CN1699620A - Process for preparing a catalyst for synthesis of carbon nano tube - Google Patents
Process for preparing a catalyst for synthesis of carbon nano tube Download PDFInfo
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- CN1699620A CN1699620A CN 200410022571 CN200410022571A CN1699620A CN 1699620 A CN1699620 A CN 1699620A CN 200410022571 CN200410022571 CN 200410022571 CN 200410022571 A CN200410022571 A CN 200410022571A CN 1699620 A CN1699620 A CN 1699620A
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- carbon nanotube
- catalyzer
- catalyst
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- carbon nanometer
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Abstract
The present invention provides a preparation method of catalyst for synthesis of carbon nanometer tubes, relating to the preparation of catalyst for synthesis of carbon nanometer tubes by gas phase catalysis deposition. Aliphatic salt of no.VIII group metal is used as organic complex precursor, which is decomposed at 200-1200 degree C to form highly dispersed oxide of nanometer grade. The diameter of the carbon nanometer tube can be adjusted and controlled. The aliphatic salt can avoid segregation of some metallic elements, which always happens to water solvent system. In addition, aliphatic acid also has the effect of both compounding agent and surfactant, so various metallic ions can be highly homogeneously and stably mixed in it. Through optimization, the single wall nanometer tube of high quality can be prepared. The present method has the advantages of simple equipment, convenient operation and short production period. Besides, the diameter of carbon nanometer tube is controllable. It has the potential of industrialization for carbon nanometer tube catalyst production.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method, particularly a kind of Preparation of Catalyst that is used for the catalytic chemical vapor deposition technique synthesizing carbon nanotubes belongs to the material field.
Background technology
Carbon nanotube is the new carbon of finding the nineties in 20th century, because special structure shows excellent mechanical property, electricity, magnetic performance.At electrochemical capacitor, the application of aspects such as matrix material makes progress at present.The batch preparation of the batch preparations of carbon nanotube, especially Single Walled Carbon Nanotube becomes the focus of research.The main method of preparation carbon nanotube has three major types, laser laser ablation method, arc process, chemical Vapor deposition process (CVD method) at present.Laser ablation method can obtain highly purified product.But high-power laser equipment price is high, and is not easy to amplify.Though arc process equipment is simple, and the quality height of product.But the cost of carbon nanotube is than CVD method height.The CVD method can be divided into two major types, and a class is the floating catalytic method; Another kind of is the stagnant catalyst method for preparing catalyzer in advance.HiPco method experimental result with U.S. Rice University in the floating catalytic method is best, and they are reactant with CO and carbon back iron, controls the productive rate of carbon nanotube of single wall and the distribution of diameter by the reaction conditions of high temperature and high pressure.Though this method can obtain Single Walled Carbon Nanotube in batches, to the requirement height of conversion unit and reaction conditions.In the way of stagnant catalyst, better with the CoMoCAT method result of Dai Houjie.They are carrier with SiO2, and the bimetal salt of load cobalt and molybdenum obtains the catalyzer of proper growth Single Walled Carbon Nanotube.But process is long, and also needing the big carbon monoxide of toxicity is carbon source, and working pressure has the multi-walled pipes part unavoidably also than higher in the product.Also has the method for preparing the catalyzer of carbon nano-tube with the organic coordination compound presoma in addition.With easy organic ligand by just decomposing more than 200 ℃, for example citric acid in the aqueous solution with metal ion complexing mutually, remove organic ligand by thermal degradation at last and obtain oxide compound.The general part that adopts of this method is small molecules such as citric acid, EDTA.Because the different coordination ability of different metal ionic, segregation takes place at some ion of process that forms composite precursor in small molecules part easily, thereby influences the dispersion of reactive metal in the catalyzer.Also there is the researchist to adopt macromolecular ligand such as polyoxyethylene glycol and metal ion network and prepare catalyzer mutually.Because the macromole chain length of macromolecular ligand has iris action to metal ion, thereby obtains higher metal dispersity.Concrete process is water-soluble PEG, and metal nitrate is heated and stirred together, and is water-soluble, and slowly dehydration just obtains the gel that mixes.The heating gel is sloughed the catalyzer that organic moiety just obtains the suitable carbon nanotube.Part all reacts in the aqueous solution but macromolecular ligand still is small molecules, always can not avoid segregation completely.And in soap, because lipid acid itself has the effect of Synergist S-421 95 and tensio-active agent, each metal ion species is can blended very even.Owing in this way, do not have the existence of water, avoided the hydrolytic precipitation segregation phenomena of metal ion, thereby can obtain superfine, the nanocatalyst of high dispersive.And the catalyzer of nano level high dispersive is the key that obtains the high quality carbon nanotube.When containing VIb family, Mn, Re, Rb element in the catalyzer, can improve the dispersity of iron, cobalt, nickel element in addition.It is simple, easy to operate, with short production cycle that this method is produced catalyst equipment, suitable industrialized production.Especially under the catalyst elements proportion of composing of optimizing, the catalyzer that this method obtains can be used for producing high-quality Single Walled Carbon Nanotube.
Below in conjunction with embodiment content of the present invention is described.
Embodiment 1:
Get CH
3(CH
2)
16COOH 60.00g is placed in the 100ml beaker, is heated to 100 ℃, stirs fusion 20min.Add Co (CH
3COO)
2.4H
2O 1.24g, Mg (CH
3COO)
2.4H
2O 20.00g continues to stir 2 hours, emits pungent gas when stirring.Cool to room temperature obtains a homogeneous gel.Put into retort furnace, 600 ℃ are burnt 40min, just obtain a beige catalyzer.This catalyzer is at 850 ℃, H
280ml/min, CH
440mi/min reacts half an hour in the silica tube of diameter 3cm.Gained black product is high-quality Single Walled Carbon Nanotube through transmission electron microscope observing.Accompanying drawing is represented the pattern of this catalyzer gained carbon nanotube, and wherein scale is 20nm, and diameter of single-wall carbon nano tube is at 0.7-3nm, length at tens of microns at hundreds of microns.Except single-walled pipe also has a small amount of double-walled and multi-walled carbon nano-tubes, wherein single-walled pipe purity is greater than 75%.0.1043 the gram catalyzer obtains the black product that 0.1116 gram contains catalyzer.
Embodiment 2:
CH
3(CH
2)
16COOH 60.00g is placed in the 100ml beaker, is heated to 100 ℃, stirs fusion 20min.Add Co (CH
3COO)
2.4H
2O 1.24g, Mg (CH
3COO)
2.4H
2O 20.00g, ((CH
3COO)
2Mo)
20.21g. continue to stir 2 hours, when stirring, emit pungent gas.Cool to room temperature obtains a homogeneous gel.Put into retort furnace, 500 ℃ are burnt 60min, just obtain catalyzer.This catalyzer is at 750 ℃, H
280ml/min, CH
3CH
2OH 20mi/min, reaction is 1 hour in the silica tube of diameter 3cm.Gained black product is the single-walled pipe of diameter less than 3nm through the transmission electron microscope observing main body, and the decolorizing carbon of doing the resulting product of carbon source with alcohol lacks than methane simultaneously.0.1241 the gram catalyzer obtains the black product that 0.1750 gram contains catalyzer.
Embodiment 3:
CH
3(CH
2)
16COOH 120.00g is placed in the 200ml beaker, is heated to 100 ℃, stirs fusion 20min.Add Al (NO
3)
3.9H
2O 37.51g, Fe (NO
3)
3.9H
2O 1.26g, Ni (NO
3) .6H
2O 0.73g. continues to stir 2 hours, emits pungent gas when stirring.Cool to room temperature obtains a homogeneous gel.Put into retort furnace, 400 ℃ are burnt 8hours, just obtain catalyzer.This catalyzer is at 950 ℃, H
280ml/min, C
2H
420mi/min reacts half an hour in the silica tube of diameter 3cm.Gained black product is the single-walled pipe of diameter less than 3nm through the transmission electron microscope observing main body.0.1348 the gram catalyzer obtains the black product that 0.1685 gram contains catalyzer.
Embodiment 4:
Is 1: 6 by Fe in the catalyst product in Si, takes by weighing Fe (NO
3)
3.9H
2O and TEOS.Under agitation earlier with Fe (NO
3)
3.9H
2O joins in the stearic acid fusing, and dehydration fully adds TEOS then, and after 2 hours, naturally cooling becomes gel in 100 ℃ of stirrings.Burnt 5 hours in 700 ℃ again, just obtain catalyzer.Get this catalyzer 2.45 grams, prior to 700 ℃ of reduction half an hour in the hydrogen of 200ml/min, the back obtains the carbon nanotube of 5-20nm in 750 ℃ of CO that feed 400ml/min.Weigh behind the purifying, obtain 4.96 gram carbon nanotubes.The carbon nanotube tube wall is thinner.
Embodiment 5:
Get CH
3(CH
2)
10COOH 45.00g is placed in the 100ml beaker, is heated to 100 ℃, stirs fusion 20min.Add Co (CH
3COO)
2.4H
2O 1.24g, Mg (CH
3COO)
2.4H
2O 20.00g continues to stir 2 hours, emits pungent gas when stirring.Cool to room temperature obtains a homogeneous gel.Put into retort furnace, 500 ℃ are burnt 40min.This catalyzer is at 850 ℃, H
280ml/min, CH
440mi/min reacts half an hour in the silica tube of diameter 3cm.Gained black product is high-quality Single Walled Carbon Nanotube through transmission electron microscope observing.Wherein the carbon nanotube main body is the single-walled pipe that diameter is no more than 3nm, length at tens of micron at hundreds of microns.0.2137 the gram catalyzer obtains the black product that 0.2311 gram contains catalyzer.
Claims (9)
1. one kind is used for carbon nanotube synthetic Preparation of catalysts method, is that handle contains at least a VIII family metal fatty acid salt presoma 200 ℃-1200 ℃ heating 5 minutes-10 hours, thereby obtains the catalyzer of suitable carbon nanotube growth.
2. according to the process of claim 1 wherein its mixture of soap that contains Co, Ni, Fe, Ru, Rh, Pd, Ir, Pt in the presoma.
3. according to each method of claim 1-2, wherein further contain the silicon that is dissolved in soap, magnesium, group of the lanthanides, compound of aluminium element and composition thereof in the presoma.
4. each method of claim 1-3, wherein the carbon nanotube of resulting Catalyst Production comprises multi-walled carbon nano-tubes.
5. sharp each method that requires 1-3, wherein in the presoma mol ratio of the mol ratio of VIII family metallic element and non-VIII family metallic element between 0.005-0.1.
6. according to the method for claim 5, wherein the carbon nanotube that makes of the catalyzer that is produced further contains Single Walled Carbon Nanotube.
7. according to each method of claim 5-6, in the soap presoma of VIII family, further be dissolved with compound of the VIb family of in catalyzer, playing katalysis, Mn, Re, Rb and composition thereof.
Claim 5 or 7 each method, wherein the catalyzer of gained can be used for obtaining the Single Walled Carbon Nanotube of purity 60%-99%.
9. according to each method of claim 1-8, wherein soap is the salt of palmitinic acid, stearic acid, laurostearic acid, TETRADECONIC ACID.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531362B (en) * | 2009-04-17 | 2010-11-10 | 北京化工大学 | Method for one-step growth of carbon nanotube by taking carbon composite as catalyst |
| CN102610827A (en) * | 2012-03-28 | 2012-07-25 | 长沙星城微晶石墨有限公司 | Conductive additive for preparing power lithium ion battery cathode material and preparation method thereof |
| JP2015030792A (en) * | 2013-08-02 | 2015-02-16 | 東洋インキＳｃホールディングス株式会社 | Resin composition |
| CN105645377A (en) * | 2015-12-29 | 2016-06-08 | 深圳市纳米港有限公司 | High-conductivity and easy-dispersion carbon nanotube and preparation method thereof |
| CN113277498A (en) * | 2021-05-19 | 2021-08-20 | 西北工业大学 | Transition metal-based hybrid material nanotube and preparation method and application thereof |
| CN114029050A (en) * | 2021-12-13 | 2022-02-11 | 复旦大学 | Synthesis method of supported high-load carbon-coated noble metal nanoparticle catalyst |
| CN115432695A (en) * | 2022-10-10 | 2022-12-06 | 四川天人化学工程有限公司 | Method for manufacturing carbon nano tube by replacing methane with high-concentration carbon monoxide |
-
2004
- 2004-05-21 CN CN 200410022571 patent/CN1699620A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531362B (en) * | 2009-04-17 | 2010-11-10 | 北京化工大学 | Method for one-step growth of carbon nanotube by taking carbon composite as catalyst |
| CN102610827A (en) * | 2012-03-28 | 2012-07-25 | 长沙星城微晶石墨有限公司 | Conductive additive for preparing power lithium ion battery cathode material and preparation method thereof |
| JP2015030792A (en) * | 2013-08-02 | 2015-02-16 | 東洋インキＳｃホールディングス株式会社 | Resin composition |
| CN105645377A (en) * | 2015-12-29 | 2016-06-08 | 深圳市纳米港有限公司 | High-conductivity and easy-dispersion carbon nanotube and preparation method thereof |
| CN105645377B (en) * | 2015-12-29 | 2018-11-13 | 深圳市纳米港有限公司 | Highly conductive easy dispersing Nano carbon tubes and preparation method thereof |
| CN113277498A (en) * | 2021-05-19 | 2021-08-20 | 西北工业大学 | Transition metal-based hybrid material nanotube and preparation method and application thereof |
| CN113277498B (en) * | 2021-05-19 | 2023-10-27 | 西北工业大学 | Transition metal-based hybrid material nanotube and preparation method and application thereof |
| CN114029050A (en) * | 2021-12-13 | 2022-02-11 | 复旦大学 | Synthesis method of supported high-load carbon-coated noble metal nanoparticle catalyst |
| CN114029050B (en) * | 2021-12-13 | 2022-10-11 | 复旦大学 | Synthesis method of supported high-load carbon-coated noble metal nanoparticle catalyst |
| CN115432695A (en) * | 2022-10-10 | 2022-12-06 | 四川天人化学工程有限公司 | Method for manufacturing carbon nano tube by replacing methane with high-concentration carbon monoxide |
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