CN101885481A - Method for preparing carbon nano onions - Google Patents
Method for preparing carbon nano onions Download PDFInfo
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- CN101885481A CN101885481A CN2009100839468A CN200910083946A CN101885481A CN 101885481 A CN101885481 A CN 101885481A CN 2009100839468 A CN2009100839468 A CN 2009100839468A CN 200910083946 A CN200910083946 A CN 200910083946A CN 101885481 A CN101885481 A CN 101885481A
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Abstract
The invention discloses a method for preparing carbon nano onions, which comprise s the following steps: 1) mixing a carbon raw material and a transitional metal compound and dissolving the mixture in an organic solvent, wherein the carbon raw material is aromatic heavy oil an/or polymer resin; and 2) carbonizing the product of the step 1) in an inert atmosphere to obtain the carbon nano onions. The carbon nano onions prepared by the method are formed by arranging uniform onion balls with a concentric graphite structure, and the d002 value of the carbon nano onions is extremely close to natural graphite. The method of the invention has the advantages of low raw material price, rich raw material sources, mild reaction conditions, simple process, easy control, widely selectable metal types, high yield, high purity, low cost and the like, overcomes the drawbacks of difficult shape control, small production scale and various byproducts of the conventional carbon nano onion preparation, makes large scale production easily realized and has a high value.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nano-onions.
Background technology
In recent years, the preparation of various novel carbon nanomaterials causes the great interest of people.Just found for the first time the carbon nano-onions structure as far back as Iijima in 1980.1992, Ugarte made it to be transformed into the carbon nano-onions structure with the polyhedron graphite in the carbon ash that arc-over produced under the irradiation of HRTEM electron beam.Nineteen ninety-five, Xu and Tanaka use HRTEM equally, and by low energy electron beam irradiation, at metallic nano-particle Al, Pt under the bringing out of Au, makes amorphous carbon-film change onion-like fullerene into, after carbon nanotube, causes very big sensation in scientific circles again.Carbon nano-onions (being onion shape carbon nano-particle again) is the closed nano cages shape structure of torispherical, is made up of multilayer concentric cage shape graphite, piles up for botryoidal cluster, is similar to Russia cover baby, has the d of good degree of graphitization and very approaching pure graphite
002Value, high mechanical property, electric property, optical property etc.Carbon nano-onions has wide application prospect at aspects such as lubricating oil additive, optical electron device, energy storage material (lithium ion battery, ultracapacitor, solar cell etc.), matrix material, support of the catalyst.Carbon nano-onions behind the organic functional shows good biocompatibility, has good solvability in organism.People are by transforming diamond [I.V.Ponomareva at present, L.A.Chernozatonskii.How can carbon onion transform into diamond-like structure.Microelectron Eng 2003:69:625-628], metal catalytic [T.Cabioc ' h, J.P.Riviere, M.Jaouen, J.Delafond, M.F.Denanot, Fullerene onion formation by carbon-ion implanation into copper, Synthetic Met 1996:77:253-56] etc. method prepare carbon nano-onions.
At present, the raw material of preparation carbon nano-onions mainly is a graphite, generally adopts arc discharge method, plasma to strengthen vapour deposition process and electron beam irradiation method etc.The arc-over temperature is up to 4000K, and the nano-onions shape soccerballene crystallization degree height of generation, defective be few, be convenient to research.But go out carbon nano-onions [D.Ugarbte, onion-like graphite particles, carbon 1995:33 (7): 989-993] with regard to micropreparation by the direct current arc discharge.Plasma enhancing vapour deposition process [X.H.Chen, F.M.Deng, J.X.Wang, H.S.Yang, G.T.Wu, X.B.Zhang, J.C.Peng, W.Z.Li.Chem.Phys.Lett 2001; 336:201] and electron beam irradiation method [D.Ugart, nature 1992; 359:707] etc. also can prepare some carbon nano-onions.But these methods need the lot of energy input to go to impel the carbon material thaumatropy to form high-temperature area, so the not confirmability of by product and product structure has all become carbon nano-onions to use and mass-produced restraining factors.The preparation method of the carbon nano-onions that therefore, seek a kind of simple possible, is easy to control and to develop its application be one of emphasis of this direction research at present.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of carbon nano-onions.
The preparation method of carbon nano-onions provided by the invention comprises the steps:
1) with carbon raw material and transistion metal compound mixed dissolution in organic solvent; Described carbon raw material is aromatic hydrocarbons heavy oil and/or fluoropolymer resin;
2) product with step 1) carries out carbonization reaction in inert atmosphere; Obtain carbon nano-onions.
Described aromatic hydrocarbons heavy oil can be at least a in pix carbonis praeparsta, coal-tar pitch, black petroleum products and the petroleum pitch.
Described fluoropolymer resin can be at least a in resol, Resins, epoxy, furane resin, the urea-formaldehyde resin.Described resol specifically can be alkalescent phenol resin or acidic phenol urea formaldehyde.Described urea-formaldehyde resin specifically can be furfuryl resin.
Described transistion metal compound can be at least a in cyclopentadienyl transition organometallic compound, carbonyl transition organometallic compound, acetylacetone based transition organometallic compound, transition metal acetate, transition metal nitrate and the transition metal chloride.
Described cyclopentadienyl transition organometallic compound specifically can be at least a in ferrocene, dicyclopentadienylcobalt and the nickelocene.Described carbonyl transition organometallic compound specifically can be at least a in iron carbonyl, cobalt-carbonyl and the nickle carbonoxide.Described acetylacetone based transition organometallic compound specifically can be at least a in chromium acetylacetonate, methyl ethyl diketone platinum, acetylacetone cobalt and the palladium acetylacetonate.Described transition metal acetate specifically can be at least a in venus crystals, cobaltous acetate, nickelous acetate and the ironic acetate.Described transition metal nitrate specifically can be at least a in iron nitrate, Xiao Suangu and the nickelous nitrate; Described transition metal chloride is at least a in iron(ic) chloride, cobalt chloride and the nickelous chloride.Metal can be selected based on following principle: good consistency be arranged with carbon, and a little less than the effect between metal and ligand, and synthetic easily obtaining.
Also can comprise in the described method step 2) the carbonization reaction product carry out acid-treated step.A lot of nano-metal particles are mixing in the product after charing is handled.Metallics can be removed by acidification, thereby obtain the hollow nano-onions of pure carbon form, its diameter generally between the 20-60 nanometer, wall thickness from tens layers to the tens layers graphite flake layer.The hollow nano-onions of pure carbon form is through supersound process, and bromine water is soaked, and low-temperature heat treatment under inert atmosphere with perchloric acid and deionized water rinsing, can obtain the carbon nano-onions of purifying more then.
In the described method, the mol ratio of the metal in described carbon raw material and the described transistion metal compound is decided according to need, generally can be (2-64): 1.The ratio of metal is too low, because metal is very few, can not form a large amount of carbon nano-onions.The ratio of metal is too high, and carbon is ablated in a large number, the carbonization yield that can not guarantee.
In the described method, the temperature of carbonization reaction generally is controlled between 700-1500 ℃.Temperature is low excessively, and the thermolysis of carbon raw material not exclusively or is not decomposed, and end product will contain the light component of more amount and metal not to have been given play to sufficient catalytic performance and can not form the onion structure.Temperature is too high, and reaction is violent, is difficult to control, and manufacturing cost is high.
In the described method, the time of carbonization reaction generally was controlled at 0.2-20 hour, mainly decided according to the reactive behavior of carbon source metallizing thing and temperature of reaction.Generally speaking, the reaction times is too short, and the pyrolysis of carbon raw material is incomplete, the carbon onion structure imperfection of formation.The long raising that helps carbon nano-structured crystallization degree of time, but the long time is obviously uneconomical economically.
Organic solvent in the described step 1) specifically can be at least a in ethanol, acetone, pyridine, benzene and the tetrahydrofuran (THF).
In the preparation method of carbon nano-onions provided by the present invention based on the katalysis of metal pair organic carbon raw material under the high temperature and carbon reductive action to metal.At first solve homogeneously in by a certain percentage in the solvent with the carbon raw material with as the transistion metal compound of source metal, solvent evaporated (when the carbon raw material is the thermoplastic polymer resin, adds solidifying agent and solidify) forms the island package structure.Put it into then in the charring furnace,, rise to preset temperature, behind the stop certain hour, naturally cool to room temperature, obtain carbon nano-onions by certain temperature rise rate with inert gas replacement furnace air several rear enclosed body of heater.Transistion metal compound at first decomposites nanoparticle in the pyrolytic process, and closely wrapped up by the carbon source macromole, also may form chelate compound with matrix functional group, be external phase thereby formed macromole carbon raw material, and the inside is inlaid with the structure that is similar to the island shape of catalyst nanoparticles.Because metallics has the effect that promotes to be catalyzed into carbon, so the carbonization yield that adds catalyzer height when not adding catalyzer.Along with the rising of temperature, carbon progressively is dissolved in the metal nanoparticle, separates out when saturated, having formed dissolving separates out running balance and (has dynamic activity freely, be the necessary factor that carbon can structural modification), in the precipitation process, carbon is rearranged and forms bowl-shape graphite flake.Remove dangling bonds based on minimum energy principle, graphite flake is bent to form globular onion core.Because the influence of thermograde and concentration gradient, more lamella forms the multilayer concentric soccerballene along core growth, and interlayer interacts by Van der Waals force.
The carbon nano-onions centre portions that the present invention prepares is a hollow form, outer by closely around several layers of height-oriented graphite flake layer constitute.Electromicroscopic photograph shows, carbon nano-onions fully by one by one uniformly with one heart the onion ball of graphite-structure arrange and form, d002 value and natural graphite are very approaching.The method that invention provides only need be passed through mixed dissolution, charing, acidization and just can be obtained carbon nano-onions, have that cost of material is cheap, raw material sources are abundant, reaction conditions is gentle, technology is simple, be easy to control, the metal types selectable range is wide, yield is high, purity is high, low cost and other advantages, having solved the form that exists in the preparation of carbon current nano-onions is difficult to control, can not prepare in a large number and by product defective how, easily realize scale operation, have great value.
Description of drawings
Fig. 1 is the electron micrograph of the carbon nano-onions of embodiment 1 preparation.
Fig. 2 is the electron micrograph of the carbon nano-onions of embodiment 3 preparations.
Fig. 3 is the high-resolution electron microscope photo of the carbon nano-onions of embodiment 3 preparations.
Embodiment
Following embodiment is convenient to understand better the present invention, but does not limit the present invention.Experimental technique among the following embodiment if no special instructions, is ordinary method.Used test materials among the following embodiment if no special instructions, is to buy from routine biochemistry reagent shop and obtains.
The preparation of embodiment 1, carbon nano-onions
One, the preparation of raw material
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: nine water iron nitrates (analytical pure).
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
1, with carbon raw material and transistion metal compound uniform mixing, under magnetic agitation, fully be dissolved in ethanol, steam solvent then.
2, six methynes, four ammonia are added in the acetone, the concentration that makes six methynes, four ammonia is 14% (quality percentage composition), obtains curing agent solution.The product of step 1 is added in the curing agent solution, and 150 ℃ solidified 4 hours.
3, the product with step 2 places charring furnace, is heated to 1000 ℃ under nitrogen protection, and stops 10 hours under this temperature.
4, the product of step 3 is used salt acid soak 3 days, so that metal wherein all dissolves; Carry out suction filtration then, when neutral it is dried.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
The carbon nano-onions that step 1 is obtained carries out tem study and X-ray diffraction analysis.Transmission electron microscope (TEM) photo is seen Fig. 1, and analytical results shows that all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows that the d002 value and the natural graphite of carbon nano-onions are very approaching, and particle diameter has the extraordinary concentric arrangement degree of order between 20-40nm.
The preparation of embodiment 2, carbon nano-onions
One, the preparation of raw material
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: nine water iron nitrates.
The mol ratio of carbon raw material and transistion metal compound is 16: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, and particle diameter has the extraordinary concentric arrangement degree of order between 30-60nm.
The preparation of embodiment 3, carbon nano-onions
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: nine water iron nitrates.
The mol ratio of carbon raw material and transistion metal compound is 64: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Transmission electron microscope (TEM) photo is seen Fig. 2 and Fig. 3, and tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is 0.33602nm, and very approaching with natural graphite, particle diameter has the extraordinary concentric arrangement degree of order between 20-70nm.
The preparation of embodiment 4, carbon nano-onions
One, the preparation of raw material
Step 1 with embodiment 1.
Two, the preparation of carbon nano-onions
Be heated to 1000 ℃ under nitrogen protection, and stopped 0.3 hour under this temperature, other is with the step 2 of embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is approaching with graphite, has the concentric arrangement degree of order preferably.
The preparation of embodiment 5, carbon nano-onions
One, the preparation of raw material
Step 1 with embodiment 1.
Two, the preparation of carbon nano-onions
Be heated to 1000 ℃ under nitrogen protection, and stopped 20 hours under this temperature, other is with the step 2 of embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 6, carbon nano-onions
One, the preparation of raw material
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: Xiao Suangu (analytical pure).
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 7, carbon nano-onions
One, the preparation of raw material
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: nickelous nitrate (analytical pure).
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 8, carbon nano-onions
One, the preparation of raw material
Step 1 with embodiment 1.
Two, the preparation of carbon nano-onions
Be heated to 700 ℃ under nitrogen protection, and stopped 10 hours under this temperature, other is with the step 2 of embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 9, carbon nano-onions
One, the preparation of raw material
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: ferrocene.
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 10, carbon nano-onions
One, the preparation of raw material
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: pentacarbonyl iron.
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 11, carbon nano-onions
One, the preparation of raw material
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: acetylacetone cobalt.
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 12, carbon nano-onions
One, the preparation of raw material
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: ironic acetate.
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 13, carbon nano-onions
One, the preparation of raw material
Carbon raw material: acid catalysis resol (yellow solid, molecular weight are in the 300-500 scope, and softening temperature is greater than 75 ℃); Tianjin resin processing plant, No. 171 resins.
Transistion metal compound: iron trichloride.
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 14, carbon nano-onions
One, the preparation of raw material
Step 1 with embodiment 1.
Two, the preparation of carbon nano-onions
Be heated to 1500 ℃ under nitrogen protection, and stopped 0.2 hour under this temperature, other is with the step 2 of embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 15, carbon nano-onions
One, the preparation of raw material
Step 1 with embodiment 1.
Two, the preparation of carbon nano-onions
Be heated to 700 ℃ under nitrogen protection, and stopped 20 hours under this temperature, other is with the step 2 of embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is very approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 16, carbon nano-onions
One, the preparation of raw material
Step 1 with embodiment 1.
Two, the preparation of carbon nano-onions
Be heated to 1500 ℃ under nitrogen protection, and stopped 10 hours under this temperature, other is with the step 2 of embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is approaching with natural graphite, has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 17, carbon nano-onions
One, the preparation of raw material
Carbon raw material: urea-formaldehyde resin (Zibo prestige tackiness agent difficult to understand company limited, model ZN-01).
Transistion metal compound: nine water iron nitrates (analytical pure).
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, carbon is to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is approaching with graphite, has the concentric arrangement degree of order preferably.
The preparation of embodiment 18, carbon nano-onions
One, the preparation of raw material
Carbon raw material: base catalysis resol (Tianjin resin processing plant, No. 2127 resins).
Transistion metal compound: nine water iron nitrates (analytical pure).
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
1, with carbon raw material and transistion metal compound uniform mixing, under magnetic agitation, fully be dissolved in ethanol, steam solvent then.
2, the product with step 1 places charring furnace, is heated to 1000 ℃ and stopped 10 hours in this temperature under nitrogen protection.
3, the product of step 2 is used salt acid soak 3 days, so that metal wherein all dissolves; Yet carry out suction filtration, when neutral it is dried.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is approaching with natural graphite, has the concentric arrangement degree of order preferably.
The preparation of embodiment 19, carbon nano-onions
One, the preparation of raw material
Carbon raw material: (making with extra care) black petroleum products; C constituent content 87.24, H constituent content 8.47, fragrant branch, colloid and asphalt content 94.24,145 ℃ of softening temperatures, molecular-weight average 1769.
Transistion metal compound: nine water iron nitrates (analytical pure).
Carbon raw material (calculating the amount of substance of carbon raw material according to molecular-weight average) is 2: 1 with the mol ratio of transistion metal compound.
Two, the preparation of carbon nano-onions
Step 2 with embodiment 1.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows that the diameter of carbon nano-onions is 20-80nm, and wall thickness 10-50nm has the extraordinary concentric arrangement degree of order.
The preparation of embodiment 20, carbon nano-onions
One, the preparation of raw material
Carbon raw material: Resins, epoxy (Tianjin chemical reagents corporation, E-51 resin)
Transistion metal compound: nine water iron nitrates (analytical pure).
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
1, with carbon raw material and transistion metal compound uniform mixing, under magnetic agitation, fully be dissolved in ethanol, steam solvent then.
2, the product with step 1 places charring furnace, is heated to 1000 ℃ and stopped 10 hours in this temperature under nitrogen protection.
3, the product of step 2 is used salt acid soak 3 days, so that metal wherein all dissolves; Yet carry out suction filtration, when neutral it is dried.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is approaching with natural graphite, has the concentric arrangement degree of order preferably.
The preparation of embodiment 21, carbon nano-onions
One, the preparation of raw material
Carbon raw material: furane resin; Taiyuan Jin Fen resin processing plant; Viscosity (mPa.s (20 ℃): 12; PH value: 6.5; Free phenol content: 0.5.
Transistion metal compound: nine water iron nitrates (analytical pure).
The mol ratio of carbon raw material and transistion metal compound is 2: 1.
Two, the preparation of carbon nano-onions
1, with carbon raw material and transistion metal compound uniform mixing, under magnetic agitation, fully be dissolved in ethanol, steam solvent then.
2, the product with step 1 places charring furnace, heats under nitrogen protection, and 1000 ℃ stopped 10 hours.
3, the product of step 2 is used salt acid soak 3 days, so that metal wherein all dissolves; Yet carry out suction filtration, when neutral it is dried.
Three, the tem study of carbon nano-onions and X-ray diffraction analysis
Step 3 with embodiment 1.
Tem study is the result show, all carbon all are to exist with onion shape hollow carbon form of nanoparticles.X-ray diffraction (XRD) analytical results shows the d of carbon nano-onions
002Value is approaching with natural graphite, has the concentric arrangement degree of order preferably.
Claims (9)
1. the preparation method of carbon nano-onions comprises the steps:
1) carbon raw material and transistion metal compound are dissolved in the organic solvent; Described carbon raw material is aromatic hydrocarbons heavy oil and/or fluoropolymer resin;
2) product with step 1) carries out carbonization reaction in inert atmosphere; Obtain carbon nano-onions.
2. the method for claim 1 is characterized in that: described aromatic hydrocarbons heavy oil is at least a in pix carbonis praeparsta, coal-tar pitch, black petroleum products and the petroleum pitch.
3. method as claimed in claim 1 or 2 is characterized in that: described fluoropolymer resin is at least a in resol, Resins, epoxy, furane resin and the urea-formaldehyde resin.
4. as arbitrary described method in the claim 1 to 3, it is characterized in that: described transistion metal compound is at least a in cyclopentadienyl transition organometallic compound, carbonyl transition organometallic compound, acetylacetone based transition organometallic compound, transition metal acetate, transition metal nitrate and the transition metal chloride.
5. method as claimed in claim 4 is characterized in that: described cyclopentadienyl transition organometallic compound is at least a in ferrocene, dicyclopentadienylcobalt and the nickelocene; Described carbonyl transition organometallic compound is at least a in iron carbonyl, cobalt-carbonyl and the nickle carbonoxide; Described acetylacetone based transition organometallic compound is at least a in chromium acetylacetonate, methyl ethyl diketone platinum, acetylacetone cobalt and the palladium acetylacetonate; Described transition metal acetate is at least a in venus crystals, cobaltous acetate, nickelous acetate and the ironic acetate; Described transition metal nitrate is at least a in iron nitrate, Xiao Suangu and the nickelous nitrate; Described transition metal chloride is at least a in iron(ic) chloride, cobalt chloride and the nickelous chloride.
6. as arbitrary described method in the claim 1 to 5, it is characterized in that: described method also comprises step 2) product that obtains of described carbonization reaction carries out acid treatment, removes the step of metallic particles.
7. as arbitrary described method in the claim 1 to 6, it is characterized in that: the amount of substance ratio of the metal in described carbon raw material and the described transistion metal compound is (2: 1)-(64: 1).
8. as arbitrary described method in the claim 1 to 7, it is characterized in that: step 2) in, the temperature of described carbonization reaction is that 700 ℃-1500 ℃, time are 0.3-20 hour.
9. the carbon nano-onions that arbitrary described method prepares in the claim 1 to 8.
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