CN107597118B - Catalyst for preparing clustered carbon nanotubes, preparation method thereof and clustered carbon nanotubes - Google Patents
Catalyst for preparing clustered carbon nanotubes, preparation method thereof and clustered carbon nanotubes Download PDFInfo
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- CN107597118B CN107597118B CN201710778447.5A CN201710778447A CN107597118B CN 107597118 B CN107597118 B CN 107597118B CN 201710778447 A CN201710778447 A CN 201710778447A CN 107597118 B CN107597118 B CN 107597118B
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Abstract
The invention discloses a catalyst for preparing cluster carbon nano tubes, a preparation method thereof and the cluster carbon nano tubes, wherein the preparation method of the catalyst comprises the following steps: 1) dispersing an organic matter and a metal precursor in a solvent to obtain a dispersion liquid; 2) carrying out electrospinning by using the dispersion liquid obtained in the step (1); 3) carrying out heat treatment on the electrospinning product obtained in the step (2) in a non-oxidizing atmosphere to obtain a catalyst; the metal precursor is metal salt and/or metal oxide, and the catalyst is used for preparing the carbon nano tube, so that the fasciculate carbon nano tube can be obtained, and the fasciculate carbon nano tube is composed of all the oriented carbon nano tubes.
Description
Technical Field
The invention belongs to the field of carbon nano materials, composite materials and new energy, relates to a catalyst, a preparation method and application thereof, and particularly relates to a catalyst for preparing clustered carbon nanotubes, a preparation method thereof and clustered carbon nanotubes.
Background
Carbon nanotubes were discovered in scanning electron microscopy by Japanese scientist Iijima in the nineties of the last century and have been reported in published form. The presence of such fibrous graphite materials of multiple graphite layers was indeed known in the early seventies or eighties of the earlier twentieth century, and Tates and Baker (GB1469930a1, 1977 and EP56004a2, 1982) described for the first time deposits of fibrous carbon produced by the catalytic decomposition of hydrocarbons, but without further elaboration including their diameter, etc.
The carbon nanotube material has excellent electrochemical and mechanical properties, so that the carbon nanotube material has wide application, can be used as a conductive additive in a battery to improve the performances of the battery such as cycle, multiplying power and the like, and can also be added in an organic material to play the roles of conductivity, static electricity prevention and electromagnetic shielding. The carbon nano tube is added into products such as plastics, rubber and the like, so that the mechanical property of the material can be improved, and the breaking strength can be improved. However, in the application process, whether the carbon nanotubes can be uniformly dispersed in the matrix material is the key to exert the performance advantage. The carbon nanotubes with the oriented structure can be more easily dispersed because the single carbon tubes are not entangled, and have better advantages in application.
The current methods for preparing the oriented carbon nanotube mainly comprise a substrate method, a fixed bed method, a fluidized bed method and the like. Patent CN 102471067a by bayer corporation discloses a carbon nanotube aggregate and a preparation method thereof, which prepares carbon nanotubes with an oriented structure by gas phase chemical deposition through a cobalt-based catalyst. The Weifei patent CN 101348249B of Beijing university discloses a method for preparing a carbon nanotube array on the inner surface of particles, which realizes the growth of oriented carbon nanotubes between layers by synthesizing a catalyst with a layered structure.
The method belongs to the traditional carbon nanotube preparation method, the process conditions need to be accurately controlled in the preparation process of the catalyst, the conditions are harsh, the production cost is high, and the carbon nanotubes which are all in an orientation type can not be ensured.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a catalyst for preparing clustered carbon nanotubes, a method for preparing the same, and clustered carbon nanotubes. The cluster carbon nano-tube prepared by the catalyst is composed of all the oriented carbon nano-tubes, and compared with other winding carbon nano-tubes, the cluster carbon nano-tube has the advantages of easy dispersion and convenient use, can better exert the advantages of high conductivity and high strength of the carbon nano-tube, and has wide application prospect.
In the present invention, the "catalyst for preparing bundled carbon nanotubes" refers to: the catalyst is suitable for the production process of preparing the cluster carbon nano-tube and can be used as one of raw material components for preparing the cluster carbon nano-tube.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the preparation of a catalyst, the process comprising the steps of:
(1) dispersing an organic matter and a metal precursor in a solvent to obtain a dispersion liquid;
(2) carrying out electrospinning by using the dispersion liquid obtained in the step (1);
(3) carrying out heat treatment on the electrospinning product obtained in the step (2) in a non-oxidizing atmosphere to obtain a catalyst;
wherein the metal precursor is a metal salt and/or a metal oxide.
Preferably, the organic substance in step (1) includes any one or a mixture of at least two of polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyacrylonitrile or pitch, but is not limited to the above-listed organic substances, and other organic substances commonly used in electrospinning in the art can also be used in the present invention.
Preferably, the metal salt includes any one or a mixture of at least two of metal salts of iron, nickel, cobalt, magnesium, aluminum, calcium, silicon or manganese, such as iron chloride, nickel chloride, magnesium chloride, iron nitrate, cobalt nitrate, magnesium nitrate, aluminum nitrate, manganese nitrate, calcium chloride, manganese chloride, nickel sulfate, magnesium sulfate, aluminum sulfate, etc., and the metal salt is preferably nitrate and/or chloride, but is not limited to the above-listed metal salts, and other metal salts commonly used in the art for preparing catalysts for carbon nanotubes may also be used in the present invention.
The catalyst for the carbon nano tube is used for preparing the carbon nano tube.
Preferably, the metal oxide includes any one or a mixture of at least two of oxides of iron, nickel, cobalt, magnesium, aluminum, calcium, silicon or manganese, such as iron oxide, nickel oxide, magnesium oxide, aluminum oxide, calcium oxide, silicon oxide, manganese oxide, etc., but is not limited to the above-listed metal oxides, and other metal salts commonly used in the art for preparing catalysts for carbon nanotubes may also be used in the present invention.
Preferably, the solvent in step (1) includes any one or a mixture of at least two of water, ethanol, acetone, tetrahydrofuran and N, N-dimethylformamide, but is not limited to the above-listed solvents, and other solvents commonly used in the art to dissolve the organic substances described in the present invention may also be used in the present invention.
Preferably, the mass ratio of the organic matter, the metal precursor and the solvent in the step (1) is as follows: (5-30) (1-20) (50-94) are, for example, 5:10:53, 10:3:85, 5:15:60, 20:10:90, 30:5:80, 25:2:94, 30:20:55, 5:15:70, 8:15:85, 13:17:80, or 20:20: 68.
Preferably, the dispersing in the step (1) adopts a mode comprising the following steps: any one of stirring, grinding or ball milling.
Preferably, the electrospinning in step (2) is carried out by: and (2) filling the dispersion liquid obtained in the step (1) into an injector of electrospinning equipment, connecting the injector with a high-voltage power supply, switching on the high-voltage power supply, carrying out electrospinning, and collecting at a receiving device to obtain an electrospinning product.
Preferably, the apparatus for filling the syringe with the dispersion obtained in step (1) is a peristaltic pump.
Preferably, the flow rate of the dispersion during electrospinning in step (2) is 0.1ml/h to 100ml/h, such as 0.1ml/h, 1ml/h, 3ml/h, 5ml/h, 10ml/h, 15ml/h, 17.5ml/h, 20ml/h, 25ml/h, 30ml/h, 35ml/h, 40ml/h, 50ml/h, 60ml/h, 70ml/h, 80ml/h, 90ml/h or 100ml/h, etc.
Preferably, in the process of electrospinning in step (2), the voltage generated by the high voltage power supply is 5kv to 30kv, such as 5kv, 10kv, 15kv, 20kv, 22kv, 26kv or 30 kv.
Preferably, in the process of electrospinning in step (2), the distance between the needle of the syringe and the receiving device is 10cm to 30cm, such as 10cm, 12cm, 15cm, 18cm, 20cm, 22cm, 25cm or 30 cm.
Preferably, the non-oxidizing atmosphere in step (3) is any one of an air atmosphere, a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere, or a xenon atmosphere, or a combination of at least two thereof.
Preferably, the temperature of the heat treatment in step (3) is 300 to 600 ℃, for example, 300 ℃, 325 ℃, 350 ℃, 370 ℃, 400 ℃, 425 ℃, 450 ℃, 480 ℃, 500 ℃, 550 ℃ or 600 ℃.
Preferably, the time of the heat treatment in the step (3) is 10min to 60min, such as 10min, 20min, 30min, 35min, 40min, 45min, 50min, 55min or 60 min.
In a second aspect, the present invention provides a catalyst prepared by the method of the first aspect, wherein the catalyst has a specific surface area of 8m2/g～20m2G, e.g. 8m2/g、10m2/g、12m2/g、15m2/g、16m2/g、17.5m2/g、18m2/g、19m2G or 20m2And/g, etc.
The catalyst of the present invention is suitable for use as one of the raw material components for preparing clustered carbon nanotubes, and clustered carbon nanotubes comprising all aligned carbon nanotubes can be obtained by using the catalyst for preparing carbon nanotubes.
In a third aspect, the present invention provides a bundled carbon nanotube prepared by using the catalyst of the second aspect, wherein the bundled carbon nanotube is composed of all aligned carbon nanotubes.
Preferably, the diameter of the aligned carbon nanotube in the cluster-like carbon nanotube is 5nm to 100nm, for example, 5nm, 10nm, 15nm, 20nm, 30nm, 35nm, 40nm, 50nm, 55nm, 65nm, 70nm, 80nm, 90nm, or 100 nm.
Preferably, the length of the oriented carbon nanotube in the bundled carbon nanotubes is 5 μm to 100 μm, for example, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 45 μm, 50 μm, 60 μm, 70 μm, 80 μm, or 100 μm.
Preferably, the specific surface area of the oriented carbon nanotubes in the cluster-shaped carbon nanotubes is 140m2/g～300m2G, e.g. 140m2/g、150m2/g、160m2/g、180m2/g、190m2/g、200m2/g、215m2/g、230m2/g、245m2/g、255m2/g、270m2/g、280m2/g、290m2G or 300m2And/g, etc.
Preferably, the bulk density of the oriented carbon nanotubes in the bundled carbon nanotubes is 0.01g/cm3～0.1g/cm3For example, 0.01g/cm3、0.03g/cm3、0.04g/cm3、0.05g/cm3、0.06g/cm3、0.07g/cm3、0.08g/cm3、0.09g/cm3Or 0.1g/cm3And the like.
In a fourth aspect, the present invention provides a method for preparing the bundled carbon nanotubes according to the third aspect, comprising the following steps:
and (3) putting the catalyst in the second aspect into a reaction furnace, introducing carbon source gas and inert gas, and calcining to obtain the cluster carbon nano tube.
The reaction furnace of the present invention may be a heating furnace commonly used in the art, and may be, for example, a tube furnace.
Preferably, the carbon source gas includes any one or a mixture of at least two of methane, ethylene, acetylene, propane, propylene, or gaseous ethanol, but is not limited to the above-listed carbon source gases, and other carbon-containing gases commonly used in the art for preparing carbon nanotubes may also be used in the present invention.
Preferably, the inert gas is any one of nitrogen, argon, helium, neon, krypton or xenon or a combination of at least two of the same.
Preferably, the temperature of the calcination is 500 ℃ to 900 ℃, such as 500 ℃, 550 ℃, 575 ℃, 600 ℃, 650 ℃, 700 ℃, 725 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or the like.
Preferably, the calcination time is 10min to 200min, such as 10min, 25min, 40min, 50min, 65min, 75min, 80min, 90min, 100min, 115min, 130min, 150min, 165min, 180min, or 200 min.
As a preferable technical solution of the method of the present invention, the method further comprises grinding the catalyst of claim 6, sieving the ground catalyst with a 100-mesh sieve, and then placing the obtained catalyst under the sieve into a reaction furnace for preparing the clustered carbon nanotubes.
As a further preferable technical solution of the method for preparing the bundled carbon nanotubes of the present invention, the method comprises the steps of:
(1) dispersing metal salt and/or metal oxide and an organic matter in a solvent to obtain a dispersion liquid;
(2) carrying out electrospinning by using the dispersion liquid obtained in the step (1);
(3) carrying out heat treatment on the electrospinning product obtained in the step (2) at 300-600 ℃ for 10-60 min in a nitrogen atmosphere or an air atmosphere, grinding the heat-treated product and sieving the ground product with a 100-mesh sieve;
(4) and (4) putting the undersize catalyst obtained in the step (3) into a reaction furnace, introducing carbon source gas and inert gas, and calcining at 500-900 ℃ for 10-200 min to obtain the cluster carbon nano tube.
In the preferred embodiment, "metal salt and/or metal oxide" means: the metal salt or the metal oxide may be used, or a mixture of the metal salt and the metal oxide may be used.
Compared with the prior art, the invention has the following beneficial effects:
(1) a catalyst for manufacturing a carbon nanotube excellent in performance can be obtained by dispersing an organic solvent and a metal salt and/or a metal oxide as raw materials in a solvent, electrospinning the raw materials, and then heat-treating the mixture in a non-oxidizing atmosphere.
(2) The cluster carbon nano tube has very good orientation type, has the advantages of easy dispersion and convenient use compared with other winding type carbon nano tubes, and can better exert the advantages of high conductivity and high strength of the carbon nano tube.
(3) Compared with the prior art, the method is simple, easy to operate, environment-friendly and easy for industrial production.
Drawings
FIG. 1 is an SEM image of bundled carbon nanotubes prepared in example 1;
fig. 2 is an SEM image of the carbon nanotube prepared in comparative example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
This example provides a carbon nanotube with a special shape, i.e. a cluster carbon nanotube, which is composed of all the oriented carbon nanotubes, wherein the oriented carbon nanotubes have a diameter of 5nm to 100nm, a length of 5 μm to 100 μm, and a specific surface area of 140m2/g～300m2(g) apparent density of 0.01g/cm3～0.1g/cm3。
The preparation method comprises the following steps:
(1) 30g of polyvinyl alcohol and 10g of a mixture of ferric chloride and magnesium chloride are dissolved and dispersed in 60g of water in a high-speed stirring manner to obtain a dispersion liquid;
(2) transferring the dispersion liquid into an injector through a peristaltic pump, switching on a high-voltage power supply, and carrying out electrospinning, wherein the distance between a needle head of the injector and a receiving device is 20cm, the voltage is 10kv, and the flow rate of the dispersion liquid is 10 ml/h;
(3) introducing nitrogen into the collected electrospinning product at the temperature of 300 ℃ for calcination for 60 min;
(4) and (4) crushing the product obtained in the step (3), sieving the crushed product with a 100-mesh sieve, putting the sieved product into a tube furnace, and introducing methane gas and nitrogen to calcine the product at 900 ℃ for 10min to obtain the carbon nano tube with a special shape, namely the cluster-shaped carbon nano tube.
FIG. 1 is an SEM image of the clustered carbon nanotubes prepared in example 1, wherein the carbon nanotubes are aligned carbon nanotubes and form clusters.
Example 2
This example provides a carbon nanotube with a special shape, i.e. a cluster carbon nanotube, which is composed of all the aligned carbon nanotubes, wherein the aligned carbon nanotubes have a diameter of 5nm to 100nm, a length of 5 μm to 100 μm, and a specific surface area of 140m2/g～300m2(g) apparent density of 0.01g/cm3～0.1g/cm3。
The preparation method comprises the following steps:
(1) dissolving and dispersing 5g of asphalt and 15g of a mixture of aluminum oxide and molybdenum nitrate in 65g of tetrahydrofuran in a high-speed stirring manner to obtain a dispersion liquid;
(2) transferring the dispersion liquid into an injector through a peristaltic pump, switching on a high-voltage power supply, and carrying out electrospinning, wherein the distance between a needle head of the injector and a receiving device is 15cm, the voltage is 20kv, and the flow rate of the dispersion liquid is 20 ml/h;
(3) introducing air into the collected electrospinning product at the temperature of 600 ℃ for calcining for 10 min;
(4) and (4) crushing the product obtained in the step (3), sieving the crushed product with a 100-mesh sieve, putting the sieved product into a tube furnace, and introducing methane gas and argon gas to calcine the product at 800 ℃ for 30min to obtain the carbon nano tube with a special shape, namely the cluster-shaped carbon nano tube.
Example 3
This example provides a carbon nanotube with a special shape, i.e. a cluster carbon nanotube, which is composed of all the aligned carbon nanotubes, wherein the aligned carbon nanotubes have a diameter of 5nm to 100nm, a length of 5 μm to 100 μm, and a specific surface area of 140m2/g～300m2(g) apparent density of 0.01g/cm3～0.1g/cm3。
The preparation method comprises the following steps:
(1) dissolving and dispersing 10g of polyoxyethylene and 20g of nickel nitrate in 80g of deionized water in a high-speed stirring manner to obtain a dispersion liquid;
(2) transferring the dispersion liquid into an injector through a peristaltic pump, switching on a high-voltage power supply, and carrying out electrospinning, wherein the distance between a needle head of the injector and a receiving device is 25cm, the voltage is 25kv, and the flow rate of the dispersion liquid is 50 ml/h;
(3) introducing air into the collected electrospinning product at the temperature of 400 ℃ for calcination for 45 min;
(4) and (4) crushing the product obtained in the step (3), sieving the crushed product with a 100-mesh sieve, putting the product below the sieve into a tube furnace, introducing methane gas and argon gas, and calcining the product at 600 ℃ for 80min to obtain the carbon nano tube with a special shape, namely the cluster-shaped carbon nano tube.
Example 4
This example provides a carbon nanotube with a special shape, i.e. a cluster carbon nanotube, which is composed of all the aligned carbon nanotubes, wherein the aligned carbon nanotubes have a diameter of 5nm to 100nm, a length of 5 μm to 100 μm, and a specific surface area of 140m2/g～300m2(g) apparent density of 0.01g/cm3～0.1g/cm3。
The preparation method comprises the following steps:
(1) dissolving and dispersing 20g of polyacrylonitrile and 8g of a mixture of cobalt nitrate and silicon dioxide in 90g N N dimethylformamide in a high-speed grinding manner to obtain a dispersion liquid;
(2) transferring the dispersion liquid into an injector through a peristaltic pump, switching on a high-voltage power supply, and carrying out electrospinning, wherein the distance between a needle head of the injector and a receiving device is 20cm, the voltage is 12kv, and the flow rate of the dispersion liquid is 5 ml/h;
(3) introducing air into the collected electrospinning product at the temperature of 450 ℃ for calcining for 50 min;
(4) and (4) crushing the product obtained in the step (3), sieving the crushed product with a 100-mesh sieve, putting the sieved product into a tube furnace, and introducing methane gas and argon gas to calcine the product at 650 ℃ for 120min to obtain the carbon nano tube with a special shape, namely the cluster-shaped carbon nano tube.
Comparative example 1
The conditions were the same as in example 1 except that steps (1) to (3) were not carried out and the catalyst of step (4) was directly replaced with nickel foam.
The carbon nanotubes prepared in this comparative example were disordered (see fig. 2).
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (18)
1. A method for preparing clustered carbon nanotubes using a catalyst, the method comprising: putting a catalyst into a reaction furnace, introducing a carbon source gas and an inert gas, calcining at 500-900 ℃ for 10-200 min to obtain cluster carbon nanotubes, wherein the carbon source gas comprises any one or a mixture of at least two of methane, ethylene, acetylene, propane, propylene or gaseous ethanol;
the preparation method of the catalyst comprises the following steps:
(1) dispersing an organic matter and a metal precursor in a solvent to obtain a dispersion liquid, wherein the organic matter comprises any one or a mixture of at least two of polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyacrylonitrile or asphalt;
(2) carrying out electrospinning by using the dispersion liquid obtained in the step (1);
(3) carrying out heat treatment on the electrospinning product obtained in the step (2) at 300-600 ℃ for 10-60 min in any one or combination of at least two of air atmosphere, nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere and xenon atmosphere to obtain a catalyst;
the metal precursor is a metal salt and/or a metal oxide, the metal salt comprises any one or a mixture of at least two of metal salts of iron, nickel, cobalt, magnesium, aluminum, calcium, silicon or manganese, and the metal oxide comprises any one or a mixture of at least two of oxides of iron, nickel, cobalt, magnesium, aluminum, calcium, silicon or manganese;
the bundled carbon nanotubes are all composed of aligned carbon nanotubes.
2. The method of claim 1, wherein the metal salt is a nitrate and/or chloride.
3. The method according to claim 1, wherein the solvent in step (1) comprises any one of water, ethanol, acetone, tetrahydrofuran or N, N-dimethylformamide or a mixture of at least two of the above.
4. The method according to claim 1, wherein the mass ratio of the organic substance, the metal precursor and the solvent in step (1) is: (5-30), (1-20) and (50-94).
5. The method of claim 1, wherein the dispersing of step (1) is performed in a manner comprising: any one of stirring, grinding or ball milling.
6. The method of claim 1, wherein the electrospinning in step (2) is performed by: and (2) filling the dispersion liquid obtained in the step (1) into an injector of electrospinning equipment, switching on a high-voltage power supply, carrying out electrospinning, and collecting the electrospinning product at a receiving device.
7. The method according to claim 6, wherein the apparatus for filling the syringe with the dispersion obtained in step (1) is a peristaltic pump.
8. The method of claim 6, wherein the dispersion has a flow rate of 0.1m L/h to 100m L/h during the electrospinning in step (2).
9. The method according to claim 6, wherein the voltage generated by the high voltage power supply during the electrospinning in the step (2) is 5kV to 30 kV.
10. The method of claim 6, wherein the distance between the needle of the syringe and the receiving device is 10 cm-30 cm during the electrospinning in the step (2).
11. The process according to any one of claims 1 to 10, wherein the catalyst has a specific surface area of 8m2/g~20m2/g。
12. The method of any one of claims 1 to 10, wherein the aligned carbon nanotubes in the bundled carbon nanotubes have a diameter of 5nm to 100 nm.
13. The method of any one of claims 1 to 10, wherein the aligned carbon nanotubes in the bundled carbon nanotubes have a length of 5 μm to 100 μm.
14. The method of any one of claims 1 to 10, wherein the aligned carbon nanotubes in the bundled carbon nanotubes have a specific surface area of 140m2/g~300m2/g。
15. The method according to any one of claims 1-10The method of (2), wherein the bulk density of the aligned carbon nanotubes in the bundled carbon nanotubes is 0.01g/cm3~0.1g/cm3。
16. The method of claim 1, wherein the inert gas is any one of nitrogen, argon, helium, neon, krypton, or xenon, or a combination of at least two thereof.
17. The method of claim 1, further comprising grinding the catalyst and sieving the ground catalyst through a 100 mesh sieve, and then placing the obtained undersize catalyst into a reaction furnace for preparing the clustered carbon nanotubes.
18. The process according to any one of claims 1 to 10, characterized in that the preparation of the catalyst comprises the following steps:
(1) dispersing metal salt and/or metal oxide and an organic matter in a solvent to obtain a dispersion liquid, wherein the organic matter comprises any one or a mixture of at least two of polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyacrylonitrile or asphalt;
(2) carrying out electrospinning by using the dispersion liquid obtained in the step (1);
(3) carrying out heat treatment on the electrospinning product obtained in the step (2) at 300-600 ℃ for 10-60 min in a nitrogen atmosphere or an air atmosphere, grinding the heat-treated product and sieving the ground product with a 100-mesh sieve;
(4) placing the undersize catalyst obtained in the step (3) into a reaction furnace, introducing carbon source gas and inert gas, and calcining at 500-900 ℃ for 10-200 min to obtain cluster carbon nanotubes;
the metal salt comprises any one or a mixture of at least two of metal salts of iron, nickel, cobalt, magnesium, aluminum, calcium, silicon or manganese, and the metal oxide comprises any one or a mixture of at least two of oxides of iron, nickel, cobalt, magnesium, aluminum, calcium, silicon or manganese.
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| WO2000030141A1 (en) * | 1998-11-12 | 2000-05-25 | The Board Of Trustees Of The Leland Stanford Junior University | Self-oriented bundles of carbon nanotubes and method of making same |
| CN1483668A (en) * | 2002-09-17 | 2004-03-24 | 清华大学 | Carbon nano pipe array growth method |
| JP2014122154A (en) * | 2013-11-15 | 2014-07-03 | National Institute Of Advanced Industrial & Technology | Composite material including carbon nanotube bulk structure |
| CN104404652A (en) * | 2014-11-23 | 2015-03-11 | 吉林大学 | Compound metal oxide water oxidation catalyst and electrostatic spinning preparation method thereof |
| CN105000543A (en) * | 2014-04-18 | 2015-10-28 | 中国科学院成都有机化学有限公司 | Method for preparing aligned carbon nanotubes |
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| WO2000030141A1 (en) * | 1998-11-12 | 2000-05-25 | The Board Of Trustees Of The Leland Stanford Junior University | Self-oriented bundles of carbon nanotubes and method of making same |
| CN1483668A (en) * | 2002-09-17 | 2004-03-24 | 清华大学 | Carbon nano pipe array growth method |
| JP2014122154A (en) * | 2013-11-15 | 2014-07-03 | National Institute Of Advanced Industrial & Technology | Composite material including carbon nanotube bulk structure |
| CN105000543A (en) * | 2014-04-18 | 2015-10-28 | 中国科学院成都有机化学有限公司 | Method for preparing aligned carbon nanotubes |
| CN104404652A (en) * | 2014-11-23 | 2015-03-11 | 吉林大学 | Compound metal oxide water oxidation catalyst and electrostatic spinning preparation method thereof |
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Denomination of invention: A catalyst for preparing bunched carbon nanotubes, its preparation method and bunched carbon nanotubes Effective date of registration: 20230216 Granted publication date: 20200717 Pledgee: Industrial Bank Co.,Ltd. Harbin Branch Pledgor: HARBIN WANXIN GRAPHITE VALLEY TECHNOLOGY Co.,Ltd. Registration number: Y2023230000024 |