CN1268541C - Nano onion shaped fullerenoid material and preparation - Google Patents
Nano onion shaped fullerenoid material and preparation Download PDFInfo
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- CN1268541C CN1268541C CN 200410012340 CN200410012340A CN1268541C CN 1268541 C CN1268541 C CN 1268541C CN 200410012340 CN200410012340 CN 200410012340 CN 200410012340 A CN200410012340 A CN 200410012340A CN 1268541 C CN1268541 C CN 1268541C
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- B82—NANOTECHNOLOGY
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The present invention relates to a nano onion-shaped fullerenoid material and the preparation thereof, which belongs to the technical field of synthesizing and processing engineering of a new material. The present invention adopts a radio frequency plasma technique and utilizes amorphous-state carbon containing coal, coke and the like as raw materials to disclose a nano onion-shaped fullerenoid material and preparation thereof. The nano onion-shaped fullerenoid material provides an onion-shaped fullerenoid material formed by the intercombination of a concentric sphere, a concentric ellipsoid and a concentric polyhedron, the distance among layers is from 0.33 nm to 0.35 nm, and the diameter is from 5 nm to 60 nm. The onion-shaped fullerenoid material is catalyzed by nanometer particles in the amorphous-state carbon and nanometer particles added by people or a metal organic compound catalyst, and provides a carbon functional material with good performance.
Description
One technical field
Nano-onions shape fullerene preparation methods of the present invention, belong to the synthetic and processing technology category of novel material, relate generally to fields such as Materials science such as nano material, nano-carbon material and functional nanomaterials thereof, coal science, bio-science, information science.
Two background technologies
Onion-like fullerene comprises bag onion-like fullerene, metal intercalation onion-like fullerene in monokaryon onion-like fullerene, multinuclear onion-like fullerene, the metal.The monokaryon onion-like fullerene is meant the onion-like fullerene of being made up of onion-like fullerene monomer one by one, the multinuclear onion-like fullerene is meant the onion-like fullerene that coats by the shared outer field graphite linings of two or more onion-like fullerenes or by other graphite linings and form, the bag onion-like fullerene is meant the onion-like fullerene of clad metal in concentric graphite linings in the metal, and metal intercalation onion-like fullerene is meant the onion-like fullerene that inserts atoms metal between graphite linings.At present, the method for preparing onion-like fullerene has direct current arc electric discharge, electron beam irradiation method, catalytic pyrolysis method.Wherein, the direct current arc electric discharge is with the carbon dioxide process carbon electrode discharge, forms onion-like fullerene by carbon plasma under the effect of catalyzer.The electron beam irradiation method is to adopt high resolution transmission electron microscopy electron beam irradiation carbonaceous material, changes to onion-like fullerene under the inducing of catalyzer, and this method can only generate the onion-like fullerene of trace.Catalytic pyrolysis method is that low-molecular-weight hydrocarbon is carried out catalyse pyrolysis, finally generates onion-like fullerene, and impurity is more in this method product.In these methods, comparatively extensive with the application of direct current arc electric discharge.
The direct current arc electric discharge is to utilize the discharge of carbon dioxide process carbon electrode to form onion-like fullerene by electrode self through plasma reaction, its shortcoming is that the requirement of powerful discharge counter electrode quality is very high, the general high purity graphite electrode that adopts, make its cost very high, if with the coal is raw material, then the kind of coal is had relatively high expectations, and must compare strict pre-treatment to the carbon raw material, in addition, energy consumption is bigger, moreover the high power discharge process is violent, difficult control, and the factor that influences the soccerballene productive rate is too many, except catalyzer and gaseous species, reaction also is subjected to the geometrical shape of electrode, interpole gap, the influence of all multiparameters such as pressure and size of current, and in the product that makes, onion-like fullerene and carbon nanotube and agraphitic carbon coexistence.
Three summary of the invention
Nano-onions shape fullerene preparation methods of the present invention so its purpose is utilized amorphous carbon adopting the radio-frequency plasma reaction technology, discloses a kind of preparation technology who is formed nano-onions shape fullerene material by catalyst.
Above-mentioned nano-onions shape fullerene preparation methods; it is characterized in that it being a kind of amorphous carbon that utilizes; under the catalyst effect, form concentric spheroid; the layer that ellipsoid of concentration body or concentric polyhedron combine mutually is 0.33-0.35nm with the spacing of layer; the monokaryon onion shape fullerene preparation methods of diameter 5-60nm; this method is to adopt the radio frequency plasma body technique; utilize the amorphous carbon particle as raw material; with metal; metal oxide; nonmetal; nonmetal oxide nanoparticle or organometallics are as catalyzer; with amorphous carbon particle and metal; metal oxide; nonmetal; nonmetal oxide nanoparticle or metal-organic mixture are converted into nano-onions shape fullerene material, and its preparation process is:
I pulverizes, grinds amorphous carbon, obtains the amorphous carbon particle of granularity below 200 orders;
II makes the nanoparticle of particle diameter less than the metal of 200nm, metal oxide, nonmetal and nonmetal oxide with the ball mill ball milling, purchases organometallics;
III adds the described metal of II, metal oxide, nonmetal, nonmetal oxide nanoparticle or the organometallics purchased in the amorphous carbon particle to, the metal that is added, metal oxide, nonmetal, nonmetal oxide nanoparticle or organometallics account for more than 3% of amorphous carbon granular mass, below 20%, obtain amorphous carbon particle and metal, metal oxide, nonmetal, nonmetal oxide nanoparticle or metal-organic mixture, put into the reaction chamber of radio frequency plasma body source, airtight then;
IV is with Ar, H
2Or Ar/H
2Mixed gas feed in the reaction chamber of radio frequency plasma body source with the speed of 10-60ml/min, it is 5-80Pa that regulated valve makes air pressure;
V is 150-480W with the power regulation of radio frequency plasma body source; reaction times is 30-120min; under the effect of radio-frequency plasma, amorphous carbon particle and metal, metal oxide, nonmetal, nonmetal oxide nanoparticle or metal-organic mixture are converted into nano-onions shape fullerene material.
The preparation method of above-mentioned nano-onions shape fullerene is characterized in that described amorphous carbon is coal or the coke made by coal.
Above-mentioned nano-onions shape fullerene preparation methods is characterized in that described catalyzer is the nanoparticle La of pure metal nanoparticle Al, Ca, Cu, Mn, Mo, Ni, Pt, Fe, Co, La, W, Au or Pd, metal oxide
2O
3, Al
2O
3, Mo
2O
5, TiO
2, Fe
2O
3, CaO, nonmetal nanoparticle Si, nonmetal oxide nanoparticle SiO
2, organometallics C
10H
10Fe or C
32H
16N
8Cu.
Above-mentioned nano-onions shape fullerene preparation methods is characterized in that described catalyzer accounts for the 8-15% of amorphous carbon granular mass.
Above-mentioned nano-onions shape fullerene preparation methods is characterized in that described Ar, H
2Or Ar/H
2Mixed gas feed in the reaction chamber of radio frequency plasma body source Ar/H with the speed of 15-25ml/min
2Mixed gas mix with 3: 1 volume ratio, it is 25-35Pa that regulated valve makes air pressure.
Above-mentioned nano-onions shape fullerene preparation methods is characterized in that the power regulation with described radio frequency plasma body source is 420-480W, and the reaction times is 45-60min.
Above-mentioned nano-onions shape fullerene preparation methods, it is characterized in that adopting and penetrate plasma body and can obtain purified plasma body, strengthen ionization and improve discharging efficiency, discharge stability in preparation process, energy consumption is very low, reaction is easy to control, the more important thing is, temperature external in the reaction is very low, is 100-200 ℃, and synthetic nano-onions shape fullerene material degree of graphitization is very high, comparatively pure, there is no carbon nanotube and supervene, agraphitic carbon content is very low in the product, so be the method for a kind of low temperature less energy-consumption new synthesis of nano onion shape fullerene material of being easy to control.
Above-mentioned nano-onions shape fullerene preparation methods; it is characterized in that to utilize the amorphous carbon natural resources and be present in nanometer microparticle catalytic agent in the amorphous carbon; needs according to production technique; adjusting is artificial nanoparticle or the organometallics catalytic amount that adds in amorphous carbon; adjustments of gas kind and proportioning; regulate air pressure and radio-frequency plasma power; thereby the yield of control gained nano-onions shape fullerene material; this amorphous carbon resource for utilizing nature to exist more widely, the functionalization of more effectively carrying out amorphous carbon transforms provides possibility.
Above-mentioned nano-onions shape fullerene material, can utilize key propertys such as onion-like fullerene mechanics, electricity, new function materials such as the devices such as electronic component that require as property, biomaterial, catalystic material, medical material, photoelectric material, range of application is very extensive, and application prospect is very good.
Four description of drawings
The TEM onion-like fullerene that Fig. 1 is 500,000 times
The TEM onion-like fullerene that Fig. 2 is 500,000 times
Five embodiments
Embodiment 1
Working gas with Ar forms plasma body through the high voltagehigh frequency electric field action, adopt coal as the non-crystalline state carbon source, be crushed to below 200 orders, make the Mo metal of particle diameter with the ball mill ball milling less than 200nm, nanometer Mo particle catalyst is added in the amorphous carbon particle, the nanometer Mo particle catalyst that is added accounts for 10% of amorphous carbon granular mass, obtain the mixture of amorphous carbon particle and nanometer microparticle catalytic agent, get this mixture of 0.3g and put into radio-frequency plasma emissive source reaction chamber, the flow 20ml/min of Ar, pressure 30Pa, power 480W, irradiation 60min after reaction finishes, collects the product that is deposited on the reactor wall and carries out tem observation.The result shows, the diameter of onion-like fullerene is at 5-50nm, the onion-like fullerene of forming comprising the onion-like fullerene of being made up of some concentric spheroids, by some ellipsoid of concentration bodies, the onion-like fullerene of being made up of some concentric polyhedrons.
Embodiment 2
With H
2Working gas form plasma body through the high voltagehigh frequency electric field action, adopt coal as the non-crystalline state carbon source, be crushed to below 200 orders, make the La of particle diameter with the ball mill ball milling less than 200nm
2O
3Metal oxide, with nanometer La
2O
3Particle catalyst adds in the amorphous carbon particle, the nanometer La that is added
2O
3Particle catalyst accounts for 7% of amorphous carbon granular mass, obtains the mixture of amorphous carbon particle and nanometer microparticle catalytic agent, gets this mixture of 0.3g and puts into radio-frequency plasma emissive source reaction chamber, H
2Flow 25ml/min, pressure 30Pa, power 480W, irradiation 60min after reaction finishes, collects the product be deposited on the reactor wall and carries out tem observation.The result shows, the diameter of onion-like fullerene is at 10-40nm, the onion-like fullerene of forming comprising the onion-like fullerene of being made up of some ellipsoid of concentration bodies, by some concentric polyhedrons.
Embodiment 3
Working gas with Ar forms plasma body through the high voltagehigh frequency electric field action, adopt coal as the non-crystalline state carbon source, be crushed to below 200 orders, it is nonmetal less than the Si of 200nm to make particle diameter with the ball mill ball milling, nanometer Si particle catalyst is added in the amorphous carbon particle, the nanometer Si particle catalyst that is added accounts for 12% of amorphous carbon granular mass, obtain the mixture of amorphous carbon particle and nanometer microparticle catalytic agent, get this mixture of 0.3g and put into radio-frequency plasma emissive source reaction chamber, the flow 20ml/min of Ar, pressure 30Pa, power 480W, irradiation 60min after reaction finishes, collects the product that is deposited on the reactor wall and carries out tem observation.The result shows, the diameter of onion-like fullerene is at 10-50nm, the onion-like fullerene of forming comprising the onion-like fullerene of being made up of some concentric spheroids, by some ellipsoid of concentration bodies, the onion-like fullerene of being made up of some concentric polyhedrons.
Embodiment 4
Ar/H with 3: 1
2The working gas of (volume) forms plasma body through the high voltagehigh frequency electric field action, adopts coal as the non-crystalline state carbon source, is crushed to below 200 orders, makes the SiO of particle diameter less than 200nm with the ball mill ball milling
2Nonmetal oxide is with nanometer SiO
2Particle catalyst adds in the amorphous carbon particle, the nanometer SiO that is added
2Particle catalyst accounts for 10% of amorphous carbon granular mass, obtain the mixture of amorphous carbon particle and nanometer microparticle catalytic agent, get this mixture of 0.3g and put into radio-frequency plasma emissive source reaction chamber, total gas flow rate 24ml/min, pressure 25Pa, power 480W, irradiation 60min, after reaction finishes, collect the product that is deposited on the reactor wall and carry out tem observation.The result shows, the diameter of onion-like fullerene is at 15-50nm, the onion-like fullerene of forming comprising the onion-like fullerene of being made up of some concentric spheroids, by some ellipsoid of concentration bodies, the onion-like fullerene of being made up of some concentric polyhedrons.
Embodiment 5
Working gas with Ar forms plasma body through the high voltagehigh frequency electric field action, adopt coal as the non-crystalline state carbon source, be crushed to below 200 orders, the ferrocene catalyzer is added in the amorphous carbon particle, the ferrocene catalyzer that is added accounts for 15% of amorphous carbon granular mass, obtain the mixture of amorphous carbon particle and ferrocene catalyzer, get this mixture of 0.3g and put into radio-frequency plasma emissive source reaction chamber, the flow 20ml/min of Ar, pressure 30Pa, power 480W, irradiation 60min, after reaction finishes, collect the product that is deposited on the reactor wall and carry out tem observation.The result shows, the diameter of onion-like fullerene is at 15-60nm, the onion-like fullerene of forming comprising the onion-like fullerene of being made up of some concentric spheroids, by some ellipsoid of concentration bodies, the onion-like fullerene of being made up of some concentric polyhedrons.
Claims (6)
1 one kinds of nano-onions shape fullerene preparation methods; it is characterized in that it being a kind of amorphous carbon that utilizes; under the catalyst effect, form concentric spheroid; the layer that ellipsoid of concentration body or concentric polyhedron combine mutually is 0.33-0.35nm with the spacing of layer; the monokaryon onion shape fullerene preparation methods of diameter 5-60nm; this method is to adopt the radio frequency plasma body technique; utilize the amorphous carbon particle as raw material; with metal; metal oxide; nonmetal; nonmetal oxide nanoparticle or organometallics are as catalyzer; with amorphous carbon particle and metal; metal oxide; nonmetal; nonmetal oxide nanoparticle or metal-organic mixture are converted into nano-onions shape fullerene material, and its preparation process is:
I pulverizes, grinds amorphous carbon, obtains the amorphous carbon particle of granularity below 200 orders;
II makes the nanoparticle of particle diameter less than the metal of 200nm, metal oxide, nonmetal and nonmetal oxide with the ball mill ball milling, purchases organometallics;
III adds the described metal of II, metal oxide, nonmetal, nonmetal oxide nanoparticle or the organometallics purchased in the amorphous carbon particle to, the metal that is added, metal oxide, nonmetal, nonmetal oxide nanoparticle or organometallics account for more than 3% of amorphous carbon granular mass, below 20%, obtain amorphous carbon particle and metal, metal oxide, nonmetal, nonmetal oxide nanoparticle or metal-organic mixture, put into the reaction chamber of radio frequency plasma body source, airtight then;
IV is with Ar, H
2Or Ar/H
2Mixed gas feed in the reaction chamber of radio frequency plasma body source with the speed of 10-60ml/min, it is 5-80Pa that regulated valve makes air pressure;
V is 150-480W with the power regulation of radio frequency plasma body source; reaction times is 30-120min; under the effect of radio-frequency plasma, amorphous carbon particle and metal, metal oxide, nonmetal, nonmetal oxide nanoparticle or metal-organic mixture are converted into nano-onions shape fullerene material.
2 according to the described nano-onions shape of claim 1 fullerene preparation methods, it is characterized in that described amorphous carbon is coal or the coke made by coal.
3 according to the described nano-onions shape of claim 1 fullerene preparation methods, it is characterized in that described catalyzer is the nanoparticle La of pure metal nanoparticle Al, Ca, Cu, Mn, Mo, Ni, Pt, Fe, Co, La, W, Au or Pd, metal oxide
2O
3, Al
2O
3, Mo
2O
5, TiO
2, Fe
2O
3, or CaO, nonmetal nanoparticle Si, nonmetal oxide nanoparticle SiO
2, organometallics C
10H
10Fe or C
32H
16N
8Cu.
4 according to the described nano-onions shape of claim 1 fullerene preparation methods, it is characterized in that described catalyzer accounts for the 8-15% of amorphous carbon granular mass.
5 according to claim 1 nano-onions shape fullerene preparation methods, it is characterized in that Ar, H
2Or Ar/H
2Mixed gas feed in the reaction chamber of radio frequency plasma body source Ar/H with the speed of 15-25ml/min
2Mixed gas mix with 3: 1 volume ratio, it is 25-35Pa that regulated valve makes air pressure.
6 according to claim 1 nano-onions shape fullerene preparation methods, it is characterized in that the power regulation with the radio frequency plasma body source is 420-480W, and the reaction times is 45-60min.
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| CN101597052B (en) * | 2009-07-06 | 2011-06-15 | 中国科学院化学研究所 | Method for large-scale production of fullerene by burning coal or graphite |
| CN106883914A (en) * | 2017-02-09 | 2017-06-23 | 广东三和控股有限公司 | A kind of fully synthetic gasoline engine oil and preparation method thereof |
| CN108837818B (en) * | 2018-06-20 | 2021-09-28 | 中国科学院宁波材料技术与工程研究所 | Titanium dioxide composite coating and preparation method thereof |
| CN114144256A (en) * | 2019-05-22 | 2022-03-04 | 菲尔格姆斯有限公司 | Additive for liquid fuels, fuel composition based on additive and method for preparing same |
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