CN101700882A - Method for preparing carbon nano ribbon/foam carbon composite material - Google Patents
Method for preparing carbon nano ribbon/foam carbon composite material Download PDFInfo
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- CN101700882A CN101700882A CN200910309726A CN200910309726A CN101700882A CN 101700882 A CN101700882 A CN 101700882A CN 200910309726 A CN200910309726 A CN 200910309726A CN 200910309726 A CN200910309726 A CN 200910309726A CN 101700882 A CN101700882 A CN 101700882A
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Abstract
The invention relates to a method for preparing carbon nano ribbon/foam carbon composite material, belonging to the scientific and technical field of the carbon material which is the branch of the inorganic non-metallic material. Polyamide acid is used as the source of foam carbon, nickel nitrate is used as the catalyst for the growth of carbon nano ribbon, and nickel-contained composite material is prepared in the atmosphere of hydrogen with the template method by carbonization. The obtained nickel-contained composite material is used as matrix, sulfur dioxide is used as accelerator, ethylene is used as carbon nano ribbon growth source, and the carbon nano ribbon/foam carbon composite material is prepared with the chemical vapor deposition method. The carbon nano ribbon/foam carbon composite material has the structural characteristic of the solid foam and the structure and the nature of quasi two-dimensional carbon nano ribbon and can be used as the fixed-bed reactor catalyst carrier, the high-efficiency absorbent and the like.
Description
Technical field
The invention belongs to inorganic non-metallic materials science technology branch--carbon material science and technology field.The preparation method who relates to a kind of nanometer carbon ribbon/Carbon foam matrix material.
Background technology
Along with the discovery of soccerballene, people have produced great interest and have carried out extensive studies the preparation and the character thereof of nano-micrometre carbon material.Though up to the present, CNT (carbon nano-tube) and soccerballene still are the emphasis that people study, but the nano-carbon material of other patterns also causes people's great interest and has carried out a large amount of research, various novel nano-carbon materials have been obtained, as, charcoal green onion, taper charcoal, charcoal micron tree and accurate two-dimensional nano carbon material or the like.Being different from CNT (carbon nano-tube) and carbon nano fiber is the 1-dimention nano carbon material of representative, and accurate two-dimensional nano carbon material also has very big flakiness ratio (greater than an order of magnitude) except having very big slenderness ratio.Such constitutional features has been given the character of the many uniquenesses of two-dimensional nano carbon material.The accurate two-dimensional nano carbon material that obtains comprises nano-sized carbon wall, nanometer carbon plate and nanometer carbon ribbon etc., and these nano-carbon materials may have potential application in fields such as comprising electricity catalysis because of the banded pattern of its uniqueness.The nanometer carbon ribbon as a kind of accurate two-dimensional nano carbon material because of it unique texture that possesses by extensive concern.The synthetic method of carbon ribbon comprises document (Kang at present, Z.H., E.B.Wang, B.D.Mao, Z.M.Su, G.Lei, S.Y.Lian and X.Lin.Controllable fabrication of carbonnanotube and nanobelt with a polyoxometalate-assisted mild hydrothermal process.Journal of the American Chemical Society, 2005,127 (18): 6534-6535) the disclosed hydrothermal synthesis method that utilizes prepares carbon ribbon, document (Lin, C.T., T.H.Chen, T.S.Chin, C.Y.Lee and H.T.Chiu.Quasitwo-dimensional carbon nanobelts synthesized using a template method.Carbon, 2008,46 (5): 741-746.) the disclosed template of utilizing prepares carbon ribbon and document (Liu, J.W., M.W.Shao, Q.Tang, S.Y.Zhang and Y.Qian.Synthesis of carbon nanotubes and nanobeltsthrough a medial-reduction method.Journal of Physical Chemistry B, 2003,107 (26): 6329-6332.) the disclosed metallic reducing legal system of utilizing is equipped with carbon ribbon.
These methods have following shortcoming: the first, and process is complicated and be difficult to be applied to the nanometer carbon ribbon of preparation in enormous quantities.The second, the nano-carbon material that obtains exists with powdery form, and this carbon material that exists with powdery form can run into many problems in actual applications, as is difficult to reclaim, and bed pressure reduction is big etc. when being applied to fixed bed.Therefore, we need explore a kind of simple and can realize the preparation method of the nanometer carbon ribbon assembly of scale operation.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is easy to the nanometer carbon ribbon/Carbon foam matrix material of mass-producing.
Core of the present invention is the selection of carrying nickel foam carbon matrix carbonization condition and chemical vapour deposition reaction condition.Specify as follows.Polymer foam process high temperature carbonization through polyamic acid, N,N-DIMETHYLACETAMIDE and nickel nitrate solution dipping can generate and carry a nickel foam charcoal.In this process, as select suitable carbonization condition as: atmosphere, temperature rise rate and charing temperature eventually, what will obtain having the different catalysts pattern carries the nickel foam charcoal.In chemical vapor deposition processes subsequently, by in carbon source, adding the sulfurous gas of high density, can effectively regulate the pattern of the nano-carbon material of generation, make it to become the nanometer carbon ribbon.
Preparation method of the present invention comprises the steps:
(1) be that 4: 100 ratio takes by weighing nickelous nitrate in nickel/polyamic acid solid content ratio, nickelous nitrate is dissolved in polyamic acid/dimethylacetamide solution, form solution, the template foam is flooded 2-5min in above-mentioned solution, take out the template foam after flooding, squeeze out excessive polyamic acid solution, mixture foam after the extruding is put into thermostat container, dry 5-20h under 60 ℃, mixture (PU/PAA) after solidifying is placed quartz boat, under the hydrogen atmosphere condition, in tube type resistance furnace, be warming up to 700 ℃ with 1-10 ℃/min, 1h is handled in charing, obtains carrying a nickel foam charcoal after being cooled to room temperature;
The nickel foam charcoal that carries that (2) will obtain prepares nanometer carbon ribbon/Carbon foam through chemical Vapor deposition process, and process is as follows: will carry the nickel foam charcoal and place the tube furnace flat-temperature zone, protection of inert gas is warming up to 500-600 ℃, and switching gas is N
2/ H
2Gas mixture, sample reduction 30-60min, 10-20 ℃/min is warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ N
2/ SO
2/ C
2H
4(volume ratio 70: 29: 1: 50, total flux 150mL/min), after question response carried out 3-30min, gas switched to rare gas element, is cooled to room temperature, made nanometer carbon ribbon/Carbon foam.
Described nano-sized carbon strip length is the 10-200 micron, width is at the 0.5-20 micron, there is the nickel rod at the middle part of nanometer carbon ribbon, the nanometer carbon ribbon is from the both sides nucleation of nickel rod and growth in the opposite direction, and the nanometer carbon ribbon is for arranging the zonal structure that assemble along the carbon ribbon major axis with certain orientation and individual layer by many carbon nano fibers.
Described polyamic acid/dimethylacetamide solution, its polyamic acid solid content is 5-15%.
Nickel foam charcoal charing under 700 ℃ of hydrogen atmospheres in described year obtains.
The template foam is selected from polyurethane foam, melamine foamed plastic or phenolic resin foam in the described template.
Described rare gas element is selected from nitrogen, argon gas or helium.
The present invention compared with prior art has following advantage:
(1) the nanometer carbon ribbon that obtains is the banded assembly of carbon nano fiber, structure that has and performance.
(2) the nanometer carbon ribbon that obtains is covered in the Carbon foam surface, forms whole tridimensional network, and the more Powdered nanometer carbon ribbon of its macro morphology more helps reducing fixed bed pressure and falls and be easy to and reclaim.
(3) preparation process is simple, not high to equipment requirements, and parameter is controlled easily, processing ease, is easy to amplify.
Embodiment
The present invention is further described below by embodiment.
Embodiment one
(1) be that 4: 100 ratio takes by weighing nickelous nitrate in nickel/polyamic acid solid content ratio, making nickelous nitrate be dissolved in solid content is in polyamic acid/dimethylacetamide solution of 10%, form solution, polyurethane foam is flooded 2min in above-mentioned solution, take out the template foam after flooding, squeeze out excessive polyamic acid solution, mixture foam after the extruding is put into thermostat container, dry 8h under 60 ℃, mixture (PU/PAA) after solidifying is placed quartz boat, under the hydrogen atmosphere condition, in tube type resistance furnace, be warming up to 700 ℃ with 2 ℃/min, constant temperature time: 1h is cooled to and obtains carrying a nickel foam charcoal after the room temperature;
The nickel foam charcoal 0.05g that carries that (2) will obtain places the tube furnace flat-temperature zone, and protection of inert gas is warming up to 600 ℃, and switching gas is N
2/ H
2Gas mixture, sample reduction 30min, 10 ℃/min is warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ N
2/ SO
2/ C
2H
4(volume ratio 70: 29: 1: 50, total flux 150mL/min), after question response carried out 30min, gas switched to nitrogen, is cooled to room temperature, made nanometer carbon ribbon/Carbon foam.
The surface-coated dense carbon ribbon of one deck that covered of product Carbon foam, the mantle thickness degree should surpass more than 50 microns.The length of carbon ribbon can reach 500 microns, and most of carbon ribbon width is in the 2-10 micrometer range.In addition, can find shinny nickel rod significantly from the middle part of each root carbon ribbon, the nanometer carbon ribbon is from the both sides nucleation of nickel rod and growth in the opposite direction.Carbon ribbon is not to be slick one-piece construction, but arranges the zonal structure that assemble along the carbon ribbon major axis with certain orientation and individual layer by many carbon nano fibers.
Embodiment two
(1) be that 4: 100 ratio takes by weighing nickelous nitrate in nickel/polyamic acid solid content ratio, making nickelous nitrate be dissolved in solid content is in polyamic acid/dimethylacetamide solution of 15%, form solution, melamine foamed plastic is flooded 5min in above-mentioned solution, take out the template foam after flooding, squeeze out excessive polyamic acid solution, mixture foam after the extruding is put into thermostat container, dry 5h under 60 ℃, mixture (PU/PAA) after solidifying is placed quartz boat, under the hydrogen atmosphere condition, in tube type resistance furnace, be warming up to 700 ℃ with 10 ℃/min, 1h is handled in charing, obtains carrying a nickel foam charcoal after being cooled to room temperature;
The nickel foam charcoal 1g that carries that (2) will obtain places the tube furnace flat-temperature zone, and protection of inert gas is warming up to 500 ℃, and switching gas is N
2/ H
2Gas mixture, sample reduction 60min, 20 ℃/min is warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ N
2/ SO
2/ C
2H
4(volume ratio 70: 29: 1: 50, total flux 150mL/min), after question response carried out 3min, gas switched to argon gas, is cooled to room temperature, made nanometer carbon ribbon/Carbon foam.
The product nanometer carbon ribbon/Carbon foam that obtains is similar to product among the embodiment one, but the nano-sized carbon strip length is lower slightly, is the 20-100 micron, and the carbon ribbon width is starkly lower than product among the embodiment one, about the 0.5-2 micron.
Embodiment three
(1) be that 4: 100 ratio takes by weighing nickelous nitrate in nickel/polyamic acid solid content ratio, making nickelous nitrate be dissolved in solid content is in polyamic acid/dimethylacetamide solution of 15%, form solution, phenol formaldehyde foam is flooded 3min in above-mentioned solution, take out the template foam after flooding, squeeze out excessive polyamic acid solution, mixture foam after the extruding is put into thermostat container, dry 20h under 60 ℃, mixture (PU/PAA) after solidifying is placed quartz boat, under the hydrogen atmosphere condition, in tube type resistance furnace, be warming up to 700 ℃ with 5 ℃/min, 1h is handled in charing, obtains carrying a nickel foam charcoal after being cooled to room temperature;
The nickel foam charcoal 5g that carries that (2) will obtain places the tube furnace flat-temperature zone, and protection of inert gas is warming up to 500 ℃, and switching gas is N
2/ H
2Gas mixture, sample reduction 60min, 15 ℃/min is warming up to 800 ℃ under this atmosphere, and gas switches to H
2/ N
2/ SO
2/ C
2H
4(volume ratio 70: 29: 1: 50, total flux 150mL/min), after question response carried out 20min, gas switched to helium, is cooled to room temperature, made nanometer carbon ribbon/Carbon foam.
The product nanometer carbon ribbon/Carbon foam that obtains is similar to product among the embodiment one.
Claims (6)
1. the preparation method of nanometer carbon ribbon/Carbon foam matrix material is characterized in that the concrete steps of this method are as follows:
(1) be that 4: 100 ratio takes by weighing nickelous nitrate in nickel/polyamic acid solid content ratio, nickelous nitrate is dissolved in polyamic acid/dimethylacetamide solution, form solution, the template foam is flooded 2-5min in above-mentioned solution, take out the template foam after flooding, squeeze out excessive polyamic acid solution, mixture foam after the extruding is put into thermostat container, dry 5-10h under 60 ℃, mixture (PU/PAA) after solidifying is placed quartz boat, under the hydrogen atmosphere condition, in tube type resistance furnace with 1-10 ℃/min temperature programming to 700 ℃, 1h is handled in charing, obtains carrying a nickel foam charcoal after being cooled to room temperature;
Year nickel foam charcoal 0.05-5g that (2) will obtain; prepare nanometer carbon ribbon/Carbon foam through chemical Vapor deposition process; process is as follows: will carry the nickel foam charcoal and place the tube furnace flat-temperature zone; under protection of inert gas; be warming up to 500-600 ℃; switching gas is the N2/H2 gas mixture; sample reduction 30-60min; 10-20 ℃/min temperature programming to 800 ℃ under this atmosphere, mixed gas switch to H2/N2/SO2/C2H4 (volume ratio 70: 29: 1: 50, total flux 150mL/min); after question response carries out 3-30min; gas switches to rare gas element, is cooled to room temperature, makes nanometer carbon ribbon/Carbon foam.
2. the preparation method of nanometer carbon ribbon according to claim 1/Carbon foam matrix material, it is characterized in that: described nano-sized carbon strip length is the 10-200 micron, width is at the 0.5-20 micron, there is the nickel rod at the middle part of nanometer carbon ribbon, the nanometer carbon ribbon is from the both sides nucleation of nickel rod and growth in the opposite direction, and the nanometer carbon ribbon is for arranging the zonal structure that assemble along the carbon ribbon major axis with certain orientation and individual layer by many carbon nano fibers.
3. the preparation method of nanometer carbon ribbon according to claim 1/Carbon foam matrix material is characterized in that: described polyamic acid/dimethylacetamide solution, its polyamic acid solid content is 5-15%.
4. the preparation method of nanometer carbon ribbon according to claim 1/Carbon foam matrix material is characterized in that: nickel foam charcoal charing under 700 ℃ of hydrogen atmospheres in described year obtains.
5. the preparation method of nanometer carbon ribbon according to claim 1/Carbon foam matrix material, it is characterized in that: the template foam is selected from polyurethane foam, melamine foamed plastic or phenolic resin foam in the described template.
6. the preparation method of nanometer carbon ribbon according to claim 1/Carbon foam matrix material, it is characterized in that: described rare gas element is selected from nitrogen, argon gas or helium.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225337A (en) * | 2011-04-24 | 2011-10-26 | 大连理工大学 | Preparation method of foamed nanometer carbon capsule assembly and its application in catalyzing oxidative dehydrogenation of ethylbenzene |
| CN102249214A (en) * | 2011-04-27 | 2011-11-23 | 大连理工大学 | Method for loading carbon cord on surface of carbon foam |
| CN103950917A (en) * | 2014-05-07 | 2014-07-30 | 北京理工大学 | Method for preparing porous carbon material |
| CN108380206A (en) * | 2018-02-22 | 2018-08-10 | 万华化学集团股份有限公司 | A method of based on the catalyst and preparation method that carbonize polyurethane material and using the catalyst preparation cyclopentanone |
| CN110453666A (en) * | 2019-08-19 | 2019-11-15 | 中国科学技术大学 | A kind of high temperature resistant conductive porous material preparation method and high temperature resistant spilled-oil recovery unit |
| CN110572997A (en) * | 2019-08-13 | 2019-12-13 | 西安理工大学 | preparation method of novel foam carbon electromagnetic shielding composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100538963C (en) * | 2007-01-09 | 2009-09-09 | 武汉大学 | A kind of compound field-causing electron emitter and its production and use |
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2009
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225337A (en) * | 2011-04-24 | 2011-10-26 | 大连理工大学 | Preparation method of foamed nanometer carbon capsule assembly and its application in catalyzing oxidative dehydrogenation of ethylbenzene |
| CN102249214A (en) * | 2011-04-27 | 2011-11-23 | 大连理工大学 | Method for loading carbon cord on surface of carbon foam |
| CN103950917A (en) * | 2014-05-07 | 2014-07-30 | 北京理工大学 | Method for preparing porous carbon material |
| CN108380206A (en) * | 2018-02-22 | 2018-08-10 | 万华化学集团股份有限公司 | A method of based on the catalyst and preparation method that carbonize polyurethane material and using the catalyst preparation cyclopentanone |
| CN108380206B (en) * | 2018-02-22 | 2021-04-20 | 万华化学集团股份有限公司 | Method for preparing cyclopentanone through furfuryl alcohol rearrangement hydrogenation |
| CN110572997A (en) * | 2019-08-13 | 2019-12-13 | 西安理工大学 | preparation method of novel foam carbon electromagnetic shielding composite material |
| CN110572997B (en) * | 2019-08-13 | 2020-08-18 | 西安理工大学 | Preparation method of novel foam carbon electromagnetic shielding composite material |
| CN110453666A (en) * | 2019-08-19 | 2019-11-15 | 中国科学技术大学 | A kind of high temperature resistant conductive porous material preparation method and high temperature resistant spilled-oil recovery unit |
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