CN1150985C - Transition metal oxide/silicon dioxide nano composite powder body catalyst, its synthesis method and carbon nano tube prepared by using said catalyst - Google Patents
Transition metal oxide/silicon dioxide nano composite powder body catalyst, its synthesis method and carbon nano tube prepared by using said catalystInfo
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- CN1150985C CN1150985C CNB021346666A CN02134666A CN1150985C CN 1150985 C CN1150985 C CN 1150985C CN B021346666 A CNB021346666 A CN B021346666A CN 02134666 A CN02134666 A CN 02134666A CN 1150985 C CN1150985 C CN 1150985C
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- catalyst
- transition metal
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- composite powder
- silicon dioxide
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Abstract
The present invention relates to a synthetic method for a transition metal oxide / silicon dioxide nanometer composite powder catalyst. A precursor hydrothermal method is used for synthesis. The catalyst is used for preparing a carbon nanometer tube, and the catalyst is filled in a quartz tube of a catalyst bed. The catalyst is heated to 500 to 600 DGE C under the condition of inert gas. Hydrogen gas is introduced for reducing for 0.4 to 1.5 hours. When the temperature is from 630 to 780 DEGC, acetylene and the hydrogen gas are introduced at the flow speed of 40 to 200 ml / min, the volume ratio of the acetylene to the hydrogen gas is 9: 1 to 1: 1, and the cracking reaction is generated to synthesize the carbon nanometer tube, and the reaction time is from 0.5 to 1.0 hour. The catalyst can be used for preparing a carbon nanometer tube which has the advantages of high production rate, small tube diameter and narrow distribution range.
Description
Technical field
The invention belongs to the nano material preparation technical field, more particularly, relate to a kind of transition metal oxide/silicon dioxide nano composite powder body catalyst and synthetic method thereof, and this catalyst is used to prepare the method for CNT.
Background technology
CNT has been a kind of new function material and structural material of excellent performance by generally acknowledging in the world, can be used as high density hydrogen storage material, high strength composite, fine definition FPD, nano-device and electromagnet absorbing material etc.At present, preparation CNT method mainly contains three kinds of catalystic pyrolysis, arc process and laser evaporation methods.Catalystic pyrolysis prepares CNT need use transition metal (Ni, Co, Fe) or its compound as catalyst usually, effective dispersion of catalyst granules and scale size are one of key factors of synthetic carbon nanotube, and the synthetic catalyst powder dispersiveness of at present usually used sol-gel atmosphere pressure desiccation is relatively poor, particle diameter is bigger and inhomogeneous, thereby the CNT productive rate that makes is lower, caliber is big, distribution is wide etc.
Summary of the invention
The object of the present invention is to provide a kind of transition metal oxide/silicon dioxide nano composite powder body catalyst, be used to prepare that productive rate height, caliber are little, the CNT of narrow distribution range;
Another object of the present invention is to provide the synthetic method of above-mentioned catalyst;
Another object of the present invention is to provide above-mentioned catalyst to be used to prepare the method for CNT.
Transition metal oxide/silicon dioxide nano composite powder body catalyst of the present invention adopts sol-gel process and hydro-thermal method to synthesize.
The synthetic method of catalyst of the present invention comprises the steps:
(1) be that 1: 6～1: 16 molar ratio is mixed with mixed solution with organosilicon and the transition metal nitrate aqueous solution by element silicon and transition metal, stir more than 10 hours, adding and transition metal mol ratio are 3: 1～10: 1 precipitating reagent, continue to stir 3～15 hours, form transition metal hydroxide and silica mixed gel after still aging 6～24 hours, the binary gel gets binary colloidal through washing, suction filtration;
(2) (1) gained binary colloidal is put into autoclave, add deionized water, the volume compactedness is 50%～85%, power supply is connected in the airtight back of autoclave, is warming up to 200～250 ℃ with 30～80 ℃/hour speed, insulation reaction 3～6 hours, slowly venting, the nature of cutting off the electricity supply simultaneously is cooled to room temperature, takes out sample, promptly gets the transition metal oxide/silicon dioxide composite powder body catalyst;
Wherein said organosilicon is ethyl orthosilicate, chromatographic silica gel; Transition metal is nickel or cobalt or iron; Precipitating reagent is an aqueous slkali.
The synthetic method of catalyst of the present invention, preferred precipitating reagent is ammoniacal liquor, NaOH, potassium hydroxide solution.
Effect was preferable when the synthetic method of catalyst of the present invention, stir speed (S.S.) were 150 rev/mins～700 rev/mins.
Catalyst of the present invention prepares the method for CNT by catalystic pyrolysis, that is: catalyst is put in the catalytic bed quartz ampoule, be heated to 500～600 ℃ under the atmosphere of inert gases, logical hydrogen reducing 0.4～1.5 hour, when temperature reaches 630～780 ℃, feeding volume ratio with the flow velocity of 40～200 ml/min is 9: 1～1: 1 acetylene and hydrogen, makes its cracking synthesizing carbon nanotubes, reacts 0.5～1.0 hour.
The above-mentioned method for preparing CNT, when feeding acetylene and hydrogen, temperature is preferably 680～730 ℃; The volume ratio of acetylene and hydrogen is preferably 3: 1～and 1: 1.
The present invention compared with prior art has the following advantages:
(1) little, the good dispersion of the catalyst powder particle that makes of hydro-thermal method, catalytic activity height, therefore the CNT diameter narrowly distributing that makes by this catalyst, caliber is little, purity is high; Prepared CNT external diameter is 10～35 nanometers.
(2) use the Hydrothermal Preparation catalyst powder, technology is simple, and equipment investment is few; In the preparation process of carbon pipe, used reaction gas is the cheapest acetylene gas of carbonaceous gas price, so prepare CNT with method of the present invention, cost is low, and is easy to operate, is suitable for industrialization and amplifies popularization.
The specific embodiment
Embodiment 1:
1, synthetic catalyst
(1) with ethyl orthosilicate and nickel nitrate aqueous solution silicon in molar ratio: nickel is in room temperature under to mix at 1: 8, stirs 12 hours, slowly splashes into weak aqua ammonia (nickel, ammonia mol ratio are 1: 6), stir again to leave standstill each washing, suction filtration after 12 hours, the binary colloidal predecessor.
(2) binary colloidal is placed in the autoclave through the washing suction filtration, adds deionized water, and still cavity compactedness 60% is warming up to 200 ℃ with 80 ℃/hour speed then, is incubated 3 hours, makes NiO
2/ SiO
2Composite powder body catalyst.
2, preparation CNT
Get 100 milligrams of catalyst, be warming up to 550 ℃ under the nitrogen atmosphere, logical hydrogen reducing 0.5 hour, (acetylene: hydrogen=2: 1), reaction gas flow speed 75 ml/min were reacted 0.5 hour to feed reaction gas in the time of 700 ℃, get 50 milligrams of products (having deducted catalyst), contain 30% CNT in the product, caliber 10-18 nanometer, majority is 15 nanometers.
Embodiment 2:
Identical with step with embodiment 1 other condition, change mixed solution silicon, nickel mol ratio are 1: 12, and nickel, ammonia mol ratio are 1: 9, and the medium compactedness is 70% in the still, and hydrothermal temperature is 230 ℃, makes NiO/SiO
2Composite powder body catalyst.
Get 210 milligrams of products (having deducted catalyst), carbon nanotubes is (promptly seldom amorphous carbon generates) more than 90%, caliber 10-23 nanometer, and majority is 20 nanometers.
Embodiment 3:
Identical with embodiment 2 other conditions with step, change silicon, the nickel mol ratio is 1: 14,170 milligrams of products ((having deducted catalyst)), carbon nanotubes is more than 85%, caliber 10-30 nanometer, majority is 25 nanometers.
Embodiment 4:
Identical with step with embodiment 2 other conditions, raw material is a cobalt nitrate, gets 140 milligrams of products (having deducted catalyst), carbon nanotubes 65%, and caliber 15-30 nanometer, majority is 30 nanometers.
Embodiment 5:
Identical with step with embodiment 2 other conditions, raw material is a ferric nitrate, gets 100 milligrams of products (having deducted catalyst), carbon nanotubes 50%, and caliber 15-28 nanometer, majority is 28 nanometers.
Embodiment 6:
Identical with step with embodiment 2 other conditions, changing precipitating reagent is NaOH, gets 200 milligrams of products (having deducted catalyst), carbon nanotubes 60%, and caliber 20-35 nanometer, majority is 35 nanometers.
Comparative Examples 1:
Identical with embodiment 1 other condition, step, only change step (2) and be atmosphere pressure desiccation, be about to behind the binary colloidal washing suction filtration in normal pressure to be warming up to 500 ℃ of calcinings 3 hours down earlier 80 ℃ of dryings 3 hours, grind through cooling and make catalyst powder; Use the Preparation of Catalyst CNT, get 80 milligrams of products (having deducted catalyst), carbon nanotubes 30%, caliber are distributed as the 20-60 nanometer, average about 40 nanometers of caliber.
Claims (7)
1, a kind of synthetic method of transition metal oxide/silicon dioxide nano composite powder body catalyst, it is characterized in that its synthetic method step is: (1) is that 1: 6～1: 16 molar ratio is mixed with mixed solution with organosilicon and the transition metal nitrate aqueous solution by element silicon and transition metal, stir more than 10 hours, adding and transition metal mol ratio are 3: 1～10: 1 precipitating reagent, continue to stir 3～15 hours, form the hydroxide and the silica mixed gel of transition metal after still aging 6～24 hours, the binary gel is through washing, suction filtration gets binary colloidal; (2) the prepared binary colloidal of step (1) is put into autoclave, add deionized water, the volume compactedness is 50%～85%, power supply is connected in the airtight back of autoclave, is warming up to 200～260 ℃ with 30～80 ℃/hour speed, insulation reaction 3～6 hours, slowly venting, the nature of cutting off the electricity supply simultaneously is cooled to room temperature, takes out sample, promptly gets the transition metal oxide/silicon dioxide composite powder body catalyst.Wherein said organosilicon is ethyl orthosilicate, chromatographic silica gel; Transition metal is nickel or cobalt or iron; Precipitating reagent is an aqueous slkali.
2, the synthetic method of catalyst according to claim 1, it is characterized in that described precipitating reagent be ammoniacal liquor, NaOH, potassium hydroxide solution wherein one or more.
3, the synthetic method of catalyst according to claim 1 is characterized in that the speed that stirs is 150 rev/mins～700 rev/mins.
4, the synthetic catalyst of the described method of claim 1.
5, the described catalyst of claim 4 is used to prepare the method for CNT, it is characterized in that catalyst is placed in the catalytic bed quartz ampoule, be heated to 500～600 ℃ under the atmosphere of inert gases, logical hydrogen reducing 0.4～1.5 hour, when temperature reaches 630～780 ℃, feeding volume ratio with the flow velocity of 40～200 ml/min is 9: 1～1: 1 acetylene and hydrogen, makes its cracking synthesizing carbon nanotubes, reacts 0.5～1.0 hour.
6, the method for preparing CNT according to claim 5, the temperature that it is characterized in that feeding the gaseous mixture reaction is 680～730 ℃.
7,, it is characterized in that feeding volume ratio and be 3: 1～1: 1 acetylene and hydrogen according to claim 5 or the 6 described methods that prepare CNT.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021346666A CN1150985C (en) | 2002-09-06 | 2002-09-06 | Transition metal oxide/silicon dioxide nano composite powder body catalyst, its synthesis method and carbon nano tube prepared by using said catalyst |
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| CNB021346666A CN1150985C (en) | 2002-09-06 | 2002-09-06 | Transition metal oxide/silicon dioxide nano composite powder body catalyst, its synthesis method and carbon nano tube prepared by using said catalyst |
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| CN1400049A CN1400049A (en) | 2003-03-05 |
| CN1150985C true CN1150985C (en) | 2004-05-26 |
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| CN1318298C (en) * | 2004-11-12 | 2007-05-30 | 中国科学院兰州化学物理研究所 | Synthesis process of nanometer mesoporous gold complex |
| CN102240540B (en) * | 2011-05-11 | 2012-10-17 | 北京化工大学 | Flaky gallium-containing nano photocatalyst and use thereof in light degradation of organic pollutants |
| CN106435210A (en) * | 2016-09-27 | 2017-02-22 | 宁波大地化工环保有限公司 | Preparation method of trapping agent special for precious metal |
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