CN110240144B - Method for preparing carbon nano tube by discharge plasma assisted pyrolysis - Google Patents
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Abstract
The invention belongs to the technical field of carbon nano-material preparation, and discloses a method for preparing a carbon nano-tube by discharge plasma-assisted pyrolysis. Firstly, preparing nanometer cobaltosic oxide powder by taking cobalt salt, urea and the like as raw materials; then taking nano cobaltosic oxide and cyanamide organic powder as raw materials, and obtaining carbon-containing nano tube powder through a discharge plasma-assisted pyrolysis method; finally, amorphous carbon and metal cobalt in the product are respectively removed by an oxidation method and an acid washing method, and the carbon nano tube is obtained. The invention utilizes the discharge plasma to assist pyrolysis to rapidly prepare the carbon nano tube, can reduce the preparation time of the carbon nano tube, does not need flammable and explosive organic gas containing carbon in the reaction process, simplifies the preparation process flow of the carbon nano tube, and has higher safety factor and lower raw material cost.
Description
Technical Field
The invention belongs to the technical field of carbon nano-material preparation, and particularly relates to a method for preparing a carbon nano-tube by discharge plasma-assisted pyrolysis.
Background
Because the carbon nano tube has the characteristics of light weight, perfect connection of a hexagonal structure and the like, and has outstanding advantages in the aspects of mechanical properties, thermal properties, electrical properties, optical properties and the like, the research on the preparation, the properties and the application of the carbon nano tube becomes a hot spot field pursued by scientists in various countries. In recent years, as the application range of carbon nanotubes is continuously expanded, the demand thereof is continuously increased, and therefore, how to efficiently prepare carbon nanotubes with higher purity and uniform tube diameter at low cost becomes a main research direction.
In the field of carbon nanotube preparation technology, there are 3 methods commonly used at present: arc discharge, laser ablation, and catalytic cracking (also known as chemical vapor deposition). Among these methods, the purity of the carbon nanotubes produced by the arc discharge method is not high, and the by-products are not easily removed; the development of the laser ablation method is limited by the complicated equipment and the low yield of carbon nanotubes. As for the catalytic cracking method, the method has the characteristics of simple production equipment, lower preparation temperature and relatively stronger controllability, so the method is the first method for industrially producing the carbon nano tube at present. The typical process flow of the method is as follows: firstly, exhausting air in a furnace cavity of a sintering furnace by using nitrogen or argon, and using the air as carrier gas in a heat preservation process; next, the catalyst precursor is reduced to a simple metal substance using hydrogen as a reducing gas; then, using methane, acetylene and other gases as carbon sources to realize the growth of the carbon nano tube; and finally, cooling the carbon nano tube to room temperature along with the furnace under the protective atmosphere to obtain the carbon nano tube. From the above, the catalytic cracking method has the disadvantages of complicated process and long flow; the process is time-consuming and has low efficiency; during preparation, flammable and explosive gases such as hydrogen and the like need to be introduced, so that potential safety hazards exist; the organic gas is used as a carbon source, and the raw material cost is higher.
At present, on the basis of comprehensively knowing the characteristics of the existing carbon nanotube preparation method, how to improve the defects of the methods is to rapidly prepare the carbon nanotube at lower temperature and lower cost, and ensure the safety of the preparation process, which has important significance in the technical field of the preparation of the carbon nanotube.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a method for preparing a carbon nano tube by discharge plasma-assisted pyrolysis. The method solves the obvious problems of the conventional carbon nano tube preparation method, particularly the catalytic cracking method.
The purpose of the invention is realized by the following technical scheme:
a method for preparing carbon nanotubes by discharge plasma assisted pyrolysis comprises the following preparation steps:
(1) cobalt salt is used as a raw material, urea is used as a precipitator, polyethylene glycol is used as a dispersing agent, a cobalt salt precursor is obtained through a uniform precipitation method, and the cobalt salt precursor is calcined to obtain nano cobaltosic oxide powder;
(2) adding the nano cobaltosic oxide powder obtained in the step (1) and cyanamide organic powder into an organic solvent, stirring the mixture evenly under the ultrasonic condition, and drying the mixture to obtain raw material powder;
(3) performing discharge plasma-assisted pyrolysis on the raw material powder obtained in the step (2) under a vacuum condition to obtain carbon-containing nanotube powder;
(4) removing amorphous carbon and metal cobalt in the carbon-containing nano tube powder by using an oxidation method and an acid washing method to obtain the carbon nano tube.
Preferably, the cobalt salt in step (1) is cobalt nitrate, and the step of obtaining the cobalt salt precursor by the uniform precipitation method comprises: firstly preparing a cobalt nitrate solution, then adding urea, then adding polyethylene glycol as a dispersing agent, adjusting pH and uniformly stirring, heating and refluxing to obtain a precipitate, and filtering to obtain a cobalt salt precursor.
Preferably, the calcination in step (1) means calcination at a temperature of 350 ℃ for 2 h.
Preferably, the cyanamide organic compound in step (2) is melamine, dicyandiamide or cyanamide.
Preferably, the molar ratio of the cobaltosic oxide to the cyanamide organic compound in the step (2) is 1 (5-10).
Preferably, the organic solvent in step (2) is ethanol.
Preferably, the discharge plasma assisted pyrolysis process in the step (3) is as follows: in a discharge plasma system, heating to 600-1200 ℃ at a heating rate of 100-400 ℃/min, and reacting for 10-30 min under heat preservation.
Preferably, in the step (4), the oxidation method refers to oxidation with hydrogen peroxide, and the acid washing method refers to soaking with nitric acid.
The principle of the invention is as follows: the carbon nano tube is prepared by taking cyanamide organic matters as main raw materials, namely serving as a reducing agent of cobaltosic oxide serving as a catalyst oxide and serving as a carbon source required by the growth of the carbon nano tube, and performing a discharge plasma-assisted pyrolysis method at low cost, quickly and efficiently.
The preparation method of the invention has the following main advantages and beneficial effects:
(1) the carbon nano tube is prepared by the discharge plasma-assisted catalytic pyrolysis method, so that the rapid temperature rise can be realized, the decomposition of the organic carbon source is accelerated, and the preparation time is reduced, so that the whole preparation process of the carbon nano tube can be rapidly and efficiently completed.
(2) The invention does not need to introduce hydrogen as a reducing agent of the catalyst oxide in the preparation process of the carbon nano tube and does not need to introduce carbon-containing organic gas as a carbon source required by the growth of the carbon nano tube, thereby having higher experimental safety coefficient and lower raw material cost.
Drawings
FIG. 1 is a transmission electron micrograph of a carbon nanotube prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of carbon nanotubes prepared in example 1 of the present invention.
Fig. 3 is a raman spectrum of the carbon nanotube prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The method for preparing the carbon nanotube by the discharge plasma assisted pyrolysis comprises the following specific preparation steps:
(1) firstly, preparing 0.35mol/L cobalt nitrate solution, then adding urea into the solution according to the molar ratio of the cobalt nitrate to the urea of 3.5:1, finally adding a proper amount of polyethylene glycol as a dispersing agent, adjusting the pH value to about 5, uniformly stirring by using a magnetic stirrer, transferring the solution into a single-neck flask, heating and refluxing at 96 ℃ for 3 hours to obtain a precipitate, and filtering to obtain a catalyst precursor. And drying the precursor, and calcining the dried precursor in a muffle furnace at 350 ℃ for 2h to obtain the nano cobaltosic oxide.
(2) Adding the nano cobaltosic oxide and the melamine into an ethanol solution according to the molar ratio of 1:10, stirring for 6 hours under the ultrasonic condition, and then drying in vacuum to obtain raw material powder.
(3) Placing the raw material powder in a graphite mould, then placing the mould in a discharge plasma system, vacuumizing to below 10Pa, heating to 500 ℃ at the speed of 100 ℃/min, keeping the temperature for 5min, continuously heating to 1200 ℃ at the speed of 100 ℃/min, keeping the temperature for reaction for 10 min, and cooling along with a furnace to obtain the powder containing the carbon nano tube.
(4) And taking out the powder, and soaking the powder in 30 wt% of hydrogen peroxide and 6mol/L of nitric acid for 24 hours respectively to remove amorphous carbon and catalyst cobalt, thereby finally obtaining the purified carbon nano tube.
The scanning electron micrograph, the transmission electron micrograph and the raman spectroscopy of the carbon nanotube prepared in this example are shown in fig. 1, fig. 2 and fig. 3, respectively.
As shown in fig. 1, a large amount of carbon nanotubes are distributed and the impurities are less when observed by a scanning electron microscope. The spherical particles at the head of the carbon nano tube are catalyst cobalt particles.
As shown in fig. 2, the product was a carbon nanotube as observed by transmission electron microscopy. The tube wall was clear and flat, indicating good crystallization.
Raman spectra of carbon nanotubes, as shown in FIG. 3, where I D /I G The ratio of (A) to (B) is 0.64, further proving that the prepared CNTs have good crystallinity.
Example 2
The method for preparing the carbon nanotube by the discharge plasma assisted pyrolysis comprises the following specific preparation steps:
(1) firstly, preparing 0.35mol/L cobalt nitrate solution, then adding urea into the solution according to the molar ratio of the cobalt nitrate to the urea being 3.5:1, finally adding a proper amount of polyethylene glycol as a dispersing agent, adjusting the pH value to about 5, uniformly stirring by using a magnetic stirrer, then transferring the solution into a single-neck flask, heating and refluxing at 96 ℃ for 3 hours to obtain a precipitate, and filtering to obtain a catalyst precursor. And drying the precursor, and calcining the dried precursor in a muffle furnace at 350 ℃ for 2h to obtain the nano cobaltosic oxide.
(2) Adding the nano cobaltosic oxide and melamine into an ethanol solution according to a molar ratio of 1:10, stirring for 6 hours under an ultrasonic condition, and then drying in vacuum to obtain raw material powder.
(3) Placing the raw material powder in a graphite mould, then placing the mould in a discharge plasma system, vacuumizing to below 10Pa, heating to 500 ℃ at the speed of 100 ℃/min, keeping the temperature for 5min, continuously heating to 600 ℃ at the speed of 100 ℃/min, keeping the temperature for reaction for 10 min, and cooling along with a furnace to obtain the powder containing the carbon nano tube.
(4) And taking out the powder, and soaking the powder in 30 wt% of hydrogen peroxide and 6mol/L of nitric acid for 24 hours respectively to remove amorphous carbon and catalyst cobalt, thereby finally obtaining the purified carbon nanotube.
Example 3
The method for preparing the carbon nanotube by the discharge plasma assisted pyrolysis comprises the following specific preparation steps:
(1) firstly, preparing 0.35mol/L cobalt nitrate solution, then adding urea into the solution according to the molar ratio of the cobalt nitrate to the urea being 3.5:1, finally adding a proper amount of polyethylene glycol as a dispersing agent, adjusting the pH value to about 5, uniformly stirring by using a magnetic stirrer, then transferring the solution into a single-neck flask, heating and refluxing at 96 ℃ for 3 hours to obtain a precipitate, and filtering to obtain a catalyst precursor. And drying the precursor, and then calcining the dried precursor in a muffle furnace at 350 ℃ for 2h to obtain the nano cobaltosic oxide.
(2) Adding the nano cobaltosic oxide and the melamine into an ethanol solution according to the molar ratio of 1:10, stirring for 6 hours under the ultrasonic condition, and then drying in vacuum to obtain raw material powder.
(3) Placing the raw material powder in a graphite mould, then placing the mould in a discharge plasma system, vacuumizing to below 10Pa, heating to 500 ℃ at the speed of 400 ℃/min, keeping the temperature for 5min, continuously heating to 900 ℃ at the speed of 400 ℃/min, keeping the temperature for reaction for 10 min, and cooling along with a furnace to obtain the powder containing the carbon nano tube.
(4) And taking out the powder, and soaking the powder in 30 wt% of hydrogen peroxide and 6mol/L of nitric acid for 24 hours respectively to remove amorphous carbon and catalyst cobalt, thereby finally obtaining the purified carbon nanotube.
Example 4
The method for preparing the carbon nanotube by the discharge plasma assisted pyrolysis comprises the following specific preparation steps:
(1) firstly, preparing 0.35mol/L cobalt nitrate solution, then adding urea into the solution according to the molar ratio of the cobalt nitrate to the urea of 3.5:1, finally adding a proper amount of polyethylene glycol as a dispersing agent, adjusting the pH value to about 5, uniformly stirring by using a magnetic stirrer, transferring the solution into a single-neck flask, heating and refluxing at 96 ℃ for 3 hours to obtain a precipitate, and filtering to obtain a catalyst precursor. And drying the precursor, and calcining the dried precursor in a muffle furnace at 350 ℃ for 2h to obtain the nano cobaltosic oxide.
(2) Adding the nano cobaltosic oxide and the melamine into an ethanol solution according to the molar ratio of 1:10, stirring for 6 hours under the ultrasonic condition, and then drying in vacuum to obtain raw material powder.
(3) Placing the raw material powder in a graphite mould, then placing the mould in a discharge plasma system, vacuumizing to below 10Pa, heating to 500 ℃ at the speed of 100 ℃/min, keeping the temperature for 5min, continuously heating to 900 ℃ at the speed of 100 ℃/min, keeping the temperature for reaction for 30min, and cooling along with a furnace to obtain the powder containing the carbon nano tube.
(4) And taking out the powder, and soaking the powder in 30 wt% of hydrogen peroxide and 6mol/L of nitric acid for 24 hours respectively to remove amorphous carbon and catalyst cobalt, thereby finally obtaining the purified carbon nanotube.
Example 5
The method for preparing the carbon nanotube by the spark plasma assisted pyrolysis comprises the following specific preparation steps:
(1) firstly, preparing 0.35mol/L cobalt nitrate solution, then adding urea into the solution according to the molar ratio of the cobalt nitrate to the urea of 3.5:1, finally adding a proper amount of polyethylene glycol as a dispersing agent, adjusting the pH value to about 5, uniformly stirring by using a magnetic stirrer, transferring the solution into a single-neck flask, heating and refluxing at 96 ℃ for 3 hours to obtain a precipitate, and filtering to obtain a catalyst precursor. And drying the precursor, and calcining the dried precursor in a muffle furnace at 350 ℃ for 2h to obtain the nano cobaltosic oxide.
(2) Adding the nano cobaltosic oxide and the melamine into an ethanol solution according to the molar ratio of 1:5, stirring for 6 hours under the ultrasonic condition, and then drying in vacuum to obtain raw material powder.
(3) Placing the raw material powder in a graphite mould, then placing the mould in a discharge plasma system, vacuumizing to below 10Pa, heating to 500 ℃ at the speed of 100 ℃/min, keeping the temperature for 5min, continuously heating to 900 ℃ at the speed of 100 ℃/min, keeping the temperature for reaction for 10 min, and cooling along with a furnace to obtain the carbon nanotube-containing powder.
(4) And taking out the powder, and soaking the powder in 30 wt% of hydrogen peroxide and 6mol/L of nitric acid for 24 hours respectively to remove amorphous carbon and catalyst cobalt, thereby finally obtaining the purified carbon nanotube.
Example 6
The method for preparing the carbon nanotube by the discharge plasma assisted pyrolysis comprises the following specific preparation steps:
(1) firstly, preparing 0.35mol/L cobalt nitrate solution, then adding urea into the solution according to the molar ratio of the cobalt nitrate to the urea of 3.5:1, finally adding a proper amount of polyethylene glycol as a dispersing agent, adjusting the pH value to about 5, uniformly stirring by using a magnetic stirrer, transferring the solution into a single-neck flask, heating and refluxing at 96 ℃ for 3 hours to obtain a precipitate, and filtering to obtain a catalyst precursor. And drying the precursor, and calcining the dried precursor in a muffle furnace at 350 ℃ for 2h to obtain the nano cobaltosic oxide.
(2) Adding the nano cobaltosic oxide and dicyandiamide into an ethanol solution according to the molar ratio of 1:10, stirring for 6 hours under the ultrasonic condition, and then drying in vacuum to obtain raw material powder.
(3) Placing the raw material powder in a graphite mould, then placing the mould in a discharge plasma system, vacuumizing to below 10Pa, heating to 500 ℃ at the speed of 100 ℃/min, keeping the temperature for 5min, continuously heating to 900 ℃ at the speed of 100 ℃/min, keeping the temperature for reaction for 10 min, and cooling along with a furnace to obtain the powder containing the carbon nano tube.
(4) And taking out the powder, and soaking the powder in 30 wt% of hydrogen peroxide and 6mol/L of nitric acid for 24 hours respectively to remove amorphous carbon and catalyst cobalt, thereby finally obtaining the purified carbon nano tube.
Example 7
The method for preparing the carbon nanotube by the discharge plasma assisted pyrolysis comprises the following specific preparation steps:
(1) firstly, preparing 0.35mol/L cobalt nitrate solution, then adding urea into the solution according to the molar ratio of the cobalt nitrate to the urea being 3.5:1, finally adding a proper amount of polyethylene glycol as a dispersing agent, adjusting the pH value to about 5, uniformly stirring by using a magnetic stirrer, then transferring the solution into a single-neck flask, heating and refluxing at 96 ℃ for 3 hours to obtain a precipitate, and filtering to obtain a catalyst precursor. And drying the precursor, and calcining the dried precursor in a muffle furnace at 350 ℃ for 2h to obtain the nano cobaltosic oxide.
(2) Adding the nano cobaltosic oxide and the cyanamide into an ethanol solution according to the molar ratio of 1:10, stirring for 6 hours under the ultrasonic condition, and then drying in vacuum to obtain raw material powder.
(3) Placing the raw material powder in a graphite mould, then placing the mould in a discharge plasma system, vacuumizing to below 10Pa, heating to 500 ℃ at the speed of 100 ℃/min, keeping the temperature for 5min, continuously heating to 900 ℃ at the speed of 100 ℃/min, keeping the temperature for reaction for 10 min, and cooling along with a furnace to obtain the powder containing the carbon nano tube.
(4) And taking out the powder, and soaking the powder in 30 wt% of hydrogen peroxide and 6mol/L of nitric acid for 24 hours respectively to remove amorphous carbon and catalyst cobalt, thereby finally obtaining the purified carbon nanotube.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A method for preparing carbon nano tubes by discharge plasma assisted pyrolysis is characterized by comprising the following preparation steps:
(1) cobalt salt is used as a raw material, urea is used as a precipitator, polyethylene glycol is used as a dispersing agent, a cobalt salt precursor is obtained through a uniform precipitation method, and the cobalt salt precursor is calcined to obtain nano cobaltosic oxide powder;
(2) adding the nano cobaltosic oxide powder obtained in the step (1) and cyanamide organic powder into an organic solvent, stirring the mixture evenly under the ultrasonic condition, and drying the mixture to obtain raw material powder;
(3) placing the raw material powder obtained in the step (2) in a graphite mould, then placing the mould in a discharge plasma system, and obtaining carbon-containing nano tube powder through a discharge plasma-assisted pyrolysis method under a vacuum condition;
(4) removing amorphous carbon and metal cobalt in the carbon-containing nano tube powder by using an oxidation method and an acid washing method to obtain a carbon nano tube;
the discharge plasma assisted pyrolysis process in the step (3) comprises the following steps: in a discharge plasma system, the temperature is raised to 500 ℃ and kept for 5min, and then raised to 600-1200 ℃ at the temperature raising rate of 100-400 ℃/min, and the temperature is kept for reaction for 10-30 min.
2. The method for preparing carbon nanotubes by spark plasma assisted pyrolysis as claimed in claim 1, wherein: the cobalt salt in the step (1) is cobalt nitrate, and the step of obtaining the cobalt salt precursor by the uniform precipitation method comprises the following steps: firstly, preparing a cobalt nitrate solution, then adding urea as a precipitator, adding polyethylene glycol as a dispersing agent, adjusting pH, uniformly stirring, heating and refluxing to obtain a precipitate, and filtering to obtain a cobalt salt precursor.
3. The method for preparing carbon nanotubes by spark plasma assisted pyrolysis as claimed in claim 1, wherein: the calcination in the step (1) refers to calcination at a temperature of 350 ℃ for 2 h.
4. The method for preparing carbon nanotubes by spark plasma assisted pyrolysis according to claim 1, wherein: in the step (2), the cyanamide organic substance refers to melamine, dicyandiamide or cyanamide.
5. The method for preparing carbon nanotubes by spark plasma assisted pyrolysis according to claim 1, wherein: in the step (2), the molar ratio of the cobaltosic oxide to the cyanamide organic substance is 1 (5-10).
6. The method for preparing carbon nanotubes by spark plasma assisted pyrolysis according to claim 1, wherein: the organic solvent in the step (2) is ethanol.
7. The method for preparing carbon nanotubes by spark plasma assisted pyrolysis according to claim 1, wherein: in the step (5), the oxidation method refers to oxidation by using hydrogen peroxide, and the acid washing method refers to soaking by using nitric acid.
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