CN110040720B - Preparation method of high-purity narrow-diameter-distribution small-diameter double-wall carbon nano tube - Google Patents
Preparation method of high-purity narrow-diameter-distribution small-diameter double-wall carbon nano tube Download PDFInfo
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Abstract
The invention relates to the field of structure control preparation of carbon nanotubes, in particular to a preparation method of a double-wall carbon nanotube with high purity, narrow diameter distribution and small diameter. A floating catalyst chemical vapor deposition method is adopted, toluene and ethylene are used as carbon sources, ferrocene is used as a catalyst precursor, sulfur is used as a growth promoter, and hydrogen is used as carrier gas to grow the carbon nano tube. The number of double-wall carbon nano tubes in the product accounts for 50-70% of the total number of the carbon nano tubes, and the balance is single-wall carbon nano tubes. And (3) performing heat treatment on the product in air, oxidizing to remove amorphous carbon and single-wall carbon nanotubes in the product, wherein the number of the double-wall carbon nanotubes accounts for more than 95% of the total number of the carbon nanotubes after treatment, the double-wall carbon nanotubes have complete structures, the diameters of the double-wall carbon nanotubes are intensively distributed in 1.8-2.3 nm, and the centralized oxidation temperature is higher than 800 ℃. Finally, the preparation of the double-wall carbon nano tube with high purity, narrow diameter distribution and small diameter is realized.
Description
Technical Field
The invention relates to the field of structure control preparation of carbon nanotubes, in particular to a preparation method of a double-wall carbon nanotube with high purity, narrow diameter distribution and small diameter.
Background
The double-wall carbon nano tube can be regarded as a one-dimensional hollow tubular structure formed by coaxially curling double-layer graphene, and has good flexibility, ultrahigh specific surface area and excellent mechanical and electrical properties. And, because the peculiar double-deck pipe wall structure, compare in single-walled carbon nanotube, double-walled carbon nanotube has higher mechanical strength, and the form of mass transfer is diversified between the interior outer wall, has more abundant diversified application. Moreover, the outer tube wall of the double-walled carbon nanotubes protects the inner tube wall, and the structurally sound inner wall maintains good mechanical and electron transport properties even if the outer wall is functionalized to some extent (1 Yao Zhao, Jinquan Wei, Robert Vajtai, Pulickel M.Ajayan & Enrique V.Barrera.SCIENTIFIC report.1 (83): SEP 6 (2011)). Therefore, the double-wall carbon nano tube can functionalize the outer wall thereof to improve the compatibility of the double-wall carbon nano tube with other substances, can keep the excellent properties of the single-wall carbon nano tube such as mechanics, electricity, heat and the like, and has attractive application potential. Therefore, it is necessary to develop a structure-controlled preparation technique of double-walled carbon nanotubes.
At present, double-walled carbon nanotubes are generally prepared by a supported chemical vapor deposition method (reference 2Guoqing Ning, Yi Liu, Fei Wei, Qian Wen, Guohua Luo. J Phys Chem C,2007,111: 1969-. The supported chemical vapor deposition method needs to support the catalyst on a porous matrix, so a post-treatment process is needed to remove the carrier in the product, and the problems of complex preparation process, structural defects introduced in the carrier removing process and the like exist. The floating catalyst chemical vapor deposition method (floating method) takes an organic metallocene as a catalyst precursor, the catalyst precursor is carried into a reaction zone by utilizing carrier gas, the metallocene is decomposed in a high-temperature zone and forms metal nano-particles, and a carbon source is decomposed, permeated and separated out of the double-wall carbon nano-tube on the metal particles under proper conditions. Other impurities are not introduced in the whole preparation process, and the preparation method can be used for continuous preparation, so that the macroscopic quantity double-wall carbon nano tube with high quality and high purity is expected to be prepared. However, the double-walled carbon nanotube sample grown by the floating method has the problems of low purity, poor structural uniformity, large diameter (>3nm), mixture of double-walled carbon nanotubes and other carbon nanotubes in most products, and the like, and further performance and application research is limited. At present, the controllable preparation technology of the double-walled carbon nano-tube with high purity and small diameter is still blank at home and abroad. Therefore, the controllable preparation technology of the double-wall carbon nano tube with high purity, high crystallinity, high quality, uniform diameter and small diameter has important academic significance and application value.
Disclosure of Invention
The invention aims to provide a preparation method of a high-purity, narrow-diameter-distribution and small-diameter double-wall carbon nanotube, which realizes the enrichment of the high-purity, high-crystallinity, uniform-diameter and small-diameter double-wall carbon nanotube by means of the combination of the optimization of thermodynamic and kinetic conditions for the growth of the small-diameter double-wall carbon nanotube, the control of the growth process and the subsequent weak oxidation treatment.
The technical scheme of the invention is as follows:
a preparation method of a double-wall carbon nano tube with high purity, narrow diameter distribution and small diameter adopts a floating catalyst chemical vapor deposition method, hydrogen is used as carrier gas, methylbenzene and ethylene are used as carbon sources, ferrocene is used as a catalyst precursor, sulfur is used as an accelerant to grow the carbon nano tube, the number of the double-wall carbon nano tube in the obtained product accounts for 50-70% of the total number of the carbon nano tube, and the balance is the single-wall carbon nano tube; and then, the prepared product is spread in a horizontal tube furnace, and amorphous carbon and single-walled carbon nanotubes in the product are removed by heat treatment and oxidation in the air, so that the enrichment of the double-walled carbon nanotubes with high purity, narrow diameter distribution and small diameter is realized.
The preparation method of the double-wall carbon nano tube with high purity, narrow diameter distribution and small diameter comprises the following specific steps: under the protection of hydrogen, heating a chemical vapor deposition horizontal tube furnace to 1100-1300 ℃, adjusting the hydrogen flow to 1000-3000 sccm, introducing 0.5-30 sccm of ethylene, and simultaneously injecting a mixed solution prepared from toluene, ferrocene and sulfur powder at a constant speed of 0.5-1 ml/h, wherein the mass ratio of the mixed solution is 100 (3-5): (0.1-1), and growing the carbon nano tube for 0.5-5 h.
The preparation method of the high-purity narrow-diameter-distribution small-diameter double-wall carbon nano tube preferably comprises the steps of heating a chemical vapor deposition horizontal tube furnace to 1150-1250 ℃ under the protection of hydrogen, adjusting the hydrogen flow to 1700-2400 sccm, introducing 3-15 sccm of ethylene, simultaneously injecting a mixed solution prepared from methylbenzene, ferrocene and sulfur powder at a constant speed of 0.5-0.8 ml/h, wherein the mass ratio of the mixed solution is (3-5) and (0.25-0.65), and growing the carbon nano tube for 0.5-2 h.
The preparation method of the double-wall carbon nano tube with high purity, narrow diameter distribution and small diameter comprises the steps of placing a product prepared by a floating catalyst chemical vapor deposition method in a horizontal tube furnace in an air atmosphere at room temperature, then heating the horizontal tube furnace to 500-540 ℃ at the speed of 10-20 ℃/min, keeping the temperature for 0.5-3 hours, and naturally cooling the product to the room temperature along with the furnace.
According to the preparation method of the double-wall carbon nano tube with high purity, narrow diameter distribution and small diameter, the double-wall carbon nano tube in the product is highly enriched, the number of the double-wall carbon nano tube accounts for more than 95% of the total number of the carbon nano tube, the diameter of the double-wall carbon nano tube is uniform, and more than 85% of the diameter of the double-wall carbon nano tube is intensively distributed in the range of 1.8-2.3 nanometers.
The preparation method of the double-wall carbon nano tube with high purity, narrow diameter distribution and small diameter has high crystallinity of the double-wall carbon nano tube, few defects and concentrated oxidation temperature of more than 800 ℃.
The design idea of the invention is as follows:
the invention utilizes the intrinsic physical property that the small-diameter single-wall carbon nano tube has higher reaction activity, and provides an innovative idea of combining the optimization of the growth condition of the double-wall carbon nano tube and the weak oxidation treatment in the air to prepare the high-purity small-diameter double-wall carbon nano tube. Namely: firstly, a mixture of a small-diameter single-wall carbon nanotube and a double-wall carbon nanotube is prepared by controlling thermodynamic and kinetic conditions, and then the single-wall carbon nanotube is removed by weak oxidation treatment in air without damaging the structure of the double-wall carbon nanotube. The invention finally realizes the controllable preparation of the small-diameter double-wall carbon nano tube, improves the purity of the double-wall carbon nano tube, keeps the structural integrity of the intrinsic carbon layer of the double-wall carbon nano tube, and obtains the small-diameter double-wall carbon nano tube with high purity, pure outer wall, extremely low carbon impurity content and uniform diameter.
The invention has the advantages and beneficial effects that:
1. the invention adopts a floating catalyst chemical vapor deposition method, firstly prepares a mixed product of double-wall carbon nanotubes and single-wall carbon nanotubes, and then carries out weak oxidation treatment on the product at a proper temperature in an air atmosphere to remove carbon impurities and single-wall carbon nanotubes in the product, thereby finally realizing high enrichment of the double-wall carbon nanotubes with high purity, narrow diameter distribution and small diameter, and the content of the double-wall carbon nanotubes in the product carbon nanotubes is more than 95 percent.
2. The diameter of the double-wall carbon nano tube obtained by the method is uniform, more than 85% of the diameter is intensively distributed in the range of 1.8-2.3 nanometers, and the diameter of the double-wall carbon nano tube is equivalent to that of a single-wall carbon nano tube prepared by a common floating catalyst chemical vapor deposition method, but the double-wall tube wall has stronger mechanical strength, higher stability, richer functionalized forms and more application potential.
3. The invention is based on a mode of combining floating catalyst chemical vapor deposition preparation and low-temperature weak oxidation post-treatment, and the whole process flow is simple and easy to repeat and prepare in scale.
Drawings
FIG. 1 is a scanning electron micrograph of the carbon nanotube prepared in example 1. Wherein, the picture (a) is a prepared carbon nano tube; (b) the figure shows the carbon nanotubes after the weak oxidation treatment.
FIG. 2 is a high-resolution TEM image of the carbon nanotubes prepared in example 1. Wherein, the picture (a) is a prepared carbon nano tube; (b) the figure shows the carbon nanotubes after the weak oxidation treatment.
FIG. 3 is a diameter distribution statistical chart of double-walled carbon nanotubes after the weak oxidation treatment in example 1.
FIG. 4 thermogravimetric curves of the carbon nanotubes prepared in example 1. Wherein, the picture (a) is a prepared carbon nano tube; (b) the figure shows the carbon nanotubes after the weak oxidation treatment. In the figure, the abscissa Temp represents temperature (. degree. C.), the left ordinate Mass represents Mass percent (%), and the right ordinate DSC represents heat flow rate (mW/mg).
Detailed Description
In the specific implementation process, hydrogen is used as carrier gas, toluene and ethylene are used as carbon sources, ferrocene is used as a catalyst precursor, sulfur is used as a growth promoter, the growth of the carbon nano tube is carried out, then the prepared product is flatly paved in a horizontal tube furnace, and amorphous carbon and a single-walled carbon nano tube in the product are removed by in-situ oxidation in a mode of heat treatment in air, so that the enrichment of the high-purity, narrow-diameter distribution and small-diameter double-walled carbon nano tube is realized. Under the optimized condition, the number of double-wall carbon nano tubes in the prepared product accounts for 50-70% of the total number of the carbon nano tubes, and the balance is single-wall carbon nano tubes; after the weak oxidation treatment, the number of the double-wall carbon nano tubes accounts for more than 95 percent of the total number of the carbon nano tubes. The diameter of the double-wall carbon nano tube is uniform (more than 85 percent of the diameter of the double-wall carbon nano tube is intensively distributed in 1.8-2.3 nanometers), the crystallinity is high, the defects are few, and the centralized oxidation temperature is higher than 800 ℃.
The present invention will be described in more detail below with reference to examples and the accompanying drawings.
Example 1.
Firstly, preparing a mixed solution of toluene, ferrocene and sulfur powder with the mass ratio of 100:3:0.25, and carrying out ultrasonic treatment for 10 minutes for later use. Under the protection of low-flow hydrogen, heating a chemical vapor deposition horizontal tubular furnace to 1200 ℃, then adjusting the hydrogen flow to 1800sccm, introducing 7sccm ethylene, and simultaneously injecting a mixed solution prepared from toluene, ferrocene and sulfur powder at a constant speed of 0.6ml/h to grow the carbon nano tube for 1 h.
And flatly paving the prepared product obtained in the step at the center of a constant-temperature area of a horizontal tube furnace with two open ends, then heating the horizontal tube furnace to 530 ℃ at the speed of 15 ℃/min, keeping the temperature for 2 hours, removing amorphous carbon and single-walled carbon nanotubes in the product through in-situ weak oxidation, and naturally cooling the sample to room temperature along with the furnace.
And characterizing the samples in a preparation state and after the weak oxidation treatment by using a scanning electron microscope and a transmission electron microscope. As shown in fig. 1, the scanning electron microscope characterization shows that the samples in the preparation state (fig. 1a) and after the weak oxidation treatment (fig. 1b) are very pure, and the surface of the carbon tube has no granular impurities. As shown in fig. 2, transmission electron microscopy characterization shows that the as-prepared sample (fig. 2a) is a mixture of single-walled and double-walled carbon nanotubes, and the number of the walls and the number of the carbon nanotubes are counted under the transmission electron microscopy, and the result shows that the number of the double-walled carbon nanotubes accounts for more than 65% of the total number of the carbon nanotubes; after the weak oxidation treatment (fig. 2b), the single-walled carbon nanotubes are greatly reduced, the double-walled carbon nanotubes account for more than 97% of the total number of the carbon nanotubes, and the double-walled carbon nanotubes have complete carbon layer structures before and after the weak oxidation treatment. As shown in fig. 3, the diameters of 100 double-walled carbon nanotubes are measured under a transmission electron microscope and a diameter distribution graph is drawn, the diameters of the double-walled carbon nanotubes are distributed in the range of 1.7 to 3.1 nanometers, wherein 88% of the diameters of the double-walled carbon nanotubes are distributed in the range of 1.8 to 2.3 nanometers in a concentrated manner, and the concentrated oxidation temperature of the double-walled carbon nanotubes is 805 ℃.
Thermogravimetric analysis is carried out on the samples after preparation state and weak oxidation treatment so as to represent crystallinity change and purity of the macro sample. As shown in fig. 4, the mass percent curve of the prepared carbon nanotube (fig. 4a) shows significant weight loss in two temperature ranges of 450-550 ℃ and 750-820 ℃, corresponding to the weight loss of the mass percent curve, and the DSC curve shows a plurality of discrete exothermic peaks corresponding to the oxidative decomposition reaction of the carbonaceous product. Wherein, the low-temperature (450-550 ℃) oxidative decomposition reaction is carried out by amorphous carbon with higher reaction activity and the small-diameter single-walled carbon nano-tube, and the high-temperature (750-820 ℃) oxidation decomposition reaction is carried out by the double-walled carbon nano-tube; the mass percent curve of the sample (figure 4b) after the weak oxidation treatment shows weight loss in the temperature range of 750-820 ℃, and a DSC curve shows an obvious exothermic peak around 805 ℃ corresponding to the weight loss of the mass percent curve, so that the high crystallinity and the structural uniformity of the double-wall carbon nano tube are shown corresponding to the decomposition reaction of the double-wall carbon nano tube. Comparing the thermogravimetric analysis results of the carbon nano tube after the preparation state and the weak oxidation treatment, the oxidative decomposition temperature of the double-wall carbon nano tube in the preparation state carbon nano tube has no obvious difference with the oxidative decomposition temperature of the double-wall carbon nano tube after the weak oxidation treatment, and the results show that the structural damage of the double-wall carbon nano tube caused by the weak oxidation treatment process is extremely small, which is consistent with the representation results of a transmission electron microscope. In addition, the impurity residues of the prepared carbon nanotube sample and the carbon nanotube sample after the weak oxidation treatment are respectively 4.5 wt% and 7 wt%, which indicates the high purity of the sample, and is consistent with the characterization result of a scanning electron microscope.
Example 2.
Firstly, preparing a mixed solution of toluene, ferrocene and sulfur powder with the mass ratio of 100:3:0.19, and carrying out ultrasonic treatment for 10 minutes for later use. Under the protection of low-flow hydrogen, heating a chemical vapor deposition horizontal tubular furnace to 1100 ℃, then adjusting the hydrogen flow to 1500sccm, introducing 8sccm ethylene, and simultaneously injecting a mixed solution prepared by toluene, ferrocene and sulfur powder at a constant speed of 0.6ml/h to grow the carbon nano tube for 2 h.
And flatly paving the prepared product obtained in the step at the center of a constant-temperature area of a horizontal tube furnace with two open ends, then heating the horizontal tube furnace to 530 ℃ at the speed of 10 ℃/min, keeping the temperature for 1.5 hours, removing amorphous carbon and single-walled carbon nanotubes in the product through in-situ weak oxidation, and then naturally cooling the sample to room temperature along with the furnace.
The samples in the preparation state and after the weak oxidation treatment are characterized by a scanning electron microscope and a transmission electron microscope, and the scanning electron microscope shows that the samples in the preparation state and after the weak oxidation treatment are very pure, and no granular impurities exist on the surface of the carbon tube; transmission electron microscope characterization shows that the weak oxidation treatment enables the number proportion of the double-wall carbon nano tubes in the carbon nano tubes to be improved from 58% to more than 95%. The diameter of the double-walled carbon nano-tube is distributed in the range of 1.7-2.5 nanometers, wherein 85% of the diameter of the double-walled carbon nano-tube is distributed in the range of 1.8-2.3 nanometers. The concentrated oxidation temperature of the double-walled carbon nanotube is 801 ℃.
Example 3.
Firstly, preparing a mixed solution of toluene, ferrocene and sulfur powder with the mass ratio of 100:5:0.35, and carrying out ultrasonic treatment for 10 minutes for later use. Under the protection of low-flow hydrogen, heating a chemical vapor deposition horizontal tubular furnace to 1150 ℃, then adjusting the hydrogen flow to 1500sccm, introducing 8sccm ethylene, and simultaneously injecting a mixed solution prepared from toluene, ferrocene and sulfur powder at a constant speed of 0.6ml/h to grow the carbon nano tube for 2 h.
And flatly paving the prepared product obtained in the step at the center of a constant-temperature area of a horizontal tube furnace with two open ends, then heating the horizontal tube furnace to 515 ℃ at the speed of 15 ℃/min, keeping the temperature for 2.5 hours, removing amorphous carbon and single-walled carbon nanotubes in the product by in-situ weak oxidation, and then naturally cooling the sample to room temperature along with the furnace.
The samples in the preparation state and after the weak oxidation treatment are characterized by a scanning electron microscope and a transmission electron microscope, and the scanning electron microscope shows that the samples in the preparation state and after the weak oxidation treatment are very pure, and no granular impurities exist on the surface of the carbon tube; transmission electron microscope characterization shows that the weak oxidation treatment enables the number of the double-wall carbon nano tubes in the carbon nano tubes to be increased from 62% to more than 96%. The diameter of the double-walled carbon nano-tube is distributed in the range of 1.7-3.0 nanometers, wherein 85% of the diameter of the double-walled carbon nano-tube is distributed in the range of 1.8-2.3 nanometers. The concentrated oxidation temperature of the double-walled carbon nanotube is 802 ℃.
Comparative example 1.
Firstly, preparing a mixed solution of toluene, ferrocene and sulfur powder with the mass ratio of 100:2:0.95, and carrying out ultrasonic treatment for 10 minutes for later use. Under the protection of low-flow hydrogen, heating a chemical vapor deposition horizontal tubular furnace to 1200 ℃, then adjusting the hydrogen flow to 1500sccm, introducing 5sccm ethylene, and simultaneously injecting a mixed solution prepared from toluene, ferrocene and sulfur powder at a constant speed of 0.9ml/h to grow the carbon nano tube for 2 h.
The transmission electron microscope shows that the number of the double-walled carbon nano tubes of the obtained product accounts for more than 35% of the total number of the carbon nano tubes, the balance is the single-walled carbon nano tubes, the diameter of the double-walled carbon nano tubes is distributed in 2-3.5 nanometers, and a large amount of impurity carbon is attached to the surfaces of the carbon nano tubes. The weak oxidation treatment of this sample does not allow to obtain high purity double-walled carbon nanotubes.
Comparative example 2.
Firstly, preparing a mixed solution of toluene, ferrocene and sulfur powder with the mass ratio of 100:2:0.38, and carrying out ultrasonic treatment for 10 minutes for later use. Under the protection of low-flow hydrogen, heating a chemical vapor deposition horizontal tubular furnace to 1150 ℃, then adjusting the hydrogen flow to 2000sccm, introducing 5sccm ethylene, and simultaneously injecting a mixed solution prepared from toluene, ferrocene and sulfur powder at a constant speed of 1.2ml/h to grow the carbon nano tube for 1 h.
The transmission electron microscope characterization shows that the carbon nanotube with different wall numbers in the obtained product has the following ratio: the single-wall carbon nano tube accounts for 98 percent, the double-wall carbon nano tube accounts for 1 percent, and the three-wall carbon nano tube accounts for 1 percent.
The results of the examples and the comparative examples show that the invention can realize the controllable preparation of the mixture of the double-wall carbon nanotube with high purity, high content and small diameter (> 50%) and the single-wall carbon nanotube by regulating the thermodynamic and kinetic conditions of the floating catalyst chemical vapor deposition growth carbon nanotube, and can prepare the double-wall carbon nanotube with high purity, narrow diameter distribution and small diameter in a large scale by combining the subsequent air oxidation treatment, and the finally obtained double-wall carbon nanotube has complete structure, high crystallinity and high purity. The method has simple process flow and is easy to repeat and prepare in large scale.
Claims (3)
1. A preparation method of a double-wall carbon nano tube with high purity, narrow diameter distribution and small diameter is characterized in that a floating catalyst chemical vapor deposition method is adopted, hydrogen is used as carrier gas, methylbenzene and ethylene are used as carbon sources, ferrocene is used as a catalyst precursor, sulfur is used as an accelerant to grow the carbon nano tube, the number of the double-wall carbon nano tube in the obtained product accounts for 50-70% of the total number of the carbon nano tube, and the balance is the single-wall carbon nano tube; then the prepared product is spread in a horizontal tube furnace, and the amorphous carbon and the single-walled carbon nanotube in the product are removed by heat treatment and oxidation in the air, thereby realizing the enrichment of the double-walled carbon nanotube with high purity, narrow diameter distribution and small diameter; after heat treatment and oxidation, the number of the double-wall carbon nano tubes accounts for more than 95% of the total number of the carbon nano tubes, the diameters of the double-wall carbon nano tubes are uniform, and more than 85% of the diameters of the double-wall carbon nano tubes are intensively distributed in the range of 1.8-2.3 nanometers;
the specific steps for preparing the carbon nano tube are as follows: heating a chemical vapor deposition horizontal tubular furnace to 1100-1300 ℃ under the protection of hydrogen, adjusting the hydrogen flow to 1000-3000 sccm, introducing 0.5-30 sccm of ethylene, and simultaneously injecting a mixed solution prepared from toluene, ferrocene and sulfur powder at a constant speed of 0.5-1 mL/h, wherein the mass ratio of the mixed solution is 100 (3-5) (0.1-1), and growing the carbon nano tube for 0.5-5 h;
placing a product prepared by a floating catalyst chemical vapor deposition method in a horizontal tube furnace in an air atmosphere at room temperature, then heating the horizontal tube furnace to 500-540 ℃ at the speed of 10-20 ℃/min, keeping the temperature for 0.5-3 hours, and naturally cooling the product to the room temperature along with the furnace.
2. The method for preparing a high-purity, narrow-diameter-distribution and small-diameter double-wall carbon nanotube according to claim 1, wherein the chemical vapor deposition horizontal tube furnace is heated to 1150-1250 ℃ under the protection of hydrogen, the hydrogen flow is adjusted to 1700-2400 sccm, 3-15 sccm of ethylene is introduced, and a mixed solution prepared from toluene, ferrocene and sulfur powder is injected at a constant speed of 0.5-0.8 mL/h, the mass ratio of the mixed solution is 100 (3-5): (0.25-0.65), and the growth of the carbon nanotube is carried out for 0.5-2 h.
3. The method for producing a high-purity, narrow-diameter-distribution, small-diameter double-walled carbon nanotube according to any one of claims 1 to 2, wherein the double-walled carbon nanotube has high crystallinity and few defects, and the concentrated oxidation temperature is more than 800 ℃.
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