CN112707385A - Method for preparing carbon nano tube - Google Patents

Method for preparing carbon nano tube Download PDF

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CN112707385A
CN112707385A CN202110057027.4A CN202110057027A CN112707385A CN 112707385 A CN112707385 A CN 112707385A CN 202110057027 A CN202110057027 A CN 202110057027A CN 112707385 A CN112707385 A CN 112707385A
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mesoporous silica
molecular template
silica molecular
carbon nanotubes
carbon source
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卓恩宗
夏玉明
许哲豪
郑浩旋
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HKC Co Ltd
Beihai HKC Optoelectronics Technology Co Ltd
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HKC Co Ltd
Beihai HKC Optoelectronics Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/16Preparation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00Structure or properties of carbon nanotubes
    • C01B2202/20Nanotubes characterized by their properties
    • C01B2202/22Electronic properties

Abstract

The application relates to the technical field of nano material preparation, in particular to a preparation method of a carbon nano tube, which comprises the following steps: providing a mesoporous silica molecular template; depositing a carbon source on the mesoporous silica molecular template by adopting an atomic layer deposition method, and then removing the mesoporous silica molecular template to obtain the carbon nano tube. The process does not need the participation of a catalyst, and the obtained high-density and high-purity carbon nano tube has good application prospect in the flexible display.

Description

Method for preparing carbon nano tube
Technical Field
The application belongs to the technical field of nano material preparation, and particularly relates to a preparation method of a carbon nano tube.
Background
With the rapid development of the electronic industry, the demand for low energy consumption, multifunction and environment-friendly electronic products is increasing, and flexible electronic devices become important fields for the development of the next generation of electronic industry due to their unique flexibility, ductility, high-efficiency and multi-functionality, and portability, and attract more and more attention. Among them, transistors are used as amplifiers and switches of driving parts of many electronic devices, and are applied to many electronic devices, so that flexible thin film transistors are also a research hotspot in recent years. Touch screen materials also need to be flexible, and Indium Tin Oxide (ITO) is difficult to meet the requirements, so new conductive materials such as flexible metal grids, nano silver wires (AgNWs), Carbon Nanotubes (CNTs), graphene, conductive polymers and the like are exposed.
Carbon nanotubes carbon, as a one-dimensional nanomaterial, are lightweight and have many exceptional mechanical and electrochemical properties. The preparation of carbon nanotubes generally includes an arc method, a laser evaporation method and a chemical vapor deposition method; the parameters of the arc method are not easy to regulate and control, and the equipment for exciting the evaporation method is expensive and has complex process; the chemical vapor deposition method has low growth temperature and easily-controlled parameters, but the purity and density of the prepared carbon nanotubes need to be improved due to the participation of a catalyst, the reaction process is far away from an equilibrium state and the like.
Disclosure of Invention
The present application aims to provide a method for preparing carbon nanotubes, and aims to solve the technical problem of how to improve the purity and density of carbon nanotubes.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
the application provides a preparation method of a carbon nano tube, which comprises the following steps:
providing a mesoporous silica molecular template;
depositing a carbon source on the mesoporous silica molecular template by adopting an atomic layer deposition method, and then removing the mesoporous silica molecular template to obtain the carbon nano tube.
In one embodiment, the step of depositing a carbon source on the mesoporous silica molecular template by using an atomic layer deposition method comprises:
placing the mesoporous silica molecular template in atomic layer deposition equipment, and then sequentially carrying out the following pulse circulation: introducing a carbon source for 0.01-0.03 s, staying the carbon source for 8-12 s, purging with argon for 4-6 s, introducing a hydrogen plasma for 0.02-0.04 s, staying the hydrogen plasma for 8-12 s, and purging with argon for 8-12 s.
In one embodiment, the pulse cycle comprises: and introducing the carbon source for 0.02s, keeping the carbon source for 10s, purging with argon for 5s, introducing the hydrogen plasma for 0.03s, keeping the hydrogen plasma for 10s, and purging with argon for 10 s.
In one embodiment, the number of pulse cycles is 50-500.
In one embodiment, before the pulse cycle, hydrogen is introduced into the atomic layer deposition equipment to preheat the atomic layer deposition equipment to 500-600 ℃.
In one embodiment, the carbon source is selected from at least one of methane, ethane, ethylene, and acetylene.
In one embodiment, the step of removing the mesoporous silica molecular template comprises: and removing the mesoporous silica molecular template by using hydrofluoric acid solution or sodium hydroxide solution for etching.
In one embodiment, the concentration of the hydrofluoric acid solution is 2-10%, or the concentration of the sodium hydroxide solution is 10-30%.
In one embodiment, the mesoporous silica molecular template has a pore diameter of 2-50nm and a pore volume of 0.2-1m3/g。
In one embodiment, the mesoporous silica molecular template is a silica-silica molecular template prepared by mixing tetraethoxysilane: hydrochloric acid: polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer: ethanol ═ (0.1 to 1): (0.1-0.5): (0.01:0.1): the raw materials of (5-30) are obtained by sol-gel self-assembly.
According to the preparation method of the carbon nano tube, a mesoporous silica molecular template is used as a deposition matrix, an atomic layer deposition technology is adopted, a carbon source is deposited on the mesoporous silica molecular template, and then the mesoporous silica molecular template is removed to obtain the pure carbon nano tube with good three-dimensional shape retention; during the deposition process, when carbon source molecules reach the surface of the deposition substrate, the carbon source molecules are chemically adsorbed on the surface of the substrate and undergo a self-limiting surface reaction, and high-density carbon nanotubes are formed through the self-limiting reaction, and the process does not need the participation of a catalyst, so that the purity of the carbon nanotubes is improved. The high-density and high-purity carbon nano tube obtained by the preparation method has good application prospect in a flexible display.
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In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing a carbon nanotube according to an embodiment of the present disclosure.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
An embodiment of the present application provides a method for preparing a carbon nanotube, as shown in fig. 1, the method includes the following steps:
s01: providing a mesoporous silica molecular template;
s02: depositing a carbon source on the mesoporous silica molecular template by adopting an atomic layer deposition method, and then removing the mesoporous silica molecular template to obtain the carbon nano tube.
According to the preparation method of the carbon nano tube, the mesoporous silica molecular template is used as a deposition matrix, an atomic layer deposition technology is adopted, a carbon source is deposited on the mesoporous silica molecular template, and then the mesoporous silica molecular template is removed to obtain the pure carbon nano tube with good three-dimensional shape retention; in the above carbon source deposition process, when carbon source molecules reach the surface of the deposition substrate, the carbon source molecules are chemically adsorbed on the surface of the substrate and undergo a self-limiting surface reaction, and a high-density carbon nanotube is formed through such a self-limiting reaction, and the process does not require the participation of a catalyst, thereby increasing the purity of the carbon nanotube. The high-density and high-purity carbon nano tube obtained by the preparation method has good application prospect in a flexible display.
The mesoporous silica has a novel highly ordered material, can provide a controllable nano reactor for the preparation of nano materials, and by adjusting the mesoscopic or microstructure of the mesoporous silica molecular template, replicas with different topological structures are obtained, which not only can be used as a nano reactor with uniform size to synthesize low-dimensional nano materials, but also can be used for the preparation of ordered high-dimensional nano materials, so that the mesoporous silica molecular template is used as a deposition matrix in the application. The Atomic Layer Deposition (ALD) technology is a novel chemical vapor deposition technology, and is a method for forming a nanomaterial by alternately introducing a vapor phase precursor pulse into a reaction chamber and performing a chemisorption reaction on the surface of a deposition substrate, wherein when vapor phase precursor molecules reach the surface of the deposition substrate, the vapor phase precursor molecules are chemisorbed on the surface of the deposition substrate and perform a surface reaction, and the atomic layer deposition surface reaction has self-limiting properties, namely, chemisorption self-limiting (CS) and sequential reaction self-limiting (RS), and the self-limiting property is the basis of the atomic layer deposition, so that the nanomaterial is formed by continuously repeating the self-limiting reaction, and the excellent conformal stoichiometric nanomaterial is produced. Due to the surface chemical self-limiting adsorption property of ALD, the method can be applied to filling of nano-holes and high-depth groove structures. Therefore, the mesoporous silica molecular template and the atomic layer deposition are combined, and the carbon source can be deposited to generate the carbon nano tube with high purity and density on the premise of not needing a catalyst.
In the step S01, in the mesoporous silica molecular template, the pore diameter of the mesoporous silica is 2-50nm, and the pore volume is 0.2-1m3(ii) in terms of/g. The mesoporous silica molecular template within the size range is more beneficial to filling of carbon source precursors, and the reversed-phase carbon nano tube is prepared by utilizing the molecular template with the size, and the microscopic ordered size can endow the carbon nano tube material with excellent physical propertiesSuch as quantum effects, etc.
In one embodiment, the mesoporous silica may be SBA15/MCM41, etc., and has a high specific surface area up to 2000m2The carbon source precursor has uniform pore diameter and stable chemical property, and the molecular template framework cannot be damaged when the carbon source precursor is immersed or reacted in the later period.
In one embodiment, the mesoporous silica molecular template is prepared by sol-gel self-assembly. Specifically, the mesoporous silica molecular template is prepared by mixing Tetraethoxysilane (TEOS): hydrochloric acid: polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123): ethanol ═ (0.1 to 1): (0.1-0.5): (0.01:0.1): the raw materials of (5-30) are obtained by sol-gel self-assembly.
For example, the mesoporous silica molecular template is specifically prepared by the following steps:
1. firstly, liquid TEOS is measured according to the following molar ratio: HCl: p123: c2H5OH ═ 0.1 to 1: (0.1-0.5): (0.01:0.1): (5-30) obtaining a mixed liquid;
2. rapidly dispersing the mixed liquid at 30-60 ℃ and 1200rpm for 30-300 min;
3. after uniform dispersion, reducing the temperature to room temperature (25 ℃), and standing for 2-10 h;
4. the mesoporous silica film is obtained by a rotary deposition or immersion deposition method.
In the above process, mesoporous silica membranes with different pore diameters can be obtained by controlling the amount of TEOS.
In one embodiment, the step of depositing a carbon source on the mesoporous silica molecular template by using an atomic layer deposition method comprises:
placing the mesoporous silica molecular template in atomic layer deposition equipment, and then sequentially carrying out the following pulse circulation: introducing a carbon source for 0.01-0.03 s, staying the carbon source for 8-12 s, purging with argon for 4-6 s, introducing a hydrogen plasma for 0.02-0.04 s, staying the hydrogen plasma for 8-12 s, and purging with argon for 8-12 s.
Through the pulse circulation procedure, a carbon source can be well deposited on the mesoporous silica molecular template to form the carbon nano tube. Further, in a preferred embodiment, the pulse cycle comprises: and introducing the carbon source for 0.02s, keeping the carbon source for 10s, purging with argon for 5s, introducing the hydrogen plasma for 0.03s, keeping the hydrogen plasma for 10s, and purging with argon for 10 s. Further, the number of pulse cycles is 50 to 500. By repeating the above number of pulse cycles, the carbon nanotubes formed by the self-limiting reaction have better conformality.
In one embodiment, before the pulse cycle, hydrogen is introduced into the atomic layer deposition equipment to preheat the atomic layer deposition equipment to 500-600 ℃. By introducing hydrogen and heating the deposition matrix in the equipment, when the temperature reaches the temperature required by the carbon nano tube, namely about 500-600 ℃, the carbon source and the hydrogen plasma can be sequentially introduced to carry out the pulse circulation. Can be prepared by adjusting the ratio of carbon source to hydrogen (e.g., adjusting the volume ratio of carbon source: H)21: 20-100) to obtain the carbon nanotube.
In one embodiment, the carbon source is selected from at least one of methane, ethane, ethylene, and acetylene. The carbon source can form a good carbon atom precursor.
In one embodiment, the step of removing the mesoporous silica molecular template comprises: and etching by using an acid solution or an alkali solution to remove the mesoporous silica molecular template. Specifically, the acid solution is a hydrofluoric acid solution of 2-10% (mass fraction), or the alkali solution is a sodium hydroxide solution of 10-30% (mass fraction). The acid solution or the alkali solution can well etch the mesoporous silicon dioxide to obtain the pure carbon nano tube.
In conclusion, the carbon nano tube is prepared by using the ALD method and taking the mesoporous silica molecular template as the deposition substrate under the condition of not needing a catalyst. Compared with the common chemical vapor deposition method, the preparation method has higher efficiency and lower cost and is suitable for industrial use; the obtained carbon nano tube is easy to control, high in density and purity, good in compactness, capable of improving transmission capacity and light transmittance, excellent in conductivity, transparency and other properties, and suitable for being applied to flexible devices of panels with various sizes, such as large, medium and small, in combination with specific examples.
Example 1
The preparation method of the carbon nano tube comprises the following steps:
(1) preparing a mesoporous silica molecular template:
mixing the molar ratio of TEOS: HCl: p123: c2H5OH ═ 0.1 to 1: (0.1-0.5): (0.01:0.1): (5-30) mixing the raw materials to obtain a mixed liquid; rapidly dispersing the mixed liquid at 30-60 ℃ and 1200rpm for 30-300 min; after uniform dispersion, reducing the temperature to room temperature (25 ℃), and standing for 2-10 h; the mesoporous silica molecular template is obtained by a method of rotary deposition or dipping deposition.
In this embodiment, mesoporous silica molecular templates with different pore capacities and pore diameters can be obtained by adjusting different contents of TEOS, and the specific results are shown in table 1 below. And then, the molecular template is taken as a matrix to prepare the carbon nano tube.
TABLE 1
TEOS content (%) Pore volume (m)3/g) Pore size (nm) Class of mesoporous silica molecular templates
0.5 0.39 10.6 Molecular template A
1.5 0.52 18.8 Molecular template B
2.5 0.68 31.7 Molecular template C
(2) Atomic layer deposition
The mesoporous silica molecular template is used as a matrix, atomic layer deposition is carried out according to the procedure in the table 2, and then the mesoporous silica molecular template is removed by etching with 10% hydrofluoric acid solution, so as to obtain the carbon nano tube.
TABLE 2
Figure BDA0002901006020000071
Three molecular templates prepared by the method are taken as matrixes, and CH is taken4As a carbon source, the conductivity data of the corresponding carbon nanotubes finally prepared are shown in table 3 below.
TABLE 3
Mesoporous silica molecular template Conductivity of CNT
Molecular template A 0.1s/cm
Molecular template B 0.22s/cm
Molecular template C 0.15s/cm
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. A method for preparing carbon nanotubes is characterized by comprising the following steps:
providing a mesoporous silica molecular template;
depositing a carbon source on the mesoporous silica molecular template by adopting an atomic layer deposition method, and then removing the mesoporous silica molecular template to obtain the carbon nano tube.
2. The method of preparing carbon nanotubes according to claim 1, wherein the step of depositing a carbon source on the mesoporous silica molecular template by atomic layer deposition comprises:
placing the mesoporous silica molecular template in atomic layer deposition equipment, and then sequentially carrying out the following pulse circulation: introducing a carbon source for 0.01-0.03 s, staying the carbon source for 8-12 s, purging with argon for 4-6 s, introducing a hydrogen plasma for 0.02-0.04 s, staying the hydrogen plasma for 8-12 s, and purging with argon for 8-12 s.
3. The method of manufacturing carbon nanotubes of claim 2, wherein the pulse cycle comprises: and introducing the carbon source for 0.02s, keeping the carbon source for 10s, purging with argon for 5s, introducing the hydrogen plasma for 0.03s, keeping the hydrogen plasma for 10s, and purging with argon for 10 s.
4. The method of preparing carbon nanotubes according to claim 2, wherein the number of pulse cycles is 50 to 500.
5. The method of claim 2, wherein hydrogen is introduced into the atomic layer deposition apparatus to preheat the carbon nanotubes to 500-600 ℃ before the pulse cycle is performed.
6. The method for producing carbon nanotubes according to claim 1, wherein the carbon source is at least one selected from the group consisting of methane, ethylene and acetylene.
7. The method of preparing carbon nanotubes of any one of claims 1 to 6, wherein the step of removing the mesoporous silica molecular template comprises: and etching by using an acid solution or an alkali solution to remove the mesoporous silica molecular template.
8. The method of preparing carbon nanotubes according to claim 7, wherein the acid solution is a 2-10% hydrofluoric acid solution or the alkali solution is a 10-30% sodium hydroxide solution.
9. The method of preparing carbon nanotubes of any one of claims 1 to 6, wherein the mesoporous silica molecular template has a pore diameter of 2 to 50nm and a pore volume of 0.2 to 1m3/g。
10. The method for preparing carbon nanotubes according to any one of claims 1 to 6, wherein the mesoporous silica molecular template is prepared by mixing tetraethoxysilane: hydrochloric acid: polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer: ethanol ═ (0.1 to 1): (0.1-0.5): (0.01:0.1): the raw materials of (5-30) are obtained by sol-gel self-assembly.
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Application publication date: 20210427