CN101215431B - Silicon oxide coating nano carbon composite material and preparation method thereof - Google Patents
Silicon oxide coating nano carbon composite material and preparation method thereof Download PDFInfo
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- CN101215431B CN101215431B CN2008100521075A CN200810052107A CN101215431B CN 101215431 B CN101215431 B CN 101215431B CN 2008100521075 A CN2008100521075 A CN 2008100521075A CN 200810052107 A CN200810052107 A CN 200810052107A CN 101215431 B CN101215431 B CN 101215431B
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Abstract
The invention discloses nano-carbon composite material which is coated by silicon oxide and a process for preparation, which utilizes nano-carbon basal body and organo-silicone to be raw material, and the organo-silicone is separated in high temperature on the nano-carbon basal body in gas phase to deposit and coat silicon oxide, the thickness of silicon oxide layer on a single nano-carbon tube can be led to be 5-300nm through controlling a reacting condition. The carbon basal body is nano carbon, which comprises nano-carbon fiber and a nano-carbon tube, and the diameter is between 1nm and 500 nm. The specific process for preparation comprises producing nano carbon in air current, quickly separating the organo-silicone in high temperature in the air current which contains nano carbon, and the pyrolysis temperature is between 600 DEG C and 1500 DEG C. The invention is a process which can quickly control to synthesize a large amount of coaxial nano fibers whose structures are even. The invention has the advantages of simple, high effective, high yield rate and the like.
Description
Technical field
The present invention relates to CNT (carbon nano-tube) Composite Preparation field, particularly a kind of silicon oxide coating nano carbon pipe matrix material and the method for preparing the coaxial fiber of silicon oxide enveloped carbon nanometer tube.
Background technology
Photoelectric device, biosensor and the field of energy conversion of coaxial fiber in future that coats the one-dimensional nano carbon pipe of high mechanical strength and electroconductibility with the electrical isolation silicon oxide of photolytic activity and excellent biological compatibility has important potential application.After silicon oxide is coated in carbon nano tube surface, can obviously strengthen carbon nanotube field emission performance (W.K.Yi, T.Jeong, S.G.Yu, et al,, Adv.Mater., 2002,14, p1464; ), make carbon nanotube have optionally gas-sensitive property, and can improve the high-temperature oxidation resistance of carbon nanotube.Particularly in the biologic applications field, the biocompatibility that silica coating has, can be used as the inertia protective layer of isolating CNT (carbon nano-tube) micro sensor and organism (W.G.Fan, L.Gao, Chem.Lett., 2005,34, p954-955).In addition, the silicon oxide of coating on the CNT (carbon nano-tube) surface is to be used for the ideal carrier of other functional group of chemical bond-linking and CNT (carbon nano-tube).
Chinese patent CN1904149A has reported that a kind of rapid heating organo-siloxane prepares the method for silica white nano-wire.But not the method for preparing silicon oxide coating nano carbon composite material.
The method of existing synthetic co-axial nano fiber mainly is based on liquid phase collosol and gel chemical reaction, comprises a series of complex processes such as the original CNT (carbon nano-tube) of purifying or functionalization, chemical bond-linking silicon oxide presoma, gelation and pyrolysis.The synthesis cycle of this synthetic method is longer, and is difficult for obtaining the uniform silica coating of diameter.And electrical property and mechanical property that acidifying of original CNT (carbon nano-tube) being carried out in order to realize silicon oxide evenly is coated on CNT (carbon nano-tube) surface or functionalization can influence CNT (carbon nano-tube) itself.Therefore also do not have so far a kind of not with the electrical property of sacrificing CNT (carbon nano-tube) itself and mechanical property simultaneously again can be efficiently the method for the coaxial fibers of the uniform silicon oxide enveloped carbon nanometer tube of composite structure in a large number.
Chinese patent CN1994876A has reported a kind of preparation method of nano silica dioxide granule enveloping carbon nanotube composite powder.This method is not to be that pyrolytic reaction realizes the coating of silicon oxide to carbon nanotube by liquid phase collosol and gel chemical reaction, and relates to complex chemical treatment processes such as dispersed carbon pipe.
Summary of the invention
The purpose of this invention is to provide a kind of efficient synthetic silica coating nano carbon pipe matrix material and preparation method, is that template fast pyrogenation organo-siloxane in gas-phase reaction obtains the coaxial conjugated fibre of silicon oxide coating nano carbon with the nano-sized carbon.The present invention is a kind of method of co-axial nano fiber of fast controllable synthetic a large amount of even structure, has characteristics such as easy, efficient, high yield, is particularly suitable for commercialization and prepares the co-axial nano fiber.
The invention provides a kind of preparation silicon oxide coating nano carbon composite material is to deposit on the nano-sized carbon matrix with the pyrolysis organo-siloxane to coat silicon oxide.Described carbon base body is a nano-sized carbon, comprises carbon nano fiber, CNT (carbon nano-tube), diameter 1～500nm; Silicon oxide coats bed thickness 5-300nm.
Described carbon nanotube is single wall, double-walled or multiple-wall carbon nanotube.
Described silicon oxide carbon coated nano composite material is the coaxial fiber of silicon oxide coating nano carbon pipe.
Described organo-siloxane is organic monomer or the polymkeric substance that contains Si-O main chain or skeleton structure, can be liquid, gel and solid.It is at 600～1500 ℃ of thermolytic rate massfractions at least 30%, and is preferable more than 50%.
The preparation method of silicon oxide coating nano carbon composite material provided by the invention comprises: separate organo-siloxane in the air-flow interior heat that contains nano-sized carbon, produce the silicon oxide coating nano carbon material, 600～1500 ℃ of pyrolysis temperatures.
Described organo-siloxane is sent into the air-flow pyrolysis that contains nano-sized carbon with methods such as liquid phase injection and solid phase conveyings.
Described carrier gas is hydrogen or rare gas element.
Described nano-sized carbon is growth in situ or directly introducing in air-flow.The growth in situ nano-sized carbon comprises fixed catalytic, laser method, plasma method etc. by pyrochemistry vapor phase stream method.Directly introducing is that gas phase is mixed, and gas-liquid mixed or gas-solid mix to be introduced.
Described in vapor phase stream the carbon source material of original position growing nano carbon be C
xH
yO
z, x=1～8 wherein, y=4～14, z=0～2, the best is an ethanol, ethene, toluene etc.
The catalyzer that uses during described growing nano carbon is the metal-salt that contains transition metal such as iron, cobalt, nickel.The best is a ferrocene.
The invention provides a kind of silicon oxide coating nano carbon composite material and preparation method, is that template quick cracking organic silicon oxygen alkane in gas-phase reaction obtains silicon oxide coating nano carbon composite material with the nano-sized carbon.The present invention is a kind of co-axial nano fiber of fast controllable synthetic a large amount of even structure and the method that synthetic other inorganics coating nano-sized carbon form coaxial configurations, has easyly, efficient, is easy to characteristics such as commercial applications.
Description of drawings
Fig. 1 is the used experimental installation sketch of the present invention.
The sem photograph of the silicon oxide enveloped carbon nanometer tube fiber that Fig. 2 makes for example 1 of the present invention.
The transmission electron microscope picture of the silicon oxide enveloped carbon nanometer tube fiber that Fig. 3 makes for example 2 of the present invention.
Embodiment
As shown in the figure, 1 inlet mouth, 2 sample feeding rod, 3 tongued and grooved flanges, 4 organo-siloxanes, 5 process furnace, 6 air outlets, 7 reactors.
Further specify embodiment and effect with following non-limiting example:
Example 1
After ethanol and ferrocene pressed mass ratio and mix at 80: 1, with the speed of 7ml/h, being injected into temperature was 1150 ℃, is connected with 600ml/min H
2In the reactor of air-flow, the poly-silicone resin (thermolytic rate massfraction 80%, viscosity: 2000mPa.s, 20 ℃) of 100mg dimethyl is introduced pyrolysis in the above-mentioned reactor, in reactor, grow pure white cotton-shaped product.Electron microscopic observation is the CNT (carbon nano-tube) structure that silicon oxide coats, and silicon oxide coating bed thickness 30nm (Fig. 2, Fig. 3).
Example 2
This example uses different organo-siloxanes on the basis of example 1, dimethyl silicone oil (thermolytic rate massfraction 90%).Concrete experimental procedure is identical with example 1, grows the cotton-shaped product of a large amount of grey in reactor.Electron microscopic observation, product all are the CNT (carbon nano-tube) structures that silicon oxide coats, and silicon oxide coats bed thickness 50nm.
Example 3
This example uses different organo-siloxanes on the basis of example 1; Tetraethoxysilane (thermolytic rate massfraction 95%).Concrete experimental procedure is identical with example 1, grows the cotton shape product of a large amount of grey in reactor.Electron microscopic observation, product all are the CNT (carbon nano-tube) structures that silicon oxide coats, and silicon oxide coats bed thickness 50nm.
Example 4
This example uses different organo-siloxanes on the basis of example 1; Silica carbon mixed gel is (containing hydrogen silicone oil and tetramethyl-tetrem thiazolinyl cyclotetrasiloxane mass ratio are 1: 1 mixing back cross-linking products, thermolytic rate massfraction 40%) 1..Concrete experimental procedure is identical with example 1, grows a large amount of greyish white cotton-shaped products in reactor.Electron microscopic observation, product all are the CNT (carbon nano-tube) structures that silicon oxide coats, and silicon oxide coats bed thickness 25nm
Example 5
This example uses different organo-siloxanes on the basis of example 1; The concrete experimental procedure of silicon sulfide ketone (thermolytic rate massfraction 70%) is identical with example 1, grows a large amount of greyish black cotton-shaped products in reactor.Electron microscopic observation, product partly are the CNT (carbon nano-tube) structures that silicon oxide coats, and silicon oxide coats bed thickness 50～150nm.
Example 6
This example becomes the introducing mode of CNT (carbon nano-tube) in advance on the basis of example 1 and mixes with organo-siloxane.
The 0.1mg single-wall nano-carbon tube film is pre-soaked in the poly-silicone resin (thermolytic rate massfraction 80%) of 100mg dimethyl.Being incorporated into temperature by the sample presentation device is 1150 ℃, and in the reactor of 600ml/min hydrogen stream, reaction stops the back and grow pale powder shape product in reactor.Electron microscopic observation, the CNT (carbon nano-tube) structure that exists silicon oxide to coat in its product.Wherein silicon oxide coats bed thickness 25nm.
Example 7
This example changes growing nano carbon pipe on the basis of example 1 mode is the high temperature chemical vapor deposition method of fixed catalytic.Concrete steps are for being 850 ℃ in temperature, be connected with the 500ml/min argon gas, be placed with in advance in the fixed-bed catalytic chemical gas phase pyrolysis oven of Fe/MgO catalyzer of prepared by co-precipitation, logical ethene (flow is 75ml/min), after reaction for some time, 100ml dimethyl silicone oil (thermolytic rate massfraction 90%) is incorporated into above-mentioned reactive system.The several minutes reaction finishes the back and grow the grey powdery product in reactor.Electron microscopic observation, the carbon structural nano that exists silicon oxide to coat in its product.
Example 8
This example changes the organo-siloxane pyrolysis temperature on the basis of example 6 be 800 ℃.Other concrete experimental procedures are with example 6.Its product of electron microscopic observation can be observed the CNT (carbon nano-tube) structure that silicon oxide coats.Silicon oxide coats bed thickness 50～100nm.
Example 9
This example changes the organo-siloxane pyrolysis temperature on the basis of example 6 be 1200 ℃.Other concrete experimental procedures are with example 6.Its product of electron microscopic observation can be observed the CNT (carbon nano-tube) structure that silicon oxide coats.Silicon oxide coats bed thickness 50nm.
Example 10
This example will be introduced organo-siloxane on the basis of example 3 mode is carried by sample presentation device solid phase and is changed the syringe pump gas phase into and spray into.Concrete steps adopt the gas phase mode of spraying into can realize that successive is incorporated into pyrolysis in the vapor phase stream with organo-siloxane with example 3.Its product of electron microscopic observation is mainly the CNT (carbon nano-tube) structure that silicon oxide coats.Wherein silicon oxide coats bed thickness 50nm.
Example 11
This example will be introduced organo-siloxane on the basis of example 3 mode changes the injection of hollow steel tube liquid phase into by the conveying of sample presentation device solid phase.Concrete steps adopt the liquid phase injection mode can realize that successive is incorporated into pyrolysis in the vapor phase stream with organo-siloxane with example 3.Its product of electron microscopic observation is mainly the CNT (carbon nano-tube) structure that silicon oxide coats.Wherein silicon oxide coats bed thickness 50nm
Example 12
This example changes gas in the vapor phase stream on the basis of example 1 flow is 200ml/min, and other step is with example 1.Its product of electron microscopic observation, major part are the CNT (carbon nano-tube) structures that silicon oxide coats.Wherein silicon oxide coats bed thickness 40nm.
Example 13
This example changes gas in the vapor phase stream on the basis of example 1 flow is 1000ml/min, and other step is with example 1.Its product of electron microscopic observation, major part are the CNT (carbon nano-tube) structures that silicon oxide coats.Wherein silicon oxide coats bed thickness 25nm.
Example 14
This example changes organo-siloxane on the basis of example 2 pyrolysis atmosphere is an Ar gas, and other step is with example 2.In reaction tubes, collect black powder and fibrous product.Electron microscopic observation, the carbon structural nano that wherein exists silicon oxide to coat.Wherein silicon oxide coats bed thickness 50～300nm.
Claims (6)
1. the preparation method of a silicon oxide coating nano carbon composite material, it is to be raw material with carbon base body and organo-siloxane, the pyrolysis organo-siloxane, and deposition coats silicon oxide on the nano-sized carbon matrix, be the coaxial fiber of silicon oxide coating nano carbon pipe, coat silicon oxide bed thickness 5-300nm; The nano-sized carbon matrix is a CNT (carbon nano-tube), and diameter 1～500nm is characterized in that:
Separate organo-siloxane in the air-flow interior heat that contains nano-sized carbon, produce silicon oxide coating nano carbon composite material, 600～1500 ℃ of pyrolysis temperatures.
2. by the described preparation method of claim 1, it is characterized in that organo-siloxane being sent into the air-flow pyrolysis that contains nano-sized carbon with liquid phase injection or solid phase carrying method.
3. by the described preparation method of claim 1, it is characterized in that described nano-sized carbon is included in growth in situ or directly introducing in the air-flow.
4. by the described preparation method of claim 3, it is characterized in that described direct introducing is that gas phase is mixed introducing, gas-liquid mixed is introduced or the gas-solid mixing is introduced.
5. by the described preparation method of claim 3, the carbon source material that it is characterized in that growth in situ in the described vapor phase stream is C
xH
yO
z, x=1～8, y=4～14, z=0～2.
6. by the described preparation method of claim 5, it is characterized in that described carbon source material is ethanol, ethene or dimethylbenzene, and the adding catalyzer is: the metal-salt of iron, cobalt or nickel transition metal.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103173041B (en) * | 2013-03-08 | 2014-06-04 | 北京化工大学 | Method for making core-shell polyhedral oligomeric silsesquioxane (POSS) coated multi-walled carbon nanotube (MWNT) |
| CN105819897B (en) * | 2016-03-15 | 2018-04-24 | 苏州赛福德备贸易有限公司 | The preparation method of carbon nanotubes coating ceramic |
| CN105819421A (en) * | 2016-03-15 | 2016-08-03 | 苏州赛福德备贸易有限公司 | Preparation method of ceramic coated carbon nanotube |
| CN115466937B (en) * | 2022-09-19 | 2024-05-03 | 苏州第一元素纳米技术有限公司 | Silicon oxide coated carbon nano tube and preparation device, method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1841679A (en) * | 2005-03-29 | 2006-10-04 | 中国科学院化学研究所 | Nano material and application in FET nanometer component |
| CN1994876A (en) * | 2006-12-22 | 2007-07-11 | 中国科学院上海硅酸盐研究所 | Preparation method of nano silica dioxide granule enveloping carbon nanotube composite powder |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1841679A (en) * | 2005-03-29 | 2006-10-04 | 中国科学院化学研究所 | Nano material and application in FET nanometer component |
| CN1994876A (en) * | 2006-12-22 | 2007-07-11 | 中国科学院上海硅酸盐研究所 | Preparation method of nano silica dioxide granule enveloping carbon nanotube composite powder |
Non-Patent Citations (2)
| Title |
|---|
| Jiangang Hu, et al.Nanowires with a carbon nanotube core and siliconoxidesheath.Carbon44 8.2006,44(8),1581-1583. |
| Jiangang Hu, et al.Nanowires with a carbon nanotube core and siliconoxidesheath.Carbon44 8.2006,44(8),1581-1583. * |
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