CN1294076C - Carbon atom wire and process for preparing carbon nanotube and carbon atom wire by pyrolyzing solid-state carbon source - Google Patents
Carbon atom wire and process for preparing carbon nanotube and carbon atom wire by pyrolyzing solid-state carbon source Download PDFInfo
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- CN1294076C CN1294076C CNB021245177A CN02124517A CN1294076C CN 1294076 C CN1294076 C CN 1294076C CN B021245177 A CNB021245177 A CN B021245177A CN 02124517 A CN02124517 A CN 02124517A CN 1294076 C CN1294076 C CN 1294076C
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Abstract
The present invention relates to a new substance, namely a carbon atom wire which is not reported until now. The external appearance of the present invention is black powder in a solid state, the present invention has the structure that carbon atoms are connected in a wire shape, the diameter is from 1.5 to 2 angstroms, wherein the carbon content is higher than 95%, and the oxygen content is less than 5%. The present invention also provides a method for preparing carbon nanotubes and carbon atom wires by pyrolysis with a solid state carbon source, the carbon contained macromolecule of starch, or cellulose, or polyacrylic resin is used as a carbon source, a transitional metal is used as a catalyst, decomposition is carried out in a reducing atmosphere at the temperature of 450 to 600 DEG C, the post-treatment is carried out at the temperature of 600 DEG C to 1000 DEG C, and the carbon nanotubes or carbon atom wires are obtained. The transitional metal, is Fe, or Co, or Ni, or the alloy of Fe, Co and Ni. The reducing gas is H2 or CO, and N2, or Ar, or other inert gas is used for diluting. The present invention uses the solid state raw material of low price, and the large-scale preparation of carbon nanotubes or carbon atom wires with low cost is realized. The obtained product contains less impurities, such as amorphous carbon, etc., the yield of the carbon nanotubes and the carbon atom wires is high, and the diameter is uniform.
Description
Technical field
The present invention relates to provide a kind of and do not see the novel substance-carbon atom wire of any report so far as yet and be carbon source, adopt pyrolysis and Catalytic processes to prepare a kind of method of carbon nanotube and carbon atom wire with the solid carbon-contg polymer.
Background technology
Carbon nanotube is found to have only so far in a decade or so short, and its particular structure and performance have attracted many field scientists' such as chemistry, physics, Materials science extensive concern.It is in the preparation of matrix material and nano photoelectronic devices, the electronic field emission source, and the energy storage, aspects such as catalysis have boundless application prospect.But carbon nanotube still can not be with the accessible price scale production so far, and this becomes the bottleneck problem of its widespread usage of restriction.How at lower cost the scale preparation carbon nanotube becomes one of current various countries scientist problem demanding prompt solution.The preparation of carbon nanotube mainly contains arc discharge method, laser ablation method and chemical Vapor deposition process at present.Arc discharge method and laser ablation method are low because of the yield of its carbon nanotube, high being difficult to of production cost produce in batches.Chemical Vapor deposition process is a kind of method of the present preparation carbon nanotube that the most generally adopts.This method is decomposed carbonization with some hydrocarbon polymers elevated temperature heat in the presence of transition-metal catalyst and is generated carbon nanotube.The hydrocarbon polymer as carbon source that generally adopts has acetylene at present, as: patent EP1061043A1, WO 9925652A1, WO 9965821A1, CN 1165209A; Ethene, as: patent WO 2000030141A1; WO 2000017102A1; Methane, as: patent CN 1266018A.These pyrolysis carbon sources all are gaseous substances, the transportation difficulty, and plant factor is low in the preparation process, yields poorly, and causes production cost to increase greatly.People such as Y.Gogotsi are at J.Mater.Res., reported on 15 (12), 2591 (2000) they with hydrothermal method at 700-800 ℃, 60-100Mpa pressure and Ni exist down and prepare carbon nanotube with polyethylene/water mixture.This article is not reported the purity and the yield situation of its product, but the high pressure of 60-100Mpa is awful for large-scale production.People such as N.I.Maksimova are at J.Mol.Catal.A:Chem., 158 (1), 301 (2000) reported they with polyethylene and polyvinyl alcohol in 600-750 ℃ at N
2Make the Preparation of Catalyst carbon nanotube with ironic hydroxide under the air-flow.By transmission electron microscope photo that they delivered as can be known, contain a large amount of impurity such as decolorizing carbon in the product that they obtained, the carbon nanotube yield is very low.People such as N.I.Maksimova point out that in the text poly pyrolysis produces 98% gaseous state, liquid product.So neither prepare carbon nanotube from solid matter in itself in 600-750 ℃ of preparation carbon nanotube by polyethylene.
Summary of the invention
The present invention will provide a kind of novel substance of not seeing any report so far as yet---carbon atom wire, provide a kind of method for preparing carbon atom wire, wish a kind of technological line that is different from existing preparation carbon nanotube method of developing simultaneously, providing a kind of is that carbon source prepares carbon atom wire, prepares the technical scheme of carbon nanotube with new processing method with the solid matter, in the hope of making the novel substance carbon atom wire and reducing the production cost of carbon nanotube significantly, help realizing the large-scale industrial production of carbon nanotube.
Particular content of the present invention is:
1, carbon atom wire, this is a novel substance of not seeing any report so far as yet, its outward appearance is the black solid powder.The constructional feature of carbon atom wire is that carbon atom links to each other with wire.Its skeleton symbol is expressed as follows:
Its structural representation is seen Figure 12.By the image (seeing accompanying drawing 1) of high resolution transmission electron microscopy (HRTEM) as can be known, the diameter of carbon atom wire is the 1.5-2 dust.Consider around the carbon atom two atoms the most contiguous to be arranged from size.Fig. 2 and Fig. 3 are the X diffraction experiment results of carbon atom wire.It shows: carbon atom wire does not have lattice structure each other, is lack of alignment substantially.Fig. 4 and Fig. 5 are the photoelectron spectruies (XPS) of carbon atom wire.X-ray source is AlK α.Its quantitative analysis shows: substantially only contain two kinds of elements of carbon and oxygen (the molybdenum element peak among Fig. 2 and Fig. 3 is on the sample compressing tablet) in the carbon atom wire, carbon content is more than 95%, oxygen level less than 5%.Carbon atom wire intermediary carbon atom links to each other with two carbon atoms the most contiguous, and the carbon atom of carbon atom wire end links to each other with Sauerstoffatom.Fig. 6 and Fig. 7 also are the photoelectron spectruies (XPS) of carbon atom wire, but its bound energy scope is only near the carbon peak.Cls's among Fig. 6 is the bimodal of 284.4eV and 284.0eV in conjunction with the peak.Accompanying drawing 8 and 9 is Auger spectrograms of carbon atom wire.As seen from the figure, the CKLL Auger kinetic energy of carbon atom wire is 270.6eV.Carbon atom wire has good electrical conductivity, has largest specific surface area, carbon atom wire does not have fixed spacing each other, can embed easily-the Tuo embedding, therefore other ions, atom or the molecule of mixing that mix-go be to be used for secondary cell, ultracapacitor, catalysis, the ideal material of absorption, the various ripples of shielding.The preparation success of this material still is that practical application all has very significant meaning for fundamental research.
2, to contain carbon macromolecule; particularly starch or treated starch (following general designation starch), Mierocrystalline cellulose or modified-cellulose (following general designation Mierocrystalline cellulose) or polyacrylic resin are carbon source; with the transition metal is catalyzer; heating stage by stage under protection of reducing atmosphere; promptly heat up, under 0.1～2Mpa pressure, in 450～600 ℃ of thermal degradation with 5 ℃～30 ℃/minute speed; 600 ℃～1000 ℃ aftertreatments obtain carbon atom wire or carbon nanotube product at last.Polyacrylic resin described here is meant by vinylformic acid or its homologue autohemagglutination or the superpolymer that forms with other monomer copolymerization.Described transition metal is recommended Fe, Co, Ni or its alloy, and they are reduced in preparation process by its corresponding nitrate, acetate, muriate, organic compound, oxide compound or oxyhydroxide and generate, or directly add with the nano-powder of metal.Described reducing gas is H
2Or CO.Reducing gas inert gas dilution, rare gas element are N
2Or Ar or other rare gas elementes, the Dilution ratio of reducing gas and rare gas element is 1: 9～10: 0.Making carbon atom wire or the diameter that diameter is several dusts through above method is several carbon nanotubes to the hundreds of nanometer.Implementation method of the present invention is as follows: with starch, Mierocrystalline cellulose or polyacrylic resin or wherein the mixture of two or three material mix drying thoroughly with the solution that contains nitrate, acetate, muriate, organic compound or oxide compound, oxyhydroxide, metal nano powder or its mixture of Fe, Co, Ni or other transition metal.In starch or Mierocrystalline cellulose and polyacrylic resin mixture, starch or Mierocrystalline cellulose or its mixture, with the ratio of polyacrylic resin be 1: 0～0: 1.Solid-state carbon source starch, Mierocrystalline cellulose or polyacrylic resin or its mixture are 1: 1 * 10 with the ratio of the metal content of Fe, Co, Ni or other transition-metal catalysts
-3～1: 0.Starch, Mierocrystalline cellulose or polyacrylic resin or its mixture of the dried Fe of containing, Co or Ni catalyzer are placed in porcelain burning boat or other suitable vessel, place reactor or the fluidized-bed isolated with air.Through vacuumizing, fill N
2, Ar or other rare gas element, three times to go out intrasystem air displacement repeatedly.At H
2Or CO air-flow or H
2And N
2, H
2With Ar, CO and N
2, be warmed up to 450 ℃～600 ℃ with 5～30 ℃/min speed under CO and the Ar air-flow.H
2Or CO air-flow or H
2And N
2, H
2With Ar, CO and N
2Or CO and Ar gas flow rate are decided according to the reaction vessel volume size.At 450 ℃～600 ℃ constant temperature 4～6h, so that Fe, Co or Ni salt decompose and is reduced into respective metal; Thermolysis also takes place simultaneously in starch, Mierocrystalline cellulose and acrylic resin.After this be warmed up to 600～1000 ℃ of aftertreatments, constant temperature 8～15h with the speed of 5 ℃～30 ℃/min again.Naturally be cooled to room temperature then.
The application recommends following scheme and parameter:
Reactant is yam starch or gossypin, and contains 76% polyacrylic resin, the polyacrylic acid iron resin aqueous solution of 0.034%Fe, and transition metal is Fe (NO
3)
3
The mass ratio of yam starch or gossypin, polyacrylic acid iron resin aqueous solution, transition metal is 2.3: 0.23: 1;
Post-processing temperature is 800 ℃;
Described polyacrylic resin is polymerized with mass ratio by vinylformic acid and vinylbenzene at 4: 1;
Gains are carbon atom wire.
The present invention is when providing novel substance-carbon atom wire, the brand-new technology approach of preparation carbon atom wire and carbon nanotube is provided, and most important character is that pyrolysis is that the carbon source catalyse pyrolysis prepares carbon atom wire or/and carbon nanotube with solid matters such as starch, Mierocrystalline cellulose or polyacrylic resins.Suitable temperature, the super-refinement of catalyzer and suitable amounts and catalyzer and the high molecular uniform mixing of carbon source are the keys that improves carbon atom wire content in the product.Starch, Mierocrystalline cellulose and polyacrylic resin are cheap, and the requirement of the equipment and technology of use is also lower, compare with existing carbon nanotube preparation technology, can reduce production costs greatly, realize scale preparation carbon nanotube at lower cost.Impurity such as the decolorizing carbon that contains in the product are few, resulting carbon atom wire and carbon nanotube yield height, and diameter is even.
Description of drawings
Fig. 1 is the resulting pattern of product under high resolution transmission electron microscopy (HRTEM) through purification processes in the embodiment of the invention 3;
Fig. 2 is X-ray diffraction (XRD) figure of the resulting product of crossing through purification processes among the embodiment 3, and ray is CuK α;
Fig. 3 is X-ray diffraction (XRD) figure of the resulting product of crossing through purification processes among the embodiment 4, and ray is CuK α;
Fig. 4 is photoelectron spectrum (XPS) figure of the resulting product of crossing through purification processes among the embodiment 3, and ray is AlK α, and the bound energy scope is 0-1000eV;
Fig. 5 is photoelectron spectrum (XPS) figure of the resulting product of crossing through purification processes among the embodiment 4, and ray is AlK α, and the bound energy scope is 0-1000eV;
Fig. 6 is photoelectron spectrum (XPS) figure of the resulting product of crossing through purification processes among the embodiment 3, and ray is AlK α, and the bound energy scope is 276-298eV;
Fig. 7 is photoelectron spectrum (XPS) figure of the resulting product of crossing through purification processes among the embodiment 4, and ray is AlK α, and the bound energy scope is 276-298eV;
Fig. 8 is auger electron spectroscopy (AES) figure of the resulting product of crossing through purification processes among the embodiment 3, and ray is AlK α;
Fig. 9 is auger electron spectroscopy (AES) figure of the resulting product of crossing through purification processes among the embodiment 4, and ray is AlK α;
Figure 10 is the resulting pattern of product under transmission electron microscope (TEM) without any purification processes in the embodiment of the invention 1;
Figure 11 is the resulting pattern of product under transmission electron microscope (TEM) without any purification processes among the embodiment 2;
Figure 12 is the carbon atom wire structural representation.
Embodiment
Embodiment 1, with 2g 0.2mol/L Fe (NO
3)
3Solution and 3.5g yam starch mix the back and add porcelain burning boat, vacuum hydro-extraction 1h under the room temperature, put into its reaction tubes can with the isolated tube furnace of outside air, vacuumize, fill Ar gas, three times to get rid of original air in the boiler tube repeatedly, feeds the Ar of 30mL/min and the H of 30mL/min under 0.2Mpa pressure
2Steady air flow.Speed with 15 ℃/min is warming up to 500 ℃, constant temperature 5h, and the speed with 15 ℃/min is warming up to 700 ℃ again, is cooled to room temperature behind the constant temperature 15h naturally, stops the supple of gas or steam.Discharging gets product 1.0g.Resulting product viewed pattern under transmission electron microscope (TEM) without any purification processes is seen Figure 10.By this TEM image as can be known, impurity such as the decolorizing carbon that contains seldom, products obtained therefrom purity is very high, wherein round shape thing is a catalyst Fe, the carbon nanotube caliber is evenly distributed, and is about 15nm.
Embodiment 2: substantially the same manner as Example 1, but reactant is a gossypin.Figure 11 resulting pattern of product under transmission electron microscope of this embodiment of serving as reasons without any purification processes.By this TEM image as can be known, products obtained therefrom purity is also very high, and the caliber of gained carbon nanotube is also very even, is about 20nm.
Embodiment 3: reactant is the 2.3g yam starch, 0.23g polyacrylic acid iron resin aqueous solution (wherein contain polyacrylic resin 76%, Fe 0.034%, and all the other are water) and 1.0g 2.0%Fe (NO
3)
3, post-processing temperature is 800 ℃.Polyacrylic resin is polymerized with mass ratio by vinylformic acid and vinylbenzene at 4: 1.This embodiment gets product 0.63g.Resulting carbon atom wire is seen Fig. 1 at the following viewed pattern of high resolution transmission electron microscopy (HRTEM) after purification processes.X-ray diffraction (XRD) figure of resulting carbon atom wire after purification processes sees Fig. 2.Photoelectron spectrum (XPS) figure of resulting carbon atom wire after purification processes sees Fig. 4 and Fig. 6.Auger electron spectroscopy (AES) figure of resulting carbon atom wire after purification processes sees Fig. 8.
Embodiment 4: substantially the same manner as Example 3, but reactant is a gossypin.X-ray diffraction (XRD) figure of resulting carbon atom wire after purification processes sees Fig. 3.Photoelectron spectrum (XPS) figure of resulting carbon atom wire after after the purification processes sees Fig. 5 and Fig. 7.Auger electron spectroscopy (AES) figure of resulting carbon atom wire after purification processes sees Fig. 9.
Embodiment 5: substantially the same manner as Example 1, and the cobalt metal of catalyzer for getting by the Cobaltous diacetate reduction.Fill N
2Gas, three times to get rid of original air in the boiler tube repeatedly, feeds the N of 30mL/min
2H with 30mL/min
2Steady air flow; Heat up with the speed of 5 ℃/min, 450 ℃ of following thermal degradation, more than 450 ℃ to heating aftertreatment below 1000 ℃.
Embodiment 6: substantially the same manner as Example 1, but reactant is the mixture of starch and polyacrylic acid sago cycas fat; Catalyzer is the nanometer fine powder of Ni.Obstructed Ar gas or N
2Gas only fills H
2Steady air flow; Heat up with the speed of 30 ℃/min, 600 ℃ of following thermal degradation, more than 600 ℃ to heating aftertreatment below 900 ℃.
Embodiment 7: substantially the same manner as Example 1, but reactant is the mixture of Mierocrystalline cellulose and starch; Reducing gas is the steady air flow of CO; Temperature rise rate is 10 ℃/min.
Embodiment 8: substantially the same manner as Example 1, but reactant be starch, Mierocrystalline cellulose and with the mixture of polyacrylic acid sago cycas fat; Catalyzer is the nanometer fine powder of Ag; Heat up with the speed of 20 ℃/min, 500 ℃ of following thermal degradation, more than 500 ℃ to heating aftertreatment below 1000 ℃.Reducing gas is the Ar of 27mL/min and the H of 3mL/min
2Steady air flow.
Embodiment 9: substantially the same manner as Example 1, but reducing gas is the steady air flow of the Ar of the CO of 27mL/min and 9mL/min.
Embodiment 10: substantially the same manner as Example 1, but Fe (NO
3)
3Solution changes Fe into
2AC
3Solution.
Embodiment 11: substantially the same manner as Example 1, but Fe (NO
3)
3Solution changes FeCl into
3Solution.
Embodiment 12: substantially the same manner as Example 1, but Fe (NO
3)
3Solution changes Fe into
2O
3
Embodiment 13: substantially the same manner as Example 1, but Fe (NO
3)
3Solution changes Fe (OH) into
3
Embodiment 14: substantially the same manner as Example 1, but Fe (NO
3)
3Solution changes the nanometer powder of metal Fe into.
Embodiment 15～20, and is basic identical with embodiment 1 and 10～14, but Fe wherein changes Co into.
Embodiment 21～26, and is basic identical with embodiment 1 and 10～14, but Fe wherein changes Ni into.
Claims (7)
1, a kind of carbon atom wire, it is characterized in that: outward appearance is the black solid powder, and structure is that carbon atom links to each other with wire, and diameter is the 1.5-2 dust, carbon atom wire intermediary carbon atom links to each other with two carbon atoms the most contiguous, and the carbon atom of carbon atom wire end links to each other with Sauerstoffatom.
2, according to the described carbon atom wire of claim 1, it is characterized in that: contain two kinds of elements of carbon and oxygen in the carbon atom wire, carbon content is more than 95%, and oxygen level is less than 5%.
3, according to claim 1 or 2 described carbon atom wires, it is characterized in that: photoelectron spectrum shows that the bound energy peak of the Cls of carbon atom wire is 284.5-284.0eV, and the x-ray source of photoelectron spectrum is AlK α.
4, according to claim 1 or 2 described carbon atom wires, it is characterized in that: the CKLL Auger kinetic energy of carbon atom wire is 270.5eV.
5, a kind of solid-state carbon source pyrolysis prepares the method for carbon nanotube and/or carbon atom wire, is carbon source with the carbon containing polymer substance, is catalyzer with the transition metal, at H
2Or CO air-flow or H
2And N
2, H
2With Ar, CO and N
2, CO and Ar air-flow protection of reducing atmosphere under heating stage by stage: the speed with 5 ℃～30 ℃/min heats up; under 0.1～2Mpa pressure; in 450～600 ℃ of thermal degradation, 600 ℃～1000 ℃ aftertreatments obtain carbon nanotube at last or/and the carbon atom wire product.
6, prepare the method for carbon nanotube and/or carbon atom wire according to the described solid-state carbon source pyrolysis of claim 5, it is characterized in that: described carbon containing polymer substance is selected from starch, Mierocrystalline cellulose or polyacrylic resin.
7, the method for preparing carbon nanotube and/or carbon atom wire according to claim 5 or 6 described solid-state carbon source pyrolysis, it is characterized in that: described transition metal is Fe, Co, Ni or its alloy, they are reduced in preparation process by its corresponding nitrate, acetate, muriate, organic compound, oxide compound or oxyhydroxide and generate, or directly add with the nano-powder of metal
Concrete steps are: with starch, Mierocrystalline cellulose or polyacrylic resin or wherein two or three material mixture with contain Fe, the nitrate of Co or Ni, acetate, muriate, organic compound or oxide compound, oxyhydroxide, the solution of metal nano powder or its mixture is mixed thoroughly, dry, starch or Mierocrystalline cellulose or its mixture are 1: 0～0: 1 with the ratio of polyacrylic resin in starch or Mierocrystalline cellulose and the polyacrylic resin mixture, solid-state carbon source starch, Mierocrystalline cellulose or polyacrylic resin or its mixture and Fe, the ratio of the metal content of Co or Ni catalyzer is 1: 1 * 10
-3～1: 0, with starch, Mierocrystalline cellulose or the polyacrylic resin of the dried Fe of containing, Co or Ni catalyzer or its mixture be placed on porcelain burn boat or in, place reactor or the fluidized-bed isolated, through vacuumizing, fill N with air
2Or Ar, three times so that intrasystem air displacement is gone out, at H repeatedly
2Or CO air-flow or H
2And N
2, H
2With Ar, CO and N
2, be warmed up to 450 ℃～600 ℃ with 5～30 ℃/min speed, H under CO and the Ar air-flow
2Or CO air-flow or H
2And N
2, H
2With Ar, CO and N
2Or CO and Ar gas flow rate visual response vessel volume size and decide, at 450 ℃～600 ℃ constant temperature 4～6h, so that Fe, Co or the decomposition of Ni salt and be reduced into respective metal; Thermolysis also takes place simultaneously in starch, Mierocrystalline cellulose and polyacrylic resin, after this is warmed up to 600～1000 ℃ with the speed of 5 ℃～30 ℃/min again, and constant temperature 8～15h is to form carbon nanotube and/or carbon atom wire.
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| CN1323029C (en) * | 2004-12-10 | 2007-06-27 | 中国科学院长春应用化学研究所 | Polyolefin burning process of synthesizing carbon nanotube |
| CN101185904B (en) * | 2007-01-18 | 2011-01-19 | 江苏工业学院 | Selectivity liquid phase hydrogenation catalyst and preparation method and use thereof |
| CN101613100B (en) * | 2008-06-25 | 2011-07-20 | 中国科学院大连化学物理研究所 | Micro-wave preparation method for biomass-based graphitized carbon and carbon-carbon composite material |
| CN101898760A (en) * | 2010-07-23 | 2010-12-01 | 东北林业大学 | Method for catalyzing polymer with multi-metallic catalyst to compound carbon nano-tube in situ |
| CN102002652B (en) * | 2010-12-08 | 2012-06-27 | 上海交通大学 | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof |
| US20130116114A1 (en) * | 2011-11-07 | 2013-05-09 | K Tube Technology LLC | Systems, Devices, and/or Methods for Preparation of Graphene and Graphene Hybrid Composite Via the Pyrolysis of Milled Solid Carbon Sources |
| WO2013070339A1 (en) * | 2011-11-07 | 2013-05-16 | K Tube Technology LLC | Systems, devices, and/or methods for solar cells comprising a light amplification element |
| CN102491308A (en) * | 2011-11-25 | 2012-06-13 | 卓心康 | Method for synthesis of carbon nanostructure material by using organic material |
| CN102527695A (en) * | 2012-01-05 | 2012-07-04 | 中国科学院生态环境研究中心 | Method for preparing nano iron/carbon compound material by kitchen waste |
| JP5942277B2 (en) * | 2012-07-06 | 2016-06-29 | パナソニックＩｐマネジメント株式会社 | Carbon-based material, electrode catalyst, electrode, gas diffusion electrode, electrochemical device, fuel cell, and method for producing carbon-based material |
| CN103318872B (en) * | 2013-07-03 | 2014-10-22 | 北京理工大学 | Preparation method of carbon nano tubes |
| CN103794803A (en) * | 2014-01-22 | 2014-05-14 | 江西师范大学 | Preparation method and application of nitrogen and phosphorus codoped carbon oxygen reduction catalyst for microbial fuel cell |
| CN105772708B (en) * | 2016-03-10 | 2018-02-02 | 合肥工业大学 | A kind of method that nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite is prepared using biomass castoff |
| CN112604681A (en) * | 2020-12-14 | 2021-04-06 | 陕西科技大学 | Formaldehyde degradation material and preparation method and application thereof |
| CN112604680A (en) * | 2020-12-14 | 2021-04-06 | 陕西科技大学 | Formaldehyde decomposition material and preparation method and application thereof |
| CN114634174A (en) * | 2020-12-16 | 2022-06-17 | 东北林业大学 | Method for synthesizing carbon nano tube by using starch or cellulose biomass as carbon source |
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| CN1193600A (en) * | 1997-02-04 | 1998-09-23 | 中国科学院金属研究所 | Manufacture of carbon tubes in nanon size |
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