WO2009135344A1 - Method of self-assembly growing carbon nanotubess by chemical-vapor-deposition without the use of metal catalyst - Google Patents
Method of self-assembly growing carbon nanotubess by chemical-vapor-deposition without the use of metal catalyst Download PDFInfo
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- WO2009135344A1 WO2009135344A1 PCT/CN2008/001207 CN2008001207W WO2009135344A1 WO 2009135344 A1 WO2009135344 A1 WO 2009135344A1 CN 2008001207 W CN2008001207 W CN 2008001207W WO 2009135344 A1 WO2009135344 A1 WO 2009135344A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01B32/16—Preparation
Definitions
- the present invention relates to a method of synthesizing self-assembled carbon nanotubes by chemical vapor deposition under the conditions of a metal-free catalyst. Background technique
- the preparation methods of carbon nanotubes mainly include arc discharge method, laser evaporation method and catalyst-assisted chemical vapor deposition method.
- the preparation of carbon nanotubes by arc discharge method is characterized by rapid growth, easy control of process parameters, but growth temperature.
- catalyst-assisted chemical vapor deposition is the use of free carbon produced by hydrocarbon cracking Ion, two methods for precipitating carbon nanotubes at one end of the catalyst, which have the advantages of easy control of the reaction process, strong applicability, simple preparation method, high product purity, and large-scale production, and are widely used.
- hydrocarbon cracking Ion two methods for precipitating carbon nanotubes at one end of the catalyst, which have the advantages of easy control of the reaction process, strong applicability, simple preparation method, high product purity, and large-scale production, and are widely used.
- the performance and application of the carbon nanotubes are greatly affected by the residual catalyst particles in the product.
- Carbon nanotubes can be used in many fields such as teaching devices, capacitors, transistors, hydrogen storage materials, composite materials, etc., but most of them should use ⁇ 3 ⁇ 4 net carbon nanotubes to make their performance Optimal state.
- the purification of the product is the main means to remove the residual catalyst particles in the carbon nanotubes to obtain pure carbon nanotubes. However, the purification process increases the production cost, the yield is low, and the structure of the carbon nanotubes may be damaged or introduced.
- the use of a catalyst-free preparation process is another way to obtain pure carbon nanotubes, such as: non-catalytic arc discharge method, non-catalytic flame method, thermal plasma sputtering, etc., but the arc discharge method is used to turn over carbon nanotubes.
- the technical problem to be solved by the present invention is to provide a method for synthesizing carbon nanotubes, which can directly obtain self-assembled carbon nanotubes by chemical vapor deposition under the condition of a metal-free catalyst.
- a method for chemically vapor-depositing a metal-free catalyst for self-assembled carbon nanotubes characterized in that: a mixture of a carbon source gas and a carrier gas is introduced into an environment having a temperature of 940 ° C to 980 ° C, a carbon source gas The decomposition products are deposited on a substrate of 650 to 750 ° C to form self-assembled carbon nanotubes.
- the carbon source gas is a gaseous carbonaceous compound.
- the carrier gas is one of nitrogen, hydrogen, argon or a mixed gas of two or more thereof.
- the equipment that provides the heating and decomposition reaction environment is a sorghum furnace.
- the substrate is located at an outlet end of the high temperature furnace.
- the high-temperature furnace Before the mixture is introduced into the high-temperature furnace, the high-temperature furnace is evacuated, and then heated to 940° (: ⁇ 980° (:.) under the protection of the carrier gas.
- the high temperature furnace is a horizontal vacuum tube high temperature furnace.
- the substrate is a corundum, quartz plate, silicon wafer or alumina substrate.
- the flow ratio of the carbon source gas and the carrier gas is 1: 2 ⁇ 1: ⁇
- the temperature was maintained at 940 ° C to 980 ° C for 15 hours.
- the beneficial effects of the invention are:
- the carbon nanotubes prepared by the process are not "metal catalyst particles", and the product has high purity (80% to 90%), and is prepared to be low in latitude and strong in conformability, but in the phase-catalyzed auxiliary vapor deposition process, The method yields low (mg level).
- Another feature of the preparation process is that carbon nanotubes can be grown at temperatures between 940 ° C and 980 ° C. For high temperature materials, carbon nanotube or carbon nanotube films can be grown in situ without damaging the materials. In the process of preparing carbon nanotubes using the invention, no metal catalyst is used, and various effects of the base metal catalyst particles on the intrinsic properties of the carbon nanotubes are avoided. Since the method is not limited by the catalyst, the carbon nanotubes are directly grown on the substrate, and continuous production is expected.
- 1 is a schematic diagram of preparation of carbon nanotubes
- Figure 2 is a temperature distribution curve of the longitudinal distance along the center in the furnace of the present embodiment
- Figure 3 is an SEM image of the product of this example.
- Figure 4 is a TEM image of the product of this example.
- Figure 5 is another TEM image of the product of this example. detailed description
- the equipment used in this embodiment is a horizontal vacuum tube furnace, which is heated to 940 ° C ⁇ 980 ° C under the protection of a carrier gas, and is supplied with carbon source gas.
- the carbon source is cracked when flowing through the high temperature region, and Deposited on a substrate in a low temperature region to form carbon nanotubes.
- r indicates the diameter of the corundum tube of the horizontal vacuum tube furnace.
- the temperature at the center of the cavity is 920 ⁇ (below the programmed temperature of 3 (TC, as shown in Table 1), and the temperature at which the substrate is placed is between 650 ° C and 750 ° C.
- This temperature gradient It is very advantageous to form carbon nanotubes.
- Table 1 The temperature distribution data of the longitudinal distance along the center in the furnace of this embodiment is shown in Table 1, and the corresponding temperature distribution curve is shown in Fig. 2.
- Table 1 shows the distribution of the temperature in the furnace along the longitudinal direction of the center.
- the corundum lining is repeatedly washed 3 to 5 times with an ultrasonic cleaning device, and dried; (the substrate may also be a quartz plate, a silicon wafer, an alumina lining, etc.)
- the SEM image of the obtained product is shown in Fig. 3; the ⁇ image is shown in Figs. 4 and 5.
Abstract
A method of self-assembly growing carbon nanotubes by chemical-vapor-deposition without the use of metal catalyst is provided, wherein a horizontal vacuum-tube type high-temperature furnace is heated to 940~980 °C and the temperature is held under the protection of a carrier gas, then a mixed gas of carbon source gas and carrier gas is fed, The decomposed product of the carbon source gas is deposited on a substrate in the low temperature area of the high-temperature furnace, and hence to self-assembly grow carbon nanotubes. The said carbon source gas is a carbon-containing material in gaseous state. The said carrier gas is one or two or more selected from nitrogen, hydrogen, and argon. Since the use of metal catalyst is omitted, the obtained carbon nanotubes contain no metal catalyst; therefor the purity of the product is improved with a low cost, and the product can be produced continuously.
Description
化学气相沉积合成无金属催化剂自组生长碳纳米管的方法 Method for synthesizing carbon nanotubes by chemical vapor deposition and synthesizing metal-free catalyst
技术领域 Technical field
本发明涉及一种在无金属催化剂的条件下化学气相沉积合成自组生长的 碳纳米管的方法。 背景技术 The present invention relates to a method of synthesizing self-assembled carbon nanotubes by chemical vapor deposition under the conditions of a metal-free catalyst. Background technique
碳纳米管作为纳米材料中最具潜力的材料之一， 其制备工艺的研究受到 广泛关注。 目前， 碳纳米管的制备方法主要有电弧放电法、 激光蒸发法和催 化剂辅助化学气相沉积法等， 其中， 电弧放电法制备碳纳米管的特点为生长 快速， 工艺参数较易控制， 但生长温度高， 设备复杂， 产物杂质多， 产率低 且难纯化， 不适合批量生产； 激光蒸发法制备的产物质量高， 但产量低； 催 化剂辅助化学气相沉积法是利用碳氢化 物裂解产生的自由碳离子， 在催化 剂一端析出生成碳纳米管的二种方法， 该^^目对其它方法具有反应过程易于 控制、 适用性强、 制备方法简便、 产品纯度高、 可规模化生产等优点， 被广 泛应用于制备碳纳米管。 但是， 由于产物中残留催化剂颗粒， 使碳纳米管的 性能及应用受到很大影响。 As one of the most promising materials in nanomaterials, carbon nanotubes have received extensive attention in the preparation of their processes. At present, the preparation methods of carbon nanotubes mainly include arc discharge method, laser evaporation method and catalyst-assisted chemical vapor deposition method. Among them, the preparation of carbon nanotubes by arc discharge method is characterized by rapid growth, easy control of process parameters, but growth temperature. High, complex equipment, high product impurities, low yield and difficult to purify, not suitable for mass production; high quality products produced by laser evaporation, but low yield; catalyst-assisted chemical vapor deposition is the use of free carbon produced by hydrocarbon cracking Ion, two methods for precipitating carbon nanotubes at one end of the catalyst, which have the advantages of easy control of the reaction process, strong applicability, simple preparation method, high product purity, and large-scale production, and are widely used. For the preparation of carbon nanotubes. However, the performance and application of the carbon nanotubes are greatly affected by the residual catalyst particles in the product.
： 碳纳米管可以应甩于场发教器件、 电容器、 晶体管、 储氢材料、：复合材 '料等众多领域， 但大部分应翔 要采用 ^¾净的碳纳米管才能使其性能迖到最 优状态。 对产物进行纯化是 a前去除碳纳米管中残留催化剂颗粒， 获得纯净 碳纳米管的主要手段， 然而纯化过程提高了生产成本， 收率低， 同时可能导 致碳纳米管的结构受损或引入新的杂质; 利用无催化剂制备工艺是另一种获 得纯净碳纳米管的途径， 如： 无催化电弧放电法、 无催化火焰法、 热等离子 溅射等技术， 但是电弧放电法翻备碳纳米管的特点为生长快速， 工艺参数较 易控制， 但生长温度高， 设备复杂， 产物杂质多， 产率低且难纯化， 不适合 批量生产； 火焰法制备产物含有大量碳粒、 烟粒和纳米碳纤维等副产物， 难 纯化； 热等离子溅射技^:设备复杂， 生产成本高， 不适合产业化生产。 发明内容 : Carbon nanotubes can be used in many fields such as teaching devices, capacitors, transistors, hydrogen storage materials, composite materials, etc., but most of them should use ^3⁄4 net carbon nanotubes to make their performance Optimal state. The purification of the product is the main means to remove the residual catalyst particles in the carbon nanotubes to obtain pure carbon nanotubes. However, the purification process increases the production cost, the yield is low, and the structure of the carbon nanotubes may be damaged or introduced. The use of a catalyst-free preparation process is another way to obtain pure carbon nanotubes, such as: non-catalytic arc discharge method, non-catalytic flame method, thermal plasma sputtering, etc., but the arc discharge method is used to turn over carbon nanotubes. It is characterized by rapid growth and easy control of process parameters, but high growth temperature, complicated equipment, high product impurities, low yield and difficult to purify, not suitable for mass production; flame preparation products contain a large amount of carbon particles, soot particles and nano carbon fibers. By-product, difficult to purify; hot plasma sputtering technology ^: complex equipment, high production costs, not suitable for industrial production. Summary of the invention
本发明所要解决的技术问题是， 提供一种合成碳纳米管的方法， 在无金 属催化剂条件下， 采用化学气相沉积方法直接获得自组生长碳纳米管。 The technical problem to be solved by the present invention is to provide a method for synthesizing carbon nanotubes, which can directly obtain self-assembled carbon nanotubes by chemical vapor deposition under the condition of a metal-free catalyst.
本发明为解决上述技术问题所采甩的技术方案是：
一种化学气相沉积合成无金属催化剂自组生长碳纳米管的方法， 其特征 在于： 将碳源气体和载气的混合气通入温度为 940°C〜980°C的环境中， 碳源 气体的分解产物在 650 〜 750°C的衬底上沉积形成自组生长碳纳米管。 The technical solution adopted by the present invention to solve the above technical problems is: A method for chemically vapor-depositing a metal-free catalyst for self-assembled carbon nanotubes, characterized in that: a mixture of a carbon source gas and a carrier gas is introduced into an environment having a temperature of 940 ° C to 980 ° C, a carbon source gas The decomposition products are deposited on a substrate of 650 to 750 ° C to form self-assembled carbon nanotubes.
所述的碳源气体为气态含碳化合物。 The carbon source gas is a gaseous carbonaceous compound.
所述载气为氮气、 氢气、 氩气之一种或其 2种或多种的混合气体。 The carrier gas is one of nitrogen, hydrogen, argon or a mixed gas of two or more thereof.
提供加热和分解反应环境的设备为高蕰炉。 The equipment that provides the heating and decomposition reaction environment is a sorghum furnace.
所述的衬底位于所述高温炉内的出气端。 The substrate is located at an outlet end of the high temperature furnace.
在对所述高温炉内通入混合气之前， 将所述高温炉抽真空， 再在载气的 保护下升温至 940° (：〜 980° (：。 Before the mixture is introduced into the high-temperature furnace, the high-temperature furnace is evacuated, and then heated to 940° (: ～ 980° (:.) under the protection of the carrier gas.
所述的高温炉为卧式真空管 高温炉。 The high temperature furnace is a horizontal vacuum tube high temperature furnace.
所述的衬底为刚玉、 石英片、 硅片或氧化铝衬底。 The substrate is a corundum, quartz plate, silicon wafer or alumina substrate.
所述碳源气体和载气的流量比 1 : 2〜1： ο The flow ratio of the carbon source gas and the carrier gas is 1: 2~1: ο
在所述的 940°C〜980°C温度:下保温 1 5小时。 本发明的有益效果有： The temperature was maintained at 940 ° C to 980 ° C for 15 hours. The beneficial effects of the invention are:
由于不使用催化剂， 该 ΐ艺制备的碳纳米管不^"金属催化剂颗粒， 产物 纯度高 （80%〜90%) ， 制备成 ί低， 适 性强， 但相 ¾"催化辅助气相沉积工 艺， 该方法产量较低 （毫克级）。 该制备工艺另一个特点在于其温度在 940°C~980°C之间就可以生长碳纳米管，对于耐高温材料可实现不破坏材料的 情况下原位生长碳纳米管或碳纳米管薄膜。 使用该发明制备碳纳米管的过程 中， 不使用金属催化剂， 避免†金属催化剂 粒对碳纳米管本征性能产生的 各种影响。 由于该方法不受催化剂的限制， 直接在衬底上生长碳纳米管， 有 望实现连续化生产。 Since the catalyst is not used, the carbon nanotubes prepared by the process are not "metal catalyst particles", and the product has high purity (80% to 90%), and is prepared to be low in latitude and strong in conformability, but in the phase-catalyzed auxiliary vapor deposition process, The method yields low (mg level). Another feature of the preparation process is that carbon nanotubes can be grown at temperatures between 940 ° C and 980 ° C. For high temperature materials, carbon nanotube or carbon nanotube films can be grown in situ without damaging the materials. In the process of preparing carbon nanotubes using the invention, no metal catalyst is used, and various effects of the base metal catalyst particles on the intrinsic properties of the carbon nanotubes are avoided. Since the method is not limited by the catalyst, the carbon nanotubes are directly grown on the substrate, and continuous production is expected.
附图说明 DRAWINGS
图 1是碳纳米管制备示意简图； 1 is a schematic diagram of preparation of carbon nanotubes;
图 2是本实施例炉内沿中心纵向距离的温度分布曲线; Figure 2 is a temperature distribution curve of the longitudinal distance along the center in the furnace of the present embodiment;
图 3是本实施例产物的 SEM图像； Figure 3 is an SEM image of the product of this example;
图 4 是本实施例产物的 TEM图像； Figure 4 is a TEM image of the product of this example;
图 5 是本实施例产物的另一幅 TEM图像。
具体实施方式 Figure 5 is another TEM image of the product of this example. detailed description
下面结合附图和具体实施方式对本发明作进一步说明。 The invention is further described below in conjunction with the drawings and specific embodiments.
实施例 1 : Example 1
如图 1， 本实施例所用设备为卧式真空管式炉， 在载气的保护下升温至 940°C〜980°C， 通入碳源气体， 碳源在流经高温区时裂解， 并在低温区的衬底 上沉积， 形成碳纳米管。 如图 2， r表示卧式真空管式炉的刚玉管管径， 本实施 例所使用的高温炉腔体内部中心部位与衬底所放置位置存在一个温度梯度， 当高温炉加热至程序设置温度 （如 950°C时， 腔体中心部位温度为 920Ό (低于 程序温度 3(TC， 如表 1所示),而衬底所放置位置温度则在 650°C〜750°C左右， 这个温度梯度非常有利于形成碳纳米管。 本实施例炉内沿中心纵向距离的温 度分布数据见表 1， 对应:的温度分布曲线如图 2所示。 As shown in Fig. 1, the equipment used in this embodiment is a horizontal vacuum tube furnace, which is heated to 940 ° C ~ 980 ° C under the protection of a carrier gas, and is supplied with carbon source gas. The carbon source is cracked when flowing through the high temperature region, and Deposited on a substrate in a low temperature region to form carbon nanotubes. As shown in Fig. 2, r indicates the diameter of the corundum tube of the horizontal vacuum tube furnace. In this embodiment, there is a temperature gradient between the inner center portion of the high temperature furnace chamber and the substrate. When the high temperature furnace is heated to the programmed temperature ( For example, at 950 °C, the temperature at the center of the cavity is 920 Ό (below the programmed temperature of 3 (TC, as shown in Table 1), and the temperature at which the substrate is placed is between 650 ° C and 750 ° C. This temperature gradient It is very advantageous to form carbon nanotubes. The temperature distribution data of the longitudinal distance along the center in the furnace of this embodiment is shown in Table 1, and the corresponding temperature distribution curve is shown in Fig. 2.
表 1本实施例炉内沿中心纵向 巨离温度分布。 Table 1 shows the distribution of the temperature in the furnace along the longitudinal direction of the center.
本实施例具体制备碳纳米管的步骤如下: The steps for specifically preparing carbon nanotubes in this embodiment are as follows:
( 1 )使用刚玉片作为衬底， 用超声清洗仪对刚玉衬片反复清洗 3〜5次， 干 燥； （衬底还可使用石英片、 硅片、 氧化铝衬片等） (1) Using a corundum sheet as a substrate, the corundum lining is repeatedly washed 3 to 5 times with an ultrasonic cleaning device, and dried; (the substrate may also be a quartz plate, a silicon wafer, an alumina lining, etc.)
(2 )将干 ' 后的刚玉衬片放入卧式真空管式炉内，其放置位置在出气端一 侧， 距离加热区域中心点（即图 1中的0点）约: 9〜13cm (见图 1， 图 1高温炉的 纵向长度为 13.5 X 2cm，即 27cm); (2) Place the corundum lining of the dry 'in the horizontal vacuum tube furnace, the placement position is on the side of the outlet end, and the center point of the heating area (ie 0 point in Figure 1) is about 9~13cm (see Figure 1, Figure 1 high temperature furnace longitudinal length of 13.5 X 2cm, or 27cm);
(3 )对管式炉抽真空， 排餘炉管:内杂质气体， 然后通入氮气至常压； (3) vacuuming the tube furnace, draining the furnace tube: inside the impurity gas, and then introducing nitrogen gas to normal pressure;
(4)在氮气的保护下， 将温度升至 950°C， 通入 C /N2混合气体， 保温 ί.5 小时； (4) Under the protection of nitrogen, raise the temperature to 950 ° C, pass the C / N 2 mixed gas, and keep it for 5 hours;
( 5 )温度降至室温，取出产物； (5) The temperature is lowered to room temperature, and the product is taken out;
所得产物的 SEM图像如图 3所示； 其 ΤΕΜ图像如图 4和图 5所示。
The SEM image of the obtained product is shown in Fig. 3; the ΤΕΜ image is shown in Figs. 4 and 5.
Claims
1、 一种化学气相沉积合成无金属催化剂自组生长碳纳米管的方法， 其特征在 于： 将碳源气体和载气的混合气通入温度为 940T〜 980°C的环境中， 在无金 属催化剂条件下， 碳源气体的分解产物在 650° (：〜 750°C的衬底上沉积形成自 组生长碳纳米管。 A method for chemically vapor-depositing a metal-free catalyst for self-assembled carbon nanotubes, characterized in that: a mixture of a carbon source gas and a carrier gas is introduced into an environment having a temperature of 940T to 980 ° C, in the absence of metal Under the catalyst conditions, the decomposition products of the carbon source gas are deposited on a substrate of 650 ° (: 750 ° C) to form self-assembled carbon nanotubes.
2、 .如权利要求 1所述的化学气相沉积合成无金属催化剂自组生长碳纳米管的 方法， 其特征在于： 所述的碳源气体为气态含碳化合物。 A method of chemically vapor-depositing a metal-free catalyst for self-assembled carbon nanotubes according to claim 1, wherein: said carbon source gas is a gaseous carbonaceous compound.
3、如权利要求 1所述的化学气相沉积合成无金属催化剂自组生长碳纳米管的 方法， 其特征在于： 所述载气为氮气、 氢气、 氩气之一种或其 2种或多种的 混合气体。 .' 3. The method for chemically vapor-depositing a metal-free catalyst for self-organizing carbon nanotubes according to claim 1, wherein: the carrier gas is one of nitrogen, hydrogen, argon or two or more thereof. Mixed gas. .'
4、 如权利要求 1所述的化学气相沉积着成无金属截化剂自组生长碳纳米管 的方法， 其特征在于： 提供加热和分解反应环境的设备为高温炉。 4. The method according to claim 1, wherein the apparatus for providing a heating and decomposing reaction environment is a high temperature furnace.
5、 如权利要求 4所述的化学气相沉积合成无金属德化剂自组生长碳纳米管 的方法， 其特征在于： 所述的衬底位于 高温炉内的出气端。 5. The method according to claim 4, wherein the substrate is located at an outlet end of the high temperature furnace.
6、 如权利要求 4所述的化 气相沉积合成无金属催化剂自组生长碳纳米管 的方法， 其特征在于： 在对所述高温炉内通入混合气之前 将所述高温炉抽 真空， 再在载气的保护下升温至 940°C〜980°C。 6. The method for chemically vapor-depositing a metal-free catalyst for self-assembled carbon nanotubes according to claim 4, wherein: the high temperature furnace is evacuated before the mixture is introduced into the high temperature furnace, and then The temperature was raised to 940 ° C to 980 ° C under the protection of a carrier gas.
7、 如权利要求 4所述的化学气相沉^ ¾合成无金属催化剂自组生长碳纳米管 的方法， 其特征在于： 所述的高温炉为卧式真空管式高温炉。 7. The method according to claim 4, wherein the high temperature furnace is a horizontal vacuum tube type high temperature furnace.
8、 如权利要求 1 任一项所述的化学气相沉积合成无金属催化剂自组生长碳 纳米管的方法， 其特征在于: 所述的衬底为刚玉、 石英片、 硅片或氧化铝衬 底。 The method for chemically vapor-depositing a metal-free catalyst for self-assembled carbon nanotubes according to any one of claims 1 to 3, wherein the substrate is corundum, quartz, silicon or alumina substrate. .
9、 如权利要求 1 所述的化学气相沉积合成无金属催化剂自组生长碳纳米管 的方法， 其特征在于: 所述碳源气体和载气的流量比 1 : 2〜1： 4。 9. The method according to claim 1, wherein the carbon source gas and the carrier gas have a flow ratio of 1: 2 to 1: 4.
10、 如权利要求 1至 9任一项所述的化学气相沉积合成无金属催化剂自组生 长碳纳米管的方法，其特征在于：在所述的 940°C〜980°C温度下保温 1〜5小 时
The method for chemically vapor-depositing a metal-free catalyst for self-assembled carbon nanotubes according to any one of claims 1 to 9, wherein the temperature is maintained at a temperature of 940 ° C to 980 ° C. 5 hours
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| CN101476176B (en) * | 2009-01-09 | 2012-09-19 | 深圳大学 | Method for gas-phase growth of carbon fibre |
| CN102502578B (en) * | 2011-10-26 | 2013-11-13 | 上海交通大学 | Chemical vapor synthesis method for growing carbon nanotubes in mode of being attached to wall of pore channel of template |
| EP2892859A2 (en) | 2012-09-04 | 2015-07-15 | OCV Intellectual Capital, LLC | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
| CN106587002A (en) * | 2016-11-23 | 2017-04-26 | 东莞劲胜精密组件股份有限公司 | Preparation method for carbon micro-tube |
| CN107338508B (en) * | 2017-06-15 | 2020-06-19 | 华南理工大学 | Method for synthesizing ultralong solid carbon fiber by autocatalysis chemical vapor deposition |
| CN107651663B (en) * | 2017-09-18 | 2020-10-09 | 中国科学院宁波材料技术与工程研究所 | Surface functionalized carbon material and preparation method and application thereof |
| CN108598448A (en) * | 2018-06-27 | 2018-09-28 | 合肥工业大学 | A kind of three-dimensional structure carbon coating cobalt acid manganese nano-material and preparation method and application |
| CN113757555B (en) * | 2021-08-25 | 2023-05-02 | 中盐金坛盐化有限责任公司 | Method for reducing performance degradation of hydrogen on pipeline material |
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| US20050183663A1 (en) * | 2003-11-07 | 2005-08-25 | Shang-Che Cheng | Systems and methods for manufacture of carbon nanotubes |
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| CN112323091A (en) * | 2020-11-01 | 2021-02-05 | 南开大学 | Preparation method of carbon-coated transition metal catalyst with bamboo-like carbon nanotube through yolk-eggshell structure |
| CN112323091B (en) * | 2020-11-01 | 2022-02-22 | 南开大学 | Preparation method of carbon-coated transition metal catalyst with bamboo-like carbon nanotube through yolk-eggshell structure |
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