CN105347326B - A kind of preparation method of carbon nanometer cucurbit structural material - Google Patents
A kind of preparation method of carbon nanometer cucurbit structural material Download PDFInfo
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- CN105347326B CN105347326B CN201510798838.4A CN201510798838A CN105347326B CN 105347326 B CN105347326 B CN 105347326B CN 201510798838 A CN201510798838 A CN 201510798838A CN 105347326 B CN105347326 B CN 105347326B
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Abstract
A kind of preparation method of carbon nanometer cucurbit structural material, as follows：（1）The carriers such as ceramic boat or quartz boat and catalyst are put into tube furnace, in atmospheric conditions, 800 1200 DEG C are warming up in the atmosphere of buffer gas；（2）800 1200 DEG C of temperature are maintained, buffer gas is passed through, buffer gas is passed through tube furnace again after presoma, in the deposited on supports such as ceramic boat or quartz boat carbon nanometer cucurbit structural material, the 30min of growth time 1；（3）The buffer gas by presoma is closed, room temperature is cooled in buffer gas.Preparation technology of the present invention is simple, consumes energy low, product purity height can be mass-produced；The carbon nanomaterial of prepared calabash shaped has the advantages that big surface area, is easy to what is combined well with matrix, can be used directly to carry out physical characteristic detection, and apply in various application products.
Description
Technical field
The invention belongs to functional material field, it is related to the preparation method of carbon nano-structured material.
Background technology
Carbon nanomaterial refers to the dispersed phase yardstick at least one-dimensional carbon material less than 100nm.Dispersed phase both can be by carbon
Atom is constituted, it is possibility to have non-carbon is constituted.The carbon nanomaterial that document is at most reported is CNT.Since Japan
Iijima is since 1991 find CNT, due to its peculiar one-dimentional structure, Wuli-Shili-Renli system approach and potential application
Prospect, and the physico educational circles in countries in the world and the concern of material educational circles scientist are enjoyed always.CNT is by individual layer or many
Hollow, seamless " micro-pipe " that layer graphite flake is wound around central shaft by certain helical angle, every layer by a carbon atom
Pass through sp2After 3 carbon atoms of hydridization and surrounding are bonded completely the hexagonal groups that are constituted into the face of cylinder.
The application study of carbon nanomaterial relates generally to medical sensing material（Biology sensor etc.）, energy storage material
（Lithium battery, ultracapacitor and other electrochemical energy storages etc.）, energy conversion material（Fuel cell etc.）, environment measuring
And repair materials（Applied to chemistry and physical sensing material, sorbing material etc.）.At present, the primary synthetic methods of carbon nanomaterial
There are arc process, chemical vapor deposition（CVD）Method, solid-phase pyrolysis and laser method etc., wherein chemical vapor deposition（CVD）Method is not only
Preparation method is easy, easy control of process conditions, and raw material is cheap, and the advantages of being adapted to large-scale production, the product impurity of gained contains
Amount is low, and degree of graphitization is high, so as the main method for preparing carbon nanomaterial.Due to the difference of control condition, except usual
Linear, tubular it is carbon nano-structured outside, also obtained the CNT of many other shapes.Due to unique pattern and structure
Feature, so that with special performance.
Carbon nanometer cucurbit structure is coaxial cone, cone be by concentric cylindrical type graphite linings along outer surface by
Tapered short set structure is formed, and the innermost layer of cone is that the SWNT or many walls of one or several a diameter of nanometers are received
Rice carbon pipe, they are either directly formed by stacking by the CNT of the different numbers of plies or different structure by Van der Waals force,
Either same number of plies CNT bunchy is formed by stacking, and each position is made up of an entirety carbon in a seamless fashion.
The ladder-shaper structure that these carbon nanometer cucurbit structural material outer surface is made up of the graphite linings being gradually shortened is substantial amounts of active sites, can
Excellent carrier as catalyst or ion, in Catalyst and electrochemical kinetics energy field（Such as high-performance lithium ion
Battery and ultracapacitor）With wide application and development prospect.Conical structure compares SWNT not only significantly
Its mechanical radial strength is enhanced, and top dimension is within several nanometers, is the needle point and field hair of preferable scanning probe
Penetrate material.In addition, carbon nanometer cucurbit structure has several nanometers and each independent internal diameter, storage can be used as simultaneously and transported not
With multiple autonomous channels of liquid, or even each independent combined nano syringe is made, be engaged in the cell of nanometer level
Repair and study on the modification, so as to obtain extensive use in fields such as biological and chemicals.Furthermore, compared to more smooth CNT,
With the new carbon nano-structured of calabash shaped structure, it is clear that in superpower field of compound material be more excellent reinforcement.Separately
Outside, this New Type of Carbon nanometer cucurbit structure as a carbon it is overall because with CNT per se with excellent electricity, light
Learn and mechanical property, the development of full carbon nanomaterial electronic device will be most likely promoted.
The content of the invention
It is an object of the invention to provide a kind of carbon nanometer cucurbit structural material preparation method, simple with equipment, operation is held
Easily, energy consumption is low, the advantages of product purity is high.
The present invention is achieved by the following technical solutions.
The preparation method of carbon nanometer cucurbit structural material of the present invention, as follows.
（1）The carriers such as ceramic boat or quartz boat and catalyst are put into tube furnace, in atmospheric conditions, buffer gas
Atmosphere in be warming up to 800-1200 DEG C.
（2）800-1200 DEG C of temperature is maintained, buffer gas is passed through, buffer gas is passed through tube furnace again after presoma,
In the deposited on supports such as ceramic boat or quartz boat carbon nanometer cucurbit structural material, growth time 1-30min.
（3）The buffer gas by presoma is closed, room temperature is cooled in buffer gas.
Step of the present invention（1）Described in buffer gas be hydrogen, argon gas, nitrogen in one or more of mixed gas；
Catalyst is ferrocene, dicyclopentadienyl nickel or cobaltocene；
Step of the present invention（1）Middle heating rate is 20-40 DEG C/min.
Step of the present invention（2）Described in presoma, in carbon source add growth promoter constitute, wherein, the carbon source
For carbon containing organic molecule, optional benzene, methane, acetylene, ethanol etc.；Growth promoter be containing growth promoter of sulfur, can for thiophene,
Carbon disulfide or hydrogen sulfide；Carbon source and the volume ratio of growth promoter are 1/500-1/5 in the presoma.
Step of the present invention（2）The buffer gas flow of middle process presoma is 10-500sccm/s.
The present invention has following beneficial effect.
（1）Preparation technology of the present invention is simple, consumes energy low, product purity height can be mass-produced.
（2）The carbon nanomaterial of prepared calabash shaped of the invention has big surface area, is easy to be combined well with matrix
The advantages of.
（3）The present invention, as growth promoter, can improve the shape of carbon nanometer cucurbit structural material using sulfur-bearing chemicals
Into.
（4）The present invention can control calabash shaped using various experiment parameter such as flows of growth time, carbon-source gas etc. are adjusted
The length of carbon nanomaterial.
（5）The carbon nanometer cucurbit structural material that the present invention is obtained can be used directly to carry out physical characteristic detection, and use
Into various application products.
Brief description of the drawings
Fig. 1 is the experimental provision structural representation for the carbon nanomaterial that invention prepares calabash shaped.
Fig. 2 is the field emission scanning electron microscope figure of the carbon nanomaterial of calabash shaped prepared by embodiment 1（SEM schemes）.
Fig. 3 is the transmission electron microscope picture of the carbon nanomaterial of calabash shaped prepared by embodiment 1（TEM schemes）.
Fig. 4 is the transmission electron microscope picture of the carbon nanomaterial of calabash shaped prepared by embodiment 2（TEM schemes）.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Method described in example below, is conventional method unless otherwise specified；The material agents, such as without special
Illustrate, commercially obtain.
Embodiment 1.
Presoma is mixed by the thiophene of 100ml benzene and 10% content.Experimental provision used is as shown in figure 1, luxuriant by two
The carriers such as iron, ceramic boat or quartz boat are put into tube furnace quartz ampoule on such as position of figure, in atmospheric conditions, are passed through hydrogen
Flow is 180sccm and is that carbon source is closed after 2min is exhausted in 100sccm by the hydrogen flowing quantity of presoma, then with 27.5
DEG C/s heat temperature raisings.When temperature reaches 1100 DEG C, hydrogen is adjusted to 30sccm, while being passed through the hydrogen by presoma
Flow 50sccm, by moving quartz ampoule, ferrocene is moved into quartz ampoule, kept after 1100 DEG C of 10min, forerunner is passed through in closing
The hydrogen of body and 180sccm will be adjusted to as buffer gas hydrogen flowing quantity, be moved back to ferrocene originally by moving quartz ampoule
Position, cool to room temperature, you can obtain the carbon nanomaterial of calabash shaped.The carbon nanomaterial of the calabash shaped of gained
SEM and TEM figures are Fig. 2 and Fig. 3.
Embodiment 2.
Presoma is mixed by the thiophene of 100ml benzene and 20% content.Experimental provision used is as shown in figure 1, luxuriant by two
The carriers such as iron, ceramic boat or quartz boat are put into tube furnace quartz ampoule on such as position of figure, in atmospheric conditions, are passed through hydrogen
Flow is 180sccm and is that carbon source is closed after 2min is exhausted in 100sccm by the hydrogen flowing quantity of presoma, then with 27.5
DEG C/s heat temperature raisings.When temperature reaches 1100 DEG C, hydrogen is adjusted to 50sccm, while being passed through the hydrogen by presoma
Flow 50sccm, by moving quartz ampoule, ferrocene is moved into quartz ampoule, kept after 1100 DEG C of 20min, forerunner is passed through in closing
The hydrogen of body and the hydrogen flowing quantity as buffer gas is adjusted to 180sccm, original is moved back to by moving quartz ampoule by ferrocene
The position come, cools to room temperature, you can obtain the carbon nanomaterial of calabash shaped.The carbon nanomaterial of the calabash shaped of gained
SEM figures are Fig. 4.
Embodiment 3.
Presoma is mixed by the thiophene of 100ml benzene and 30% content.Experimental provision used is as shown in figure 1, luxuriant by two
The carriers such as iron, ceramic boat or quartz boat are put into tube furnace quartz ampoule on such as position of figure, in atmospheric conditions, are passed through hydrogen
Flow is 180sccm and is that carbon source is closed after 2min is exhausted in 100sccm by the hydrogen flowing quantity of presoma, then with 27.5
DEG C/s heat temperature raisings.When temperature reaches 1150 DEG C, hydrogen is adjusted to 100sccm, while being passed through the hydrogen by presoma
Throughput 200sccm, by moving quartz ampoule, ferrocene is moved into quartz ampoule, kept after 1100 DEG C of 10min, closed and pass through
The hydrogen of presoma and the hydrogen flowing quantity as buffer gas is adjusted to 180sccm, moved ferrocene by moving quartz ampoule
Original position is gone back to, is cooled to room temperature, you can obtain the carbon nanomaterial of calabash shaped.Such as Fig. 2.
Embodiment 4.
Presoma is mixed by the thiophene of 100ml absolute ethyl alcohols and 10% content.Experimental provision used as shown in figure 1,
The carriers such as ferrocene, ceramic boat or quartz boat are put into tube furnace quartz ampoule on such as position of figure, in atmospheric conditions, led to
Enter hydrogen flowing quantity to be 180sccm and be to close carbon source after 2min is exhausted in 100sccm by the hydrogen flowing quantity of presoma, then
With 25 DEG C/s heat temperature raisings.When temperature reaches 1100 DEG C, hydrogen is adjusted to 20sccm, while being passed through by presoma
Hydrogen flowing quantity 60sccm, by moving quartz ampoule, ferrocene is moved into quartz ampoule, kept after 1100 DEG C of 10min, closed and pass through
The hydrogen of presoma and 180sccm will be adjusted to as buffer gas hydrogen flowing quantity, be moved back to ferrocene by moving quartz ampoule
Position originally, cools to room temperature, you can obtain the carbon nanomaterial of calabash shaped.
Embodiment 5.
Presoma is mixed by the thiophene of 100ml absolute ethyl alcohols and 30% content.Experimental provision used as shown in figure 1,
The carriers such as ferrocene, ceramic boat or quartz boat are put into tube furnace quartz ampoule on such as position of figure, in atmospheric conditions, led to
Enter hydrogen flowing quantity to be 180sccm and be to close carbon source after 2min is exhausted in 100sccm by the hydrogen flowing quantity of presoma, then
With 30 DEG C/s heat temperature raisings.When temperature reaches 1050 DEG C, hydrogen is adjusted to 40sccm, while being passed through by presoma
Hydrogen flowing quantity 120sccm, by moving quartz ampoule, ferrocene is moved into quartz ampoule, kept after 1050 DEG C of 5min, closed and pass through
The hydrogen of presoma and 180sccm will be adjusted to as buffer gas hydrogen flowing quantity, be moved back to ferrocene by moving quartz ampoule
Position originally, cools to room temperature, you can obtain the carbon nanomaterial of calabash shaped.
Claims (1)
1. a kind of preparation method of carbon nanometer cucurbit structural material, it is characterized in that as follows：
（1）Ceramic boat or quartz boat and catalyst are put into tube furnace, in atmospheric conditions, without the slow of presoma
800-1200 DEG C is warming up in the atmosphere of qi of chong channel ascending adversely body；
（2）800-1200 DEG C of temperature is maintained, while the buffer gas by presoma is passed through to tube furnace, in ceramic boat or stone
Carbon nanometer cucurbit structural material, growth time 1-30min are deposited on Ying Zhou；
（3）The buffer gas by presoma is closed, room temperature is cooled in the buffer gas without presoma；
Step（1）Described in buffer gas be hydrogen, argon gas, nitrogen in one or more of mixed gas；Catalyst is two
Luxuriant iron, dicyclopentadienyl nickel or cobaltocene；
Step（2）Described in presoma, in carbon source adding growth promoter is constituted, wherein, the carbon source has to be carbon containing
Machine molecule；Growth promoter is containing growth promoter of sulfur；
Step（1）Described in heating rate be 20-40 DEG C/min；
Step（2）Described in presoma carbon source and the volume ratio of growth promoter be 1/500-1/5；
Step（2）The buffer gas flow of middle process presoma is 10-500sccm；
Step（2）Described carbon containing organic molecule is benzene, methane, acetylene or ethanol；
Step（2）Described is thiophene, carbon disulfide or hydrogen sulfide containing growth promoter of sulfur.
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| CN106129346A (en) * | 2016-06-23 | 2016-11-16 | 南昌大学 | A kind of acid accumulator negative pole lead material containing carbon nanometer calabash structural material and preparation method thereof |
| CN106710722B (en) * | 2017-01-18 | 2018-05-04 | 福州大学 | A kind of Ni wraps up mesoporous SiO2The preparation method of conductive powder body |
| CN106601373B (en) * | 2017-01-18 | 2018-04-13 | 福州大学 | A kind of Ag wraps up mesoporous SiO2The preparation method of conductive powder body |
| CN106710721B (en) * | 2017-01-18 | 2018-06-12 | 福州大学 | A kind of preparation method of Ag packages nickel slag conductive powder body |
| CN112897508A (en) * | 2021-03-11 | 2021-06-04 | 南昌大学 | Preparation method of carbon nano pear-shaped structure material |
| CN113086969A (en) * | 2021-04-02 | 2021-07-09 | 南昌大学 | High-quality carbon nano-pearl chain structure and large-scale preparation method thereof |
| CN114887552B (en) * | 2022-05-20 | 2023-03-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Injection structure for preparing carbon nanotube material and application thereof |
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