CN111470488A - Growth method of one-dimensional carbon chain - Google Patents
Growth method of one-dimensional carbon chain Download PDFInfo
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- CN111470488A CN111470488A CN201910983779.6A CN201910983779A CN111470488A CN 111470488 A CN111470488 A CN 111470488A CN 201910983779 A CN201910983779 A CN 201910983779A CN 111470488 A CN111470488 A CN 111470488A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/34—Length
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- 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
- C01B2202/36—Diameter
Abstract
The invention belongs to the field of preparation processes of one-dimensional carbon chain materials, and particularly relates to a growth method of one-dimensional carbon chains. The invention provides a growth method of a one-dimensional carbon chain, which comprises the following steps: heat treatment, heat treatment and low-pressure heat treatment; the single-walled carbon nanotube used by the growth method is a metal single-walled carbon nanotube and/or a semiconductor single-walled carbon nanotube, and the diameter of the single-walled carbon nanotube is 0.7-2.0 nm. In the technical scheme provided by the invention, the average diameter of the single-walled carbon nanotube as the raw material is controlled, and the Raman spectrum detection proves that the controlled growth of the one-dimensional carbon chain is realized by matching with a subsequent growth method; meanwhile, the yield of the long carbon chain by the growth method provided by the invention can be twice of that of the prior art. The one-dimensional carbon chain growth method provided by the invention solves the technical defect that a one-dimensional carbon chain growth method capable of controlling the length of a one-dimensional carbon chain is lacked in the prior art.
Description
Technical Field
The invention belongs to the field of preparation processes of one-dimensional carbon chain materials, and particularly relates to a growth method of one-dimensional carbon chains.
Background
A one-dimensional carbon chain is a form of the simplest structure in an allotrope of carbon, and has excellent mechanical, electrical and optical properties because its completely one-dimensional structure causes carbon atoms to be bonded in an sp hybridized manner. The research finds that: the band gap of the one-dimensional carbon chain is directly related to the length of the one-dimensional carbon chain, and the short carbon chain has a wide band gap of 2.5-5.5 electron volts and shows insulativity; and the band gap of the long carbon chain is narrow, so that the semiconductor type is shown, and the long carbon chain has a plurality of flexible application prospects in the field of semiconductors. Therefore, it is very important to effectively control and synthesize a carbon chain with a suitable length.
In the prior art, the carbon chain synthesis method mainly comprises two methods: chemical organic synthesis and growth in a confined environment inside carbon nanotubes, while the two methods are able to reach the longest lengths of 44 carbon atoms and more than 6000 carbon atoms, respectively. The latter is relatively simpler and faster and has controllable size, but is limited by the synthesis quality of the carbon nanotubes, and the prior art has not been able to truly make controllable adjustment of the carbon chain length.
Therefore, a method for growing a one-dimensional carbon chain is developed to solve the technical defect that a method for growing a one-dimensional carbon chain capable of controlling the length of the one-dimensional carbon chain is lacking in the prior art, and the problem to be solved by the technical staff in the field is needed.
Disclosure of Invention
In view of this, the present invention provides a method for growing a one-dimensional carbon chain, which is used to solve the technical defect that a method for growing a one-dimensional carbon chain capable of controlling the length of the one-dimensional carbon chain is lacking in the prior art.
The invention provides a growth method of a one-dimensional carbon chain, which comprises the following steps:
step one, heat treatment: cooling the single-walled carbon nanotube after heat treatment;
step two, heat treatment: cooling the cooled product obtained in the first step after heat treatment;
step three, low-pressure heat treatment: heating the cooled product obtained in the second step to 1300-1700 ℃ in a low-pressure environment, then carrying out low-pressure heat treatment, and cooling to room temperature after the heat treatment is finished to obtain a product;
in the first step, the single-walled carbon nanotube is a metal-type single-walled carbon nanotube and/or a semiconductor-type single-walled carbon nanotube, and the diameter of the single-walled carbon nanotube is 0.7-2.0 nm.
Preferably, in the first step, the heat treatment is performed in an environment of a protective atmosphere, wherein the protective atmosphere is: air with humidity less than 30% or oxygen-argon mixed gas with oxygen content of 10% -80%.
Preferably, in the first step, the temperature of the heat treatment is 300-500 ℃, and the time of the heat treatment is 0.5-2 hours.
Preferably, the growing method further comprises: purifying, wherein the purifying step is performed between the first step and the second step;
the purification method comprises the following steps: and (3) soaking the product obtained in the step one in a hydrochloric acid solution, and filtering, washing, rinsing and drying the soaked product in sequence to obtain a purified product.
Preferably, in the purification step, the concentration of the hydrochloric acid solution is 5-37%;
the soaking method comprises the following steps: standing for 1-24 h or performing ultrasonic treatment in water bath for 10-60 min.
Preferably, in the purification step, the filtration method is: filtering with 0.22 micron polytetrafluoroethylene filter membrane;
in the purification step, the washing method comprises the following steps: washing with deionized water for 2-4 times;
in the purification step, the rinsing method comprises the following steps: rinsing the solution with the concentration of more than 90% for 1-2 times;
in the purification step, the drying method comprises the following steps: drying for 0.2-1 hour at the temperature lower than 80 ℃.
Preferably, in the second step, the heat treatment is performed in an environment of a protective atmosphere, wherein the protective atmosphere is: air with humidity less than 30% or oxygen-argon mixed gas with oxygen content of 10% -80%.
Preferably, in the second step, the temperature of the heat treatment is 300-500 ℃, and the time of the heat treatment is 0.5-2 hours.
Preferably, in the third step, the temperature rising speed is 5-20 ℃/min, and the temperature lowering speed is 10-50 ℃/min.
Preferably, in the third step, the low-pressure heat treatment is performed in a protective atmosphere, wherein the protective atmosphere is argon;
in the third step, the pressure of the low-pressure heat treatment is 10-3～10-5Pa, and the time of the low-pressure heat treatment is 0.5-2 h.
In summary, the present invention provides a method for growing a one-dimensional carbon chain, the method comprising: heat treatment, heat treatment and low-pressure heat treatment; the single-walled carbon nanotube used by the growth method is a metal single-walled carbon nanotube and/or a semiconductor single-walled carbon nanotube, and the average diameter of the single-walled carbon nanotube is 0.7-2.0 nm. In the technical scheme provided by the invention, the average diameter of the single-walled carbon nanotube as the raw material is controlled, and the Raman spectrum detection proves that the controlled growth of the one-dimensional carbon chain is realized by matching with a subsequent growth method; meanwhile, the yield of the long carbon chain by the growth method provided by the invention can be twice of that of the prior art. The one-dimensional carbon chain growth method provided by the invention solves the technical defect that a one-dimensional carbon chain growth method capable of controlling the length of a one-dimensional carbon chain is lacked in the prior art.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for growing a one-dimensional carbon chain according to an embodiment of the present invention;
FIG. 2 is a Raman spectrum diagram of the final product obtained from single-walled carbon nanotubes with the average diameter of the raw material of 1.0 nanometer;
FIG. 3 is a Raman spectrum of the final product obtained from single-walled carbon nanotubes with an average diameter of 1.1 nm;
FIG. 4 is a Raman spectrum of the final product obtained from single-walled carbon nanotubes with an average diameter of 1.3 nm;
FIG. 5 is a Raman spectrum of the final product obtained from the semiconductor-type single-walled carbon nanotube with the average diameter of the raw material of 1.3 nm;
FIG. 6 is a Raman spectrum diagram of the final product obtained from the metal-type single-walled carbon nanotube with the average diameter of the raw material of 1.3 nm;
FIG. 7 is a Raman spectrum of the final product obtained from single-walled carbon nanotubes with an average diameter of 1.4 nm;
FIG. 8 is a Raman spectrum diagram of the final product obtained from the single-walled carbon nanotube with the average diameter of the raw material of 1.7 nanometers.
Detailed Description
The embodiment of the invention provides a growth method of a one-dimensional carbon chain, which is used for solving the technical defect that the growth method of the one-dimensional carbon chain capable of controlling the length of the one-dimensional carbon chain is lacked in the prior art.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to illustrate the present invention in more detail, the following will specifically describe a method for growing a one-dimensional carbon chain provided in the examples of the present invention with reference to the examples.
Example 1
In this example, the raw material was a single-walled carbon nanotube having an average diameter of 1.0 nm.
Placing a single-walled carbon nanotube with the diameter of 1.0 nanometer in a tube furnace, heating to 400 ℃ in dry air with the humidity not more than 30%, keeping for 1 hour for heat treatment, and then naturally cooling to room temperature to obtain a first product 1.
And (3) putting the first product 1 into a hydrochloric acid solution with the concentration of 37%, carrying out water bath ultrasonic treatment for 60 minutes, filtering the obtained material solution by using a polytetrafluoroethylene filter membrane with the pore size of 0.22 micrometer, washing for 2 times by using deionized water and rinsing for 1 time by using ethanol with the concentration of more than 90%, and drying to obtain the purified single-walled carbon nanotube paper with the diameter of 1.0 nanometer, namely a second product 1.
And (3) placing the second product 1 in a tube furnace, heating to 400 ℃ in a mixed gas atmosphere of oxygen and argon (40% of oxygen and 60% of argon), keeping for 1 hour for heat treatment, and naturally cooling to room temperature to obtain single-walled carbon nanotube paper with an open port and a diameter of 1.0 nanometer, namely a third product 1.
And (3) placing the third product 1 in an alumina boat, placing the alumina boat in a high-temperature furnace, introducing high-purity argon with the purity of more than 99.999 percent as protective gas, slowly heating to 1400 ℃ at the heating rate of 10 ℃/min for heat treatment for 1 hour, and slowly cooling to room temperature at the cooling rate of 20 ℃/min to obtain the one-dimensional carbon chain grown in the carbon nano tube.
FIG. 2 is a Raman spectrum characterization chart of the sample obtained in this example, and the Raman mode peak of the one-dimensional carbon chain observable from FIG. 2 is located around 1840 wave number, corresponding to the one-dimensional carbon chain with the length of 4-9 nm.
Example 2
In this example, the raw material was single-walled carbon nanotubes having an average diameter of 1.1 nm.
Placing single-walled carbon nanotubes with the average diameter of 1.1 nm in a tube furnace, heating to 400 ℃ in mixed gas of oxygen and argon (40% of oxygen and 60% of argon), keeping for 1 hour for heat treatment, and then naturally cooling to room temperature to obtain a first product 2.
And (3) putting the first product 2 into a hydrochloric acid solution with the concentration of 20%, carrying out water bath ultrasonic treatment for 40 minutes, filtering the obtained material solution by using a polytetrafluoroethylene filter membrane with the pore size of 0.22 micrometer, washing the material solution for 2 times by using deionized water and rinsing the material solution for 1 time by using ethanol with the concentration of more than 90%, and drying the material solution to obtain the purified single-walled carbon nanotube paper with the diameter of 1.1 nanometer, namely a second product 2.
And (3) placing the second product 2 in a tube furnace, heating to 400 ℃ in dry air with the humidity not more than 30%, keeping for 1 hour for heat treatment, and naturally cooling to room temperature to obtain the single-walled carbon nanotube paper with the diameter of 1.1 nm with an open port, namely the third product 2.
Putting the third product 2 in an alumina boat, putting the alumina boat in a high-temperature furnace, introducing high-purity argon with the purity of more than 99.999 percent as protective gas, and reducing the pressure in the tubular high-temperature furnace to 10 by using a mechanical pump molecular pump combination-3～10-5Pa, then slowly heating to 1400 ℃ at a heating rate of 10 ℃/min for heat treatment for 1 hour, and then slowly cooling to room temperature at a cooling rate of 20 ℃/min, thus obtaining the one-dimensional carbon chain grown in the carbon nano tube.
FIG. 3 is a Raman spectrum characterization chart of the sample obtained in this example, and the Raman mode peak of the one-dimensional carbon chain observable from FIG. 3 is located between 1780 and 1900 wavenumbers, corresponding to the one-dimensional carbon chain of 4 nm to 900 nm in length.
Example 3
In this example, the raw material was single-walled carbon nanotubes having an average diameter of 1.3 nm.
Placing the semiconductor single-walled carbon nanotube with the average diameter of 1.3 nanometers in a tube furnace, heating to 400 ℃ in mixed gas of oxygen and argon (10% of oxygen and 90% of argon), keeping for 1 hour for heat treatment, and then naturally cooling to room temperature to obtain a first product 3.
And (3) putting the first product 3 into a hydrochloric acid solution with the concentration of 5%, carrying out water bath ultrasonic treatment for 10 minutes, filtering the obtained material solution by using a polytetrafluoroethylene filter membrane with the pore size of 0.22 micrometer, washing for 2 times by using deionized water and rinsing for 1 time by using ethanol with the concentration of more than 90%, and drying to obtain the purified single-walled carbon nanotube paper with the diameter of 1.3 nanometers, namely a second product 3.
The second product 3 was placed in a tube furnace, heated to 400 ℃ in a dry mixture of oxygen and argon (80% oxygen and 20% argon, and held for 1 hour for heat treatment, and then cooled naturally to room temperature to obtain single-walled carbon nanotube paper with an open end having a diameter of 1.3 nm, i.e., the third product 3.
Putting the third product 3 in an alumina boat, putting the alumina boat in a high-temperature furnace, introducing high-purity argon with the purity of more than 99.999 percent as protective gas, and reducing the pressure in the tubular high-temperature furnace to 10 by using a mechanical pump molecular pump combination-3～10-5Pa, then slowly heating to 1460 ℃ at a heating rate of 20 ℃/min for heat treatment for 1 hour, and then slowly cooling to room temperature at a cooling rate of 10 ℃/min, thus obtaining the one-dimensional carbon chain grown in the carbon nano tube.
To verify the purity of the samples, the samples were thoroughly characterized using Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM). The surface of the carbon nano tube is smooth, the purity of the sample is high, no catalyst exists, a one-dimensional carbon chain exists in the carbon nano tube, and the length distribution can be observed from 4 nanometers to 30 nanometers.
FIG. 3 is a Raman spectrum characterization chart of the sample obtained in this example, and the Raman mode peak of the one-dimensional carbon chain observed in FIG. 3 is located between 1780 and 1900 wavenumbers, corresponding to the one-dimensional carbon chain of 4 nm to 900 nm in length. Compared with the raman spectra of the embodiment 1 and the embodiment 2, the strength of the one-dimensional carbon chain raman mode of the embodiment is greatly improved, which shows that the yield of the one-dimensional carbon chain prepared by using the carbon nanotube as the raw material is very high.
Example 4
In this example, the raw materials were metal-type and semiconductor-type single-walled carbon nanotubes having an average diameter of 1.3 nm, respectively.
Respectively placing metal type single-walled carbon nanotubes and semiconductor type single-walled carbon nanotubes with the diameter of 1.3 nanometers in a tube furnace, heating to 400 ℃ in a mixed gas of wet oxygen and argon (80% of oxygen and 20% of argon), keeping for 1 hour for heat treatment, and then naturally cooling to room temperature to obtain a first product 4.
And (3) putting the first product 4 into a hydrochloric acid solution with the concentration of 20%, carrying out water bath ultrasonic treatment for 60 minutes, filtering the obtained material solution by using a polytetrafluoroethylene filter membrane with the pore size of 0.22 micrometer, washing for 2 times by using deionized water and rinsing for 1 time by using ethanol with the concentration of more than 90%, and drying to obtain the purified single-walled carbon nanotube paper with the diameter of 1.3 nanometers, namely a second product 4.
The second product 4 was placed in a tube furnace, heated to 400 ℃ in a mixed gas of oxygen and argon (10% oxygen and 0% argon), and kept for 1 hour for heat treatment, and then naturally cooled to room temperature, to obtain single-walled carbon nanotube paper with an open end having a diameter of 1.3 nm, i.e., a third product 4.
Putting the third product 4 in an alumina boat, putting the alumina boat in a high-temperature furnace, introducing high-purity argon with the purity of more than 99.999 percent as protective gas, and reducing the pressure in the tubular high-temperature furnace to 10 by using a mechanical pump molecular pump combination-3～10-5Pa, then slowly heating to 1460 ℃ at the heating rate of 10 ℃/min for heat treatment for 1 hour, and then slowly cooling to room temperature at the cooling rate of 20 ℃/min, thus obtaining the one-dimensional carbon chain grown in the carbon nano tube.
In order to verify the length distribution of the one-dimensional carbon chain, raman spectrum characterization was performed on the one-dimensional carbon chain, as shown in fig. 5 and 6, and a raman mode peak of the one-dimensional carbon chain was observed, which is located between 1780 and 1900 wavenumbers, and corresponds to the one-dimensional carbon chain with a length of 4 nm to 900 nm.
Compared with the example 3, the position and the intensity of the one-dimensional carbon chain Raman mode peak have no obvious change, which shows that the one-dimensional carbon chain prepared by using the single-walled carbon nanotube separated by the metal type or the semiconductor type as the raw material and the mixed single-walled carbon nanotube with similar diameter distribution have no great change, so that the diameter of the single-walled carbon nanotube mainly determines the growth length and the yield of the one-dimensional carbon chain and has little relation with the conductivity.
Example 5
In this example, the raw material was single-walled carbon nanotubes having an average diameter of 1.4 nm.
Placing the single-walled carbon nanotube with the average diameter of 1.4 nanometers in a tube furnace, heating to 400 ℃ in dry air with the humidity not more than 30%, keeping for 1 hour for heat treatment, and then naturally cooling to room temperature to obtain a first product 5.
And (3) putting the first product 5 into a hydrochloric acid solution with the concentration of 20%, carrying out water bath ultrasonic treatment for 60 minutes, filtering the obtained material solution by using a polytetrafluoroethylene filter membrane with the pore size of 0.22 micrometer, washing for 2 times by using deionized water and rinsing for 1 time by using ethanol with the concentration of more than 90%, and drying to obtain the purified single-walled carbon nanotube paper with the diameter of 1.4 nanometers, namely the second product 5.
The second product 5 was placed in a tube furnace, heated to 400 ℃ in a mixed gas of oxygen and argon (40% oxygen and 60% argon), and kept for 1 hour for heat treatment, and then naturally cooled to room temperature, to obtain single-walled carbon nanotube paper with an open end having a diameter of 1.4 nm, i.e., a third product 5.
Placing the third product 5 in an alumina boat, placing in a high temperature furnace, introducing high purity argon with purity of more than 99.999% as protective gas, and reducing the pressure in the tubular high temperature furnace to 10 by using a mechanical pump molecular pump combination-3～10-5Pa, then slowly heating to 1500 ℃ at the heating rate of 10 ℃/min for heat treatment for 1 hour, and then slowly cooling to room temperature at the cooling rate of 20 ℃/min, wherein the final product is the one-dimensional carbon chain grown in the carbon nano tube.
In order to verify the length distribution of the one-dimensional carbon chain, the raman spectrum characterization is performed on the one-dimensional carbon chain, and as shown in fig. 7, a raman mode peak of the one-dimensional carbon chain is observed, is located at about 1852 wave numbers, and corresponds to the one-dimensional carbon chain with the length of 4-9 nanometers. Compared with the examples 1, 2, 3 and 4, the wave number range of the one-dimensional carbon chain Raman mode is extremely small, which shows that the length distribution is very narrow; however, the intensity of the Raman mode is the lowest, which indicates that the yield of the one-dimensional carbon chain prepared by using the carbon nano tube as the raw material is lower. In production practice, suitable raw materials can be adjusted and selected according to specific yield requirements or one-dimensional carbon chain length distribution requirements.
Example 6
In this example, the raw material was single-walled carbon nanotubes having an average diameter of 1.7 nm.
Placing a single-walled carbon nanotube with the average diameter of 1.7 nanometers in a tube furnace, heating to 400 ℃ in mixed gas of oxygen and argon (50% of oxygen and 50% of argon), keeping for 1 hour for heat treatment, and then naturally cooling to room temperature to obtain a first product 7.
And (3) putting the first product 7 into a hydrochloric acid solution with the concentration of 20%, carrying out water bath ultrasonic treatment for 60 minutes, filtering the obtained material solution by using a polytetrafluoroethylene filter membrane with the pore size of 0.22 micrometer, washing for 2 times by using deionized water and rinsing for 1 time by using ethanol with the concentration of more than 90%, and drying to obtain the purified single-walled carbon nanotube paper with the diameter of 1.7 nanometers, namely the second product 7.
And (3) placing the second product 7 in a tube furnace, heating to 400 ℃ in dry air with the humidity not more than 30%, keeping the temperature for 1 hour for heat treatment, and naturally cooling to room temperature to obtain the single-walled carbon nanotube paper with the diameter of 1.7 nanometers with an open port, namely the third product 7.
Placing the third product 7 in an alumina boat, placing in a high temperature furnace, and reducing the pressure in the tubular high temperature furnace to 10 with a mechanical pump molecular pump combination-3～10-5Pa, then slowly heating to 1500 ℃ at the heating rate of 10 ℃/min for heat treatment for 1 hour, and then slowly cooling to room temperature at the cooling rate of 20 ℃/min, thus obtaining the one-dimensional carbon chain grown in the carbon nano tube.
In order to verify the length distribution of the one-dimensional carbon chain, raman spectrum characterization is performed on the one-dimensional carbon chain, as shown in fig. 8, a raman mode peak of the one-dimensional carbon chain is observed, and is located between 1830 and 1860 wave numbers, and corresponds to the one-dimensional carbon chain with the length of 4 nanometers to 20 nanometers.
Compared with other examples, the wave number range of the one-dimensional carbon chain Raman mode is smaller, which shows that the length distribution is narrower; however, the strength is low, which indicates that the yield of the one-dimensional carbon chain prepared by using the carbon nanotube as a raw material is low.
According to the technical scheme, the one-dimensional carbon chain growth method provided by the invention has the following advantages:
1. in the growth method provided by the invention, the controlled growth of the one-dimensional carbon chain with controllable length distribution is successfully realized by utilizing the single-walled carbon nanotubes with different average diameters for the first time.
2. In the growth method provided by the invention, the yield of the long carbon chain which is nearly two times higher than the prior art is successfully obtained by screening the single-walled carbon nanotube with small diameter.
3. In the growth method provided by the invention, the controlled growth of the one-dimensional carbon chains with consistent and almost the same length is successfully realized by controlling the diameter of the single-walled carbon nanotube.
4. In the growth method provided by the invention, a relevant mechanism influencing the growth length of the carbon chain is disclosed, namely the carbon chain length is directly related to the inner diameter of the carbon nano tube and is not related to the conductivity type of the carbon nano tube.
5. In the growth method provided by the invention, high-temperature heat treatment is utilized, more than 90% of single-wall carbon nano tubes are converted into double-wall carbon nano tubes under the condition of not adding a carbon source, and one-dimensional carbon chains are grown in the tubes.
6. In the growth method provided by the invention, the single-walled carbon nanotube with the average diameter of 1.3 nanometers is taken as a template, more super-long one-dimensional carbon chains can be grown, and the longest length of the super-long one-dimensional carbon chains can reach hundreds of nanometers.
In summary, the present invention provides a method for growing a one-dimensional carbon chain, the method comprising: heat treatment, purification, heat treatment and low pressure heat treatment; the single-walled carbon nanotube used by the growth method is a metal single-walled carbon nanotube and/or a semiconductor single-walled carbon nanotube, and the average diameter of the single-walled carbon nanotube is 0.7-2.0 nm. In the technical scheme provided by the invention, the average diameter of the single-walled carbon nanotube as the raw material is controlled, and the Raman spectrum detection proves that the controlled growth of the one-dimensional carbon chain is realized by matching with a subsequent growth method; meanwhile, the yield of the long carbon chain by the growth method provided by the invention can be twice of that of the prior art. The one-dimensional carbon chain growth method provided by the invention solves the technical defect that a one-dimensional carbon chain growth method capable of controlling the length of a one-dimensional carbon chain is lacked in the prior art.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A growth method of a one-dimensional carbon chain is characterized by comprising the following steps:
step one, heat treatment: cooling the single-walled carbon nanotube after heat treatment;
step two, heat treatment: cooling the cooled product obtained in the first step after heat treatment;
step three, low-pressure heat treatment: heating the cooled product obtained in the second step to 1300-1700 ℃ in a low-pressure environment, then carrying out low-pressure heat treatment, and cooling to room temperature after the heat treatment is finished to obtain a product;
in the first step, the single-walled carbon nanotube is a metal-type single-walled carbon nanotube and/or a semiconductor-type single-walled carbon nanotube, and the diameter of the single-walled carbon nanotube is 0.7-2.0 nm.
2. The growth method according to claim 1, wherein in step one, the heat treatment is performed in an environment of a protective atmosphere, and the protective atmosphere is: air with humidity less than 30% or oxygen-argon mixed gas with oxygen content of 10% -80%.
3. The growing method according to claim 1, wherein in the first step, the temperature of the heat treatment is 300-500 ℃, and the time of the heat treatment is 0.5-2 h.
4. The growing method of claim 1, further comprising: purifying, wherein the purifying step is performed between the first step and the second step;
the purification method comprises the following steps: and (3) soaking the product obtained in the step one in a hydrochloric acid solution, and filtering, washing, rinsing and drying the soaked product in sequence to obtain a purified product.
5. The growing method according to claim 4, wherein in the purification step, the concentration of the hydrochloric acid solution is 5-37%;
the soaking method comprises the following steps: standing for 1-24 h or performing ultrasonic treatment in water bath for 10-60 min.
6. The growing method according to claim 4, wherein in the purifying step, the filtering method comprises: filtering with 0.22 micron polytetrafluoroethylene filter membrane;
in the purification step, the washing method comprises the following steps: washing with deionized water for 2-4 times;
in the purification step, the rinsing method comprises the following steps: rinsing the solution with the concentration of more than 90% for 1-2 times;
in the purification step, the drying method comprises the following steps: drying for 0.2-1 hour at the temperature lower than 80 ℃.
7. The growth method according to claim 1, wherein in step two, the heat treatment is performed in an environment of a protective atmosphere: air with humidity less than 30% or oxygen-argon mixed gas with oxygen content of 10% -80%.
8. The growing method according to claim 1, wherein in the second step, the temperature of the heat treatment is 300 to 500 ℃, and the time of the heat treatment is 0.5 to 2 hours.
9. The growing method according to claim 1, wherein in the third step, the temperature-raising speed is 5-20 ℃/min, and the temperature-lowering speed is 10-50 ℃/min.
10. The growth method according to claim 1, wherein in step three, the low pressure heat treatment is performed in a protective atmosphere, and the protective atmosphere is argon;
in the third step, the pressure of the low-pressure heat treatment is 10-3～10-5Pa, said low pressureThe heat treatment time is 0.5-2 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340086A (en) * | 2022-08-01 | 2022-11-15 | 中山大学 | Method for improving carbon chain yield |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368569B1 (en) * | 1998-10-02 | 2002-04-09 | University Of Kentucky Research Foundation | Method of solubilizing unshortened carbon nanotubes in organic solutions |
| CN101293629A (en) * | 2007-06-08 | 2008-10-29 | 北京大学 | Process for producing carbon nano-tube or nano-wire bifurcate structure |
| CN101481086A (en) * | 2009-01-22 | 2009-07-15 | 上海交通大学 | Non-damaged in situ construction method for nano-node |
| CN102020267A (en) * | 2010-12-30 | 2011-04-20 | 上海大学 | Purification method of single-wall carbon nano tube |
| CN102205957A (en) * | 2011-04-07 | 2011-10-05 | 上海大学 | Method for generating carbon chain in multi-wall carbon nanotube |
| JP4977982B2 (en) * | 2005-08-29 | 2012-07-18 | ソニー株式会社 | Method for producing linear carbon material and method for producing functional device |
| CN102730666A (en) * | 2011-04-15 | 2012-10-17 | 上海大学 | Method for preparing carbon nano-wires |
| CN110143583A (en) * | 2019-07-06 | 2019-08-20 | 金雪莉 | A kind of magnanimity prepares the method and device of carbon nanomaterial |
-
2019
- 2019-10-16 CN CN201910983779.6A patent/CN111470488A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368569B1 (en) * | 1998-10-02 | 2002-04-09 | University Of Kentucky Research Foundation | Method of solubilizing unshortened carbon nanotubes in organic solutions |
| JP4977982B2 (en) * | 2005-08-29 | 2012-07-18 | ソニー株式会社 | Method for producing linear carbon material and method for producing functional device |
| CN101293629A (en) * | 2007-06-08 | 2008-10-29 | 北京大学 | Process for producing carbon nano-tube or nano-wire bifurcate structure |
| CN101481086A (en) * | 2009-01-22 | 2009-07-15 | 上海交通大学 | Non-damaged in situ construction method for nano-node |
| CN102020267A (en) * | 2010-12-30 | 2011-04-20 | 上海大学 | Purification method of single-wall carbon nano tube |
| CN102205957A (en) * | 2011-04-07 | 2011-10-05 | 上海大学 | Method for generating carbon chain in multi-wall carbon nanotube |
| CN102730666A (en) * | 2011-04-15 | 2012-10-17 | 上海大学 | Method for preparing carbon nano-wires |
| CN110143583A (en) * | 2019-07-06 | 2019-08-20 | 金雪莉 | A kind of magnanimity prepares the method and device of carbon nanomaterial |
Non-Patent Citations (2)
| Title |
|---|
| LEI SHI ET AL: ""Carbon nanotubes from enhanced direct injection pyrolytic synthesis as templates for long linear carbon chain formation"", 《PHYSICA STATUS SOLIDI B-BASIC SOLID STATE PHYSICS》 * |
| 李允令: ""一维碳原子链的制备及表面增强拉曼光谱研究"", 《中国优秀硕士学位论文全文数据库 基础科学辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340086A (en) * | 2022-08-01 | 2022-11-15 | 中山大学 | Method for improving carbon chain yield |
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