CN115367737B - Three-dimensional array carbon nano tube and preparation method thereof - Google Patents
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 46
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
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- 239000005751 Copper oxide Substances 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Abstract
The invention relates to a three-dimensional array carbon nanotube and a preparation method thereof, belonging to the technical field of nano material preparation; the diameter of the single carbon nano tube is 30-50nm, and the length is 2-3 mu m. The preparation method comprises the following steps: step 1: growing an oxide nano array on a substrate as a template, and drying completely in an oven; step 2: coating a carbon layer on the oxide nano array obtained in the step 1; step 3: and performing chemical vapor deposition CVD reaction at 400-800 ℃, removing the template in the reaction process and completing the surface carbonization process to finally obtain the three-dimensional array carbon nanotube. The invention has simple preparation process, low cost, easy regulation and control and mass production. Can be used in the fields of catalysis, energy sources, composite materials and the like. Compared with the disordered stacked carbon nanotubes prepared in the traditional way, the method prepares the highly ordered vertical nitrogen doped carbon nanotubes (V-CNTs).
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a three-dimensional array carbon nano tube and a preparation method thereof.
Background
In electrochemical energy storage devices, optimizing the geometry of the support as well as the atomic and electronic structure can significantly affect electrochemical activity and stability. Monoatomic or nanoclusters dispersed on support materials such as metals, metal oxides, covalent organic frameworks, metal organic frameworks, and carbon-based materials have been widely used to catalyze photochemical and electrochemical reactions. The structure determines the property, and the three-dimensional nano array structure has a relatively orderly, continuous and completely exposed active surface, can obviously promote mass transportation and charge transfer at an electrode/electrolyte interface and in an electrode, and is expected to be an excellent carrier of single atoms and nanoclusters. The carbon nano tube is a hollow tubular one-dimensional nano material with a perfect hexagonal structure, and has the advantages of excellent mechanical, electric conduction, heat conduction and chemical stability, large specific surface area, incomplete coordination of surface atoms and the like due to the unique structure (excellent length-diameter ratio) and chemical bonds (covalent bonds between carbon atoms), and can load more active sites. And various defects in gaps and structures among the carbon nanotubes provide rich transportation channels and storage spaces for active substances. In recent years, it has found wide application in electrochemical energy storage, composite materials and other electronic fields.
The preparation method of the carbon nano tube mainly comprises a laser evaporation method, an arc discharge method and a chemical vapor deposition method. Among them, the laser evaporation method is expensive in equipment and high in synthesis cost. Although the arc discharge method has high growth speed of the carbon nano tube, the carbon nano tube has a high required temperature, and the structural parameters are difficult to control, so that the carbon nano tube is less used by researchers. The chemical vapor deposition method has the advantages of easy parameter regulation and control and low growth temperature, and realizes the mass production of the carbon nano tubes.
At present, carbon nanotubes synthesized by a chemical vapor deposition method are in a disordered stacking state due to strong interaction force among the tubes, so that the utilization rate of surface active substances of the carbon nanotubes and the reaction dynamics of subsequent application are directly influenced.
Disclosure of Invention
The technical problems to be solved are as follows:
In order to avoid the defects of the prior art, the invention provides a three-dimensional array carbon nano tube and a preparation method thereof, wherein the diameter of a single nano tube is 30-50nm, and the length is 2-3 mu m; firstly, growing an oxide nano array on a substrate as a template, and then obtaining the three-dimensional array carbon nano tube by a hydrothermal and Chemical Vapor Deposition (CVD) two-step method.
The technical scheme of the invention is as follows: a three-dimensional array carbon nano tube, wherein the diameter of a single carbon nano tube is 30-50nm, and the length is 2-3 mu m.
The invention further adopts the technical scheme that: the carbon nanotubes are doped with at least one element selected from the group consisting of nitrogen, phosphorus, sulfur, and boron.
The preparation method of the three-dimensional array carbon nano tube comprises the following specific steps:
step 1: growing an oxide nano array on a substrate as a template, and drying completely in an oven;
Step 2: coating a carbon layer on the oxide nano array obtained in the step 1;
Step 3: and performing chemical vapor deposition CVD reaction at 400-800 ℃, removing the template in the reaction process and completing the surface carbonization process to finally obtain the three-dimensional array carbon nanotube.
The invention further adopts the technical scheme that: in the step 1, the substrate is at least one of carbon cloth, carbon paper and electrospun fibers.
The invention further adopts the technical scheme that: in the step 1, the oxide nano array is at least one of ferroferric oxide, cobalt oxide, manganese oxide, tin oxide, zinc oxide and copper oxide.
The invention further adopts the technical scheme that: in the step 1, the preparation of the oxide nano-array is assisted by atomic layer deposition, hydrothermal or sol-gel method.
The invention further adopts the technical scheme that: in the step 1, the drying temperature is 0-60 ℃; the drying mode is at least one of room temperature drying, vacuum drying or freeze drying.
The invention further adopts the technical scheme that: in the step 2, the carbon source required by the carbon coating adopts at least one of sucrose, fructose, starch, glucose, agarose, dopamine hydrochloride and polydopamine.
The invention further adopts the technical scheme that: in the step 3, the chemical vapor deposition process parameters are as follows: repeatedly washing the oxide array C@oxide NAs coated with the carbon layer with deionized water and ethanol, and drying; then placing the steel in a tube furnace for high-temperature annealing; wherein the air flow is 1-300sccm, the reaction temperature is 400-800 ℃, the reaction time is 200-600min, the heating rate is 1-8 ℃/min, and the reaction is cooled to room temperature after the reaction is completed.
The invention further adopts the technical scheme that: in the step 3, the template is removed by at least one of high-temperature sintering, nitric acid, perchloric acid, hydrofluoric acid, toluene, potassium hydroxide and sodium hydroxide.
The atmosphere of the chemical vapor deposition is the mixed gas of argon/hydrogen, nitrogen and argon inert atmosphere.
Advantageous effects
The invention has the beneficial effects that: the invention discloses a novel three-dimensional array carbon nanotube material and a preparation method thereof. Firstly, preparing an oxide nano array by adopting a method of combining atomic layer deposition and hydrothermal as a template; then obtaining the three-dimensional array carbon nano tube by a hydrothermal and Chemical Vapor Deposition (CVD) two-step method; the preparation process is simple, the cost is low, the regulation and control are easy, and the large-scale production can be realized. Can be used in the fields of catalysis, energy sources, composite materials and the like. The specific effects are as follows:
1. In contrast to the disordered stacked carbon nanotubes prepared in the conventional manner (as shown in fig. 1), the present invention prepares highly ordered vertical nitrogen-doped carbon nanotubes (V-CNTs) (as shown in fig. 2, 3).
2. In the high current density state, the regular morphology of the structural array can accelerate the release of bubbles as shown in fig. 4.
3. The prepared Pt@V-CNTs/CC electrode has an overpotential of 59.83mV at a concentration of 100mA cm -2 and shows good catalytic performance.
Drawings
Fig. 1 shows a scanning electron microscope image of a conventional carbon nanotube prepared in a comparative example.
Fig. 2 shows a three-dimensional array carbon nanotube scanning electron microscope image prepared in one embodiment of the present invention.
Fig. 3 shows a three-dimensional array carbon nanotube transmission electron microscope image prepared in one embodiment of the present invention.
Fig. 4 shows a schematic representation of the three-dimensional array and the conventional disordered stack structure prepared in one embodiment of the invention during bubble release.
FIG. 5 shows an X-ray photoelectron spectrum after atomic layer deposition of platinum (Pt@V-CNT) for a three-dimensional array of carbon nanotubes prepared in one embodiment of the invention.
Detailed Description
The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
Example 1
An oxide nano array template is prepared by adopting a method combining atomic layer deposition and hydrothermal. Firstly, growing a zinc oxide film with the thickness of about 20nm on the surface of carbon cloth by an Atomic Layer Deposition (ALD) method as a seed layer; then carrying out a hydrothermal process, mixing and stirring 0.025mol L -1 of zinc nitrate hexahydrate and hexamethylenetetramine for 10 minutes, and immersing the carbon cloth with the seed layer in the solution; and transferring the mixture into a 50ml reaction furnace, and reacting for 10 hours at 95 ℃ to obtain the zinc oxide nanoneedle (ZnO NWs/CC) to finish the preparation of the oxide nano array template.
The three-dimensional array carbon nanotubes are obtained by a two-step method of hydrothermal and Chemical Vapor Deposition (CVD). Firstly, putting ZnO NWs/CC into a mixed solution of 10ml DI, 20ml ethanol and 100mg dopamine hydrochloride, and immersing carbon cloth growing with an oxide nano-array template into the solution; the mixture was then placed in an oven at 95 ℃ for 10 hours to prepare a precursor. Finally, in the CVD process, the precursor is arranged in a tube furnace in argon-hydrogen (Ar/H 2) atmosphere, the heating rate is 2 ℃ for min -1, and the temperature is further increased to 800 ℃ for heating for 3 hours, so that the three-dimensional array carbon nano tube (V-CNTs/CC) is obtained (shown in figure 2).
Example 2
Unlike example 1, in the CVD process, the precursor was set in a tube furnace in Ar/H 2 atmosphere at a heating rate of 5℃min -1, and further heated to 800℃for 3 hours to obtain V-CNTs/CC (as shown in FIG. 3).
Example 3
Unlike example 1, in the hydrothermal process, the concentration of zinc nitrate hexahydrate and hexamethylenetetramine was increased to 0.05mol L -1 to prepare an oxide template, resulting in V-CNTs/CC.
Example 4
Unlike example 1, in the CVD process, the precursor was heated at 800℃for 4 hours to obtain V-CNTs/CC.
Comparative example
The comparative example was prepared by two steps of hydrothermal and chemical vapor deposition. During the hydrothermal reaction, 0.975g of cobalt nitrate hexahydrate, 0.465g of ammonium fluoride, 1.5g of urea, and 0.675g of ferric nitrate nonahydrate were dissolved in 100ml of deionized water and stirred for 10 minutes. Thereafter, a Carbon Cloth (CC) was immersed in the solution, and placed in an oven to react at 120 ℃ for 6 hours, to obtain a cobalt iron catalyst (cofe@cc). Then, placing CoFe@CC into a chemical vapor deposition reaction furnace, taking melamine as a carbon source, preserving heat for 2 hours at 400 ℃, heating at a rate of 5 ℃/min, then, heating to 800 ℃ for two hours, and cooling to room temperature to finally obtain the carbon nanotubes (CNTs/CC). In this example, the carbon nanotubes are randomly stacked on each other, and the catalyst on top of the individual carbon nanotubes is difficult to remove (as shown in fig. 1).
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (4)
1. A three-dimensional array carbon nanotube, characterized in that: the diameter of the single carbon nano tube is 30-50 nm, and the length is 2-3 mu m; the preparation method of the three-dimensional array carbon nano tube comprises the following specific steps:
Step 1: growing an oxide nano array on a substrate as a template, and drying completely in an oven; firstly, growing a zinc oxide film of 20 nm on the surface of carbon cloth by using an atomic layer deposition method as a seed layer; then carrying out a hydrothermal process, mixing and stirring 0.025 mol L -1 zinc nitrate hexahydrate and hexamethylenetetramine for 10 minutes, and immersing the carbon cloth with the seed layer in the solution; transferring the mixture into a reaction furnace of 50ml, and reacting at 95 ℃ for 10 h to obtain zinc oxide nanoneedles, thereby completing the preparation of the oxide nano array template;
Step 2: coating a carbon layer on the oxide nano array obtained in the step 1; the carbon source required by the carbon coating adopts at least one of sucrose, fructose, starch, glucose, agarose, dopamine hydrochloride and polydopamine;
Step 3: performing Chemical Vapor Deposition (CVD) reaction at 800 ℃, removing a template in the reaction process and completing the surface carbonization process to finally obtain the three-dimensional array carbon nanotube;
the chemical vapor deposition process parameters are as follows: repeatedly washing the oxide nano array coated with the carbon layer with deionized water and ethanol, and drying; then placing the steel in a tube furnace for high-temperature annealing; wherein the air flow is 1-300 sccm, the reaction time is 200-600 min, the heating rate is 1-8 ℃/min, and the reaction is cooled to room temperature after the reaction is completed.
2. The three-dimensional array of carbon nanotubes of claim 1, wherein: the carbon nanotubes are doped with at least one element selected from the group consisting of nitrogen, phosphorus, sulfur, and boron.
3. The three-dimensional array of carbon nanotubes of claim 1, wherein: in the step 1, the drying temperature is 0-60 ℃; the drying mode is at least one of room temperature drying, vacuum drying or freeze drying.
4. The three-dimensional array of carbon nanotubes of claim 1, wherein: in the step 3, the template is removed by at least one of nitric acid, perchloric acid, hydrofluoric acid, potassium hydroxide and sodium hydroxide.
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