CN1480393A - Bamboo Knotlike nano carbon tube material containing nitrogen and synthetic method - Google Patents
Bamboo Knotlike nano carbon tube material containing nitrogen and synthetic method Download PDFInfo
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- CN1480393A CN1480393A CNA031414362A CN03141436A CN1480393A CN 1480393 A CN1480393 A CN 1480393A CN A031414362 A CNA031414362 A CN A031414362A CN 03141436 A CN03141436 A CN 03141436A CN 1480393 A CN1480393 A CN 1480393A
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- nitrogenous
- carbon nanotube
- ferric oxide
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- corrugated carbon
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Abstract
A bamboo joint shaped nitrogen-contained carbon nanotube is prepared through catalytic reaction between organic amine (diethanamine, triethanamine, dipropanamine, or tripropanamine) and molecular sieve carrying iron oxide as catalyst at 600-1200 deg.C. Its advantages are bigger pore diameter and longer distance between layers.
Description
Technical field
The present invention relates to the relevant nitrogenous corrugated carbon nanotube material and preparation method thereof that in new system, synthesizes.
Background technology
CNT (carbon nano-tube) is found a kind of carbon structure in 1991.Desirable CNT (carbon nano-tube) is seamless, the hollow tube body that is rolled into by the Graphene lamella that carbon atom forms.The lamella of Graphene generally can be from one deck to layers up to a hundred.What contain one deck Graphene lamella is called Single Walled Carbon Nanotube (SWNT), then is called multiple-wall carbon nanotube (MWNT) more than one deck.The diameter of SWNT is generally 1～6nm, and minimum diameter is approximately 0.5nm, and is suitable with the diameter of C36 molecule, but the diameter of SWNT is unstable especially later on greater than 6nm, and subsiding of SWNT pipe can be taken place, and length then can reach the hundreds of nanometer to several microns.The interlamellar spacing of MWNT is about 0.34 nanometer, and to tens nanometers, length is generally in micron dimension in several nanometers for diameter, and elder can reach several millimeters.Because CNT (carbon nano-tube) has bigger length-to-diameter ratio, is quasi-one-dimensional nanometer material so can regard it as.
The main preparation method method of CNT (carbon nano-tube) has arc process, pyrolysis method and laser evaporation method.Wherein arc process and Wolfgang-Kratschmer legal system are equipped with fullerene seemingly, and in inert gas atmosphere, two root graphite electrode direct-current discharges produce CNT (carbon nano-tube) on the negative electrode.Pyrolysis method adopts transition metal to make catalyzer exactly, and under the condition of 700-1600K, the decomposition by hydrocarbon polymer obtains CNT (carbon nano-tube).The laser ablation method adopts the graphite target in the laser ablation High Temperature Furnaces Heating Apparatus, and CNT (carbon nano-tube) just is present in the graphite evaporate that rare gas element carries secretly.The process of arranging again takes place in the carbon atom of the forming process free state of CNT (carbon nano-tube) or carbon atom group.The diameter of the CNT (carbon nano-tube) that catalysis method obtains and diameter Distribution depend primarily on reaction conditionss such as the kind, growth temperature of preparation method, catalyzer.
The doped carbon nanometer pipe of synthetic new texture can improve even create the performance that makes new advances.Study CN both at home and abroad
xThe Theoretical Calculation work of material appears in the newspapers; Synthetic nitrogen modification carbon material is a film like, and the purpose of research is to be used for improving its hardness and to obtain Electronic Performance preferably, and synthetic method is carbon material electrion or laser ablation under nitrogen atmosphere; This method complicated operation, the cost height, and material is a film like.Not seeing with catalysis process at present both at home and abroad as yet is that raw material obtains nitrogen modification corrugated carbon nanotube material and preparation method thereof with simple organic amine molecule.
Summary of the invention
The purpose of this invention is to provide nitrogenous corrugated carbon nanotube material that a kind of method is simple, cost is high, not respond well and preparation method thereof.
Its mole of removing in HF acid after catalyzer, the 120 ℃ of oven dry of said nitrogen modification bamboo-like carbon nano tubes novel material consists of xC: yN in the catalysis method synthetic nitrogen modification bamboo-like carbon nano tubes novel material provided by the invention; The value of x is 0.60～0.99, and the value of y is 0.01～0.40.
X, y value are more preferably in the above-mentioned materials: x is 0.75～0.90, and y is 0.10～0.25.When above-mentioned materials contained catalyzer, the mass ratio of itself and catalyzer was 0.01～0.80.
The catalyzer method of removing provided by the present invention is with an amount of or excessive HF acid, sulfuric acid, nitric acid or hydrochloric acid soln, and dipping is enough long-time, such as 0.5～24h; Use suction filtration then, again with a large amount of distilled water cleanings, suction filtration; To obtain black solid at last and place 120 ℃ of baking ovens to remove moisture, do not contained the nitrogen modification bamboo-like carbon nano tubes novel material of catalyzer.
Preparation method of the present invention is: will contain the ferric oxide amount and be 0.01～0.80 molecular sieve or nano iron oxide catalyst and place tube furnace, under Ar or nitrogen atmosphere, import organic amine, in 600～1200 ℃ of reactions 0.1～6.0 hour, can obtain containing the modification corrugated carbon nanotube material of catalyzer.The molecular sieve that contains ferric oxide obtains with dipping method, and oven dry, roasting get final product then.
Above-mentioned reaction good conditions is: catalyzer contains ferric oxide amount 0.05～0.70,650～1000 ℃ of temperature of reaction, 0.20～4.0 hour reaction times.
Above-mentioned reaction better condition is: catalyzer contains ferric oxide amount 0.10～0.60,700～900 ℃ of temperature of reaction, 0.30～2.0 hour reaction times.
Nitrogen carbon source provided by the invention is following any or their mixture: hexamethylenetetramine, methylamine, ethamine, propylamine, quadrol, diethylamine, triethylamine, dipropyl amine, tripropyl amine, butylamine, hexylamine, hexahydroaniline, hexanediamine.
During catalysis method synthetic nitrogen modification bamboo-like carbon nano tubes novel material Preparation of Catalyst provided by the present invention: with porous molecular screen, support ferric oxide with dipping method, or just contain ferro element when synthesizing porous molecular sieve or oxide compound, quality group becomes aFe
2O
3: bR, R are porous molecular screen or oxide compound; Then with it 80～150 ℃ of oven dry, in air, be heated to 300～1200 ℃ again it be prepared into the ferruginous form in ferric oxide or the skeleton that supports; Wherein said roasting condition is at 300～1200 ℃, roasting 0.5～24 hour; Wherein the value of a is 0.01～0.80, and the value of b is 0.99～0.20.Above-mentioned reaction good conditions is that the oven dry back was 500～800 ℃ of following roastings 1.5～6 hours.The quality ratio of components that contains the porous molecular screen of ferric oxide is aFe
2O
3: bR, wherein a is 0.01～0.80, b is 0.20～0.99; Better ratio of components a is 0.10～0.60, and b is 0.40～0.90.
Said porous molecular screen be the micro porous molecular sieve that generally adopts in the prior art, mesoporous molecular sieve and in-micro porous molecular sieve.Source of iron comprises iron nitrate, ironic oxalate, Ferrox, freshly prepd ironic hydroxide or ferrous hydroxide precipitation.Source of iron is mixed with an amount of distilled water, flood porous molecular screen then.
The material that the present invention obtains usable acid is before use removed catalyzer, also can directly use, and is more convenient.
The material that the present invention obtains is mainly used in the raw material or the high-power electrode materials that discharges and recharges power supply of energy storage, ultracapacitor.
The present invention has adopted catalysis method synthetic nitrogen modification corrugated carbon nanotube material, and its advantage is: (1) has strengthened the mechanical property of carbon nanotube; (2) specific surface and interlamellar spacing have been significantly improved; (3) this material tentatively shows the new capability of super large charge/discharge capacity and efficient, considerably beyond the carbon nano-tube material of general method preparation, is suitable for being used as the raw material or the high-power electrode materials that discharges and recharges power supply of ultracapacitor; (4) catalysis process synthesis condition gentleness, raw material is cheap, be easy to get, and is suitable for scale operation.
Catalysis method synthetic nitrogen modification corrugated carbon nanotube material provided by the present invention is done main carbon source with organic amine, with catalysis process obtain larger aperture, than the nitrogenous modification bamboo-like carbon nano tubes novel material of high-ratio surface and interlamellar spacing.
Description of drawings
Fig. 1 is the TEM figure of many carbon nanotubes
Fig. 2 is the TEM figure of single-root carbon nano-tube
Embodiment
Example one .1.0g is baked SAPO-11 molecular sieve (synthetic method is referring to chemical journal, 2002 6 phase 1122～1124 pages) in 800 ℃ of high temperature airs, places the 5mL beaker; Claim 0.030g Fe (NO)
39H
2O is dissolved in the 1.2mL distilled water, then this solution impregnation is stirred to the SAPO-11 molecular sieve, leaves standstill 12 hours; Placed 150 ℃ of oven for drying then 12 hours, 1000 ℃ of roastings are 0.5 hour in the air, reduce to room temperature naturally; Place the tube furnace of the band silica tube of Ar protection gas then, be warming up to 1200 ℃, the 2mL tripropyl amine is gone into by catalyzer by the Ar protection band of gas, sneaks into the 20mL acetylene gas simultaneously, through finishing this process in 0.5 hour.Stop heating then, continue logical Ar protection gas to dropping to room temperature.Take out the black sample and be the nitrogenous modification corrugated carbon nanotube material that contains catalyzer, C and nitrogen mol ratio are 0.99: 0.01.
Example two .1.0g are baked SAPO-11 molecular sieve (synthetic method is referring to chemical journal, 2002 6 phase 1122～1124 pages) in 800 ℃ of high temperature airs, places the 5mL beaker; Claim 0.25g Fe (NO)
39H
2O is dissolved in the 1.2mL distilled water, then this solution impregnation is stirred to the SAPO-11 molecular sieve, leaves standstill 12 hours; Placed 150 ℃ of oven for drying then 12 hours, 300 ℃ of roastings are 24 hours in the air, reduce to room temperature naturally; Place the tube furnace of the band silica tube of nitrogen protection gas then, be warming up to 620 ℃, 2g hexamethylenetetramine and 0.05mL diethylamine are gone into by catalyzer by the nitrogen protection band of gas, through finishing this process in 0.5 hour.Stop heating then, continue logical nitrogen protection gas to dropping to room temperature.Take out the black sample and be the nitrogenous modification bamboo-like carbon nano tubes novel material that contains catalyzer, C and nitrogen mol ratio are 0.62: 0.38.
Example three .0.25g are baked SBA-15 molecular sieve (synthetic method is referring to SCI, 2000 1 phase 21～23 pages) in 800 ℃ of high temperature airs, places the 5mL beaker; Claim 0.1g Fe (NO)
39H
2O is dissolved in the 1.2mL distilled water, then this solution impregnation is stirred to the SBA-15 molecular sieve, leaves standstill 12 hours; Placed 150 ℃ of oven for drying then 12 hours; Place the tube furnace of the band silica tube of Ar protection gas then, be warming up to 820 ℃, the 2mL diethylamine is gone into by catalyzer by the Ar protection band of gas, through finishing this process in 0.5 hour.Stop heating then, continue logical Ar protection gas to dropping to room temperature.Take out the black sample and be the nitrogenous modification corrugated carbon nanotube material that contains catalyzer, C and nitrogen mol ratio are 0.80: 0.20.
Claims (13)
1. nitrogenous corrugated carbon nanotube material, the mole that it is characterized in that nitrogenous corrugated carbon nanotube material is xC: yN when forming expression; The value of x is 0.60～0.99; The value of y is 0.40～0.01.
2. nitrogenous corrugated carbon nanotube material according to claim 1 is characterized in that containing catalyzer, and promptly removing the nitrogenous corrugated carbon nanotube material before the catalyzer and the mass ratio of catalyzer is 0.01～0.80.
3. nitrogenous bamboo-like carbon nano tubes novel material according to claim 1 and 2, it is characterized in that synthetic method is: in tube furnace, organic amine is reacted by containing ferric oxide multi-porous molecular sieve or oxide catalyst under Ar or nitrogen atmosphere, can obtain nitrogenous bamboo-like carbon nano tubes novel material, actual conditions is: it is 0.01～0.80 that (1) catalyzer contains the ferric oxide amount; (2) temperature of reaction is 600～1200 ℃; (3) 0.1～6.0 hour reaction times.
4. nitrogenous corrugated carbon nanotube material according to claim 3 is characterized in that synthesis condition is: it is 0.05～0.70 that (1) catalyzer contains the ferric oxide amount; (2) temperature of reaction is 650～1000 ℃; (3) 0.2～4.0 hour reaction times.
5. nitrogenous corrugated carbon nanotube material according to claim 4 is characterized in that synthesis condition is: it is 0.10～0.60 that (1) catalyzer contains the ferric oxide amount; (2) temperature of reaction is 700～900 ℃; (3) 0.3～2.0 hour reaction times.
6. nitrogenous corrugated carbon nanotube material according to claim 3 is characterized in that nitrogenous carbon source is following any or their mixture: hexamethylenetetramine, methylamine, ethamine, propylamine, quadrol, diethylamine, triethylamine, dipropyl amine, tripropyl amine, butylamine, hexylamine, hexahydroaniline, hexanediamine.
7. nitrogenous corrugated carbon nanotube material according to claim 6 is characterized in that nitrogenous carbon source is that organic amine mixes use with methane or acetylene.
8. nitrogenous corrugated carbon nanotube material according to claim 3 is to support ferric oxide with dipping method when it is characterized in that containing the porous molecular screen Preparation of Catalyst of ferric oxide, and the oven dry back was 300～1000 ℃ of following roastings 0.5～24 hour.
9. nitrogenous corrugated carbon nanotube material according to claim 8 is to support ferric oxide with dipping method when it is characterized in that containing the porous molecular screen Preparation of Catalyst of ferric oxide, and the oven dry back was 500～800 ℃ of following roastings 1.5～6 hours.
10. the porous molecular screen catalystic material that contains ferric oxide according to claim 3, the quality ratio of components that it is characterized in that containing the porous molecular screen of ferric oxide is aFe
2O
3: bR, wherein a is 0.01～0.80, b is 0.20～0.99.
11. the porous molecular screen catalystic material that contains ferric oxide according to claim 10, the quality ratio of components that it is characterized in that containing the porous molecular screen of ferric oxide is aFe
2O
3: bR, wherein a is 0.10～0.60, b is 0.40～0.90.
12. according to claim 1 or 2 described nitrogenous corrugated carbon nanotube materials, it is characterized in that this material before use usable acid remove catalyzer, also can directly use.
13. nitrogenous corrugated carbon nanotube material according to claim 1 is characterized in that this material can be used for the raw material or the high-power electrode materials that discharges and recharges power supply of energy storage, ultracapacitor.
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| CNA031414362A CN1480393A (en) | 2003-07-07 | 2003-07-07 | Bamboo Knotlike nano carbon tube material containing nitrogen and synthetic method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101069588B (en) * | 2007-05-25 | 2010-05-19 | 上海第二工业大学 | Air-battery smart nano health-care shoe pad |
| CN103480407A (en) * | 2013-09-27 | 2014-01-01 | 神华集团有限责任公司 | Iron-based catalyst auxiliary as well as preparation method and application thereof |
| CN105788881A (en) * | 2016-04-26 | 2016-07-20 | 暨南大学 | Preparation method of nitrogen-doped bamboo-like carbon nonatube |
| CN109019568A (en) * | 2018-10-10 | 2018-12-18 | 深圳大学 | A kind of preparation method of graphene nanobelt |
-
2003
- 2003-07-07 CN CNA031414362A patent/CN1480393A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101069588B (en) * | 2007-05-25 | 2010-05-19 | 上海第二工业大学 | Air-battery smart nano health-care shoe pad |
| CN103480407A (en) * | 2013-09-27 | 2014-01-01 | 神华集团有限责任公司 | Iron-based catalyst auxiliary as well as preparation method and application thereof |
| CN103480407B (en) * | 2013-09-27 | 2015-11-04 | 神华集团有限责任公司 | Fe-series catalyst auxiliary agent and its preparation method and application |
| CN105788881A (en) * | 2016-04-26 | 2016-07-20 | 暨南大学 | Preparation method of nitrogen-doped bamboo-like carbon nonatube |
| CN109019568A (en) * | 2018-10-10 | 2018-12-18 | 深圳大学 | A kind of preparation method of graphene nanobelt |
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