CN115353094A - Solid phase purification method of carbon nano tube - Google Patents
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- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000000746 purification Methods 0.000 title claims abstract description 32
- 239000007790 solid phase Substances 0.000 title claims abstract description 27
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/17—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
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Abstract
The invention discloses a solid phase purification method of a carbon nano tube, which comprises the following steps: premixing the carbon nano tube and the nitrogenous organic matter through ball milling treatment to obtain a premix; the pre-mixture is calcined under an inert atmosphere. The solid phase purification method of the carbon nano tube can remove the residual transition metal impurities in the production process of the rough carbon nano tube with high selectivity, avoid the damage to the tube wall of the carbon nano tube, simultaneously keep the excellent mechanical and electrical properties of the carbon nano tube, and has the advantages of simple process, high purification efficiency, low cost, greenness and cleanness.
Description
Technical Field
The invention belongs to the technical field of purification of carbon nanotubes, and particularly relates to a solid phase purification method of a carbon nanotube.
Background
The carbon nano tube is a one-dimensional quantum material based on hexagonal crystal lattices formed by carbon atoms, has excellent mechanical, electrical, chemical and biological properties, and has wide application prospect. The conventional method for preparing carbon nanotubes comprises: arc discharge, glow discharge, laser ablation, solid phase pyrolysis, chemical vapor deposition, gas combustion, and the like, wherein chemical vapor deposition is currently used in a wide range. However, the chemical vapor deposition method uses transition metals (Fe, co, ni, etc.) as catalysts to prepare carbon nanotubes, and the prepared carbon nanotubes usually have residual transition metal nanoparticle impurities, which affect the performance and application of the carbon nanotubes, and thus, the crude carbon nanotubes need to be purified. At present, the carbon nano tube is usually subjected to a liquid-phase acid washing method to remove transition metal nano particle impurities in the carbon nano tube, but the liquid-phase acid washing method has the defects of low purification degree of the carbon nano tube, reduced performance, generation of acid-containing wastewater and the like. Therefore, there is an urgent need to develop a more efficient, green and clean method for purifying carbon nanotubes.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: at present, the carbon nanotube is usually cleaned by liquid-phase acid cleaning method to remove the transition metal nanoparticle impurities in the carbon nanotube, and one or more mixed acids of hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid and the like are used in ultrasonic treatment and H treatment 2 O 2 Reacting with transition metal nano particles in the rough carbon nano tube under the condition of potassium permanganate or heating to generate soluble salt, and then filtering and washing to remove the soluble salt so as to achieve the purpose of purifying the carbon nano tube. However, the liquid-phase acid washing method can only remove the transition metal nanoparticles exposed on the surface of the carbon nanotubes, and it is difficult to obtain high-purity carbon nanotubes; the liquid-phase acid washing method has poor reaction selectivity, can damage the tube wall structure of the carbon nano tube, and reduces the mechanical and electrical properties of the carbon nano tube; the liquid-phase acid washing method has a complex process flow, and a large amount of acid-containing wastewater is generated in the treatment process. Therefore, there is an urgent need to develop a more efficient, green and clean method for purifying carbon nanotubes.
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a solid phase purification method of a carbon nano tube, which can remove residual transition metal impurities in the production process of the crude carbon nano tube with high selectivity, avoid the damage to the tube wall of the carbon nano tube, simultaneously keep the excellent mechanical and electrical properties of the carbon nano tube, and has the advantages of simple process, high purification efficiency, low cost, green and clean properties.
The solid phase purification method of the carbon nano tube comprises the following steps: premixing a carbon nano tube and a nitrogenous organic matter through ball milling treatment to obtain a premix; the pre-mixture is calcined under an inert atmosphere.
The solid phase purification method of the carbon nano tube according to the embodiment of the invention has the following advantages and technical effects: the method of the embodiment of the invention purifies the rough carbon nano tube with transition metal impurities left in the production process, firstly, nitrogen-containing organic matter and the rough carbon nano tube are selected to be premixed by ball milling, the nitrogen-containing organic matter and the carbon nano tube are fully and uniformly mixed, and part of the tail end closed end of the carbon nano tube is opened by mechanical force, so that the residual transition metal nano particles are exposed, the full contact between the nitrogen-containing organic matter and the metal nano particles in the carbon nano tube is facilitated, and the removal of the metal nano particles is facilitated; then, the premix is calcined in an inert atmosphere, and the nitrogen-containing organic substance is capable of generating CN during pyrolysis x And (3) reacting the volatile substances with the fully exposed transition metal nano particles to generate volatile substances of transition metals, and then carrying the volatile substances of the transition metals out of the carbon nano tube along with the inert gas, so that the purposes of removing transition metal impurities and purifying the carbon nano tube are achieved, the removal rate of the transition metal impurities can exceed 90%, and meanwhile, the method can avoid the damage of acid treatment on the tube wall of the carbon nano tube and can keep the excellent mechanical and electrical properties of the carbon nano tube.
In some embodiments, the nitrogen-containing organic includes at least one of cyanamide, dicyandiamide, melamine, urea, melem.
In some embodiments, the weight ratio of the nitrogen-containing organic to the carbon nanotubes is from 0.1 to 300.
In some embodiments, the rotational speed of the ball milling process is 200 to 350rpm.
In some embodiments, the ball milling treatment time is 5 to 50 hours.
In some embodiments, the inert atmosphere comprises at least one of nitrogen, argon, helium.
In some embodiments, the temperature of the firing is 500 to 1200 ℃.
In some embodiments, the firing is at a ramp rate of 1 to 20 ℃ min -1 。
In some embodiments, the calcination time is from 1 to 50 hours.
In some embodiments, the carbon nanotubes are crude carbon nanotubes produced by chemical vapor deposition.
Drawings
FIG. 1 is an X-ray diffraction pattern of crude carbon nanotubes of example 2 of the present invention.
FIG. 2 is an X-ray diffraction pattern of carbon nanotubes treated by the solid phase purification method according to example 2 of the present invention.
FIG. 3 shows the electrochemical impedance spectra of the purified Carbon Nanotubes (CNTs) of example 6 of the present invention and the purified carbon nanotubes (A-CNTs) of comparative example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The solid phase purification method of the carbon nano tube comprises the following steps: premixing the carbon nano tube and the nitrogenous organic matter through ball milling treatment to obtain a premix; the pre-mixture is calcined under an inert atmosphere.
According to the solid phase purification method of the carbon nano tube, the crude carbon nano tube with the transition metal impurities left in the production process is purified, firstly, nitrogen-containing organic matters and the crude carbon nano tube are selected to be premixed through ball milling, the nitrogen-containing organic matters and the carbon nano tube are fully and uniformly mixed, partial end closed ports of the carbon nano tube are opened through mechanical force, and then the carbon nano tube is subjected to solid phase purificationThe residual transition metal nano particles are exposed, so that the nitrogen-containing organic matter can be in full contact with the metal nano particles in the carbon nano tubes, and the metal nano particles can be removed; then, the premix is calcined in an inert atmosphere, and the nitrogen-containing organic substance is capable of generating CN during pyrolysis x And (3) reacting the volatile substances with the fully exposed transition metal nano particles to generate volatile substances of transition metals, and then carrying the volatile substances of the transition metals out of the carbon nano tube along with the inert gas, so that the purposes of removing transition metal impurities and purifying the carbon nano tube are achieved, the removal rate of the transition metal impurities can exceed 90%, and meanwhile, the method can avoid the damage of acid treatment on the tube wall of the carbon nano tube and can keep the excellent mechanical and electrical properties of the carbon nano tube.
In some embodiments, the nitrogen-containing organic includes at least one of cyanamide, dicyandiamide, melamine, urea, melem. In the embodiment of the invention, nitrogen-containing organic matters are preferred, and the nitrogen-containing organic matters have high nitrogen content and can generate CN with more volatility x The substance is beneficial to improving the purification effect of the carbon nano tube and reducing the content of impurities.
In some embodiments, the nitrogen-containing organic is preferably dicyanodiamine. In the embodiment of the invention, CN generated by different nitrogenous organic matters in the pyrolysis process x CN produced by decomposition of dicyanodiamine, slightly different in kind x Is easier to combine with the surface atoms of the transition metal nano particles in the rough carbon nano tube, and is beneficial to improving the removal effect of metal impurities.
In some embodiments, the nitrogen-containing organic compound is further preferably a nitrogen-containing organic compound formed by combining dicyanodiamine and melem, and optionally, the mass ratio of dicyanodiamine to melem is 2:1. in the examples of the present invention, CN derived from the decomposition of two different nitrogen-containing organic compounds, dicyanodiamine and melem x And a synergistic effect exists between the metal impurities, so that the removal effect of the metal impurity nano particles is improved.
In some embodiments, the weight ratio of the nitrogen-containing organic to the carbon nanotubes is from 0.1 to 300, preferably from 1:1 to 300. In the embodiment of the invention, the adding amount of the nitrogen-containing organic matter is optimized, and if the using amount of the nitrogen-containing organic matter is too high, the surface of the carbon nano tube is wrapped by carbon nitride, so that the conductivity of the carbon nano tube is reduced; if the dosage of the nitrogen-containing organic matter is too low, the metal nano particles can not be completely removed, and the aim of removing metal impurities can not be achieved.
In some embodiments, the rotational speed of the ball milling process is 200 to 350rpm; the time of the ball milling treatment is 5 to 50 hours, preferably 10 to 50 hours. In the embodiment of the invention, the ball milling treatment process opens the end seal of the carbon nano tube by mechanical force, which is beneficial to the contact of nitrogen-containing organic matters and metal nano particles in the carbon nano tube and the removal of the metal nano particles.
In some embodiments, the inert atmosphere comprises at least one of nitrogen, argon, helium. The roasting is carried out in an inert atmosphere, the vacuumizing is not needed, and the requirement on equipment is low.
In some embodiments, the temperature of the roasting is 500 to 1200 ℃, preferably 500 to 1000 ℃; the temperature rise rate of the roasting is 1-20 ℃ min -1 Preferably 5 to 20 ℃ per min -1 (ii) a The roasting time is 1-50 h, preferably 3-30 h. In the embodiment of the invention, the roasting temperature and time are optimized, and the volatile CN is favorable x The generation of substances and the volatilization removal of generated volatile substances of transition metals are beneficial to improving the purification effect of the carbon nano tube.
In some embodiments, the carbon nanotubes are crude carbon nanotubes produced by chemical vapor deposition.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
0.3g of crude carbon nanotubes and 5g of cyanamide were mixed uniformly and transferred to a ball mill jar, and the rotation speed of the ball mill was set at 300rpm, and the mixture was milled for 24 hours. Transferring the ground mixture into a quartz boat, putting the quartz boat into a tube furnace, introducing argon, and keeping the temperature at 10 ℃ for min -1 The temperature rising rate is increased to 800 ℃, and the temperature is kept for 8 hours. Cooling chamberObtaining the purified carbon nano tube after warming.
Example 2
2g of crude carbon nanotubes and 6g of dicyanodiamide were mixed uniformly and transferred to a ball mill pot, the rotation speed of the ball mill was set at 250rpm, and the mixture was ground for 12 hours. Transferring the ground mixture into a quartz boat, putting the quartz boat into a tube furnace, introducing nitrogen, and keeping the temperature at 20 ℃ for min -1 The temperature rising rate is increased to 500 ℃, and the temperature is kept for 30 hours. And cooling to room temperature to obtain the purified carbon nano tube.
As can be seen from fig. 1, in addition to the diffraction peaks (26.3 °, 43.1 °, 54.2 °) of the carbon nanotubes, the XRD spectrum of the crude carbon nanotubes also detected the diffraction peaks (44.5 ° and 51.9 °) of metal Ni, indicating that the crude carbon nanotubes contain a certain amount of residual metal Ni impurities.
From fig. 2, it can be seen that the diffraction peaks (44.5 ° and 51.9 °) of metal Ni of the crude carbon nanotubes after solid-phase purification were disappeared, and only the diffraction peaks (26.3 ° and 43.1 ° and 54.2 °) of the carbon nanotubes were detected, indicating that the metal Ni impurities were effectively removed from the crude carbon nanotubes after solid-phase purification.
Example 3
0.15g of the crude carbon nanotubes and 15g of melamine were mixed uniformly and transferred to a ball mill jar, the rotation speed of the ball mill was set at 350rpm, and the mixture was ground for 24 hours. Transferring the ground mixture into a quartz boat, putting the quartz boat into a tube furnace, introducing helium gas, and keeping the temperature at 5 ℃ for min -1 The temperature rising rate is increased to 1000 ℃, and the temperature is kept for 3 hours. And cooling to room temperature to obtain the purified carbon nano tube.
Example 4
2g of crude carbon nanotubes and 6g of urea were mixed uniformly and transferred to a ball mill pot, and the rotation speed of the ball mill was set at 250rpm for 12 hours. Transferring the ground mixture into a quartz boat, putting the quartz boat into a tube furnace, introducing helium gas, and keeping the temperature at 20 ℃ for min -1 The temperature rising rate is increased to 500 ℃, and the temperature is kept for 30 hours. And cooling to room temperature to obtain the purified carbon nano tube.
Example 5
0.4g of the crude carbon nanotubes and 0.6g of dicyanodiamide were mixed uniformly and transferred to a ball mill pot, the rotation speed of the ball mill was set at 280rpm, and the mixture was milled for 50 hours. Transferring the ground mixture intoPutting the quartz boat into a tube furnace, introducing argon, and keeping the temperature at 10 ℃ for min -1 The temperature rising rate is increased to 1000 ℃, and the temperature is kept for 5 hours. And cooling to room temperature to obtain the purified carbon nano tube.
Example 6
0.15g of crude carbon nanotubes, 5g of miller amine and 10g of dicyanodiamine are mixed uniformly and then transferred into a ball milling tank, the rotating speed of the ball mill is set to 350rpm, and the mixture is milled for 24 hours. Transferring the ground mixture into a quartz boat, putting the quartz boat into a tube furnace, introducing helium gas, and keeping the temperature at 5 ℃ for min -1 The temperature rising rate is increased to 1000 ℃, and the temperature is kept for 3 hours. And cooling to room temperature to obtain purified Carbon Nanotubes (CNTs).
Example 7
The same procedure as in example 6 was repeated, except that no melem was added and 15g of dicyanodiamine was added as the nitrogen-containing organic substance.
Example 8
The same procedure as in example 6 was repeated, except that dicyanodiamine was not added and 15g of Melamine was added as the nitrogen-containing organic substance.
Comparative example 1
The method is the same as the method of example 6, except that the carbon nanotubes purified in example 6 are acid-washed, specifically: adding the purified Carbon Nanotubes (CNTs) into a single-neck round-bottom flask containing 100mL of a 5M HCl solution, installing a condenser tube, and heating and stirring at 120 ℃ for reacting for 6 hours. Cooling to room temperature, filtering, washing with water and ethanol, and drying in a vacuum oven at 60 ℃ for 12h to obtain the acid-washed carbon nanotubes (A-CNTs).
The purified Carbon Nanotubes (CNTs) of example 6 and the acid-washed carbon nanotubes (a-CNTs) of comparative example 1 were tested by electrochemical impedance spectroscopy, and the results are shown in fig. 3. As can be seen from fig. 3, the charge transfer resistance of the carbon nanotubes (a-CNTs) obtained after the acid treatment was 165 Ω, while the charge transfer resistance of the Carbon Nanotubes (CNTs) obtained by the solid phase purification method was only 143 Ω, indicating that the carbon nanotubes obtained by the solid phase purification method had better conductivity. As can be seen from table 1, the residual content of Ni impurities in the carbon nanotubes after the 5M HCl pickling process is reduced from 0.03wt% to 0.01wt%, but the high-temperature pickling process partially destroys the C = C conjugated structure of the tube wall of the carbon nanotubes, which results in poor conductivity of the pickled carbon nanotubes (a-CNTs), increased contact resistance, and reduced performance of the purified carbon nanotubes.
Comparative example 2
The same procedure as in example 6 was repeated except that the carbon nanotubes, melem and dicyanodiamine were mixed uniformly without ball milling and then directly subjected to calcination.
The results of measuring the Ni impurity content of the carbon nanotubes before and after purification in examples 1 to 8 and comparative examples 1 to 2 are shown in table 1.
TABLE 1
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although the above embodiments have been shown and described, it should be understood that they are exemplary and should not be construed as limiting the present invention, and that many changes, modifications, substitutions and alterations to the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the present invention.
Claims (10)
1. A method for solid phase purification of carbon nanotubes, comprising: premixing a carbon nano tube and a nitrogenous organic matter through ball milling treatment to obtain a premix; the pre-mixture is calcined under an inert atmosphere.
2. The method for the solid-phase purification of carbon nanotubes according to claim 1, wherein said nitrogen-containing organic compound comprises at least one of cyanamide, dicyandiamide, melamine, urea, and melem.
3. The method for solid-phase purification of carbon nanotubes according to claim 1, wherein the weight ratio of the nitrogen-containing organic substance to the carbon nanotubes is from 0.1 to 1.
4. The method for the solid-phase purification of carbon nanotubes according to claim 1, wherein the rotation speed of the ball milling process is 200 to 350rpm.
5. The method for the solid-phase purification of carbon nanotubes according to claim 1, wherein the time of the ball milling treatment is 5 to 50 hours.
6. The method for the solid-phase purification of carbon nanotubes of claim 1, wherein said inert atmosphere comprises at least one of nitrogen, argon, helium.
7. The method for the solid-phase purification of carbon nanotubes according to claim 1, wherein the temperature of the calcination is 500 to 1200 ℃.
8. The method for the solid-phase purification of carbon nanotubes according to claim 1, wherein the temperature increase rate of the calcination is 1 to 20 ℃ min -1 。
9. The method for the solid-phase purification of carbon nanotubes according to claim 1, wherein the calcination time is 1 to 50 hours.
10. The method for the solid-phase purification of carbon nanotubes according to claim 1, wherein the carbon nanotubes are crude carbon nanotubes obtained by chemical vapor deposition.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116281961A (en) * | 2023-03-10 | 2023-06-23 | 北京化工大学 | Port selective functionalized carbon nanotube and preparation method thereof |
| CN118125426A (en) * | 2024-04-30 | 2024-06-04 | 湖南金阳石墨烯研究院有限公司 | Purification method of chemical vapor deposition carbon nano tube |
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