CN115974053A - Honeycomb-structure carbon nanotube and preparation method thereof - Google Patents
Honeycomb-structure carbon nanotube and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a honeycomb structure carbon nano tube and a preparation method thereof, firstly, an oxygen-free carbon precursor is taken as a reactant, and a carbon nano tube vertical array is prepared by a chemical vapor deposition method; then cleaning to remove surface impurities; then putting the purified carbon nano tube vertical array into a reactor, and depositing metal particles on the top end of the carbon nano tube vertical array by a physical deposition method; and finally, introducing water vapor at a high temperature for a period of time to prepare the honeycomb-structure carbon nano tube. The method has simple and practical process and low cost, and can realize the regulated growth of the carbon nano tube with the honeycomb structure through a two-step method. The prepared carbon nano tube with the honeycomb structure has higher purification efficiency on particles and toxic and harmful gases, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of carbon nanotube preparation, and particularly relates to a carbon nanotube with a honeycomb structure and a preparation method thereof.
Background
Since 1991, carbon nanotubes have been found to have been developed, and the techniques for preparing carbon nanotubes have been developed rapidly, among which chemical vapor deposition, arc discharge, and laser ablation have become the mainstream means for carbon nanotubes. The chemical vapor deposition method is widely used due to its advantages of simple preparation process, easily available raw materials, high yield of carbon nanotubes, etc. The precise growth of the carbon nano tube in the aspects of diameter, tube length and morphological structure can be realized by regulating and controlling reaction parameters (temperature, catalyst concentration, catalyst particle size, reaction time, growth promoter) and the like in the chemical vapor deposition process. For example: the particle size of the catalyst is reduced, so that the preparation of the small-diameter carbon nano tube can be realized, the reaction time is prolonged to increase the tube length of the carbon nano tube, and the deposition density of the catalyst on the support is increased to realize the growth of the vertical array carbon nano tube.
The properties and properties of carbon nanotubes are highly dependent on structure and morphology: the carbon nano tube vertical array with high orientation has excellent electrical property, the net-shaped interwoven carbon nano tube has better particle separation performance, and the carbon nano tube with the spiral structure and a plurality of defect sites is more suitable to be used as a catalyst carrier. Therefore, the physical properties of the carbon nanotubes must be controlled to enable industrial application of the carbon nanotubes. For this reason, the precise preparation of carbon nanotubes having a horizontal array, a vertical array, a helical structure, a bead structure, a Y-shape, a cross-shape, and the like has been achieved.
A novel carbon nanotube, namely a honeycomb-structured carbon nanotube, is provided, and the structure endows the carbon nanotube with large specific surface area, high gas permeability and good electrical conductivity. The existing carbon nanotube preparation technology is difficult to realize the effective preparation of the honeycomb structure, and the yield of the carbon nanotube with the honeycomb structure is low, so that the application of the carbon nanotube is limited. Therefore, it is highly desirable to develop a preparation technique suitable for carbon nanotubes having a honeycomb structure.
Disclosure of Invention
The technical problem to be solved is as follows: the prior carbon nanotube preparation technology is difficult to realize the controllable preparation of the honeycomb structure, and the yield of the carbon nanotube with the honeycomb structure is low, so the application of the carbon nanotube is greatly limited; in order to solve the technical problem, the invention provides a carbon nano tube with a honeycomb structure and a preparation method thereof, which have simple operation steps and strong practicability.
The technical scheme is as follows:
a preparation method of a carbon nanotube with a honeycomb structure comprises the following steps:
step one, preparing a carbon nano tube vertical array: putting the cleaned support body into a quartz tube of a tube furnace, heating under the protection of nitrogen with the flow rate of 10-1000ml/min, keeping the temperature after the temperature reaches 680-850 ℃, introducing a reactant formed by mixing 30-60ml of carbon precursor and a catalyst into the quartz tube for constant-temperature reaction for 20-120min, and preparing the carbon nano tube vertical array;
and step two, purifying the carbon nano tube vertical array: soaking the carbon nano tube vertical array prepared in the first step in 10-25ml of cleaning solution at room temperature for 60min to remove catalyst particles and other impurities on the surface of the carbon nano tube vertical array, then slowly cleaning the carbon nano tube vertical array with deionized water for three times, and then drying the carbon nano tube vertical array at 90 ℃ for 120min to obtain a purified carbon nano tube vertical array;
step three, preparing the carbon nano tube with the honeycomb structure: depositing metal particles on the top end of the purified carbon nano tube vertical array by a deposition method, then putting the carbon nano tube vertical array with the top end loaded with the metal particles into a tube furnace, and introducing 5ml of water vapor to react for 30min at the temperature of 650 ℃ in nitrogen atmosphere to obtain the carbon nano tube with the honeycomb structure.
Furthermore, the support body in the first step is a high-temperature resistant compact material or a high-temperature resistant porous material with a flat surface.
Further, the high-temperature resistant compact material is a quartz piece, a silicon chip or stainless steel; the high-temperature-resistant porous material is alumina ceramic, silicon carbide ceramic or silicon nitride ceramic.
Further, the heating rate is 5-10 ℃/min.
Further, the carbon precursor is a liquid low-carbon organic matter; the liquid low-carbon organic matter only contains two elements of carbon and hydrogen, the liquid low-carbon organic matter is one or more of benzene, toluene, xylene and cyclohexane, and the catalyst is iron, cobalt and nickel metallocene or corresponding metal salt.
Further, the concentration of the solution formed by mixing the carbon precursor and the catalyst is 8-12mg/mL, the dosage of the carbon precursor is 40-60mL, the dosage of the catalyst is 0.32-0.72g, and the constant temperature is 680-850 ℃.
Further, the cleaning solution in the second step is one or more of 30-50% nitric acid, 30-37% hydrochloric acid and 30-45% sulfuric acid.
Further, the deposition method in the third step comprises an atomic layer deposition method or a physical vapor deposition method, and the deposited metal particle elements are determined according to the types of the catalysts in the first step and are one or more of iron, cobalt and nickel.
Furthermore, the deposition condition is determined according to the diameter of the carbon nano tube in the second step, and the particle size of the deposited metal particles is required to be larger than or equal to the diameter of the carbon nano tube.
The application also requests to protect the carbon nano tube with the honeycomb structure, which is prepared by the preparation method of the carbon nano tube with the honeycomb structure.
Has the beneficial effects that:
1. the method has simple and practical process and no pollution, and realizes the high-efficiency preparation of the carbon nano tube with the honeycomb structure by regulating and controlling relevant parameters through the synergistic effect of the two-step deposition method.
2. The prepared carbon nano tube with the honeycomb structure can be widely applied to the fields of filtration treatment of fine particles in air, toxic and harmful gas purification, catalyst carriers, capacitance elements and the like, and has good application prospect.
Drawings
Fig. 1 is a microscopic morphology and structure characterization diagram of the carbon nanotube with a honeycomb structure according to the present application, wherein (a) is an SEM photograph of the whole carbon nanotube with a honeycomb structure, (b) is a mapping diagram of C element in the carbon nanotube with a honeycomb structure, (C) is a mapping diagram of Fe element in the carbon nanotube with a honeycomb structure, (d) is a TEM photograph of lattice diffraction of a single carbon nanotube, (e) is a thermogravimetric change curve of the carbon nanotube with a honeycomb structure in an air atmosphere, and (f) is an XRD diagram of the carbon nanotube with a honeycomb structure.
Fig. 2 is a graph showing the comparison result of the membrane parameters and the application data between the carbon nanotube with the honeycomb structure and the carbon nanotubes with other shapes, wherein (a) is the specific surface area of the carbon nanotube with different structures, (b) the diameter of the carbon nanotube with different structures, (c) the pore size distribution of the membrane prepared by the carbon nanotube with different structures, (d) the gas permeability of the membrane prepared by the carbon nanotube with different structures, (e) the filtration efficiency of the membrane prepared by the carbon nanotube with different structures on 300nm dust, and (f) the filtration pressure drop of the membrane prepared by the carbon nanotube with different structures on 300nm dust.
Detailed Description
The present invention will be further explained with reference to examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
A preparation method of a carbon nano tube with a honeycomb structure comprises the steps of putting a cleaned flat quartz plate into a reactor of a tube furnace, heating to 850 ℃ under the protection of 10ml/min nitrogen, preserving heat, introducing a reactant formed by mixing 30ml of cyclohexane and 0.24g of ferrocene into a quartz tube, and reacting for 20min at a constant temperature to prepare the carbon nano tube vertical array.
And then soaking the prepared carbon nano tube vertical array in 10ml of 30% nitric acid solution at room temperature for 60min, then slowly cleaning the array with deionized water for three times, and then drying the array at 90 ℃ for 120min, wherein the diameter of the single carbon nano tube after characterization and purification is 10nm.
Depositing Fe nanoclusters with the particle size of 12nm on the top end of the purified carbon nanotube vertical array by using a physical vapor deposition method, then putting the carbon nanotube vertical array loaded with the Fe nanoclusters into a tubular furnace, and introducing 5ml of water vapor into the tubular furnace at the temperature of 650 ℃ in a nitrogen atmosphere to react for 30min to obtain the carbon nanotube with the honeycomb structure.
Example 2
A preparation method of a carbon nano tube with a honeycomb structure comprises the steps of putting a cleaned flat silicon carbide ceramic wafer into a reactor of a tube furnace, heating to 680 ℃ under the protection of 1000ml/min of nitrogen, preserving heat, introducing a reactant formed by mixing 60ml of dimethylbenzene and 0.48g of nickel nitrate into a quartz tube, and reacting for 120min at a constant temperature to prepare the carbon nano tube vertical array. And then soaking the prepared carbon nano tube vertical array in 25ml of 50% nitric acid solution at room temperature for 60min, then slowly cleaning the array with deionized water for three times, and then drying the array at 90 ℃ for 120min, wherein the diameter of a single carbon nano tube after characterization and purification is 5nm. Depositing Ni nanoclusters with the particle size of 6nm on the top ends of the carbon nanotubes by using an atomic layer deposition method, then putting the carbon nanotube vertical array loaded with the Ni nanoclusters into a tubular furnace, and introducing 5ml of water vapor to react for 30min at the temperature of 650 ℃ in a nitrogen atmosphere to obtain the carbon nanotubes with the honeycomb structures.
Example 3
A preparation method of a carbon nano tube with a honeycomb structure comprises the steps of putting a clean flat alumina ceramic support body into a reactor of a tube furnace, heating to 720 ℃ under the protection of 100ml/min nitrogen, preserving heat, introducing a reactant formed by mixing 40ml of normal hexane and 0.32g of cobalt chloride into a quartz tube, and reacting for 60min at a constant temperature to prepare the carbon nano tube vertical array. And then soaking the prepared carbon nano tube vertical array in 15ml of 40% sulfuric acid solution at room temperature for 60min, then slowly cleaning the carbon nano tube vertical array with deionized water for three times, and then drying the carbon nano tube vertical array at 90 ℃ for 120min, wherein the diameter of a single carbon nano tube after characterization and purification is 20nm. Depositing Co nanoclusters with the particle size of 22nm on the top ends of the carbon nanotubes by a magnetron sputtering method, then putting the Co nanocluster-loaded carbon nanotube vertical array into a tube furnace, and introducing 5ml of water vapor in a nitrogen atmosphere at 650 ℃ for reacting for 30min to obtain the carbon nanotubes with the honeycomb structure.
Example 4
A preparation method of a carbon nano tube with a honeycomb structure comprises the steps of putting a cleaned flat alumina ceramic support body into a reactor of a tube furnace, heating to 780 ℃ under the protection of 100ml/min nitrogen, preserving heat, introducing reactants formed by mixing 10ml of dimethylbenzene, 10ml of methylbenzene, 10ml of cyclohexane and 0.24g of ferrocene into a quartz tube, reacting for 60min at a constant temperature, and preparing to obtain the carbon nano tube vertical array. And then soaking the prepared carbon nano tube vertical array in a mixed solution consisting of 10ml of 40% sulfuric acid solution and 10ml of 38% hydrochloric acid solution at room temperature for 60min, then slowly cleaning the carbon nano tube vertical array with deionized water for three times, and then drying the carbon nano tube vertical array at 90 ℃ for 120min, wherein the diameter of a single carbon nano tube after characterization and purification is 8nm. Depositing Fe nanoclusters with the particle size of 10nm on the top ends of the carbon nanotubes by a magnetron sputtering method, then putting the Fe nanocluster-loaded carbon nanotube vertical array into a tube furnace, and introducing 5ml of water vapor to react for 30min at the temperature of 650 ℃ in a nitrogen atmosphere to obtain the carbon nanotubes with the honeycomb structure.
As shown in fig. 2, the carbon nanotubes with a honeycomb structure prepared in the application have a larger specific surface area and a thinner diameter, and the prepared membrane has higher gas permeability and smaller pore size distribution, so that the prepared carbon nanotube membrane with a honeycomb structure has lower filtration pressure drop and higher filtration efficiency for 300nm dust particles, and the performance of the membrane is remarkably improved compared with that of membrane materials prepared from carbon nanotubes with other structures.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a carbon nanotube with a honeycomb structure is characterized by comprising the following steps:
step one, preparing a carbon nano tube vertical array: putting the cleaned support body into a quartz tube of a tube furnace, heating under the protection of nitrogen with the flow rate of 10-1000ml/min, preserving heat after the reaction temperature reaches 680-850 ℃, introducing a reactant formed by mixing 30-60ml of carbon precursor and a catalyst into the quartz tube for constant-temperature reaction for 20-120min, and preparing to obtain the carbon nano tube vertical array;
and step two, purifying the carbon nano tube vertical array: soaking the carbon nano tube vertical array prepared in the first step in 10-25ml of cleaning solution at room temperature for 60min to remove catalyst particles and other impurities on the surface of the carbon nano tube vertical array, then slowly cleaning the carbon nano tube vertical array with deionized water for three times, and then baking the carbon nano tube vertical array at 90 ℃ for 120min to obtain a purified carbon nano tube vertical array;
step three, preparing the carbon nano tube with the honeycomb structure: depositing metal particles on the top end of the purified carbon nano tube vertical array by a deposition method, then putting the carbon nano tube vertical array with the top end loaded with the metal particles into a tube furnace, and introducing 5ml of water vapor in a nitrogen atmosphere at 650 ℃ to react for 30min to obtain the carbon nano tube with the honeycomb structure.
2. The method for preparing carbon nanotubes with a honeycomb structure according to claim 1, wherein: in the first step, the support body is a high-temperature resistant compact material or a high-temperature resistant porous material with a smooth surface.
3. The method for preparing carbon nanotubes with a honeycomb structure according to claim 2, wherein: the high-temperature resistant compact material is a quartz piece, a silicon chip or stainless steel; the high-temperature-resistant porous material is alumina ceramic, silicon carbide ceramic or silicon nitride ceramic.
4. The method for preparing carbon nanotubes with a honeycomb structure according to claim 1, wherein: the heating rate is 5-10 ℃/min.
5. The method for preparing carbon nanotubes with a honeycomb structure according to claim 1, wherein: the carbon precursor is a liquid low-carbon organic matter; the liquid low-carbon organic matter only contains two elements of carbon and hydrogen, the liquid low-carbon organic matter is one or more of benzene, toluene, xylene and cyclohexane, and the catalyst is iron, cobalt and nickel metallocene or corresponding metal salt.
6. The method for preparing carbon nanotubes with a honeycomb structure according to claim 1, wherein: the concentration of the solution formed by mixing the carbon precursor and the catalyst is 8-12mg/mL, the dosage of the carbon precursor is 40-60mL, the dosage of the catalyst is 0.32-0.72g, and the constant temperature is 680-850 ℃.
7. The method for preparing carbon nanotubes with a honeycomb structure according to claim 1, wherein: and the cleaning solution in the second step is one or more of 30-50% of nitric acid, 30-37% of hydrochloric acid and 30-45% of sulfuric acid.
8. The method for preparing carbon nanotubes with a honeycomb structure according to claim 1, wherein: the deposition method in the third step comprises an atomic layer deposition method or a physical vapor deposition method, and the deposited metal particle elements are determined according to the types of the catalysts in the first step and are one or more of iron, cobalt and nickel.
9. The method for preparing carbon nanotubes with a honeycomb structure according to claim 1, wherein: the deposition condition is determined according to the diameter of the carbon nano tube in the second step, and the particle size of the deposited metal particles is required to be larger than or equal to the diameter of the carbon nano tube.
10. The carbon nanotube having a honeycomb structure produced by the method according to any one of claims 1 to 9.
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