CN110980692A - Conical carbon nanotube array and preparation method thereof - Google Patents
Conical carbon nanotube array and preparation method thereof Download PDFInfo
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- CN110980692A CN110980692A CN201911170049.0A CN201911170049A CN110980692A CN 110980692 A CN110980692 A CN 110980692A CN 201911170049 A CN201911170049 A CN 201911170049A CN 110980692 A CN110980692 A CN 110980692A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 72
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 55
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052786 argon Inorganic materials 0.000 claims abstract description 26
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013067 intermediate product Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 49
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000002390 adhesive tape Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 7
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 16
- 238000002791 soaking Methods 0.000 abstract description 14
- 238000007743 anodising Methods 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 7
- UYVVPOTVRSGDSX-UHFFFAOYSA-L [Cr](=O)(=O)(O)O.[P] Chemical compound [Cr](=O)(=O)(O)O.[P] UYVVPOTVRSGDSX-UHFFFAOYSA-L 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 5
- 239000000203 mixture Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002072 nanorope Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- C01B32/168—After-treatment
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- Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a conical carbon nanotube array and a preparation method thereof. The density of the tube array was 107‑109/mm2The length of the conical carbon nano tube is 200-2000nm, and the diameter of the conical bottom tube is 30-200 nm; the method comprises the steps of anodizing an aluminum sheet in an oxalic acid solution, a sulfuric acid solution or a phosphoric acid solution, soaking the aluminum sheet in a phosphorus-chromic acid mixed solution, anodizing the obtained intermediate product in the same acid solution, soaking the intermediate product in the same acid solution for more than 10 times, heating the obtained aluminum oxide template with the conical holes in an argon atmosphere to 600-fold temperature of 700 ℃, sequentially placing the aluminum oxide template in a mixed atmosphere of argon and acetylene and keeping the temperature in the argon atmosphere, fixing carbon nanotubes in the conical holes of the obtained aluminum oxide template, and then placing the aluminum oxide template in a sodium hydroxide solution to dissolve the aluminum oxide template to obtain the target product. The carbon nano-tube array has large specific surface area and ordered arrangement of the conical carbon nano-tubes, and is easy to be widely and commercially applied to the fields of nano electronic devices, field emission and flat panel display, sensor manufacturing and the like.
Description
Technical Field
The invention relates to a nanotube array and a preparation method thereof, in particular to a conical carbon nanotube array and a preparation method thereof.
Background
In recent years, the research on carbon nano technology has been actively conducted, and various nano carbon crystals, needles, rods, barrels, etc. have been developed, and carbon nano materials have been widely used in many fields because of their excellent physical and chemical properties. Such as an article entitled "Carbon nanoropes and graphene-like nanosheets by hot film CVD" growth means and electron field emission ", mater.chem.C., 2013,1,7703-7708 (" research on growth of Carbon nanorod arrays and graphene-like nanoplatelets and their mechanism and field emission properties by chemical vapor deposition "; journal of materials chemistry C2013, volume 1, volume 46, page 7703-7708). The density of the carbon nanorod array mentioned therein is about 2.5X 107/mm2The carbon nano rods forming the array have the rod length of about 270 nanometers and the rod diameter of about 150 nanometers; the preparation method comprises the steps of sputtering a layer of gold nano-film on a clean silicon wafer, and preparing the carbon nano-rods by using plasma enhanced hot filament CVD. Although the product can be used for electron field emission under the condition of high vacuum and used as a nanometer device, the product and the preparation method thereof have the defects; secondly, the product is not a carbon nano array in ordered arrangement, so that the application range is restricted; thirdly, the preparation method does not only need to use a catalyst, namely the gold nano-film, and can not obtain products with larger specific surface area and ordered arrangement.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a conical carbon nanotube array with larger specific surface area and ordered arrangement.
Another technical problem to be solved by the present invention is to provide a method for preparing the tapered carbon nanotube array.
In order to solve the technical problem of the invention, the technical scheme adopted is that the conical carbon nano tube array is composed of a conical carbon nano array attached to a substrate, and particularly:
the conical carbon nano array is a conical carbon nano tube array;
the density of the conical carbon nanotube array is 107-109/mm2A plurality of tapered carbon nanotubes;
the length of the conical carbon nano tube forming the conical carbon nano tube array is 200-2000nm, and the diameter of the conical bottom tube is 30-200 nm.
In order to solve another technical problem of the present invention, another technical solution is that the method for preparing the tapered carbon nanotube array includes an anodic oxidation method, and particularly includes the following main steps:
step 1, firstly, placing an aluminum sheet in 0.2-0.4mol/L oxalic acid solution at the temperature of 2-25 ℃ under the direct current voltage of 35-45V, or in 0.2-0.4mol/L sulfuric acid solution under the direct current voltage of 20-30V, or in 0.1-0.2mol/L phosphoric acid solution under the direct current voltage of 120-260V for anodic oxidation for at least 2h, and then placing the aluminum sheet in a mixed solution of phosphoric acid and chromic acid at the temperature of 55-65 ℃ for soaking for at least 3h to obtain an intermediate product;
step 2, putting the intermediate product into the same acid solution with the same temperature and the same concentration in the step 1, anodizing for at least 20s under the same direct current voltage, then soaking the intermediate product into a phosphoric acid solution with the temperature of 30-50 ℃ and the weight of 3-10 wt% for at least 1min, and repeating the process for at least 10 times to obtain an alumina template with a conical hole shape;
step 3, firstly placing the alumina template with the conical hole shape in argon atmosphere, heating to 600-700 ℃, then placing the alumina template in the mixed atmosphere of argon and acetylene at the same temperature for 1.8-2.2h, and then preserving heat for at least 0.5h in the argon atmosphere at the same temperature to obtain the alumina template with the carbon nano tube in the conical hole;
and 4, firstly fixing the carbon nano tubes in the tapered holes of the alumina template, and then putting the alumina template fixed with the carbon nano tubes in a sodium hydroxide solution to dissolve the alumina template, so as to prepare the tapered carbon nano tube array.
As a further improvement of the preparation method of the conical carbon nanotube array:
preferably, the mixed solution of phosphorus and chromic acid is a mixed solution of 6 wt% phosphoric acid and 1.8 wt% chromic acid.
Preferably, the alumina template with the conical hole shape is firstly placed in the argon atmosphere for at least 1h before the temperature is raised to 600-700 ℃.
Preferably, the argon atmosphere is argon at a flow rate of 120 sccm.
Preferably, the mixed atmosphere of argon and acetylene is a mixed gas of argon at a flow rate of 120sccm and acetylene at a flow rate of 4 sccm.
Preferably, the carbon nanotubes in the tapered holes of the alumina template are fixed by glue or adhesive tape.
Preferably, the temperature of the sodium hydroxide solution is 40 ℃ and the concentration is 3 mol/L.
Compared with the prior art, the beneficial effects are that:
firstly, the prepared target product is characterized by using a scanning electron microscope, and the target product is a substrate attached with a conical carbon nanotube array according to the result and the preparation method; wherein the density of the conical carbon nanotube array is 107-109/mm2The length of the conical carbon nano tube forming the conical carbon nano tube array is 200-2000nm, and the diameter of the conical bottom tube is 30-200 nm. The target product assembled by the tapered carbon nano tubes not only greatly improves the specific surface area and the application occasion and range of the target product due to the characteristics of the carbon nano materials, but also because the carbon nano materials are the carbon nano tubes and the carbon nano tubes are the arrays which are orderly arranged.
Secondly, the preparation method is simple, scientific and effective. Not only the conical carbon nanotube array which is a target product with larger specific surface area and ordered arrangement is prepared; the catalyst is not needed, and the preparation method has the characteristics of convenience in preparation, easiness in large-area preparation of products and low cost; further, the target product is easy to be widely applied to the fields of nano electronic devices, field emission and flat panel display, sensor manufacturing and the like in a commercial mode.
Drawings
Fig. 1 is one of the results of characterization of an alumina template having carbon nanotubes disposed in tapered pores obtained during the preparation process using a Scanning Electron Microscope (SEM). Fig. 1, a, b, is a plan SEM image of an alumina template with carbon nanotubes disposed in tapered holes.
FIG. 2 is one of the results of the characterization of the objective product obtained by the preparation method using a scanning electron microscope. Fig. 2, in which a and b are plan SEM images of the object product, c is an SEM image of the object product tilted at 45 degrees, and d is an SEM image of a cross section of the object product.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
First commercially available or manufactured on its own:
aluminum sheets;
oxalic acid solution;
a sulfuric acid solution;
phosphoric acid solution;
a mixed solution of phosphoric acid and chromic acid, which is a mixed solution of 6 wt% phosphoric acid and 1.8 wt% chromic acid;
argon gas;
acetylene;
a sodium hydroxide solution;
glue and adhesive tape.
Then:
example 1
The preparation method comprises the following specific steps:
step 1, putting an aluminum sheet in 0.2mol/L oxalic acid solution at 2 ℃ and under 45V direct current voltage, or in 0.2mol/L sulfuric acid solution and under 30V direct current voltage, or in 0.1mol/L phosphoric acid solution and under 260V direct current voltage, and anodizing for 2 h. And then soaking the mixture in a phosphorus-chromic acid mixed solution at the temperature of 55 ℃ for 5 hours to obtain an intermediate product.
Step 2, putting the intermediate product into the same acid solution with the same temperature and the same concentration in the step 1, and anodizing for 20s under the same direct current voltage; and soaking the template in 3 wt% phosphoric acid solution at 30 deg.C for 5min, and repeating the above process for 10 times to obtain alumina template with conical pores.
And 3, firstly placing the alumina template with the conical hole shape in an argon atmosphere with the flow of 120sccm for 1h, and then heating to 600 ℃. Placing the mixture in a mixed atmosphere of argon and acetylene at the same temperature for 2.2h, and then preserving heat for 0.5h in an argon atmosphere with the same temperature and the flow of 120 sccm; wherein the mixed atmosphere of argon and acetylene is a mixed gas of argon with a flow rate of 120sccm and acetylene with a flow rate of 4sccm, and the alumina template with the carbon nanotubes arranged in the tapered holes as shown in FIG. 1 is obtained.
And 4, fixing the carbon nano tube in the tapered hole of the alumina template by using glue or an adhesive tape. Then the alumina template fixed with the carbon nano tube is placed in sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 3mol/L to dissolve the alumina template, and the conical carbon nano tube array similar to that shown in figure 2 is prepared.
Example 2
The preparation method comprises the following specific steps:
step 1, putting the aluminum sheet into 0.25mol/L oxalic acid solution at 8 ℃ and under 43V direct current voltage, or in 0.25mol/L sulfuric acid solution and under 28V direct current voltage, or in 0.13mol/L phosphoric acid solution and under 225V direct current voltage, and anodizing for 2.5 h. And then soaking the mixture in a mixed solution of phosphorus and chromic acid at 58 ℃ for 4.5 hours to obtain an intermediate product.
Step 2, putting the intermediate product into the same acid solution with the same temperature and the same concentration in the step 1, and anodizing for 30s under the same direct current voltage; soaking the template in 5 wt% phosphoric acid solution at 35 deg.C for 4min, and repeating the above steps for 13 times to obtain alumina template with conical pores.
And 3, firstly, placing the alumina template with the conical hole shape in an argon atmosphere with the flow of 120sccm for 1.3h, and then heating to 630 ℃. Placing the mixture in a mixed atmosphere of argon and acetylene at the same temperature for 2.1h, and then preserving heat for 0.6h in an argon atmosphere with the same temperature and the flow of 120 sccm; wherein the mixed atmosphere of argon and acetylene is a mixed gas of argon with a flow rate of 120sccm and acetylene with a flow rate of 4sccm, and the alumina template with the carbon nanotubes arranged in the tapered holes as shown in FIG. 1 is obtained.
And 4, fixing the carbon nano tube in the tapered hole of the alumina template by using glue or an adhesive tape. Then the alumina template fixed with the carbon nano tube is placed in sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 3mol/L to dissolve the alumina template, and the conical carbon nano tube array similar to that shown in figure 2 is prepared.
Example 3
The preparation method comprises the following specific steps:
step 1, putting an aluminum sheet in 0.3mol/L oxalic acid solution at 13 ℃ and under 40V direct current voltage, or in 0.3mol/L sulfuric acid solution and under 25V direct current voltage, or in 0.15mol/L phosphoric acid solution and under 190V direct current voltage, and anodizing for 3 h. And then soaking the mixture in a phosphorus-chromic acid mixed solution at 60 ℃ for 4 hours to obtain an intermediate product.
Step 2, putting the intermediate product into the same acid solution with the same temperature and the same concentration in the step 1, and anodizing for 40s under the same direct current voltage; and soaking the template in 7 wt% phosphoric acid solution at 40 deg.C for 3min, and repeating the above steps for 15 times to obtain alumina template with conical pores.
And 3, firstly, placing the alumina template with the conical hole shape in an argon atmosphere with the flow of 120sccm for 1.5h, and then heating to 650 ℃. Placing the mixture in a mixed atmosphere of argon and acetylene at the same temperature for 2 hours, and then preserving heat for 0.7 hour in an argon atmosphere with the same temperature and the flow of 120 sccm; wherein the mixed atmosphere of argon and acetylene is a mixed gas of argon with a flow rate of 120sccm and acetylene with a flow rate of 4sccm, and the alumina template with the carbon nanotubes arranged in the tapered holes as shown in FIG. 1 is obtained.
And 4, fixing the carbon nano tube in the tapered hole of the alumina template by using glue or an adhesive tape. Then the alumina template fixed with the carbon nano tube is placed in sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 3mol/L to dissolve the alumina template, and the conical carbon nano tube array shown in figure 2 is prepared.
Example 4
The preparation method comprises the following specific steps:
step 1, putting the aluminum sheet into 0.35mol/L oxalic acid solution at 19 ℃ and under 38V direct current voltage, or in 0.35mol/L sulfuric acid solution and under 23V direct current voltage, or in 0.18mol/L phosphoric acid solution and under 155V direct current voltage, and anodizing for 3.5 h. And then soaking the mixture in a phosphorus-chromic acid mixed solution at 63 ℃ for 3.5 hours to obtain an intermediate product.
Step 2, putting the intermediate product into the same acid solution with the same temperature and the same concentration in the step 1, and anodizing for 50s under the same direct current voltage; and soaking the template in 9 wt% phosphoric acid solution at 45 deg.c for 2min, and repeating the said process for 18 times to obtain alumina template with conic pores.
And 3, firstly, placing the alumina template with the conical hole shape in an argon atmosphere with the flow of 120sccm for 1.8h, and then heating to 680 ℃. Placing the mixture in a mixed atmosphere of argon and acetylene at the same temperature for 1.9h, and then preserving heat for 0.8h in an argon atmosphere with the same temperature and the flow of 120 sccm; wherein the mixed atmosphere of argon and acetylene is a mixed gas of argon with a flow rate of 120sccm and acetylene with a flow rate of 4sccm, and the alumina template with the carbon nanotubes arranged in the tapered holes as shown in FIG. 1 is obtained.
And 4, fixing the carbon nano tube in the tapered hole of the alumina template by using glue or an adhesive tape. Then the alumina template fixed with the carbon nano tube is placed in sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 3mol/L to dissolve the alumina template, and the conical carbon nano tube array similar to that shown in figure 2 is prepared.
Example 5
The preparation method comprises the following specific steps:
step 1, putting an aluminum sheet in 0.4mol/L oxalic acid solution at 25 ℃ and under direct current voltage of 35V, or in 0.4mol/L sulfuric acid solution and under direct current voltage of 20V, or in 0.2mol/L phosphoric acid solution and under direct current voltage of 120V for anodic oxidation for 4 hours. And then soaking the mixture in a phosphorus-chromic acid mixed solution at 65 ℃ for 3 hours to obtain an intermediate product.
Step 2, putting the intermediate product into the same acid solution with the same temperature and the same concentration in the step 1, and anodizing for 60s under the same direct current voltage; soaking in 10 wt% phosphoric acid solution at 50 deg.C for 1min, and repeating the above process for 20 times to obtain alumina template with conical pores.
And 3, firstly placing the alumina template with the conical hole shape in an argon atmosphere with the flow of 120sccm for 2 hours, and then heating to 700 ℃. Placing the mixture in a mixed atmosphere of argon and acetylene at the same temperature for 1.8h, and then preserving heat for 1h in an argon atmosphere with the same temperature and the flow of 120 sccm; wherein the mixed atmosphere of argon and acetylene is a mixed gas of argon with a flow rate of 120sccm and acetylene with a flow rate of 4sccm, and the alumina template with the carbon nanotubes arranged in the tapered holes as shown in FIG. 1 is obtained.
And 4, fixing the carbon nano tube in the tapered hole of the alumina template by using glue or an adhesive tape. Then the alumina template fixed with the carbon nano tube is placed in sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 3mol/L to dissolve the alumina template, and the conical carbon nano tube array similar to that shown in figure 2 is prepared.
It is apparent that those skilled in the art can make various changes and modifications to the tapered carbon nanotube array and the method of preparing the same of the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115367737A (en) * | 2022-08-05 | 2022-11-22 | 西北工业大学 | Three-dimensional array carbon nanotube and preparation method thereof |
| CN115367737B (en) * | 2022-08-05 | 2024-04-19 | 西北工业大学 | A three-dimensional array of carbon nanotubes and a method for preparing the same |
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