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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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 239000012279 sodium borohydride Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 2
- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The chemical shearing method to prepare high-disperse short nano carbon tube with length within 200nm comprises: with wet chemical method, depositing metal nickel particle on the nano carbon tube purified by nitric acid; with redox reaction of metal nickel to etch the defect on wall further, taking chemical shear to the tube and obtaining the final product.
Description
Technical Field
The invention relates to a method in the field of nanotechnology, in particular to a chemical shearing method for preparing high-dispersion short carbon nanotubes.
Background
Carbon nanotubes have a unique one-dimensional tubular structure and mechanical, physical and chemical properties, and thus exhibit a wide application prospect in many fields. However, for most applications, a large number of short-length, open-ended, discrete carbon nanotubes are required. The carbon nano tubes prepared at present are all agglomerated together in large quantity, and the length reaches the micron level, thus the application of the carbon nano tubes is severely limited. In order to obtain the desired short carbon nanotubes, the conventional methods mainly involve physical and chemical processes. The physical process is to mix the carbon nanotubes with certain additives, grind the mixture in a specific grinding device, and cut the carbon nanotubes by utilizing various actions such as mechanical friction in the system and interlayer shearing force of the additives. This method, although it can be carried out on a larger scale, requires specialized equipment and is prone to the introduction of impurities during the milling process. Chemical processes mainly using specificThe reaction consumes the carbon on the wall of the carbon tube through the reaction, thereby achieving the purpose of cutting off and opening. At present, the chemical method for shearing the carbon nano tube mainly relates to two aspects, namely concentrated acid oxidation and fluorination heat treatment. Concentrated HNO for ever3And H2SO4The mixed acid oxidizes the single (multi) -wall carbon nano-tube to obtain the short carbon nano-tube with the length of 10-300nm, and the short carbon nano-tube can be applied to molecular electronic devices. It has also been proposed that oxidation with concentrated acid can shorten carbon nanotubes, and that during acid treatment, hydroxyl, carboxyl, carbonyl and other functional groups may be introduced to the carbon nanotube wall to disperse the carbon nanotubes in the composite material matrix. However, the strong acids used in this process are corrosive, dangerous to handle and time-consuming to handle, typically requiring hours or even tens of hours. Recently, the research of performing fluorination heat treatment on single-walled carbon nanotubes for shearing purposes has attracted much attention.
A literature search of the prior art shows that J.Kirk et al, J.AM.CHEM.SOC (J.Chem.Soc.USA school of chemistry) 9, 127(2005) 1541-one 1547, published as "Controlled Oxidative cutting of Single-Walled Carbon Nanotubes", which reports Carbon Nanotubes containing F2Fluorinating for 8-12 hours at 150 ℃ in 10% argon atmosphere, then carrying out heat treatment at 1000 ℃ in argon atmosphere to break the fluorocarbon bonds formed in the fluorination process so as to achieve the purpose of shearing the carbon nanotubes, wherein the length of the obtained single-wall carbon nanotube is 20-300nm, but the carbon nanotubes obtained by the method are still agglomerated together and are difficult to disperse.
Disclosure of Invention
The invention aims to provide a chemical shearing method for preparing high-dispersion short carbon nanotubes, aiming at the defects of the prior art, so that the high-dispersion short carbon nanotubes with the length of less than 200nm can be prepared.
The invention is realized by the following technical scheme that a wet chemical method is adopted to deposit metal nickel particles on the surface of the carbon nano tube purified by nitric acid, and then the carbon nano tube is chemically sheared by using the redox reaction of the metal nickel, so that the high-dispersion short carbon nano tube is obtained. Because the surface of the carbon nano tube after acid cleaning has a plurality of defects, carbon atoms are unstable and are easy to generate oxidation or reduction reaction, and the nickel promotes the oxidation reduction reaction to generate, thereby further etching the defects on the wall of the carbon nano tube and achieving the purpose of chemically shearing the carbon nano tube.
The preparation method comprises the following steps:
(1) purification of carbon nanotubes
The prepared original carbon nano tube is purified by nitric acid reflux, and the method specifically comprises the following steps: ultrasonically dispersing original carbon nano tubes in dilute nitric acid, refluxing, diluting with deionized water, filtering with a microporous filter membrane, and drying to obtain purified carbon nano tubes.
(2) Deposition of metallic nickel particles on carbon nanotubes
Ultrasonically dispersing the carbon nano tube obtained in the step (1) into an ethanol solution, uniformly mixing the carbon nano tube with a soluble nickel salt aqueous solution, adding an excessive alkali metal borohydride aqueous solution under strong stirring, reacting at room temperature, filtering and drying to obtain a nickel-deposited carbon nano tube, wherein the nickel content in the nickel-deposited carbon nano tube is as follows by mass percent: 30-50%;
(3) preparation of high-dispersion short carbon nano-tube
And (3) heating the carbon nano tube with the nickel deposited in the step (2) in a quartz tube with openings at two ends, then sealing two ends of the quartz tube, introducing protective gas, heating again, preserving heat, cooling to room temperature, carrying out reflux treatment on the obtained black powder with nitric acid again to remove metal nickel particles, and filtering, washing and drying to obtain the high-dispersion carbon nano tube with the length of less than 200 nm.
The preparation of the high-dispersion short carbon nano tube provided by the invention is characterized in that: the purpose of shearing the carbon nano tube is achieved by utilizing the oxidation-reduction reaction of the metallic nickel for the first time. The obtained carbon nanotube has two open ends and uniform dispersion, and the length can be below 200 nm. The size is between that of spherical fullerene and long carbon nanotube, and has very important practical application significance. For example, it can be used as connector and element of molecular electronic equipment, and can be uniformly dispersed in the composite material so as to raise the mechanical property and conductivity of said material. In addition, the carbon nano tube has wide application prospect in the fields of lithium ion battery cathode materials, fuel cell catalyst carriers, biomedicine and the like.
Drawings
FIG. 1 is a transmission electron micrograph of purified carbon nanotubes (length 600-1000 nm).
FIG. 2 is the transmission electron micrograph of the high-dispersion short carbon nanotube (length < 200nm) finally obtained.
Detailed Description
The technical scheme of the invention is further stated as follows:
in the invention, the carbon nanotube is purified by nitric acid reflux, and the following measures can be specifically adopted: ultrasonically dispersing original carbon nano tubes in dilute nitric acid, performing reflux reaction at the temperature of 120-140 ℃ for 3-5 hours, diluting the solution with deionized water until the pH value is 6-7 when the temperature is reduced to room temperature, filtering the solution with a microporous filter membrane, and drying the solution at the temperature of 80-100 ℃ for 2-6 hours to obtain purified carbon nano tubes. Wherein,
the carbon nano tube is prepared by adopting a vapor deposition method, the saturated solution of ferrocene is pyrolyzed in a 1100 ℃ tubular quartz furnace, the diameter of the obtained carbon tube is about 10-20nm, and the length of the obtained carbon tube is hundreds of nanometers to several micrometers; the ratio of the concentrated nitric acid to the deionized water in the dilute nitric acid solution is as follows: 3: 1 (volume ratio); the diameter of the filtration pore of the microporous filtration membrane is 0.2-0.45 μm; the ratio of the dilute nitric acid solution to the carbon nano tube is as follows: 50-100ml/g solution.
In the present invention, the deposition of the metallic nickel particles on the carbon nanotubes may specifically adopt the following measures: ultrasonically dispersing the obtained carbon nano tube into an ethanol solution, uniformly mixing the carbon nano tube with a soluble nickel salt aqueous solution, adding an excessive alkali metal borohydride aqueous solution under strong stirring, reacting for 20min at room temperature, filtering by using a microporous filter membrane, and drying for 2-4 hours at 60-80 ℃ to obtain a nickel-deposited carbon nano tube; the carbon nano tube deposited by nickel comprises the following nickel in percentage by mass: 30-50 percent. The proportion of the ethanol solution to the carbon nano tube is as follows: 100-200 ml/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.
In the invention, the preparation of the high-dispersion short carbon nanotube can specifically adopt the following measures: heating the obtained carbon nano tube deposited by nickel in a quartz tube with openings at two ends, wherein the heating rate is 5-10 ℃/min, the temperature is increased to 400 ℃ at 300-; then sealing both ends of the quartz tube, introducing inert gas with the flow rate of 0.2-1 liter/min, raising the temperature to 800-900 ℃ again at the speed of 5-10 ℃/min, preserving the temperature for 1-2 hours at the temperature, and cooling to the room temperature under the inert atmosphere. And (3) treating the obtained black powder again by using the method in the step (1) to remove the metallic nickel particles. Filtering, washing and drying to obtain the high-dispersion carbon nano tube with the length less than 200 nm. The inert atmosphere is nitrogen or argon.
The following embodiments are provided in combination with the technical solution of the present invention and the accompanying drawings:
example 1
Ultrasonically dispersing 2g of carbon nano-tube prepared by a vapor phase growth method in 200ml of dilute nitric acid (nitric acid: water is 1: 1 (volume ratio)), refluxing and treating for 4 hours by using a round-bottom flask under the condition of oil bath at 120 ℃, diluting to the pH value of 6-7 by using deionized water when cooling to room temperature, filtering and washing for 3 times by using a microporous filter membrane, and drying for 2 hours at 80 ℃ to obtain the purified carbon nano-tube with the length of 600-1000nm (figure 1).
Taking the purified carbon sodiumUltrasonic dispersing 0.3g of rice tube into 50ml of ethanol solution, and simultaneously mixing with the ethanol solution containing 1.34g of NiSO4·6H2O in 50ml of water solution, and stirring the mixture evenly. 0.83gKBH4Dissolved in 50ml of deionized water, and the mixture of carbon tubes and nickel sulfate is poured slowly with vigorous stirring. After reacting for 20 minutes, filtering the mixture by using a microporous filter membrane, washing the mixture for 3 times, and drying the mixture for 2 hours at the temperature of 80 ℃ to obtain the carbon nano tube with deposited nickel, wherein the mass percentage of the nickel is 50%.
The sample was uniformly spread on a quartz boat and placed in a quartz tube having both ends open for heat treatment, and the temperature was raised to 400 ℃ at a rate of 10 ℃/min and held at that temperature for 1 hour. Then, the temperature was raised to 900 ℃ at the same rate, argon gas was introduced at a flow rate of 200 ml/min, and the temperature was maintained at 900 ℃ for 1 hour.
And dispersing the carbon nano tube after heat treatment in a dilute nitric acid solution again, carrying out reflux treatment at 120 ℃ for 4 hours to remove metallic nickel, cooling, filtering, washing and drying to obtain the final high-dispersion short carbon nano tube. Fig. 2 is a transmission electron micrograph of the carbon nanotubes finally obtained in this example, in which the carbon nanotubes are uniformly dispersed, have a length of 200nm or less, and are open at both ends.
Example 2
The carbon nanotube purification method was the same as in example 1. Ultrasonic dispersing 0.2g carbon nanotube into 30ml ethanol solution while mixing with ethanol solution containing 1.0gNi (NO)3)2·6H2O in 30ml of water solution, and stirring the mixture evenly. 0.83g of KBH4Dissolved in 30ml of deionized water, and the mixture of carbon tubes and nickel sulfate is poured slowly with vigorous stirring. After reacting for 20 minutes, filtering the mixture by using a microporous filter membrane, washing the mixture for 3 times, and drying the mixture for 2 hours at the temperature of 80 ℃ to obtain the carbon nano tube with deposited nickel, wherein the mass percentage of the nickel is 40%. The heat treatment was carried out at a rate of 5 ℃/min to 350 ℃ and held for 1 hour, after which nitrogen was introduced at a flow rate of 300 ml/min and at the same rate to 850 ℃ and held for 1.5 hours. When cooled to room temperature, the metal nickel particles were removed by acid washing in the same manner as in example 1. The final high-dispersion short carbon nano-tube with the length below 300nm is obtained.
Example 3
The carbon nanotube purification method was the same as in example 1. Ultrasonic dispersing 0.5g carbon nanotube into 100ml ethanol solution while mixing with solution containing 0.94g NiSO4·6H2O in 100ml of water solution, and stirring the mixture evenly. 0.41g of NaBH4Dissolved in 100ml deionized water, and the mixed solution of carbon tubes and nickel sulfate is slowly poured into the solution under strong stirring. After reacting for 20 minutes, filtering the mixture by using a microporous filter membrane, washing the mixture for 3 times, and drying the mixture for 3 hours at the temperature of 80 ℃ to obtain the carbon nano tube with deposited nickel, wherein the mass percentage of the nickel is 30%. The heat treatment was carried out by raising the temperature to 300 ℃ at a rate of 10 ℃/min and maintaining the temperature for 1.5 hours, then introducing nitrogen at a flow rate of 400 ml/min and raising the temperature to 800 ℃ at the same rate and maintaining the temperature for 2 hours. When cooled to room temperature, the metal nickel particles were removed by acid washing in the same manner as in example 1. The final high-dispersion short carbon nano-tube with the length below 400nm is obtained.
Claims (7)
1. A chemical shearing method for preparing high-dispersion short carbon nano-tubes is characterized in that a wet chemical method is adopted to deposit metal nickel particles on the surfaces of the carbon nano-tubes purified by nitric acid, and then the carbon nano-tubes are chemically sheared by the redox reaction of metal nickel, so that the high-dispersion short carbon nano-tubes are obtained.
2. The chemical shearing method for preparing high-dispersion short carbon nanotubes according to claim 1, comprising the steps of:
(1) and (3) purifying the carbon nano tube: refluxing and purifying the prepared original carbon nano tube by using nitric acid;
(2) deposition of metallic nickel particles on carbon nanotubes: ultrasonically dispersing the carbon nano tube obtained in the step (1) into an ethanol solution, uniformly mixing the carbon nano tube with a soluble nickel salt aqueous solution, adding an excessive alkali metal borohydride aqueous solution under strong stirring, reacting at room temperature, filtering and drying to obtain a nickel-deposited carbon nano tube, wherein the nickel content in the nickel-deposited carbon nano tube is as follows by mass percent: 30-50%;
(3) preparing high-dispersion short carbon nanotubes: and (3) heating the carbon nano tube with the nickel deposited in the step (2) in a quartz tube with openings at two ends, then sealing two ends of the quartz tube, introducing protective gas, heating again, preserving heat, cooling to room temperature, carrying out reflux treatment on the obtained black powder with nitric acid again to remove metal nickel particles, and filtering, washing and drying to obtain the high-dispersion carbon nano tube with the length of less than 200 nm.
3. The chemical shearing method for preparing highly dispersed short carbon nanotubes as claimed in claim 2, wherein the step (1) of purifying the carbon nanotubes comprises: ultrasonically dispersing original carbon nano tubes in dilute nitric acid, refluxing, diluting with deionized water, filtering with a microporous filter membrane, and drying to obtain purified carbon nano tubes.
4. The chemical shearing method for preparing highly dispersed short carbon nanotubes as claimed in claim 2, wherein in step (2), said soluble nickel salt is selected from nickel nitrate hexahydrate or nickel sulfate hexahydrate.
5. The chemical shearing method for preparing highly dispersed short carbon nanotubes as claimed in claim 2, wherein in step (2), said alkali metal borohydride is selected from potassium borohydride or sodium borohydride.
6. The chemical shearing method for preparing high dispersion short carbon nanotube according to claim 1, wherein in the step (3), the nickel deposited carbon nanotube is heated in a quartz tube with two open ends, specifically: heating to 400 ℃ at 300 ℃ and keeping the temperature for 1-1.5 hours; then sealing both ends of the quartz tube, introducing protective gas, heating to 800-900 ℃ again, preserving the heat for 1-2 hours at the temperature, and cooling to room temperature under protective atmosphere.
7. The chemical shearing method for preparing highly dispersed short carbon nanotubes as claimed in claim 2 or 6, wherein the protective atmosphere is nitrogen or argon.
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| CN100411742C (en) * | 2006-10-26 | 2008-08-20 | 上海交通大学 | Mechanically shearing process of preparing one-dimensional nanometer material |
| CN101638228B (en) * | 2008-07-30 | 2011-09-21 | 中国科学院大连化学物理研究所 | Method for truncating length-controlled carbon nanotubes |
| 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 |
| CN105439123A (en) * | 2015-12-28 | 2016-03-30 | 河北师范大学 | Method for preparing nano particles |
| WO2016090958A1 (en) * | 2014-12-12 | 2016-06-16 | 宁波南车新能源科技有限公司 | Preparation method for mixed capacitor negative electrode slurry |
| CN110980695A (en) * | 2019-12-31 | 2020-04-10 | 厦门大学 | Controllable shearing method of carbon-based nano material |
| CN112897509A (en) * | 2021-02-04 | 2021-06-04 | 陕西科技大学 | Method for in-situ growing carbon nano tube with collapsed tube wall by transition metal Ni catalysis |
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| KR100314094B1 (en) * | 1999-08-12 | 2001-11-15 | 김순택 | Method for fabricating a carbon nanotube field emitter using electrophoresis process |
| US6451175B1 (en) * | 2000-08-15 | 2002-09-17 | Wisconsin Alumni Research Foundation | Method and apparatus for carbon nanotube production |
| CN1209284C (en) * | 2003-10-28 | 2005-07-06 | 黄德欢 | Method and equipment for preparing Nano carbon tube with multiple walls |
| CN1253245C (en) * | 2004-03-04 | 2006-04-26 | 厦门大学 | Method of depositing high density loading metal platinum on carbon nanometer pipe surface using oriented chemistry |
| CN1302986C (en) * | 2004-05-10 | 2007-03-07 | 华东理工大学 | Method for preparing Nano carbon tubes |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100411742C (en) * | 2006-10-26 | 2008-08-20 | 上海交通大学 | Mechanically shearing process of preparing one-dimensional nanometer material |
| 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 |
| CN101638228B (en) * | 2008-07-30 | 2011-09-21 | 中国科学院大连化学物理研究所 | Method for truncating length-controlled carbon nanotubes |
| WO2016090958A1 (en) * | 2014-12-12 | 2016-06-16 | 宁波南车新能源科技有限公司 | Preparation method for mixed capacitor negative electrode slurry |
| CN105439123A (en) * | 2015-12-28 | 2016-03-30 | 河北师范大学 | Method for preparing nano particles |
| CN110980695A (en) * | 2019-12-31 | 2020-04-10 | 厦门大学 | Controllable shearing method of carbon-based nano material |
| CN112941680A (en) * | 2021-01-28 | 2021-06-11 | 华侨大学 | Preparation method of carbon nanotube fiber-loaded nano iron oxide composite material |
| CN112897509A (en) * | 2021-02-04 | 2021-06-04 | 陕西科技大学 | Method for in-situ growing carbon nano tube with collapsed tube wall by transition metal Ni catalysis |
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