CN101618867A - Method for preparing magnetic metal particle modified carbon nanotube - Google Patents
Method for preparing magnetic metal particle modified carbon nanotube Download PDFInfo
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- CN101618867A CN101618867A CN200810012116A CN200810012116A CN101618867A CN 101618867 A CN101618867 A CN 101618867A CN 200810012116 A CN200810012116 A CN 200810012116A CN 200810012116 A CN200810012116 A CN 200810012116A CN 101618867 A CN101618867 A CN 101618867A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002923 metal particle Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000007952 growth promoter Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 claims description 7
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 2
- 239000002041 carbon nanotube Substances 0.000 abstract description 37
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 37
- 239000002245 particle Substances 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 238000000859 sublimation Methods 0.000 abstract description 2
- 230000008022 sublimation Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 125000004434 sulfur atom Chemical group 0.000 abstract 1
- 239000013528 metallic particle Substances 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 15
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 230000005389 magnetism Effects 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 239000008187 granular material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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Abstract
The invention relates to a carbon nanotube preparation technique, in particular to a method for preparing a magnetic metal (iron, cobalt or nickel) particle modified carbon nanotube. The method comprises the following steps: adopting organo-metallic compounds as a carbon source and a catalyst and simultaneously as precursors of the carbon source and the catalyst, wherein the organo-metallic compounds are compounds of organic iron, cobalt or nickel; sublimating the organo-metallic compound catalyst and sufficiently and evenly mixing the organo-metallic compound catalyst with a sulfur-bearing growth promoter in a gaseous state; and putting the mixture into a reaction area to generate the magnetic metal particle modified carbon nanotube under the entrainment of buffer gas, wherein the mol ratio of sulfur to the iron (cobalt or nickel) in the organo-metallic compound is between 0 and 1/4. By controlling the sublimation temperature of the organo-metallic compound and the concentration of sulfur atoms in the reaction area, the method achieves the growth of the magnetic metal particle modified carbon nanotube and can control the diameter of the magnetic metal (iron, cobalt or nickel) particle.
Description
Technical field:
The present invention relates to the technology of preparing of carbon nanotube, be specially a kind of preparation method of magnetic metal particle modified carbon nanotube.
Background technology:
Carbon nanotube has the unique one dimension Nano structure and the performance of many excellences, is the forward position and the focus of domestic and international physical chemistry circle and material educational circles research always.Behind the carbon nanotube surface modification, its performance in some aspects is more outstanding, or has the performance that does not originally have, thereby can satisfy the requirement of various different application, and the carbon nanotube Application Areas is significant for expanding.As, introduce oxygen-containing functional group in carbon nano tube surface, form active sites, metallic particles such as Fe, Co and Ni etc. are put into equably the active sites of carbon nano tube surface, obtain the carbon nanotube that metallic particles is evenly modified, be expected to be with a wide range of applications at aspects such as catalytic field, magnetic resolution, metal-base composites and energy storage materials.
Current, the preparation metallic particles is carbon nano-tube modified mainly to be with the realizations of various post-treating methods, both prepared carbon nanotube earlier after, by carbon nanotube is carried out surface treatment, make its surface form active sites, at last various metallic particles on the carbon nano tube surface active sites is added.In order to make carbon nano tube surface form active sites (as various oxygen-containing functional groups), post-treating method will use the strong acid such as the vitriol oil (nitric acid etc.) at 120 ℃ of following long time treatment carbon nanotubes usually, it is serious that this can make the carbon tubular construction destroy, greatly reduced material property, therefore limited its widespread use in fields such as matrix material, energy storage material and support of the catalyst.
Summary of the invention:
The object of the present invention is to provide the novel method of a kind of a large amount of preparation magneticmetal iron (cobalt, nickel) particle modified carbon nanotube, it is simple that this method has equipment, processing ease, energy consumption is low, therefore advantages such as product purity height, controllability is high and it is continuous to be expected to, mass production can be used as a kind of Perfected process that is suitable for controlled preparation.
Technical scheme of the present invention is:
The invention provides the preparation method of a kind of high quality magneticmetal (iron, cobalt, nickel) particle modified carbon nanotube, this method adopts organometallic compound carbon source, catalyzer, buffer gas and contains growth promoter of sulfur, and organo-metallic (iron, cobalt or nickel) compound catalyst is distillation fast directly; Perhaps, Organometal compound catalyst distillation and even with sulphur thorough mixing under gaseous state; Then, the input reaction zone generates magneticmetal iron (cobalt, nickel) particle modified carbon nanotube, wherein:
Adopt organometallic compound simultaneously as carbon source and catalyst precursor, organometallic compound is one or more volatile organometallic compounds of ferrocene, nickelocene or dicyclopentadienylcobalt etc., the metallocenes volatilization temperature is 100～350 ℃, is preferably in 100～250 ℃ of scopes;
Containing growth promoter of sulfur is sulphur powder or organic compounds containing sulfur, as: thiophene, dithiocarbonic anhydride or hydrogen sulfide etc.; Wherein, the iron in sulphur and the organometallic compound (cobalt, nickel) mol ratio is 0～1/4, is preferably 0～1/10;
Buffer gas is one or more a mixed gas of hydrogen, argon gas, nitrogen.Depress at standard atmosphere, buffer gas is 0.16～3m/s at the flow velocity of reaction zone, is preferably in 1.2～2m/s scope;
700 ℃～1350 ℃ of end reaction temperature, insulation 5～180min is preferably 5～20min;
Used temperature rise rate is 10～60 ℃/min, is preferably 20～40 ℃/min.
Characteristics of the present invention and beneficial effect are:
1. the present invention makes the carbon nanotube of magneticmetal (iron, cobalt, the nickel) particle modification of generation by the organometallic compound that distils fast, and the content of metallic particles is 20～40wt%; The diameter of metallic particles can be regulated in 5～50nm scope.
2. the present invention adopts organometallic compound simultaneously as carbon source and catalyst precursor, and by the content of control sulphur, thereby the growth of the carbon nanotube of realization magneticmetal (iron, cobalt, nickel) particle modification also can be controlled the diameter of metallic particles.
3. the present invention is by the control sublimation temperature of organometallic compound and the sulphur atom concentration at reaction zone, thereby realizes the growth of magnetic metal particle modified carbon nanotube and can control magneticmetal (iron, cobalt, nickel) particulate diameter.Detailed process is as follows: (1) organometallics is heated the formation gaseous state, together with the hydrocarbon polymer that is heated to form evaporable sulphur under the low temperature that gasiform sulphur powder or low discharge buffer gas bring or the chemical compound gas of low discharge sulfur-bearing, with buffer gas mix and preheating after, import reaction zone together; (2) at reaction zone, organometallics will decompose, the atoms metal that dissociates, and under the effect of air-flow, the collision of free atoms metal, the particle of formation certain size; (3) decomposition reaction takes place in the carbon of organometallics cracking production under the catalysis of a part of metallic particles, and through dissolving, diffusion process, crystallization is separated out on granules of catalyst, generates carbon nanotube; (4) excessive metallic particles is deposited on the newly-generated carbon nano tube surface, thereby forms the carbon nanotube of magneticmetal (iron, cobalt, nickel) particle modification.
Description of drawings:
Fig. 1. the carbon nanotube stereoscan photograph that metallic particles is modified.
Fig. 2. the carbon nanotube transmission electron microscope photo that metallic particles is modified.
Fig. 3. the carbon nanotube magnetism analysis that metallic particles is modified.
Fig. 4. the carbon nanotube thermogravimetic analysis (TGA) that metallic particles is modified.
Embodiment:
The carrier gas gas velocity is 1.6cm/s, the mixture of weighing 5 gram ferrocene and sulphur powder, and wherein ferrocene and sulphur powder weight ratio are 100: 1, its volatilization temperature is 200 ℃, and reaction zone temperature is 1100 ℃, and temperature rise rate is 20 ℃/min, insulation 5min finally generates product toner powder darkly.
Scanning (Fig. 1) and transmission electron microscope (Fig. 2) and magnetism analysis (Fig. 3) show that product is the carbon nanotube of Armco magnetic iron particle modification.In the present embodiment, the carbon nanotube external diameter is 50-120nm, and internal diameter is 20-60nm, and iron particulate mean diameter is～10nm; Product carries out in air heat and analyzes (Fig. 4) and show that the content of metallic particles in product is～32wt%.
Embodiment 2
Carrier gas argon gas flow velocity is 1.6cm/s, the mixture of weighing 5 gram ferrocene and sulphur powder, and wherein ferrocene and sulphur powder weight ratio are 100: 1, its volatilization temperature is 250 ℃, and reaction zone temperature is 1100 ℃, and temperature rise rate is 30 ℃/min, insulation 5min finally generates product toner powder darkly.
Scanning and transmission electron microscope and magnetism analysis show that product is the carbon nanotube of Armco magnetic iron particle modification.In the present embodiment, the carbon nanotube external diameter is 70-160nm, and internal diameter is 40-90nm, and iron particulate mean diameter is～5nm; Hot analysis revealed, the metallic particles content in product is～30wt%.
Embodiment 3
Carrier gas argon gas flow velocity is 1.6cm/s, the mixture of weighing 5 gram ferrocene and sulphur powder, and wherein ferrocene and sulphur powder weight ratio are 50: 1, its volatilization temperature is 150 ℃, and reaction zone temperature is 900 ℃, and temperature rise rate is 40 ℃/min, insulation 5min finally generates product toner powder darkly.
Scanning and transmission electron microscope and magnetism analysis show that product is the carbon nanotube of Armco magnetic iron particle modification.In the present embodiment, the carbon nanotube external diameter is 90-200nm, and internal diameter is 30-110nm, and iron particulate mean diameter is～45nm; Hot analysis revealed, the metallic particles content in product is～40wt%.
Carrier gas is that argon gas and hydrogen gas mixture (mol ratio 1: 1) flow velocity are 1.6cm/s, weighing 5 gram nickelocenes, its volatilization temperature is 100 ℃, the hydrogen that with the flow velocity is 0.02cm/s carries thiophene, reaction zone temperature is 1000 ℃, temperature rise rate is 50 ℃/min, and insulation 5min finally generates product toner powder darkly.
Scanning and transmission electron microscope and magnetism analysis show that product is the carbon nanotube of magnetic nickel particle modification.In the present embodiment, the carbon nanotube external diameter is 50-120nm, and internal diameter is 20-60nm, and nickel particulate mean diameter is～20nm; Hot analysis revealed, the metallic particles content in product is～25wt%.
Embodiment 5
Carrier gas argon gas flow velocity is 1.2cm/s, the mixture of weighing 5 gram dicyclopentadienylcobalts and sulphur powder, and wherein dicyclopentadienylcobalt and sulphur weight ratio are 70: 1, its volatilization temperature is 120 ℃, and reaction zone temperature is 1200 ℃, and temperature rise rate is 10 ℃/min, insulation 5min finally generates product toner powder darkly.
Scanning and transmission electron microscope and magnetism analysis show, the carbon nanotube that product is modified for the magnetic cobalt granule.The carbon nanotube external diameter is 50-120nm, and internal diameter is 20-60nm, and the mean diameter of cobalt granule is～15nm; Hot analysis revealed, the metallic particles content in product is～35wt.
Embodiment 6
Carrier gas argon gas flow velocity is 2cm/s, the mixture of weighing 5 gram dicyclopentadienylcobalts and nickelocene, and wherein dicyclopentadienylcobalt and nickelocene weight ratio are 1: 1, its volatilization temperature is 150 ℃, and reaction zone temperature is 1100 ℃, and temperature rise rate is 60 ℃/min, insulation 5min finally generates product toner powder darkly.
Scanning and transmission electron microscope and magnetism analysis show that product is the carbon nanotube of Armco magnetic iron and nickel particle modification.In the present embodiment, carbon nanotube external diameter 80-160nm, internal diameter are 30-70nm, and the mean diameter of metallic particles is～30nm; Hot analysis revealed, the metallic particles content in product is～30wt.
Carrier gas argon gas flow velocity is 2cm/s, the mixture of weighing 5 gram ferrocene, dicyclopentadienylcobalt and nickelocenes, wherein ferrocene, dicyclopentadienylcobalt and nickelocene weight ratio are 1: 1: 1, its volatilization temperature is 120 ℃, reaction zone temperature is 1100 ℃, temperature rise rate is 60 ℃/min, and insulation 5min finally generates product toner powder darkly.
Scanning and transmission electron microscope and magnetism analysis show that product is the carbon nanotube of Armco magnetic iron, cobalt and nickel particle modification.In the present embodiment, the carbon nanotube external diameter is 60-120nm, and internal diameter is 25-60nm, and the mean diameter of metallic particles is～20nm; Hot analysis revealed, the metallic particles content in product is～37wt.
Claims (9)
1, a kind of preparation method of magnetic metal particle modified carbon nanotube, it is characterized in that: it is carbon source and catalyzer that this method adopts organometallic compound, it is simultaneously as carbon source and catalyst precursor, organometallic compound is the compound of organic iron, cobalt or nickel, and Organometal compound catalyst directly distils; Perhaps, Organometal compound catalyst distillation and with to contain growth promoter of sulfur thorough mixing under gaseous state even; Then, under buffer gas is carried secretly, enter reaction zone and generate magnetic metal particle modified carbon nanotube, 700 ℃～1350 ℃ of end reaction temperature, soaking time 5～180min.
2, according to the preparation method of the described magnetic metal particle modified carbon nanotube of claim 1, it is characterized in that: organometallic compound is volatile organometallic compound, and its volatilization temperature is 100～350 ℃.
3, according to the preparation method of the described magnetic metal particle modified carbon nanotube of claim 1, it is characterized in that: organometallic compound is one or more of ferrocene, nickelocene or dicyclopentadienylcobalt.
4, according to the preparation method of the described magnetic metal particle modified carbon nanotube of claim 1, it is characterized in that: containing growth promoter of sulfur is sulphur powder or organic compounds containing sulfur, and the mol ratio of the iron in sulphur and the organometallic compound, cobalt or nickel is 0～1/4.
5, according to the preparation method of the described magnetic metal particle modified carbon nanotube of claim 4, it is characterized in that: the mol ratio of the iron in sulphur and the organometallic compound, cobalt or nickel is preferably 0～1/10.
6, according to the preparation method of the described magnetic metal particle modified carbon nanotube of claim 1, it is characterized in that: buffer gas is one or more a mixed gas of hydrogen, argon gas, nitrogen.
7, according to the preparation method of the described magnetic metal particle modified carbon nanotube of claim 6, it is characterized in that: depress at standard atmosphere, buffer gas is 0.16～3m/s at the flow velocity of reaction zone.
8, according to the preparation method of the described magnetic metal particle modified carbon nanotube of claim 6, it is characterized in that: depress at standard atmosphere, buffer gas is preferably 1.2～2m/s at the flow velocity of reaction zone.
9, according to the preparation method of the described magnetic metal particle modified carbon nanotube of claim 1, it is characterized in that: soaking time is preferably 5～20min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102303126A (en) * | 2011-06-20 | 2012-01-04 | 浙江师范大学 | Method for manufacturing flower-shaped nickel-carbon nanotube composite material |
| CN103318870A (en) * | 2013-07-02 | 2013-09-25 | 西北师范大学 | Preparation method of novel functionalized magnetic carbon nanotube composite material of ferrocenyl derivative |
| CN103466597A (en) * | 2013-09-02 | 2013-12-25 | 中国科学院金属研究所 | Method for growing metallic single-walled carbon nanotubes by less doping nitrogen onto carbon lattices |
| CN105731417A (en) * | 2014-12-11 | 2016-07-06 | 山东大展纳米材料有限公司 | Apparatus and method for purifying carbon nanotubes |
| CN114291811A (en) * | 2021-12-29 | 2022-04-08 | 山西大学 | Simple carbon material magnetizing method |
-
2008
- 2008-07-02 CN CN200810012116A patent/CN101618867A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102303126A (en) * | 2011-06-20 | 2012-01-04 | 浙江师范大学 | Method for manufacturing flower-shaped nickel-carbon nanotube composite material |
| CN103318870A (en) * | 2013-07-02 | 2013-09-25 | 西北师范大学 | Preparation method of novel functionalized magnetic carbon nanotube composite material of ferrocenyl derivative |
| CN103318870B (en) * | 2013-07-02 | 2015-01-21 | 西北师范大学 | Preparation method of novel functionalized magnetic carbon nanotube composite material of ferrocenyl derivative |
| CN103466597A (en) * | 2013-09-02 | 2013-12-25 | 中国科学院金属研究所 | Method for growing metallic single-walled carbon nanotubes by less doping nitrogen onto carbon lattices |
| CN103466597B (en) * | 2013-09-02 | 2016-01-13 | 中国科学院金属研究所 | The method of a small amount of doped growing metallic single-wall carbon nano-tube of nitrogen on carbon grid |
| CN105731417A (en) * | 2014-12-11 | 2016-07-06 | 山东大展纳米材料有限公司 | Apparatus and method for purifying carbon nanotubes |
| CN114291811A (en) * | 2021-12-29 | 2022-04-08 | 山西大学 | Simple carbon material magnetizing method |
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Open date: 20100106 |