CN1182026C - Process for preparing Fe-series catalyst used to synthesize nano carbon tubes - Google Patents
Process for preparing Fe-series catalyst used to synthesize nano carbon tubes Download PDFInfo
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- CN1182026C CN1182026C CNB021007098A CN02100709A CN1182026C CN 1182026 C CN1182026 C CN 1182026C CN B021007098 A CNB021007098 A CN B021007098A CN 02100709 A CN02100709 A CN 02100709A CN 1182026 C CN1182026 C CN 1182026C
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- iron
- nano carbon
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- carbon tubes
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 229910021392 nanocarbon Inorganic materials 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000002360 preparation method Methods 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 238000004062 sedimentation Methods 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002075 main ingredient Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 24
- 239000002041 carbon nanotube Substances 0.000 abstract description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000151 deposition Methods 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 239000003990 capacitor Substances 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 159000000014 iron salts Chemical class 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 241001460678 Napo <wasp> Species 0.000 description 6
- 239000011943 nanocatalyst Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002159 nanocrystal Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004050 hot filament vapor deposition Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Abstract
The present invention relates to a preparation method of an iron-based catalyst used for synthesizing carbon nanotubules, which relates to the preparation of the iron-based catalyst used for synthesizing the carbon nanotubules in a gas-phase catalytic deposition method. The preparation method uses inorganic iron salts and carbonate as main raw materials, and liquid-phase coprecipitation reactions are carried out at 25 to 80 DEG C under the condition of the existence of a few of water-soluble dispersing agents to generate intermediate precipitates with high dispersibility. An obtained suspension is hydrothermally modified at 105 to 150 DEG C, then, the precipitates are filtered, washed and roasted at 300 to 800 DEG C in an air atmosphere, and the high-dispersibility catalyst whose particle size is from 3 to 10 nm and specific surface area is from 150 to 350m<2>/g is prepared, wherein the main constituent of the high-dispersibility catalyst is iron (Fe, Co, Ni)-based oxide. The catalyst preparation technology has the advantages of simplicity, low cost and easy industrial popularization, and carbon nanotubes prepared by the catalyst synthesized by the preparation method have the advantages of thin tube wall and small and uniform tube diameter (3 to 10 nm); the carbon nanotubes can be used for preparing high-strength conductive composite materials, super capacitor elements, field emission materials, hydrogen storage materials, novel catalysts, etc.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method, particularly a kind of preparation method who is used for the Fe-series catalyst of catalytic chemical vapor deposition technique synthesize nano carbon tubes belongs to the inorganic chemical technology technical field.
Background technology
Nanometer powder is meant that particle size is the powdered material of 1-100nm.The special construction level of nano material makes it have surface effects, volume effect, quantum size effect and macro quanta tunnel effect etc., thereby have a series of novel physical, chemical property, comprising in the various fields of chemical industry having great application value.A large amount of interfaces is for example arranged in nano material, and these interfaces provide the short-range diffusion approach for atom, so nano material has higher activity and diffusivity, and performances such as chemical reaction, creep, superplasticity are had remarkable influence.Nanoparticle is made catalyzer because surfactivity is many, can improve speed of reaction greatly; In rubber, add nano material and can improve its wear resistance and dielectric characteristics; In plastics, add nano material and can improve its intensity and toughness.The nano-powder structured material can carry out sintering, doping, miscible at a lower temperature, forms advanced composite material.
The preparation of carbon nanotube is the research focus of domestic and international in recent years material and chemical circles.Carbon nanotube is owing to have particular structure and performance, and application prospect is very tempting:
1. carbon nanotube is the best field emmision material of performance up to now, can be used for making flat-panel monitor.
2. because carbon nanotube has conductor and characteristic of semiconductor, make electron devices such as diode with it, be expected to bring new leap to the microminiaturization and the high speed of computer industry.
3. can be used for making biosensor and biosensor at life science.
4. carbon nanotube is present best hydrogen storage material, and this will bring glad tidings to fuel cell car and other energy storage device.
5. utilize its huge specific surface area can make ultracapacitor.
But 6. mix the different matrix material of component property etc. with various metals, nonmetal and macromolecular material.
One of gordian technique of made of carbon nanotubes is the controlled preparation of nanocatalyst, and the carbon nanotube exterior appearance and the internal performance of different nanocatalyst preparations are all different.Carbon current nano tube catalyst preparation method is based on liquid chemical method (comprising hydrolysis of alkoxide, sol-gel, urea decomposition, co-precipitation and microemulsion method etc.).The characteristics of liquid chemical method are that process is simple, raw material is easy to get, with low cost, be easy to realize suitability for industrialized production.Because caliber, wall thickness and the winding degree of carbon nanotube are all relevant with particle diameter, composition and the dispersity of nanocatalyst, ultra-fine, the high-dispersion nano catalyzer that therefore obtains definite composition is the key and the prerequisite of preparation high-performance carbon nanotube.Up to now the nanocatalyst of being reported is subjected to the restriction of particle diameter and dispersity, can only be used for preparing the common carbon nanotube of caliber mostly greater than 10nm, and wall thickness, caliber thickness inequality, often with impurity such as agraphitic carbons, the also very outstanding (Y.D.Li of wrapping phenomena, J.L.Chen, L.Chang, et.al.Feitknecht CompoundUsed as the Precursor of the Catalyst for the Catalytic Growth of Fibers from Methane, Studies in Surface Science and Catalysis, 1998,118 (1-4): 321-329; V.Ivanov, A.Fonseca, J.B.Nagy, et.al.Catalytic Production and Purification of Nanotubules HavingFullerens-scale Diameters, Catalytic Production and Purification of Nanotubules, 1995,132 (8): 1727-1737.); Though the report of straight tube or single-walled pipe is arranged, all adopt physical method to make, caliber big (＞10 μ m), small scale, efficient low (Xie Sishen, Pan Zhengwei, the preparation of superlong directional carbon nanotube array, physics, 1999,28 (1): 1-3; H.Zhang, k.Chen, Y.He, et.al.Formation and Raman Spectroscopy of SingleWall Carbon Nanotubes Synthesized by co
2Continuous Laser Vaporization, Journal ofPhysics and Chemistry of Solids, 2001,62 (11): 2007-2010.).Utilize a large amount of preparations of high dispersive superfine nano catalyzer evenly, the work of thin-walled, the nano carbon tubes that do not twine substantially do not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used for the inorganic iron series catalysts of the even thin-walled nano carbon tubes of catalytic chemical vapor deposition technique production, this method technology is simple, easy to operate, with low cost, by this method synthetic catalyzer can be used to prepare evenly, thin-walled, caliber be less than 10nm, the nano carbon tubes that do not twine substantially.
The objective of the invention is to be achieved through the following technical solutions:
1. be that salt is main raw material with inorganic water-soluble iron, carbonate is precipitation agent, under the water soluble dispersing agent existence condition, be carried out at 25-80 ℃ and carry out the liquid phase coprecipitation reaction, generate high dispersive intermediate sedimentation thing, wherein: inorganic water-soluble iron is that salt and carbonate solution concentration are 5-20% (w/v), and the water soluble dispersing agent strength of solution is 1-5% (w/v);
2. place the autoclave of 105-150C to carry out hydrothermal modification gained suspension;
3. the aaerosol solution after the above-mentioned modification is filtered, washs and drying;
4. with the roasting in 300～800 ℃ of air atmosphere of dried intermediate sedimentation thing, can make its granularity less than 10 nanometers, specific surface area 150-350m
2/ g, main ingredient is a ferrous oxide, the ferrous oxide mass percentage content is the dispersed catalysts of 70-95%.
Employed inorganic water-soluble iron is that salt is iron(ic) chloride, nickelous chloride, cobalt chloride among the present invention, any in iron nitrate, nickelous nitrate, the Xiao Suangu; Carbonate is any in yellow soda ash, volatile salt, the bicarbonate of ammonia.Employed water soluble dispersing agent is Sodium hexametaphosphate 99 ((NaPO
3)
6), ethanol (CH
3CH
2OH), water glass (Na
2OSiO
2), Sodium dodecylbenzene sulfonate (C
18H
19SO
3Na), Tai-Ace S 150 (Al
2(SO
4)
3) in any.
Above-mentioned Fe-series catalyst is placed the poly-group of nanometer bed, utilize gas chemistry catalyzed reaction deposition principle, use earlier hydrogen reducing, feed gaseous hydrocarbons again and react under nitrogen protection, can make caliber is the even thin wall carbon nano-tube of 3-10nm.
The present invention is to be in the salts solution at inorganic iron, add the carbonate deposition agent, carry out chemical reaction and hydrothermal treatment consists under the water soluble dispersing agent existence condition, forming insoluble inorganic iron is the salt throw out, after filtration, washing, drying and thermolysis get product---and inorganic iron is a salt catalyst.Whole catalyst preparation process technology is simple, easy to operate, with low cost, be easy to realize scale operation.Liquid phase dispersion-hydrothermal modification-characteristic technologies such as medium temperature roast that the present invention adopts have guaranteed the granularity and the polymolecularity of nanocatalyst, make the macro preparation of nano carbon tubes become possibility.With the catalyst particle size of this simple and easy method preparation less than 10 nanometers, specific surface area 150-350m
2/ g.This catalyzer can be used for the even thin-walled nano carbon tubes of catalytic chemical vapor deposition technique scale operation, the nano carbon tubes of preparation is even, wall is thin, diameter little (3～10nm), agraphitic carbon is less, do not twine substantially.The nano carbon tubes of the present invention's preparation can be used for preparing high performance composite, ultracapacitor, diode, field emmision material, biosensor etc., has a extensive future.
Description of drawings
Fig. 1: produce preparation technology's schematic flow sheet of the Fe-series catalyst of nano carbon tubes for being used for the gas phase catalysis sedimentation.
Fig. 2: the transmission electron microscope pattern of expression embodiment 1 gained catalyzer.
Fig. 3: the transmission electron microscope pattern of expression embodiment 1 gained nano carbon tubes.
Fig. 4: the transmission electron microscope pattern of expression embodiment 3 gained catalyzer.
Fig. 5: the transmission electron microscope pattern of expression embodiment 3 gained nano carbon tubes.
Embodiment
This technology is with inorganic iron system's (Fe, Co, Ni) salt and carbonate (Na
2CO
3, (NH
4)
2CO
3, NH
4HCO
3) be main raw material, at water soluble dispersing agent (NaPO
3)
6, CH
3CH
2OH, Na
2OSiO
2, C
18H
19SO
3Na, Al
2(SO
4)
3) carry out coprecipitation reaction in 25-80 ℃ under the existence condition, generate high dispersive intermediate sedimentation thing; Then middle suspension is carried out hydrothermal treatment consists, to improve the particulate dispersiveness.Product behind the hydrothermal modification after filtration, washing back in the air atmosphere of lesser temps 300-800 ℃ (wherein especially to be good below 600 ℃) roasting 1-5 hour, making the high dispersive inorganic iron thus is the composite salt nanocatalyst.Its concrete operations step is as follows:
1. compound concentration is that the inorganic water-soluble iron of 5-20% (w/v) is a salts solution respectively, concentration is that carbonate solution and the concentration of 1-5% (w/v) is the water soluble dispersing agent of 1-5% (w/v), and wherein: inorganic iron is that the volume ratio of salt, carbonate and water soluble dispersing agent solution is 1: 1: 0.5;
2. under room temperature, stirring (800rpm) state, water soluble dispersing agent solution is added in the carbonate solution;
3. be that salts solution is warming up to 25-80 ℃ of reaction 1-5 hour with inorganic iron, constant temperature progressively adds the mixing solutions of carbonate and water soluble dispersing agent then under whipped state, the adding speed of mixing solutions is 5-20ml/min, the reinforced follow-up continuation of insurance temperature that finishes stirred 2 hours, then stopped reaction;
4. suspension in the middle of the gained is placed 105-150 ℃ autoclave to handle 1-4 hour, carry out hydrothermal modification;
5. the gained aaerosol solution is filtered, use deionized water and washing with alcohol respectively, under air atmosphere, placed then under 105 ℃ the condition dry 4 hours;
6. dried intermediate sedimentation thing is placed in the retort furnace,, can obtain its granularity less than 10 nanometers, specific surface area 150-350m at 300～800 ℃ of following roasting 1-5 hours
2/ g contains the nano crystal iron series catalysts of (70-95% (m)) ferrous oxide.
Describe content of the present invention in detail below in conjunction with specific embodiment.
Embodiment 1:
Preparation 5% (w/v) NiCl
2Solution 100ml, 5% (w/v) NH
4HCO
3Solution 100ml, 1% (w/v (NaPO
3)
650ml.Under room temperature, stirring (800rpm) state with (NaPO
3)
6Solution joins NH
4HCO
3In the solution, (NaPO
3)
6It is 10ml/min that solution adds speed.With NiCl
2Constant temperature after solution is warming up to 80 ℃ progressively adds NH then under whipped state
4HCO
3With (NaPO
3)
6Mixing solutions, the adding speed of solution is 5ml/min.The reinforced follow-up continuation of insurance temperature that finishes stirred 2 hours, then stopped reaction.Place 150 ℃ autoclave to carry out hydrothermal modification gained suspension and handled 2 hours, and cooled off then, filter, respectively wash 3 times with deionized water and ethanol respectively, under air atmosphere in 105 ℃ of dryings 4 hours.Dried intermediate sedimentation thing is placed in the retort furnace, and 800 ℃ of following roastings 1 hour, obtaining granularity was the nano-crystal nickel catalyzer of 10nm, and specific surface area is 150m
2/ g, be nickel oxide (85% (m)) the main composition.Fig. 2 represents the transmission electron microscope pattern of embodiment 1 gained catalyzer.
Above-mentioned catalyzer is placed the poly-group of nanometer bed, utilize gas chemistry catalyzed reaction deposition principle, use earlier hydrogen reducing, feed gaseous hydrocarbons then and react under nitrogen protection, can make caliber is the even thin wall carbon nano-tube of 10nm.Fig. 3 represents the transmission electron microscope pattern of this enforcement gained nano carbon tubes.
Embodiment 2:
Preparation 20% (w/v) Fe (NO
3)
3Solution 100ml, 20% (w/v) (NH
4)
2CO
3Solution 100ml, 5% (w/v) Na
2SiO
350ml.Under room temperature, stirring (800rpm) state with CH
3CH
2OH solution adds (NH
4)
2CO
3Solution, CH
3CH
2It is 10ml/min that OH solution adds speed.With Fe (NO
3)
3Constant temperature after solution is warming up to 25 ℃ progressively adds (NH then under whipped state
4)
2CO
3With CH
3CH
2The mixing solutions of OH, the adding speed of solution is 20ml/min.The reinforced follow-up continuation of insurance temperature that finishes stirred 2 hours, then stopped reaction.Place 105 ℃ autoclave to carry out hydrothermal modification gained suspension and handled 1 hour, and cooled off then, filter, respectively wash 3 times with deionized water and ethanol respectively, under air atmosphere in 105 ℃ of dryings 4 hours.Dried intermediate sedimentation thing is placed in the retort furnace, and 400 ℃ of roastings 2 hours, obtaining granularity was the nano crystal iron catalyzer of 3nm, and specific surface area is 350m
2/ g, be ferriferous oxide (75% (m)) the main composition.
Above-mentioned catalyzer is placed the poly-group of nanometer bed, utilize gas chemistry catalyzed reaction deposition principle, use earlier hydrogen reducing, feed gaseous hydrocarbons then and react under nitrogen protection, can make caliber is the even thin wall carbon nano-tube of 3nm.
Embodiment 3:
Preparation 10% (w/v) FeCl
3Solution 100ml, 20% (w/v) Na
2CO
3Solution 100ml, 2% (w/v) CH
3CH
250 milliliters of OH.Under room temperature, stirring (800rpm) state with C
18H
19SO
3Na solution adds Na
2CO
3Solution, C
18H
19SO
3It is 10ml/min that Na solution adds speed.With FeCl
3Constant temperature after solution is warming up to 40 ℃ progressively adds (NH then under whipped state
4)
2CO
3With C
18H
19SO
3The mixing solutions of Na, the adding speed of solution is 5ml/min.The reinforced follow-up continuation of insurance temperature that finishes stirred 2 hours, then stopped reaction.Place 120 ℃ autoclave to carry out hydrothermal modification gained suspension and handled 4 hours, and cooled off then, filter, respectively wash 3 times with deionized water and ethanol respectively, under air atmosphere in 105 ℃ of dryings 4 hours.Dried intermediate sedimentation thing is placed in the retort furnace, and 300 ℃ of following roastings 5 hours, obtaining granularity was the nano crystal iron catalyzer of 6nm, and specific surface area is 280m
2/ g, be ferriferous oxide (95% (m) the main composition.Fig. 4 represents the transmission electron microscope pattern of present embodiment gained catalyzer.
Above-mentioned catalyzer is placed the poly-group of nanometer bed, utilize gas chemistry catalyzed reaction deposition principle, use earlier hydrogen reducing, feed gaseous hydrocarbons then and react under nitrogen protection, can make caliber is the even thin wall carbon nano-tube of 6nm.Fig. 5 represents the transmission electron microscope pattern of present embodiment gained nano carbon tubes.
Embodiment 4:
Compound concentration is the Ni (NO of 10% (w/v)
3)
2Solution 100ml, 15% (w/v) (NH
4)
2CO
3Solution 100ml, 2% (w/v) CH
3CH
2OH 50ml.Under room temperature, stirring (800rpm) state with CH
3CH
2OH solution adds (NH
4)
2CO
3Solution, CH
3CH
2It is 10ml/min that OH solution adds speed.With Ni (NO
3)
2Constant temperature after solution is warming up to 60 ℃ progressively adds (NH then under whipped state
4)
2CO
3With CH
3CH
2The mixing solutions of OH, the adding speed of solution is 5ml/min.The reinforced follow-up continuation of insurance temperature that finishes stirred 2 hours, then stopped reaction.Place 120 ℃ autoclave to carry out hydrothermal modification gained suspension and handled 2 hours, and cooled off then, filter, respectively wash 3 times with deionized water and ethanol respectively, under air atmosphere in 105 ℃ of dryings 4 hours.Dried intermediate sedimentation thing is placed in the retort furnace, and 500 ℃ of following roastings 2 hours, obtaining granularity was the nano-crystal nickel catalyzer of 8 nanometers, and specific surface area is 220m
2/ g, be ferriferous oxide (92% (m)) the main composition.
Above-mentioned catalyzer is placed the poly-group of nanometer bed, utilize gas chemistry catalyzed reaction deposition principle, use earlier hydrogen reducing, feed gaseous hydrocarbons then and react under nitrogen protection, can make caliber is the even thin wall carbon nano-tube of 6nm.
Embodiment 5:
Preparation 10% (w/v) CoCl
2Solution 100ml, 15% (w/v) (NH
4)
2CO
3Solution 100ml, 5% (w/v) C
18H
19SO
3Na 50ml.Under room temperature, stirring (800rpm) state with Na
2SiO
3Solution adds (NH
4)
2CO
3Solution, Na
2SiO
3It is 10ml/min that solution adds speed.With CoCl
2Constant temperature after solution is warming up to 60 ℃ progressively adds (NH then under whipped state
4)
2CO
3With Na
2SiO
3Mixing solutions, the adding speed of solution is 5ml/min.The reinforced follow-up continuation of insurance temperature that finishes stirred 2 hours, then stopped reaction.Place 120 ℃ autoclave to carry out hydrothermal modification gained suspension and handled 2 hours, and cooled off then, filter, respectively wash 3 times with deionized water and ethanol respectively, under air atmosphere in 105 ℃ of dryings 4 hours.Dried intermediate sedimentation thing is placed in the retort furnace, 400 ℃ of following roastings 2 hours, obtain the nanometer cobalt catalyst that granularity is 7nm, specific surface area is 245m
2/ g, be cobalt/cobalt oxide (92% (m)) the main composition.
Above-mentioned catalyzer is placed the poly-group of nanometer bed, utilize gas chemistry catalyzed reaction deposition principle, use earlier hydrogen reducing, feed gaseous hydrocarbons then and react under nitrogen protection, can make caliber is the even thin wall carbon nano-tube of 7nm.
Embodiment 6:
Preparation 10% (w/v) Co (NO
3)
2Solution 100ml, 15% (w/v) (NH
4)
2CO
3Solution 100ml, 2% (w/v) Al
2(SO
4)
350ml.Under room temperature, stirring (800rpm) state with CH
3CH
2OH solution adds (NH
4)
2CO
3Solution, CH
3CH
2It is 10ml/min that OH solution adds speed.With Co (NO
3)
2Constant temperature after solution is warming up to 60 ℃ progressively adds (NH then under whipped state
4)
2CO
3With Al
2(SO
4)
3Mixing solutions, the adding speed of solution is 5ml/min.The reinforced follow-up continuation of insurance temperature that finishes stirred 2 hours, then stopped reaction.Place 120 ℃ autoclave to carry out hydrothermal modification gained suspension and handled 2 hours, and cooled off then, filter, respectively wash 3 times with deionized water and ethanol respectively, under air atmosphere in 105 ℃ of dryings 4 hours.Dried intermediate sedimentation thing is placed in the retort furnace, and 500 ℃ of following roastings 2 hours, obtaining granularity was the nanocrystalline cobalt catalyst of 8 nanometers, and specific surface area is 260m
2/ g, be cobalt/cobalt oxide (88% (m)) the main composition.
Above-mentioned catalyzer is placed the poly-group of nanometer bed, utilize gas chemistry catalyzed reaction deposition principle, use earlier hydrogen reducing, feed gaseous hydrocarbons then and react under nitrogen protection, can make caliber is the even thin wall carbon nano-tube of 8nm.
Claims (6)
1, a kind of preparation method who is used for the Fe-series catalyst of synthesize nano carbon tubes, this method comprises the steps:
1. be that salt is main raw material with inorganic water-soluble iron, carbonate is precipitation agent, under the water soluble dispersing agent existence condition, carry out the liquid phase coprecipitation reaction in 25-80 ℃, generate high dispersive intermediate sedimentation thing, wherein: inorganic water-soluble iron is that salt and carbonate solution concentration are 5-20% (w/v), and the water soluble dispersing agent strength of solution is 1-5% (w/v);
2. place 105-150 ℃ to carry out hydrothermal modification gained suspension;
3. the aaerosol solution after the above-mentioned modification is filtered, washs and drying;
4. with the roasting in 300～800 ℃ of air atmosphere of dried intermediate sedimentation thing, can make granularity less than 10 nanometers, specific surface area 150-350m
2/ g, main ingredient is a ferrous oxide, the ferrous oxide mass percentage content is the dispersed catalysts of 70-95%.
2,, it is characterized in that carrying out the liquid phase coprecipitation reaction times in 25-80 ℃ in the step (1) is 1～5 hour according to the described preparation method who is used for the Fe-series catalyst of synthesize nano carbon tubes of claim 1.
3,, it is characterized in that the time of hydrothermal modification in the step (2) is 1～4 hour according to the described preparation method who is used for the Fe-series catalyst of synthesize nano carbon tubes of claim 1.
4,, it is characterized in that the roasting 1～5 hour in 600 ℃ of following air atmosphere of the intermediate sedimentation thing described in the step (4) according to the described preparation method who is used for the Fe-series catalyst of synthesize nano carbon tubes of claim 1.
5, according to the described preparation method who is used for the Fe-series catalyst of synthesize nano carbon tubes of the arbitrary claim of claim 1-4, it is characterized in that: described inorganic water-soluble iron is that salt is iron(ic) chloride, nickelous chloride, cobalt chloride, any in iron nitrate, nickelous nitrate, the Xiao Suangu; Carbonate is any in yellow soda ash, volatile salt, the bicarbonate of ammonia.
6, according to the described preparation method who is used for the Fe-series catalyst of synthesize nano carbon tubes of claim 1-4, it is characterized in that: described water soluble dispersing agent is any in Sodium hexametaphosphate 99, ethanol, water glass, Sodium dodecylbenzene sulfonate, the Tai-Ace S 150.
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Cited By (1)
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|---|---|---|---|---|
| WO2016140443A1 (en) * | 2015-03-04 | 2016-09-09 | 주식회사 엘지화학 | Catalyst produced by using hydrothermal synthesis coprecipitation technique, and carbon nanotube manufactured by using same |
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| KR100947702B1 (en) * | 2003-02-26 | 2010-03-16 | 삼성전자주식회사 | Method for forming a patterned film and a polymeric complex of surface-modified carbon nanotubes having polymerizable moiety |
| CN1718278A (en) * | 2004-07-09 | 2006-01-11 | 北京化工大学 | Catalyst for growth of carbon nano-tube, and its prepn. method |
| DE102006007147A1 (en) * | 2006-02-16 | 2007-08-23 | Bayer Technology Services Gmbh | Process for the continuous production of catalysts |
| CN102502580B (en) * | 2011-10-27 | 2014-08-27 | 清华大学 | Carbon nano tube array and preparation method thereof as well as application of carbon nano tube array in preparation of super capacitor |
| CN104084214A (en) * | 2014-07-21 | 2014-10-08 | 深圳市三顺中科新材料有限公司 | Catalyst for preparing carbon nanotube, preparation method of catalyst, carbon nanotube, preparation method of carbon nanotube and lithium ion battery |
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| CN107101254A (en) * | 2017-05-25 | 2017-08-29 | 四川宏名新材料科技有限公司 | A kind of CNT graphene floor heating tiles |
| CN111495381A (en) * | 2019-01-31 | 2020-08-07 | 新奥石墨烯技术有限公司 | Preparation method of flaky catalyst, flaky catalyst and application of flaky catalyst in preparation of superfine carbon nano tube |
| CN110372336B (en) * | 2019-08-19 | 2021-07-30 | 陈龙 | CoNiO2Parallel-flow coprecipitation method for thermistor powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016140443A1 (en) * | 2015-03-04 | 2016-09-09 | 주식회사 엘지화학 | Catalyst produced by using hydrothermal synthesis coprecipitation technique, and carbon nanotube manufactured by using same |
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