CN110790259A - Method for preparing single-walled carbon nanotubes in batches - Google Patents
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- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
Abstract
The invention discloses a batch preparation method of single-walled carbon nanotubes, belonging to the technical field of preparation of carbon nanomaterials. The invention aims to solve the technical problem that the existing method for preparing the single-walled carbon nanotube is not easy to batch. The method comprises the following steps: adding a metal organic compound into an organic solvent, and emulsifying to prepare a catalyst precursor solution; and step two, continuously introducing the catalyst precursor solution, the reducing gas, the inert gas and the carbon source gas obtained in the step one into a reaction device which is kept at the temperature of 600-1500 ℃ for continuous reaction to obtain the single-walled carbon nanotube. The single-walled carbon nanotube obtained by the method can be applied to conductive additives of various materials. The method has the advantages of low energy consumption, environment-friendly raw materials and low price. The single-walled carbon nanotube has the advantages of high purity, good pipe diameter uniformity, batch preparation and the like.
Description
Technical Field
The invention belongs to the technical field of carbon nano-material preparation; in particular to a batch preparation method of single-walled carbon nanotubes.
Background
From the structural point of view, the shape of the carbon nanotube is a one-dimensional cylindrical hollow structure, and can also be understood as being formed by curling a graphite sheet structure, and the carbon nanotube is divided into a single-wall carbon nanotube and a multi-wall carbon nanotube. The diameter of the carbon nanotube is about several to hundreds of nanometers, the length of the carbon nanotube is generally in a micron order, and the carbon nanotube is several times or even tens of thousands of times of the diameter, so that the carbon nanotube has a larger length-diameter ratio. From the performance, the carbon nano tube has good heat conduction, electric conduction and mechanical strength, and can be used for composite materials, additives and the like, and the strength, the electric conductivity and the like of the materials are enhanced. From the aspect of preparation, methods for preparing carbon nanotubes include arc discharge, laser evaporation, chemical vapor deposition, and the like. At present, the known single-walled carbon nanotube manufacturers mainly adopt an arc discharge method to prepare or produce the single-walled carbon nanotubes in batches, and although the arc discharge method is simple, the product is complex, so that the defects of low purity, high energy consumption, poor economy and the like are caused.
Compared with the multi-wall carbon nanotube, the single-wall carbon nanotube has obvious advantages in the using process, has low addition amount, and has wider application range than the multi-wall carbon nanotube in certain directions with color requirements.
Application publication No. CN 110203906A discloses a preparation method and application of single-walled carbon nanotubes, which comprises the steps of 1) heating a catalyst in a first area in a reactor to 70-85 ℃; 2) introducing hydrocarbon gas serving as a carbon source, hydrogen and argon into a reactor, and enabling mixed gas to flow through a first area to be in contact with a catalyst; 3) obtaining the single-walled carbon nano-tube in the second area. However, the purity of the carbon nanotube obtained by the method is generally lower, further acidification purification or high-temperature purification is needed, the structure of the carbon nanotube is irreversibly damaged, and the method is not beneficial to environmental protection and consumption reduction; on the other hand, the method is not suitable for batch preparation and production.
Application publication No. CN 107792845A discloses a method for preparing single-walled carbon nanotubes, which comprises the steps of 1) adding a certain amount of non-metallic catalyst into concentrated sulfuric acid solution at room temperature, and stirring uniformly to obtain mixed solution; 2) adding a certain amount of carbohydrate powder into the mixed solution obtained in the step 1), and stirring for reaction to obtain a reaction mixture containing carbon nano tubes; 3) adding the reaction mixture obtained in the step 2) into a hydrochloric acid solution, stirring, standing, filtering the upper suspension to obtain a black substance, washing with deionized water, and drying to obtain the single-walled carbon nanotube. However, the carbon nano tube prepared by the method is a multi-wall carbon nano tube, and the tube diameter of the single-wall carbon nano tube is distributed between 1.5nm and 2nm, so that the tube diameter of the carbon nano tube prepared by the method is about 15 nm; in addition, the method uses sulfuric acid and hydrochloric acid, which is not beneficial to batch preparation.
Disclosure of Invention
The invention aims to solve the technical problem that the existing method for preparing the single-walled carbon nanotube is not easy to realize batch production; and provides a batch preparation method of single-walled carbon nanotubes.
The invention relates to a batch preparation method of single-walled carbon nanotubes, which comprises the following steps:
adding a metal organic compound into an organic solvent, and emulsifying to prepare a catalyst precursor solution;
step two, continuously introducing the catalyst precursor solution, the reducing gas, the inert gas and the carbon source gas obtained in the step one into a reaction device which is kept at the temperature of 600-1500 ℃ for continuous reaction to obtain a single-walled carbon nanotube; the single-walled carbon nanotubes can be prepared in batch by continuously introducing the reaction raw materials.
In the first step, the metal organic compound is one or any combination of carbonyl metal, metallocene and metalloporphyrin in any ratio; the metal carbonyl is carbonyl iron or carbonyl nickel and the like; the carbonyl iron is iron tricarbonyl, iron tetracarbonyl, iron pentacarbonyl, iron nonacarbonyl or iron dodecacarbonyl; the metallocene is ferrocene or nickelocene; the metalloporphyrin is porphyrin iron or porphyrin nickel.
In the first step, adding the metal organic compound into the organic solvent according to the proportion of adding 0.01 mol-10 mol of metal organic compound into each liter of organic solvent; the stirring speed is 100 rpm-5000 rpm, and the stirring time is 30 min-240 min in the emulsification treatment process.
The batch preparation method of the single-walled carbon nanotubes can also be carried out according to the following steps:
step one, adding simple substance metal into an organic solvent to obtain a suspension, and mechanically grinding to obtain a catalyst precursor solution;
and step two, continuously introducing the catalyst precursor solution, the reducing gas, the inert gas and the carbon source gas obtained in the step one into a reaction device which is kept at the temperature of 600-1500 ℃ for continuous reaction to obtain the single-walled carbon nanotube.
Firstly, the elementary metal is one or a plurality of transition metal, noble metal, alkali metal and alkaline earth metal which are combined according to any ratio; such as one or more of iron, cobalt, nickel, chromium, molybdenum, tungsten and the like, which are combined according to any ratio.
Adding the elementary metal into the organic solvent according to the proportion of adding 0.01-10 mol of the elementary metal into each liter of the organic solvent;
in the step one of any scheme, the organic solvent is one or a combination of several of aromatic compounds, aliphatic hydrocarbon compounds, alcohols and ethers; the aromatic compound is benzene, naphthalene or anthracene, the aliphatic hydrocarbon compound is cyclohexane or heptane, the alcohol is ethanol, glycerol or butanol, and the ether is diethyl ether or ethyl propyl ether.
In the second step of any scheme, the reaction device with the heat preservation temperature of 600-1500 ℃ is obtained by continuously introducing inert gas into the reaction device, raising the temperature to a certain temperature and preserving the heat for 20-60 min so as to ensure the uniform temperature of the reaction cavity.
In the second step of any of the above embodiments, the reducing gas is H2、NH3、CO、H2And (5) one of S.
In the second step of any of the above embodiments, the inert gas is N2Or Ar.
In the second step of any scheme, the carbon source gas is one or a combination of several of methane, ethylene, acetylene, propane and propylene according to any ratio.
The reducing gas in step two of any of the above embodiments: inert gas: carbon source gas: the ratio of the amounts of the metal organic compound is (2-5): (0.5-1): (0.5-5): (0.2-0.5).
The method of the invention continuously prepares the high-quality single-walled carbon nanotubes with high purity, narrow tube diameter distribution range and the like in batches, the single-walled carbon nanotubes have black powder appearance, the micro appearance is the tube bundle of the single-walled carbon nanotubes (the single-walled carbon nanotubes are distributed in the tube bundle because the surface energy of the single-walled carbon nanotubes is higher, and no single tube exists), and the single-walled carbon nanotubes have certain orientation, the tube diameter is between 1.5 and 3nm, and the specific surface area is 400m2/g-800m2More than one gram, and the carbon content is more than 65 percent (mass) and can reach more than 86 percent (mass). The method can be used as a final product without further treatment, and the good structure of the product is kept to the maximum extent so as to ensure the performance. It can be used as conductive additive for various materials, and has mechanical property enhancing effect.
The method has the advantages of low energy consumption, environment-friendly raw materials and low price.
Drawings
FIG. 1 is a TEM image of single-walled carbon nanotubes prepared in example 1;
FIG. 2 is an SEM image of single-walled carbon nanotubes prepared in example 2.
Detailed Description
Example 1: 38.69g of iron pentacarbonyl powder is dissolved in 500g of glycerol solvent, namely the amount concentration of catalytic element substances is 0.5mol/L, and the mixture is stirred for 30min at 1500rpm (carbonyl iron is easy to spontaneously combust in the air) under the anaerobic condition to emulsify the mixture, thus obtaining a catalyst precursor solution; h is to be2：N2：C3H6: the carbonyl iron is prepared according to the following steps of 2.5: 0.75: 1.5: the mass ratio of 0.5 was introduced into the reaction apparatus maintained at 850 ℃, i.e. the feed rates were respectively: h2Is 1.25L/min, N2Is 0.375L/min, C3H60.75L/min, 0.5L/min carbonyl iron solution, reacting for 2min, collecting black powder 20.15g, which is single-walled carbon nanotube with diameter of about 2nm, as shown in FIG. 1.
The specific surface area of the single-walled carbon nanotube prepared by the method of the embodiment is 524m2(ii)/g, carbon content 87%.
The mass production can be realized by continuously introducing raw materials into the reaction device.
Example 2: mixing glycerol and absolute ethyl alcohol according to a mass ratio of 1: 1, mixing to obtain a mixed solvent, dissolving 49.14g of iron pentacarbonyl powder in the mixed solvent to obtain a catalytic element substance with the concentration of 0.5mol/L, stirring for 15min at 1500rpm (carbonyl iron is easy to spontaneously combust in air) under an anaerobic condition, and emulsifying to obtain a catalyst precursor solution; h is to be2：N2：C3H6: the carbonyl iron is prepared according to the following steps of 2.5: 0.75: 1.5: the mass ratio of 0.5 was introduced into a reaction apparatus maintained at 820 ℃, i.e. the feed rates were respectively: h2Is 1.25L/min, N2Is 0.375L/min, C3H60.75L/min, 0.5L/min carbonyl iron solution, and allowing the reaction to continue for 2min, collecting black powder 32.62g, namely single-walled carbon nanotubes, as shown in figure 2.
The tube diameter of the single-walled carbon nanotube prepared by the method of the embodiment is 1.97nm, and the specific surface area is 535m2(iv)/g, carbon content 82%.
Example 3: 38.69g of nickel carbonyl powder is dissolved in 500g of glycerol solvent, namely the amount concentration of catalytic element substances is 0.5mol/L, and the mixture is stirred for 30min at 2000rpm under the anaerobic condition to be emulsified, so that catalyst precursor solution is obtained; h is to be2：N2：C3H6: nickel carbonyl in a weight ratio of 2.5: 0.75: 1.5: the mass ratio of 0.5 was fed to the reaction apparatus maintained at 780 ℃ i.e. the feed rates were respectively: h2Is 1.25L/min, N2Is 0.375L/min, C3H60.75L/min, 0.5L/min nickel carbonyl solution, reacting for 2min, collecting black powder 38.75g, namely single-walled carbon nanotube.
The tube diameter of the single-walled carbon nanotube prepared by the method of the embodiment is 2.2nm, and the specific surface area is 509m2(iv)/g, carbon content 85%.
Example 4: mixing glycerol and absolute ethyl alcohol according to a mass ratio of 1: 1 to obtain a mixed solvent, dissolving 49.14g of carbonyl nickel powder in the mixed solvent to obtain a catalytic element substance with the concentration of 0.5mol/L, stirring for 15min at 2000rpm under an anaerobic condition to emulsify the catalytic element substance to obtain the catalystA precursor solution; h is to be2：N2：C3H6: nickel carbonyl in a weight ratio of 2.5: 0.75: 1.5: the mass ratio of 0.5 was introduced into the reaction apparatus maintained at 750 ℃ i.e. the feed rates were respectively: h2Is 1.25L/min, N2Is 0.375L/min, C3H60.75L/min, 0.5L/min nickel carbonyl solution, reacting for 2min, collecting black powder 40.08g, namely single-walled carbon nanotube.
The tube diameter of the single-walled carbon nanotube prepared by the method of the embodiment is 2.5nm, and the specific surface area is 497m2(iv)/g, carbon content 89%.
Example 5: 38.69g of iron pentacarbonyl powder is dissolved in 500g of glycerol solvent, namely the amount concentration of catalytic element substances is 0.5mol/L, and the mixture is stirred for 30min at 2500rpm under the anaerobic condition (carbonyl iron is easy to spontaneously combust in the air), so that the catalyst precursor solution is obtained; h is to be2S：N2：C3H6: the carbonyl iron is prepared according to the following steps of 2.5: 0.75: 1.5: the mass ratio of 0.5 was introduced into the reaction apparatus maintained at 850 ℃, i.e. the feed rates were respectively: h2S is 1.25L/min, N2Is 0.375L/min, C3H60.75L/min, 0.5L/min carbonyl iron solution, reacting for 2min, collecting black powder 22.86g, namely single-walled carbon nanotube.
The tube diameter of the single-walled carbon nanotube prepared by the method of the embodiment is 1.78nm, and the specific surface area is 601m2(iv)/g, carbon content 86%.
Example 6: 38.69g of nickel carbonyl powder is dissolved in 500g of glycerol solvent, namely the amount concentration of catalytic element substances is 0.5mol/L, and the mixture is stirred for 30min at 2500rpm under the anaerobic condition to be emulsified, so that catalyst precursor solution is obtained; h is to be2S：N2：C3H6: nickel carbonyl in a weight ratio of 2.5: 0.75: 1.5: the mass ratio of 0.5 was fed to the reaction apparatus maintained at 780 ℃ i.e. the feed rates were respectively: h2S is 1.25L/min, N2Is 0.375L/min, C3H60.75L/min, 0.5L/min nickel carbonyl solution, reacting for 2min, and collecting black powder, namely the single-walled carbon nanotube.
The tube diameter of the single-walled carbon nanotube prepared by the method of the embodiment is 1.98nm, and the specific surface area is 587m2(iv)/g, carbon content 83%.
Example 7: 38.69g of nickel carbonyl powder is dissolved in 500g of glycerol solvent, namely the amount concentration of catalytic element substances is 0.5mol/L, and the mixture is stirred for 30min at 3000rpm under the anaerobic condition to be emulsified, so that catalyst precursor solution is obtained; h is to be2S：N2：C3H6: nickel carbonyl in a weight ratio of 2.5: 0.75: 1.5: the mass ratio of 0.5 was fed to the reaction apparatus maintained at 780 ℃ i.e. the feed rates were respectively: h2S is 1.25L/min, N2Is 0.375L/min, C3H60.75L/min, 0.5L/min nickel carbonyl solution, reacting for 2min, collecting black powder 35.57gg, that is single-walled carbon nanotube
The tube diameter of the single-walled carbon nanotube prepared by the method of the embodiment is 2.3nm, and the specific surface area is 543m2(iv)/g, carbon content 83%.
Example 8: 38.69g of nickel carbonyl powder is dissolved in 500g of glycerol solvent, namely the amount concentration of catalytic element substances is 0.5mol/L, and the mixture is stirred for 30min at 3000rpm under the anaerobic condition to be emulsified, so that catalyst precursor solution is obtained; h is to be2S：N2：C3H6: nickel carbonyl in a weight ratio of 2.5: 0.75: 1.5: the mass ratio of 0.5 was fed to the reaction apparatus maintained at 780 ℃ i.e. the feed rates were respectively: h2S is 1.25L/min, N2Is 0.375L/min, C3H60.75L/min, 0.5L/min nickel carbonyl solution, reacting for 2min, collecting black powder 38.89g, namely single-walled carbon nanotube.
The tube diameter of the single-walled carbon nanotube prepared by the method of the embodiment is 2.4nm, and the specific surface area is 512m2(iv)/g, carbon content 89%.
Example 9: 38.69g of iron pentacarbonyl powder is dissolved in 500g of glycerol solvent, namely the amount concentration of catalytic element substances is 0.5mol/L, and the mixture is stirred for 30min at 3000rpm under the anaerobic condition (carbonyl iron is easy to spontaneously combust in the air), so that the catalyst precursor solution is obtained; h is to be2：N2：CH4: the carbonyl iron is prepared according to the following steps of 2.5: 0.75: 1.5:the mass ratio of 0.5 was fed to a reaction apparatus maintained at 1000 ℃ i.e. the feed rates were respectively: h2Is 1.25L/min, N2Is 0.375L/min, CH40.75L/min, 0.5L/min carbonyl iron solution, reacting for 2min, and collecting black powder 18.64g, namely the single-walled carbon nanotube.
The tube diameter of the single-walled carbon nanotube prepared by the method of the embodiment is 1.98nm, and the specific surface area is 532m2G, carbon content 84%.
Example 10: mixing glycerol and absolute ethyl alcohol according to a mass ratio of 1: 1, mixing to obtain a mixed solvent, dissolving 49.14g of iron pentacarbonyl powder in the mixed solvent to obtain a catalytic element substance with the concentration of 0.5mol/L, stirring for 15min at 3000rpm (carbonyl iron is easy to spontaneously combust in air) under an anaerobic condition, and emulsifying to obtain a catalyst precursor solution; h is to be2：N2：CH4: the carbonyl iron is prepared according to the following steps of 2.5: 0.75: 1.5: the mass ratio of 0.5 was fed to a reaction apparatus maintained at 1000 ℃ i.e. the feed rates were respectively: h2Is 1.25L/min, N2Is 0.375L/min, CH40.75L/min, 0.5L/min carbonyl iron solution, reacting for 2min, collecting black powder 22.34g, namely single-walled carbon nanotube.
The tube diameter of the single-walled carbon nanotube prepared by the method of the embodiment is 2.2nm, and the specific surface area is 498m2(ii)/g, carbon content 88%.
Claims (10)
1. A batch preparation method of single-walled carbon nanotubes is characterized by comprising the following steps:
adding a metal organic compound into an organic solvent, and emulsifying to prepare a catalyst precursor solution;
and step two, continuously introducing the catalyst precursor solution, the reducing gas, the inert gas and the carbon source gas obtained in the step one into a reaction device which is kept at the temperature of 600-1500 ℃ for continuous reaction to obtain the single-walled carbon nanotube.
2. The batch preparation method of single-walled carbon nanotubes as claimed in claim 1, wherein the organometallic compound is one or a combination of several of hydroxyl metal, metallocene and metalloporphyrin.
3. The batch preparation method of single-walled carbon nanotubes according to claim 2, wherein the metal carbonyl is iron carbonyl or nickel carbonyl; the carbonyl iron is iron tricarbonyl, iron tetracarbonyl, iron pentacarbonyl, iron nonacarbonyl or iron dodecacarbonyl; the metallocene is ferrocene or nickelocene; the metalloporphyrin is porphyrin iron or porphyrin nickel.
4. The batch preparation method of single-walled carbon nanotubes as claimed in claim 1, wherein the step one comprises adding the metal organic compound to the organic solvent in a ratio of 0.01mol to 10mol per liter of the organic solvent; the stirring speed in the emulsification treatment is 100 rpm-5000 rpm, and the stirring time is 30 min-240 min.
5. The batch preparation method of single-walled carbon nanotubes as claimed in claim 1, wherein the organic solvent in step one is one or a combination of aromatic compounds, aliphatic hydrocarbon compounds, alcohols, and ethers.
6. The batch preparation method of single-walled carbon nanotubes as claimed in claim 5, wherein the aromatic compound is benzene, naphthalene or anthracene, the aliphatic hydrocarbon compound is cyclohexane or heptane, the alcohol is ethanol, glycerol or butanol, and the ether is diethyl ether or ethyl propyl ether.
7. The batch preparation method of single-walled carbon nanotubes as claimed in claim 1, wherein the reaction apparatus insulated at 600-1500 ℃ in the second step is obtained by continuously introducing inert gas into the reaction apparatus, heating to a certain temperature, and then insulating for 20-60 min.
8. The batch of single-walled carbon nanotubes of claim 1The preparation method is characterized in that the reducing gas in the step two is H2、NH3、CO、H2One of S; the inert gas being N2Or Ar; the carbon source gas is one or the combination of a plurality of methane, ethylene, acetylene, propane and propylene; the reducing gas: inert gas: carbon source gas: the ratio of the amounts of the metal organic compound is (2-5): (0.5-1): (0.5-5): (0.2-0.5).
9. The method for batch preparation of single-walled carbon nanotubes according to any one of claims 1 to 8, wherein the catalyst precursor solution of step one is prepared by: adding simple substance metal into an organic solvent to obtain a suspension, and mechanically grinding to obtain a catalyst precursor solution;
wherein the simple substance metal is one or a combination of several of transition metal, noble metal, alkali metal and alkaline earth metal.
10. The batch preparation method of single-walled carbon nanotubes as claimed in claim 9, wherein the elemental metal is one or a combination of iron, cobalt, nickel, chromium, molybdenum and tungsten.
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