CN115367737A - Three-dimensional array carbon nanotube and preparation method thereof - Google Patents
Three-dimensional array carbon nanotube and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
Abstract
The invention relates to a three-dimensional array carbon nano tube and a preparation method thereof, belonging to the technical field of nano material preparation; the diameter of a single carbon nano tube is 30-50nm, and the length of the single carbon nano tube 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 completely drying in an oven; and 2, step: coating a carbon layer on the oxide nano array obtained in the step 1; and 3, step 3: carrying out Chemical Vapor Deposition (CVD) reaction at 400-800 ℃, removing the template in the reaction process and finishing the surface carbonization process to finally obtain the three-dimensional array carbon nano tube. The invention has simple preparation process, low cost, easy regulation and control and large-scale production. Can be used in the fields of catalysis, energy, composite materials and the like. Compared with the disordered stacked carbon nanotubes prepared in the traditional mode, the invention 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 and the atomic and electronic structure can significantly affect electrochemical activity and stability. The monoatomic or nanocluster is dispersed on a carrier material such as a metal, a metal oxide, a covalent organic framework, a metal organic framework, and a carbon-based material, and has been widely used for catalytic photochemical and electrochemical reactions. The structure determines the property, the three-dimensional nano array structure has a relatively ordered, continuous and completely exposed active surface, can remarkably promote mass transport and charge transfer in an electrode/electrolyte interface and an electrode, and is expected to be used as an excellent carrier of single atoms and nanoclusters. The carbon nano tube is a hollow tubular one-dimensional nano material with a connection perfect hexagonal structure, and due to the unique structure (excellent length-diameter ratio) and chemical bonds (covalent bonds between carbon atoms), the carbon nano tube has the advantages of excellent mechanical, electric and thermal stability, large specific surface area, incomplete coordination of surface atoms and the like, and can load more active sites. And gaps among the carbon nanotubes and various defects in the structure provide abundant transportation channels and storage spaces for the active substances. In recent years, the material has wide application in the fields of electrochemical energy storage, composite materials and other electronics.
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. The arc discharge method has a high growth rate of carbon nanotubes, but is used by few researchers due to the high temperature required and the difficulty in controlling the structural parameters. The chemical vapor deposition method has easily controlled parameters and low growth temperature, and realizes the mass production of the carbon nano tubes.
At present, carbon nanotubes synthesized by chemical vapor deposition are mostly in a disordered stacking state due to strong interaction force between tubes, and directly influence the utilization rate of surface active substances and the reaction kinetics of subsequent application.
Disclosure of Invention
The technical problem to be solved is as follows:
in order to avoid the defects of the prior art, the invention provides the three-dimensional array carbon nanotube and the preparation method thereof, wherein the diameter of a single nanotube is 30-50nm, and the length of the single nanotube 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 two-step method of hydrothermal and Chemical Vapor Deposition (CVD).
The technical scheme of the invention is as follows: a three-dimensional array carbon nanotube, the diameter of a single carbon nanotube is 30-50nm, and the length of the single carbon nanotube is 2-3 μm.
The further technical scheme of the invention is as follows: the carbon nano tube is at least doped with at least one element of nitrogen, phosphorus, sulfur and boron.
A preparation method of a three-dimensional array carbon nanotube comprises the following specific steps:
step 1: growing an oxide nano array on a substrate as a template, and completely drying in an oven;
step 2: coating a carbon layer on the oxide nano array obtained in the step (1);
and step 3: carrying out Chemical Vapor Deposition (CVD) reaction at 400-800 ℃, removing the template in the reaction process and finishing the surface carbonization process to finally obtain the three-dimensional array carbon nano tube.
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 fiber.
The further technical scheme of the invention is as follows: 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 further technical scheme of the invention is as follows: in the step 1, the oxide nano array is prepared by adopting atomic layer deposition, hydrothermal method or sol-gel method.
The invention further adopts the technical scheme that: in the step 1, the drying temperature is 0-60 ℃; the drying method 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 for coating the carbon layer is at least one of sucrose, fructose, starch, glucose, agarose, dopamine hydrochloride and polydopamine.
The further technical scheme of the invention is as follows: in the step 3, the chemical vapor deposition process parameters are as follows: repeatedly washing and drying the oxide array C @ oxide NAs of the coated carbon layer by using deionized water and ethanol; then placing the mixture in a tube furnace for high-temperature annealing; wherein the gas 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.
The further technical scheme of the invention is as follows: 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 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 reaction as a template; then obtaining the three-dimensional array carbon nano tube by a two-step method of hydrothermal and Chemical Vapor Deposition (CVD); 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, composite materials and the like. The concrete effects are as follows:
1. compared with the disordered stacked carbon nanotubes prepared in the traditional way (shown in figure 1), the invention prepares highly ordered vertical nitrogen-doped carbon nanotubes (V-CNTs) (shown in figures 2 and 3).
2. The regular morphology of the structural array in the high current density regime accelerates the release of bubbles as shown in figure 4.
3. The prepared Pt @ V-CNTs/CC electrode is 100mA cm -2 The overpotential is 59.83mV, which 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 scanning electron microscope image of a three-dimensional array carbon nanotube prepared in one embodiment of the present invention.
Fig. 3 shows a transmission electron microscope image of a three-dimensional array carbon nanotube prepared in one embodiment of the present invention.
Fig. 4 shows different representations of a three-dimensional array and a conventional disordered stack structure prepared in one embodiment of the present invention during the release of bubbles.
FIG. 5 shows an X-ray photoelectron spectrum of atomic layer deposited platinum (Pt @ V-CNT) on three-dimensional array carbon nanotubes prepared in one embodiment of the present invention.
Detailed Description
The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
Example 1
And preparing the oxide nano array template 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 using an Atomic Layer Deposition (ALD) method as a seed layer; then carrying out a hydrothermal process, and adding 0.025mol L of the mixture -1 Mixing and stirring 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 at 95 ℃ for 10h to obtain the zinc oxide nano needle (ZnO NWs/CC) to finish the preparation of the oxide nano array template.
The three-dimensional array carbon nano tube is obtained by a two-step method of hydrothermal and Chemical Vapor Deposition (CVD). Firstly, putting ZnO NWs/CC in a mixed solution of 10ml of DI, 20ml of ethanol and 100mg of dopamine hydrochloride, and immersing a carbon cloth on which an oxide nano-array template grows in the solution; the mixture was then placed in an oven at 95 ℃ for 10 hours to prepare a precursor. Finally, in a CVD process, the precursor is exposed to argon-hydrogen (Ar/H) 2 ) Setting in a tube furnace with atmosphere, wherein the heating rate is 2 ℃ for min -1 Further increase to 800 deg.C, addAnd heating for 3h to obtain the three-dimensional array carbon nanotubes (V-CNTs/CC) (shown in figure 2).
Example 2
In contrast to example 1, in a CVD process, the precursor was in Ar/H 2 Setting in a tubular furnace with atmosphere, and heating up at 5 deg.C for min -1 And further heating to 800 ℃ for 3h to obtain V-CNTs/CC (shown in figure 3).
Example 3
In contrast to example 1, the concentration of zinc nitrate hexahydrate and hexamethylenetetramine was increased to 0.05mol L during hydrothermal treatment -1 And preparing an oxide template to obtain V-CNTs/CC.
Example 4
Different from the example 1, in the CVD process, the precursor is heated at 800 ℃ for 4h 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 iron nitrate nonahydrate were dissolved in 100ml of deionized water and stirred for 10min. Thereafter, 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). And then, placing CoFe @ CC in a chemical vapor deposition reaction furnace, taking melamine as a carbon source, preserving heat for 2 hours at 400 ℃, heating up at the rate of 5 ℃/min, then heating to 800 ℃, preserving heat for two hours, and cooling to room temperature to finally obtain the carbon nano tube (CNTs/CC). In this case, the carbon nanotubes are randomly stacked on top of each other, and the single carbon nanotube-tipped catalyst is difficult to remove (as shown in fig. 1).
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. A three-dimensional array carbon nanotube is characterized in that: the diameter of a single carbon nano tube is 30-50nm, and the length of the single carbon nano tube is 2-3 mu m.
2. The three-dimensional array carbon nanotube according to claim 1, wherein: the carbon nano tube is doped with at least one element of nitrogen, phosphorus, sulfur and boron.
3. A method for preparing the three-dimensional array carbon nano tube as claimed in claim 1 or 2, which is characterized by comprising the following steps:
step 1: growing an oxide nano array on a substrate as a template, and completely drying in an oven;
step 2: coating a carbon layer on the oxide nano array obtained in the step 1;
and 3, step 3: carrying out Chemical Vapor Deposition (CVD) reaction at 400-800 ℃, removing the template in the reaction process and finishing the surface carbonization process to finally obtain the three-dimensional array carbon nano tube.
4. The three-dimensional array carbon nanotube according to claim 3, wherein: in the step 1, the substrate is at least one of carbon cloth, carbon paper and electrospun fiber.
5. The three-dimensional array carbon nanotube according to claim 3, wherein: 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.
6. The carbon nanotube three-dimensional array according to claim 3, wherein: in the step 1, the oxide nano array is prepared by adopting atomic layer deposition, hydrothermal method or sol-gel method.
7. The carbon nanotube three-dimensional array according to claim 3, wherein: in the step 1, the drying temperature is 0-60 ℃; the drying method is at least one of room temperature drying, vacuum drying or freeze drying.
8. The three-dimensional array carbon nanotube according to claim 3, wherein: in the step 2, the carbon source required by the carbon coating layer is at least one of sucrose, fructose, starch, glucose, agarose, dopamine hydrochloride and polydopamine.
9. The carbon nanotube three-dimensional array according to claim 3, wherein: in the step 3, the chemical vapor deposition process parameters are as follows: repeatedly washing and drying the oxide array C @ oxide NAs of the coated carbon layer by using deionized water and ethanol; then placing the mixture in a tube furnace for high-temperature annealing; wherein the gas 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.
10. The three-dimensional array carbon nanotube according to claim 3, wherein: 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.
Priority Applications (1)
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