Nano particle, particle diameter are 10～100 nanometers.Accompanying drawing 12 is this Fe
3O
4The transmission electron microscope photo of nano particle.
Embodiment 20
Take by weighing 0.65g diacetyl acetone cobalt, be dissolved in the methyl alcohol of 50mL.This solution is transferred in the open container, and after lighting, flame status reached stable in about 1 minute.After treating that flame status is stable, use a sheet glass that has moisture film to collect the sustainable flour that obtains at the flame internal flame.When liquid level decline caused flame location to descend, the relative position that can suitably adjust receiving trap made it still to receive in above-mentioned position.Obtain flour.After treating that solution combustion fully, with the black flour of collecting 20mL deionized water ultra-sonic dispersion, adopt the method collection of centrifugation (4000 rev/mins) to obtain throw out, and with washed with de-ionized water 3 times of this throw out, should precipitate at last with deionized water and mix and ultra-sonic dispersion, promptly obtain the colloid aqueous solution of product.Resulting product electron diffraction and transmission electron microscope are the Co particle, and particle diameter is 5～20 nanometers.Accompanying drawing 13 is the transmission electron microscope photo of this Co nano particle.
Embodiment 21
Take by weighing 1.75g praseodynium iron and 2.5mL toluene, be dissolved in the lump in the 47.5mL ethanol.All the other operations are all with embodiment 20.Resulting product electron diffraction and transmission electron microscope are the Fe of carbon shell parcel
3O
4Nano particle, particle diameter are 10～100 nanometers, thick 2～20 nanometers of shell.Accompanying drawing 14 is the Fe of this carbon shell parcel
3O
4The transmission electron microscope photo of nano particle.
Embodiment 22
Take by weighing 0.65g diacetyl acetone cobalt and 10mL hexanaphthene, be dissolved in the lump in the 40mL methyl alcohol.All the other operations are all with embodiment 20.Resulting product electron diffraction and transmission electron microscope are the Co nano particle of carbon shell parcel, and particle diameter is 5～20 nanometers, thick 2～10 nanometers of shell.
Embodiment 23
Take by weighing 1.10g praseodynium lanthanum, be dissolved in the 50mL tetrahydrofuran (THF).All the other operations are all with embodiment 20.Resulting product electron diffraction and transmission electron microscope are the La of carbon shell parcel
2O
3Nano particle, particle diameter are 10～100 nanometers, thick 2～20 nanometers of shell.Accompanying drawing 15 is the La of this carbon shell parcel
2O
3The transmission electron microscope photo of nano particle.
Embodiment 24
Take by weighing 1.75g praseodynium iron and 0.55mL poly(oxyethylene glycol) 400, be dissolved in the lump in the 50mL ethanol.All the other operations are all with embodiment 20.Resulting product electron diffraction and transmission electron microscope are Fe
3O
4Hollow nano-sphere.Accompanying drawing 16 is this Fe
3O
4The transmission electron microscope photo of hollow nano-sphere, the diameter of hollow ball structure are 10～400 nanometers.
Embodiment 25
Take by weighing 0.88g praseodynium iron, be dissolved in the 50mL dehydrated alcohol.This solution is transferred in the open container, and after lighting, flame status reached stable in about 1 minute.After treating that flame status is stable, use a sheet glass that has moisture film to collect the sustainable hair-like material of black that obtains at the flame internal flame.When liquid level decline caused flame location to descend, the relative position that can suitably adjust receiving trap made it still to receive in above-mentioned position.。Also ultra-sonic dispersion is in the 50mL deionized water with this material collection, and centrifugation obtains black precipitate.Resulting product electron diffraction and transmission electron microscope are the CNT (carbon nano-tube) that is surrounded by metal oxide particle in head or the pipe, and its length is 10 nanometers～10 micron.Above-mentioned product was placed concentrated hydrochloric acid ultrasonic 1 hour, centrifugal collecting precipitation afterwards, and repeatedly cleaning this with deionized water, to be precipitated to the pH value be 7, it was well-dispersed in the deionized water in last ultrasonic 5 minutes, forms colloidal solution.Resulting product electron diffraction and transmission electron microscope are for removing the CNT (carbon nano-tube) of metal oxide.The colloidal solution of this CNT (carbon nano-tube) is very stable, does not have precipitation in half a year and separates out.Accompanying drawing 17 has been for having removed the transmission electron microscope photo of the CNT (carbon nano-tube) of metal oxide, and its length is 10 nanometers～10 micron.
Embodiment 26
Take by weighing 7.06g praseodynium iron and 1.90mL tetraethyl-silica alkane, be dissolved in the lump in the 50mL methyl alcohol.All the other operations are all with embodiment 1.Resulting product electron diffraction and transmission electron microscope are the γ-Fe with inorganic/inorganic heterogeneous structure
2O
3/ SiO
2Nano particle, particle diameter are 20～200 nanometers, and saturation magnetization is 42.3 magnetostatic ampere/grams.Accompanying drawing 18 is the transmission electron microscope photo of this nano particle.
Table 1
| The embodiment numbering | The soluble metal compound precursor | Organic solvent | The flame position | The nano material product |
| 1 | Praseodynium iron | Dehydrated alcohol | The flame envelope tip | γ-Fe 2O 3Nano particle |
| 2 | The same | Methyl alcohol and N-vinyl-2-Pyrrolidone | The same | The same |
| 3 | The same | Formaldehyde and tetrahydrofuran (THF) | The same | The same |
| 4 | Iron(III) chloride hexahydrate | Ethanol | The same | The same |
| 5 | Pentacarbonyl iron | Ethanol and acetone | The same | The same |
| 6 | Iron acetate | Methyl alcohol and dimethyl formamide | The same | The same |
| 7 | Ironic oxalate | Methyl alcohol and alpha-pyrrolidone | The same | The same |
| 8 | Ironic citrate | Methyl alcohol and alpha-pyrrolidone | The same | The same |
| 9 | Ferrous gluconate | Methyl alcohol | The same | The same |
| 10 | Diacetyl acetone cobalt | Methyl alcohol | The same | The CoO nano particle |
| 11 | Diacetyl acetone cobalt and praseodynium iron | Methyl alcohol | The same | CoFe 2O 4Nano particle |
| 12 | Diacetyl acetone nickel | Methyl alcohol | The same | The NiO nano particle |
| 13 | Praseodynium manganese | Methyl alcohol | The same | MnO 2Nano particle |
| 14 | The praseodynium yttrium | Ethanol | The same | Y 2O 3Nano particle |
| 15 | Seven hydration yttrium trichlorides | Methyl alcohol | The same | Y 2O 3Nano particle |
| 16 | The praseodynium lanthanum | Ethanol | The same | La 2O 3Nano particle |
| 17 | Butyl (tetra) titanate | Virahol | The same | TiO 2Nano particle |
| 18 | Butyl (tetra) titanate and praseodynium iron | Ethyl acetate | The same | FeTiO 3Nano particle |
| 19 | Praseodynium iron | Dehydrated alcohol | Flame envelope is near the internal flame place | Fe 3O 4Nano particle |
| 20 | Diacetyl acetone cobalt | Methyl alcohol | Internal flame | The Co nano particle |
| 21 | Praseodynium iron | Toluene, ethanol | The same | The Fe of carbon shell parcel 3O 4Nano particle |
| 22 | Diacetyl acetone cobalt | Hexanaphthene, methyl alcohol | The same | The Co nano particle of carbon shell parcel |
| 23 | The praseodynium lanthanum | Tetrahydrofuran (THF) | The same | The La of carbon shell parcel 2O 3Nano particle |
| 24 | Praseodynium iron | Polyoxyethylene glycol, ethanol | The same | Fe 3O 4Hollow nano-sphere |
| 25 | Praseodynium iron | Dehydrated alcohol | Internal flame | Be surrounded by the CNT (carbon nano-tube) of metal oxide particle in head or the pipe |
| 26 | Praseodynium iron | Tetraethyl-silica alkane, methyl alcohol | The flame envelope tip | γ-Fe with inorganic/inorganic heterogeneous structure 2O 3/ SiO 2Nano particle |
Claims (4)
1. the method for a preparing nano material by flame combustion, it is characterized in that: be that combustionmaterial and carbon provide body with the organic solvent, with the metallic compound that dissolves in organic solvent is the metal precursor of nano material, organic solution by the metallic compound presoma that in air, directly burns, collect the nano material that obtains at the flame internal flame and comprise the metal nanoparticle material, the metal nano material that has the carbon shell, the metal oxide nano-material that has the carbon shell, metallic oxide hollow nano-sphere or CNT (carbon nano-tube) are collected the nano-particle material that the nano material that obtains comprises the metal oxide nanoparticles material or has inorganic/inorganic heterogeneous structure at the flame flame envelope.
2. method according to claim 1, it is characterized in that: acetylacetonate, acetate, oxalate, Citrate trianion, gluconate, carbonyl-complexes, muriate that described metallic compound presoma is chosen from Fe, cobalt, nickel, manganese, the acetylacetonate of yttrium or lanthanide rare metal, muriate, perhaps at least a in the titanic acid ester.
3. method according to claim 1 and 2 is characterized in that: described organic solvent is selected from a kind of in alcohols, aldehydes, ketone, ester class, alkanes, polyacrylic, benzene, toluene, tetrahydrofuran (THF), dimethyl formamide, the type siloxane or greater than a kind of mixture.
4. method according to claim 1 is characterized in that:
Described metal nanoparticle is Co or Ni nano particle, and particle diameter is 5 nanometers～20 nanometers;
Described metal oxide nanoparticles is γ-Fe
2O
3, Fe
3O
4, CoO, NiO, MnO
2, CoFe
2O
4, NiFe
2O
4, MnFe
2O
4, TiO
2, FeTiO
3, CoTiO
3, NiTiO
3, MnTiO
3, Y
2O
3And the lanthanide rare metal oxide nanoparticles, particle diameter is 10 nanometers～300 nanometers;
The described metal nano material that has the carbon shell is the Ni nano particle that has the Co of carbon shell or have the carbon shell, and particle diameter is 5 nanometers～20 nanometers, and the carbon thickness of the shell is 2 nanometers～10 nanometers;
The described metal oxide nano-material that has the carbon shell is the Fe that has the carbon shell
3O
4, have the carbon shell CoO, have the carbon shell NiO, have the Y of carbon shell
2O
3Or have the lanthanide rare metal oxide nanoparticles of carbon shell, and particle diameter is 10 nanometers～100 nanometers, the carbon thickness of the shell is 2 nanometers～20 nanometers;
Described metallic oxide hollow nano-sphere is Fe
3O
4, CoO or NiO hollow nano-sphere, particle diameter is 10 nanometers～400 nanometers;
Described global shape with nano particle of inorganic/inorganic heterogeneous structure is circle or oval, and is made up of two different pieces, and one of them part is γ-Fe
2O
3, CoO, NiO or MnO
2Another part is SiO
2, the particle overall dimensions is 20 nanometers～200 nanometers;
Described CNT (carbon nano-tube), length are 10 nanometers～10 micron.
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