CN1807233A - Chemical shearing method for preparing high dispersion short carbon nanometer tube - Google Patents
Chemical shearing method for preparing high dispersion short carbon nanometer tube Download PDFInfo
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- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
一种制备高分散短碳纳米管的化学剪切方法，属于纳米技术领域。本发明采用湿化学的方法在经硝酸纯化的碳纳米管表面沉积金属镍颗粒再利用金属镍的氧化还原反应，对碳纳米管进行化学剪切，从而得到高分散短碳纳米管。因为经酸洗过的碳纳米管表面存在很多缺陷，碳原子不稳定，很容易发生氧化或还原反应，通过镍促使氧化还原反应的发生，从而使碳管壁上的缺陷进一步被刻蚀，达到化学剪切碳纳米管的目的。本发明制备高分散，长度可在200nm以下的短碳纳米管。
The invention discloses a chemical shearing method for preparing highly dispersed short carbon nanotubes, which belongs to the field of nanotechnology. The invention adopts a wet chemical method to deposit metal nickel particles on the surface of carbon nanotubes purified by nitric acid, and then utilizes the redox reaction of metal nickel to chemically shear the carbon nanotubes, thereby obtaining highly dispersed short carbon nanotubes. Because there are many defects on the surface of acid-washed carbon nanotubes, carbon atoms are unstable, and oxidation or reduction reactions are prone to occur. Nickel promotes the occurrence of oxidation-reduction reactions, so that the defects on the carbon tube walls are further etched to achieve The purpose of chemically shearing carbon nanotubes. The invention prepares highly dispersed short carbon nanotubes whose length can be less than 200nm.
Description
技术领域technical field
本发明涉及的是一种纳米技术领域的方法，特别是一种制备高分散短碳纳米管的化学剪切方法。The invention relates to a method in the field of nanotechnology, in particular to a chemical shearing method for preparing highly dispersed short carbon nanotubes.
背景技术Background technique
碳纳米管由于其具有独特的一维管状结构及机械、物理、化学性质，碳纳米管在许多领域表现出广泛的应用前景。但对于大多数的应用领域来说，都需要大量的长度短、端部开口、离散分布的碳纳米管。目前制备的碳纳米管都是大量团聚在一起，且长度达到微米级，严重限制了其的应用。为了得到所需的短碳纳米管，常用的方法主要涉及物理过程和化学过程。物理过程是将碳纳米管与一定的添加剂混合，在特定的研磨装置中研磨，利用体系内的机械摩擦力和添加剂的层间剪切力等多种作用使碳纳米管被截断。该方法虽然可进行较大规模的生产，但需要专门的设备，且在研磨过程中容易引入杂质。化学过程主要是利用特定的反应使碳管壁上的碳经反应而消耗，达到截断和开口的目的。目前采用化学法剪切碳纳米管主要涉及两个方面，即浓酸氧化和氟化热处理。曾经有人用浓HNO3和H2SO4的混酸氧化单(多)壁碳纳米管，得到长度为10-300nm的短碳纳米管，可应用于分子级的电子器件。还有人提出用浓酸氧化可使碳纳米管变短，且在酸处理过程中，碳管壁上可引入羟基、羧基、羰基等官能团，使其在复合材料基质中达到更好的分散。但是这种方法中使用的强酸都是具有腐蚀性的，操作危险而且处理过程耗时，一般需要几小时甚至几十小时。最近，对单壁碳纳米管进行氟化热处理以达到剪切目的的研究引起了人们的广泛关注。Due to its unique one-dimensional tubular structure and mechanical, physical, and chemical properties, carbon nanotubes show broad application prospects in many fields. But for most applications, large numbers of short-length, open-ended, discretely distributed carbon nanotubes are required. The currently prepared carbon nanotubes are all agglomerated in a large number, and the length reaches the micron level, which seriously limits its application. In order to obtain the desired short carbon nanotubes, the commonly used methods mainly involve physical and chemical processes. The physical process is to mix carbon nanotubes with certain additives, grind them in a specific grinding device, and use various effects such as mechanical friction in the system and interlayer shear force of additives to cut carbon nanotubes. Although this method can be produced on a large scale, it requires special equipment and is easy to introduce impurities during the grinding process. The chemical process mainly uses a specific reaction to consume the carbon on the carbon tube wall through reaction to achieve the purpose of truncation and opening. At present, the shearing of carbon nanotubes by chemical methods mainly involves two aspects, namely concentrated acid oxidation and fluorination heat treatment. Someone once oxidized single (multiple) walled carbon nanotubes with a mixed acid of concentrated HNO 3 and H 2 SO 4 to obtain short carbon nanotubes with a length of 10-300 nm, which can be applied to molecular-level electronic devices. It was also suggested that carbon nanotubes could be shortened by oxidation with concentrated acid, and functional groups such as hydroxyl, carboxyl, and carbonyl could be introduced into the walls of carbon nanotubes during acid treatment to achieve better dispersion in the composite matrix. However, the strong acids used in this method are all corrosive, dangerous to operate and time-consuming to process, generally requiring several hours or even dozens of hours. Recently, the study of fluorination heat treatment of single-walled carbon nanotubes for the purpose of shearing has attracted a lot of attention.
经对现有技术的文献检索发现，J.Kirk等在《J.AM.CHEM.SOC》(美国化学学会杂志)9，127(2005)1541-1547上发表的“Controlled Oxidative Cuttingof Single-Walled Carbon Nanotubes(单壁碳纳米管的可控氧化剪切)”，该文报道了碳纳米管在含F210％氩气气氛中150℃氟化8-12小时，然后在氩气气氛中1000℃热处理，使氟化过程中形成的碳氟键断裂以达到剪切碳纳米管的目的，所得的单壁碳纳米管长度为20-300nm，但是这种方法得到的碳纳米管仍然团聚在一起，很难分散。Found through literature search to prior art, " Controlled Oxidative Cutting of Single-Walled Carbon " Controlled Oxidative Cuttingof Single-Walled Carbon published on " J.AM.CHEM.SOC " (Journal of American Chemical Society) 9,127 (2005) 1541-1547 by J.Kirk etc. Nanotubes (Controlled Oxidative Shearing of Single-walled Carbon Nanotubes)", which reported that carbon nanotubes were fluorinated at 150°C for 8-12 hours in an atmosphere of 10% argon containing F 2 , and then fluorinated at 1000°C in an atmosphere of argon Heat treatment to break the carbon-fluorine bond formed in the fluorination process to achieve the purpose of shearing carbon nanotubes. The length of the resulting single-walled carbon nanotubes is 20-300nm, but the carbon nanotubes obtained by this method are still agglomerated together. Difficult to disperse.
发明内容Contents of the invention
本发明的目的是针对现有技术的不足，提供一种制备高分散短碳纳米管的化学剪切方法，使其制备高分散，长度可在200nm以下的短碳纳米管。The purpose of the present invention is to provide a chemical shearing method for preparing highly dispersed short carbon nanotubes, so as to prepare highly dispersed short carbon nanotubes whose length can be less than 200 nm.
本发明是通过以下技术方案实现的，本发明采用湿化学的方法在经硝酸纯化的碳纳米管表面沉积金属镍颗粒再利用金属镍的氧化还原反应，对碳纳米管进行化学剪切，从而得到高分散短碳纳米管。因为经酸洗过的碳纳米管表面存在很多缺陷，碳原子不稳定，很容易发生氧化或还原反应，通过镍促使氧化还原反应的发生，从而使碳管壁上的缺陷进一步被刻蚀，达到化学剪切碳纳米管的目的。The present invention is achieved through the following technical scheme. The present invention adopts wet chemical method to deposit metal nickel particles on the surface of carbon nanotubes purified by nitric acid, and then utilizes the redox reaction of metal nickel to chemically shear carbon nanotubes, thereby obtaining Highly dispersed short carbon nanotubes. Because there are many defects on the surface of acid-washed carbon nanotubes, carbon atoms are unstable, and oxidation or reduction reactions are prone to occur. Nickel promotes the occurrence of oxidation-reduction reactions, so that the defects on the carbon tube walls are further etched to achieve The purpose of chemically shearing carbon nanotubes.
本发明制备方法包括如下步骤：The preparation method of the present invention comprises the following steps:
(1)碳纳米管的纯化(1) Purification of carbon nanotubes
将制备的原始碳纳米管用硝酸回流纯化，具体为：将原始碳纳米管在稀硝酸中超声分散，回流，用去离子水稀释，再用微孔滤膜过滤，干燥，得到经提纯的碳纳米管。Purify the prepared original carbon nanotubes with nitric acid reflux, specifically: ultrasonically disperse the original carbon nanotubes in dilute nitric acid, reflux, dilute with deionized water, filter with a microporous membrane, and dry to obtain purified carbon nanotubes Tube.
(2)金属镍颗粒在碳纳米管上的沉积(2) Deposition of metallic nickel particles on carbon nanotubes
将步骤(1)得到的碳纳米管超声分散到乙醇溶液中，再与可溶性镍盐水溶液混合均匀，在强烈搅拌下加入过量的碱金属的硼氢化物水溶液，室温下反应后过滤，干燥，得到镍沉积的碳纳米管，镍沉积的碳纳米管中镍的质量百分含量为：30-50％；ultrasonically disperse the carbon nanotubes obtained in step (1) into an ethanol solution, then mix them uniformly with a soluble nickel salt solution, add an excess of alkali metal borohydride aqueous solution under strong stirring, react at room temperature, filter, and dry to obtain Nickel-deposited carbon nanotubes, the mass percentage of nickel in the nickel-deposited carbon nanotubes is: 30-50%;
(3)高分散短碳纳米管的制备(3) Preparation of highly dispersed short carbon nanotubes
将步骤(2)得到的镍沉积的碳纳米管在两端开口的石英管中加热，之后将石英管两端封口，并通入保护性气体，再次升温，并保温，然后冷却至室温，所得黑色粉末再次用硝酸回流处理，以除去金属镍颗粒，经过滤、洗涤、干燥后得到长度小于200nm的高分散碳纳米管。The nickel-deposited carbon nanotubes obtained in step (2) are heated in a quartz tube with two ends open, then the two ends of the quartz tube are sealed, and a protective gas is introduced, the temperature is raised again, and the temperature is kept, and then cooled to room temperature, the obtained The black powder is refluxed with nitric acid again to remove metal nickel particles, and after filtering, washing and drying, highly dispersed carbon nanotubes with a length of less than 200nm are obtained.
本发明提供的高分散短碳纳米管制备的特点是：首次利用了金属镍的氧化还原反应达到剪切碳纳米管的目的。所得的碳纳米管两端开口并且均匀分散，长度可在200nm以下。这一尺度介于球形的富勒烯与长碳纳米管之间，具有十分重要的实际应用意义。例如它可以用作分子级电子设备的连接器和元器件，也可以在复合材料中均匀分散，以提高材料的机械性能和传导性能。另外，这种碳纳米管在锂离子电池阴极材料，燃料电池催化剂载体，生物医学等领域将有广阔的应用前景。The characteristic of the preparation of highly dispersed short carbon nanotubes provided by the invention is that the redox reaction of metal nickel is used for the first time to achieve the purpose of shearing carbon nanotubes. Both ends of the obtained carbon nanotubes are open and uniformly dispersed, and the length can be below 200nm. This scale is between spherical fullerenes and long carbon nanotubes, and has very important practical significance. For example, it can be used as connectors and components of molecular-level electronic devices, and can also be uniformly dispersed in composite materials to improve the mechanical properties and conductivity of materials. In addition, this carbon nanotube will have broad application prospects in lithium ion battery cathode materials, fuel cell catalyst supports, biomedicine and other fields.
附图说明Description of drawings
图1为纯化后碳纳米管(长度600-1000nm)的透射电镜照片。Figure 1 is a transmission electron micrograph of purified carbon nanotubes (600-1000nm in length).
图2为最终得到的高分散短碳纳米管(长度＜200nm)的透射电镜照片。Fig. 2 is a transmission electron micrograph of the finally obtained highly dispersed short carbon nanotubes (length<200nm).
具体实施方式Detailed ways
以下对本发明技术方案进一步的陈述：Further statement to the technical scheme of the present invention below:
本发明中，所述的碳纳米管用硝酸回流纯化，具体可以采用以下措施：将原始碳纳米管在稀硝酸中超声分散，并在120-140℃的温度下回流反应3-5小时，待温度降至室温时，用去离子水稀释至pH值为6-7，再用微孔滤膜过滤，在80-100℃干燥2-6小时，得到经提纯的碳纳米管。其中，In the present invention, the carbon nanotubes are purified by reflux with nitric acid. Specifically, the following measures can be adopted: ultrasonically disperse the original carbon nanotubes in dilute nitric acid, and reflux reaction at a temperature of 120-140°C for 3-5 hours. When the temperature is lowered to room temperature, it is diluted with deionized water to a pH value of 6-7, filtered through a microporous membrane, and dried at 80-100° C. for 2-6 hours to obtain purified carbon nanotubes. in,
所述的碳纳米管是采用气相沉积的方法制得的，在1100℃管式石英炉中热解二茂铁的饱和溶液，所得碳管直径约为10-20nm，长度为几百纳米至几微米；所述的稀硝酸溶液中浓硝酸与去离子水的比例为：3∶1(体积比)；所述的微孔滤膜的滤孔直径为0.2-0.45μm；所述的稀硝酸溶液与碳纳米管的比例为：50-100ml/g溶液。The carbon nanotubes are prepared by vapor deposition, and the saturated solution of ferrocene is pyrolyzed in a tubular quartz furnace at 1100°C, and the obtained carbon tubes have a diameter of about 10-20nm and a length of several hundred nanometers to several micrometers; The ratio of concentrated nitric acid and deionized water in the described dilute nitric acid solution is: 3: 1 (volume ratio); The filter pore diameter of described microporous membrane is 0.2-0.45 μ m; The ratio of nanotubes is: 50-100ml/g solution.
本发明中，所述的金属镍颗粒在碳纳米管上的沉积，具体可以采用以下措施：将得到的碳纳米管超声分散到乙醇溶液中，再与可溶性镍盐水溶液混合均匀，在强烈搅拌下加入过量的碱金属的硼氢化物水溶液，室温下反应20min后用微孔滤膜过滤，在60-80℃干燥2-4小时，得到镍沉积的碳纳米管；所述的镍沉积的碳纳米管中镍的质量百分含量为：30-50％。所述的乙醇溶液与碳纳米管的比例为：100-200ml/g。所述的可溶性镍盐可选自六水硝酸镍或六水硫酸镍；所述的碱金属的硼氢化物可选自硼氢化钾或硼氢化钠。In the present invention, the deposition of the metal nickel particles on the carbon nanotubes may specifically adopt the following measures: ultrasonically disperse the obtained carbon nanotubes into an ethanol solution, then mix them evenly with a soluble nickel salt aqueous solution, Add excess alkali metal borohydride aqueous solution, react at room temperature for 20 minutes, filter with a microporous membrane, and dry at 60-80°C for 2-4 hours to obtain nickel-deposited carbon nanotubes; the nickel-deposited carbon nanotubes The mass percent content of nickel in the tube is 30-50%. The ratio of the ethanol solution to the carbon nanotubes is 100-200ml/g. The soluble nickel salt can be selected from nickel nitrate hexahydrate or nickel sulfate hexahydrate; the alkali metal borohydride can be selected from potassium borohydride or sodium borohydride.
本发明中，所述的高分散短碳纳米管的制备，具体可以采用以下措施：将得到的镍沉积的碳纳米管在两端开口的石英管中加热，升温速率5-10℃/分钟，升温至300-400℃，并在该温度下保持1-1.5小时；之后将石英管两端封口，并通入惰性气体，流量为0.2-1升/分钟，再次以5-10℃/分钟的速度升温至800-900℃，并在该温度下保温1-2小时，在惰性气氛下冷却至室温。所得黑色粉末再次采用步骤(1)所述的方法进行处理，以除去金属镍颗粒。经过滤、洗涤、干燥后得到长度小于200nm的高分散碳纳米管。惰性气氛为氮气或氩气。In the present invention, the preparation of the highly dispersed short carbon nanotubes may specifically adopt the following measures: heating the obtained nickel-deposited carbon nanotubes in a quartz tube with openings at both ends at a heating rate of 5-10° C./min. Raise the temperature to 300-400°C and keep it at this temperature for 1-1.5 hours; then seal both ends of the quartz tube and pass in an inert gas with a flow rate of 0.2-1 liter/min, and again at a rate of 5-10°C/min Raise the temperature to 800-900°C, keep it at this temperature for 1-2 hours, and cool to room temperature under an inert atmosphere. Gained black powder is processed by the method described in step (1) again to remove metallic nickel particles. After filtering, washing and drying, highly dispersed carbon nanotubes with a length less than 200nm are obtained. The inert atmosphere is nitrogen or argon.
结合本发明的技术方案以及附图提供以下实施例：The following embodiments are provided in conjunction with the technical solutions of the present invention and the accompanying drawings:
实施例1Example 1
将气相生长法所制的碳纳米管2g超声分散在200ml稀硝酸(硝酸∶水＝1∶1(体积比))溶液中，然后在120℃油浴条件下用圆底烧瓶回流处理4小时，待冷却至室温时，用去离子水稀释至pH值为6-7，再用微孔滤膜过滤并洗涤3次，在80℃下干燥2小时，得到提纯后的碳纳米管，长度为600-1000nm(图1)。2 g of carbon nanotubes produced by the vapor phase growth method were ultrasonically dispersed in 200 ml of dilute nitric acid (nitric acid: water=1: 1 (volume ratio)) solution, and then refluxed in a round-bottomed flask at 120 ° C for 4 hours under oil bath conditions. When cooled to room temperature, dilute with deionized water to a pH value of 6-7, then filter and wash 3 times with a microporous membrane, and dry at 80°C for 2 hours to obtain purified carbon nanotubes with a length of 600 -1000nm (Figure 1).
取上述经提纯的碳纳米管0.3g超声分散到50ml乙醇溶液中，同时与含有1.34gNiSO4·6H2O的50ml水溶液混合，搅拌均匀。0.83gKBH4溶于50ml去离子水中，在强烈搅拌下缓慢倒入碳管与硫酸镍的混合溶液。反应20分钟后，用微孔滤膜过滤后洗涤3次，在80℃下干燥2小时，得到沉积镍的碳纳米管，镍的质量百分含量为50％。0.3 g of the above-mentioned purified carbon nanotubes were ultrasonically dispersed into 50 ml of ethanol solution, and simultaneously mixed with 50 ml of aqueous solution containing 1.34 g of NiSO 4 ·6H 2 O, and stirred evenly. 0.83g KBH 4 was dissolved in 50ml deionized water, and slowly poured into the mixed solution of carbon tubes and nickel sulfate under vigorous stirring. After reacting for 20 minutes, filter with a microporous membrane, wash three times, and dry at 80° C. for 2 hours to obtain nickel-deposited carbon nanotubes, the mass percentage of nickel being 50%.
该样品均匀平铺到石英舟并置于两端开口的石英管进行热处理，以10℃/分钟的速率升温至400℃，在此温度下保持1小时。再以同样的速率升温至900℃，同时通入氩气，氩气流量为200ml/分钟，在900℃保温1小时。The sample was evenly spread on a quartz boat and placed in a quartz tube with openings at both ends for heat treatment. The temperature was raised to 400°C at a rate of 10°C/min, and kept at this temperature for 1 hour. Then the temperature was raised to 900° C. at the same rate, and argon gas was introduced at the same time. The flow rate of argon gas was 200 ml/min, and the temperature was kept at 900° C. for 1 hour.
将热处理后的碳纳米管再次分散在稀硝酸溶液中，120℃回流处理4小时去除金属镍，冷却后过滤洗涤并干燥，得到最终高分散短碳纳米管。图2为本实施例最终得到的碳纳米管透射电镜照片，碳纳米管均匀分散，长度在200nm以下，并且两端开口。The heat-treated carbon nanotubes were dispersed again in dilute nitric acid solution, refluxed at 120° C. for 4 hours to remove metallic nickel, filtered, washed and dried after cooling to obtain the final highly dispersed short carbon nanotubes. FIG. 2 is a transmission electron microscope photo of the carbon nanotubes finally obtained in this embodiment. The carbon nanotubes are uniformly dispersed, the length is less than 200 nm, and both ends are open.
实施例2Example 2
碳纳米管纯化方法同实施例1。将0.2g碳纳米管超声分散到30ml乙醇溶液中，同时与含有1.0gNi(NO3)2·6H2O的30ml水溶液混合，搅拌均匀。将0.83gKBH4溶于30ml去离子水中，在强烈搅拌下缓慢倒入碳管与硫酸镍的混合溶液。反应20分钟后，用微孔滤膜过滤后洗涤3次，在80℃下干燥2小时，得到沉积镍的碳纳米管，镍的质量百分含量为40％。热处理以5℃/分钟的速率升温至350℃并保温1小时，之后通入氮气，流量为300ml/分钟，以同样的速率升温至850℃保温1.5小时。冷却至室温时采用与实施例1相同的方法进行酸洗去除金属镍颗粒。得到最终高分散短碳纳米管，长度在300nm以下。The carbon nanotube purification method is the same as in Example 1. Ultrasonic dispersion of 0.2 g of carbon nanotubes into 30 ml of ethanol solution was mixed with 30 ml of aqueous solution containing 1.0 g of Ni(NO 3 ) 2 ·6H 2 O, and stirred evenly. Dissolve 0.83g KBH 4 in 30ml deionized water, and slowly pour into the mixed solution of carbon tubes and nickel sulfate under vigorous stirring. After reacting for 20 minutes, filter with a microporous membrane, wash three times, and dry at 80° C. for 2 hours to obtain nickel-deposited carbon nanotubes with a mass percentage of nickel of 40%. Heat treatment was heated up to 350°C at a rate of 5°C/min and kept at a temperature of 1 hour, then nitrogen gas was introduced at a flow rate of 300ml/min, and the temperature was raised to 850°C at the same rate for 1.5 hours. When cooling to room temperature, the same method as in Example 1 was used to carry out pickling to remove metallic nickel particles. The final highly dispersed short carbon nanotubes are obtained, the length of which is below 300nm.
实施例3Example 3
碳纳米管纯化方法同实施例1。将0.5g碳纳米管超声分散到100ml乙醇溶液中，同时与含有0.94gNiSO4·6H2O的100ml水溶液混合，搅拌均匀。将0.41gNaBH4溶于100ml去离子水中，在强烈搅拌下缓慢倒入碳管与硫酸镍的混合溶液。反应20分钟后，用微孔滤膜过滤后洗涤3次，在80℃下干燥3小时，得到沉积镍的碳纳米管，镍的质量百分含量为30％。热处理以10℃/分钟的速率升温至300℃并保温1.5小时，之后通入氮气，流量为400ml/分钟，以同样的速率升温至800℃保温2小时。冷却至室温时采用与实施例1相同的方法进行酸洗去除金属镍颗粒。得到最终高分散短碳纳米管，长度在400nm以下。The carbon nanotube purification method is the same as in Example 1. Ultrasonic dispersion of 0.5 g of carbon nanotubes into 100 ml of ethanol solution was mixed with 100 ml of aqueous solution containing 0.94 g of NiSO 4 ·6H 2 O, and stirred evenly. Dissolve 0.41g NaBH4 in 100ml deionized water, slowly pour into the mixed solution of carbon tubes and nickel sulfate under vigorous stirring. After reacting for 20 minutes, filter with a microporous membrane, wash three times, and dry at 80° C. for 3 hours to obtain nickel-deposited carbon nanotubes, the mass percentage of nickel being 30%. The heat treatment is heated up to 300°C at a rate of 10°C/min and kept at a temperature of 1.5 hours, then nitrogen gas is introduced at a flow rate of 400ml/min, and the temperature is raised to 800°C at the same rate and kept at a temperature of 2 hours. When cooling to room temperature, the same method as in Example 1 was used to carry out pickling to remove metallic nickel particles. The final highly dispersed short carbon nanotubes are obtained, the length of which is below 400nm.
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| CN100411742C (en) * | 2006-10-26 | 2008-08-20 | 上海交通大学 | Method for mechanically shearing one-dimensional nanomaterials |
| CN101638228B (en) * | 2008-07-30 | 2011-09-21 | 中国科学院大连化学物理研究所 | A method for shortening carbon nanotubes with controllable length |
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| CN100411742C (en) * | 2006-10-26 | 2008-08-20 | 上海交通大学 | Method for mechanically shearing one-dimensional nanomaterials |
| CN101618868B (en) * | 2008-07-03 | 2013-03-13 | 中国科学院成都有机化学有限公司 | Method for removing amorphous carbon in carbon nanotubes |
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