CN108085655A - It is a kind of（2m, m）Carbon nanotubes horizontal array and preparation method thereof - Google Patents
It is a kind of（2m, m）Carbon nanotubes horizontal array and preparation method thereof Download PDFInfo
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- CN108085655A CN108085655A CN201611040477.8A CN201611040477A CN108085655A CN 108085655 A CN108085655 A CN 108085655A CN 201611040477 A CN201611040477 A CN 201611040477A CN 108085655 A CN108085655 A CN 108085655A
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Abstract
The invention discloses a kind of (2m, m) carbon nanotubes horizontal arrays and preparation method thereof.Described method includes following steps：Ammonium salt is transferred in substrate, is then made annealing treatment, ammonium salt is pressed for ammonium molybdate or wolframic acid；Ammonium salt is reduced using hydrogen；After reduction step, be passed through into reaction vessel carbon source gas grown to get.(2m, m) carbon nanotubes horizontal array of the invention, the caliber of carbon nanotubes therein is 0.7~1.3nm, and length is 100~300 μm.For the catalyst that the present invention uses for carbide, catalytic activity is higher, and more existing metallic catalyst has higher activity, this is the key that the present invention can obtain the higher carbon nanotubes of density.The fusing point for the catalyst molybdenum carbide that the present invention uses is higher, can keep solid forms, therefore can obtain the high carbon nanotubes of chiral selectivity.The present invention selects single crystal substrates, and as growth substrate, since single crystal substrates have Double Symmetry, growing obtained carbon nanotubes has very high array.
Description
Technical field
The present invention relates to a kind of carbon nanotubes horizontal arrays and preparation method thereof, and in particular to a kind of (2m, m) carbon nanotubes
Horizontal array and preparation method thereof.
Background technology
Carbon nanotubes has abundant structure and electron energy band, therefore larger potential application valency is suffered from many fields
Value, however carbon nanotubes is hindered to move towards the structure-controllable that one of significant problem of practical application is carbon nanotubes and is prepared.Prepare tool
There is a preferable homogeneity or even the carbon nanotubes of unidextrality is huge challenge prepared by current carbon nanotubes.Meanwhile in nano-electron
In, generally require carbon nanotubes can self-contained horizontal array, and density is the higher the better.In actual report, low temperature (700 DEG C or so)
Although the carbon nanotubes of certain chiral selectivity (be less than 60%) can be obtained, carbon nanotubes it is second-rate, while not
It can be into horizontal array.In addition, that reports at present utilizes solid alloy catalyst preparation unidextrality (12,6) carbon nanotubes, life
Long efficiency is very low, although obtain carbon nanotubes have it is very highly selective, still be in horizontal array.To sum up, master-hand is obtained
The carbon nanotubes horizontal array of Sexual behavior mode is a huge challenge.
The content of the invention
The object of the present invention is to provide a kind of (2m, m) carbon nanotubes horizontal array and preparation method thereof, prepared by the present invention
The density of (2m, m) carbon nanotubes horizontal array is high, and chiral selectivity is high.
The preparation method of (2m, m) carbon nanotubes horizontal array provided by the present invention, includes the following steps：
1) ammonium salt is transferred in substrate, is then made annealing treatment；
2) ammonium salt is reduced using hydrogen；
3) after the reduction step, carbon source gas is passed through into reaction vessel and is grown to get (2m, the m) carbon
Nanotube horizontal array.
In (2m, m) type carbon nanotubes horizontal array of the invention, m is the natural number between 1~6, concretely 4 or 6.
In above-mentioned preparation method, in step 1), the ammonium salt can be ammonium molybdate or ammonium tungstate.
In above-mentioned preparation method, in step 1), the mode for shifting the ammonium salt is：
The alcoholic solution of ammonium salt is spun in the substrate, the ethanol solution of ammonium salt specifically can be used；
The molar concentration of the alcoholic solution of the ammonium salt can be 0.01~0.1mM, concretely 0.05mM；
The rate of the spin coating can be 2300~2800r/min, such as 2500r/min.
In above-mentioned preparation method, in step 1), the substrate can be single crystal substrates, such as alpha alumina-based using monocrystalline
Bottom.
In above-mentioned preparation method, in step 1), the condition of the annealing is as follows：
Temperature can be 800~1200 DEG C, concretely 1000~1100 DEG C, 1000 DEG C or 1100 DEG C；
Time can be 6~10 it is small when, concretely 8 it is small when；
By the annealing, make catalyst precursor (ammonium salt) fully oxidized and spread in the substrate.
In above-mentioned preparation method, in step 2), the condition of the reduction is as follows：
The flow velocity of hydrogen can be 100~200sccm, concretely 200sccm；
Temperature can be 400~800 DEG C, concretely 450 DEG C or 800 DEG C；
Time can be 5~20 minutes, concretely 5~10 minutes, 5 minutes or 10 minutes；
By the reduction step, the ammonium salt is reduced to solid metal particles, as grows carbon nanotubes horizontal array
The presoma of row.
In above-mentioned preparation method, in step 3), the carbon source gas can be ethylene, acetylene or alcohol vapor；
The carbon source gas be passed through mode for it is following 1) or 2)：
1) when the carbon source gas be ethylene or acetylene, by the way of being introduced directly into；
2) when the carbon source gas be alcohol vapor, using argon gas introducing by the way of.
In above-mentioned preparation method, in step 3), the rate that is passed through of the carbon source gas can be 50~150sccm, such as
100sccm。
In above-mentioned preparation method, in step 3), the condition of the growth is as follows：
Temperature can be 800~900 DEG C, such as 850 DEG C；
Time can be 15~30min, such as 15min or 30min.
(2m, m) carbon nanotubes horizontal array that the above method of the present invention is prepared falls within protection scope of the present invention.
The present invention specifically provides (8,4) carbon nanotubes horizontal array and (12,6) carbon nanotubes horizontal array.
The chiral selectivity of (2m, m) carbon nanotubes horizontal array provided by the invention is up to more than 80%~90%.
The density of (2m, m) carbon nanotubes horizontal array provided by the invention is higher, 10~30 on every micron substrate.
(2m, m) carbon nanotubes horizontal array provided by the invention, the caliber of carbon nanotubes therein is 0.7~1.3nm,
Length is 100~300 μm.
Compared with prior art, the present invention has the advantages that：
1) for the catalyst that the method for the present invention uses for carbide, catalytic activity is higher, more existing metallic catalyst tool
There is higher activity, this is the key that the present invention can obtain the higher carbon nanotubes of density.
2) fusing point for the catalyst molybdenum carbide that the method for the present invention uses is higher, can keep solid forms, therefore the present invention
The high carbon nanotubes of chiral selectivity can be obtained.
3) the method for the present invention selects single crystal substrates as growth substrate, since single crystal substrates are with Double Symmetry,
Growing obtained carbon nanotubes has very high array.
4) repeatability of present invention growth (2m, m) carbon nanotubes horizontal array is higher and growth limits from area, reason
By can above grow very big area.
Description of the drawings
Fig. 1 is the SEM figures of (12,6) carbon nanotubes horizontal array prepared by the embodiment of the present invention 1.
Fig. 2 is the AFM figures of (12,6) carbon nanotubes horizontal array prepared by the embodiment of the present invention 1.
Fig. 3 is the Raman spectrum of (12,6) carbon nanotubes horizontal array prepared by the embodiment of the present invention 1.
Fig. 4 is the high-resolution-ration transmission electric-lens figure of (12,6) carbon nanotubes horizontal array prepared by the embodiment of the present invention 1 and spreads out
Penetrate analysis (interior illustration).
Fig. 5 is the SEM figures of (8,4) carbon nanotubes horizontal array in (2m, m) prepared by the embodiment of the present invention 2.
Fig. 6 is the Raman spectrum of (8,4) carbon nanotubes horizontal array in (2m, m) prepared by the embodiment of the present invention 2.
Fig. 7 is the high-resolution-ration transmission electric-lens of (8,4) carbon nanotubes horizontal array in (2m, m) prepared by the embodiment of the present invention 2
Figure and diffraction analysis (interior illustration).
Fig. 8 is the AFM figures of the single crystal substrates of monodisperse catalyst precursor prepared by the embodiment of the present invention 1.
Fig. 9 is the AFM of the single crystal substrates of load prepared by the embodiment of the present invention 1 not after the annealing of same amount catalyst precursor
And XPS figures.
The AFM figures of the catalyst obtained after the reduction that Figure 10 is prepared for the embodiment of the present invention 1.
Figure 11 is the AFM figures of the catalyst under different reduction temperatures prepared by the embodiment of the present invention 1.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1 prepares (12,6) carbon nanotubes horizontal array
In 4 × 6mm2Monocrystalline Alpha-alumina substrate on, with the speed of 2500r/min spin coating 0.05mM on single-crystal substrates
Ammonium molybdate ethanol solution, then carried out between 1100 DEG C 8 it is small when annealing, allow the abundant oxygen of catalyst precursor ammonium molybdate
Change and spread in signle crystal alumina substrate.The substrate of annealing, which is placed in 450 DEG C of reaction vessel, uses 200sccm hydrogen reducings
Then 10min rises to 850 DEG C；Hydrogen is cut off, introduces the alcohol vapor (being carried by argon gas) of 100sccm, grows 30min, then
Cooling to get to 15 every micron (12,6) carbon nanotubes horizontal array, wherein, the caliber of carbon nanotubes for 1.1~
1.3nm, length are 100~300 μm.
The chiral selectivity of (12,6) carbon nanotubes horizontal array manufactured in the present embodiment is up to 90%.
(12,6) carbon nanotubes horizontal array manufactured in the present embodiment SEM figure as shown in Figure 1, it can be seen from this figure that
The carbon nanotubes horizontal array of growth has larger area distributions and higher density, and the collimation of carbon nanotubes is preferable.
(12,6) carbon nanotubes horizontal array manufactured in the present embodiment AFM figure as shown in Fig. 2, it can be seen from this figure that
Carbon nanotubes horizontal array has higher density, averag density about every micron 15, local density about every micron 40.
The Raman spectrum of (12,6) carbon nanotubes horizontal array manufactured in the present embodiment by the figure as shown in figure 3, can be seen
Go out, carbon nanotubes horizontal array has very high chiral selectivity.
The high-resolution-ration transmission electric-lens figure and diffraction analysis (interpolation of (12,6) carbon nanotubes horizontal array manufactured in the present embodiment
Figure) as shown in figure 4, it can be seen from this figure that the chirality of carbon nanotubes is (12,6).
Embodiment 2 prepares (8,4) carbon nanotubes horizontal array
In 4 × 6mm2Monocrystalline Alpha-alumina substrate on, with the speed of 2500r/min spin coating 0.05mM on single-crystal substrates
Ammonium tungstate ethanol solution, then carried out between 1000 DEG C 8 it is small when annealing, allow the abundant oxygen of catalyst precursor ammonium tungstate
Change and spread in signle crystal alumina substrate.The substrate of annealing, which is placed in 800 DEG C of reaction vessel, uses 200sccm hydrogen reducings
Then 5min rises to 850 DEG C；Hydrogen is cut off, introduces the alcohol vapor (being carried by argon gas) of 100sccm, grows 15min, then
Cooling to get to 10 every micron (8,4) carbon nanotubes horizontal array, wherein, the caliber of carbon nanotubes is 0.7~1.0nm,
Length is 100~300 μm.
The chiral selectivity of (8,4) carbon nanotubes horizontal array manufactured in the present embodiment is up to 80%.
The SEM of (8,4) carbon nanotubes horizontal array manufactured in the present embodiment is schemed as shown in figure 5, it can be seen from this figure that carbon
Nanotube horizontal array can realize large area deposition, averag density about every micron 10.
The Raman spectrum of (8,4) carbon nanotubes horizontal array manufactured in the present embodiment by the figure as shown in fig. 6, can be seen
Go out, carbon nanotubes horizontal array has very high chiral selectivity.
The high-resolution-ration transmission electric-lens figure and diffraction analysis (interpolation of (8,4) carbon nanotubes horizontal array manufactured in the present embodiment
Figure) as shown in fig. 7, it can be seen from this figure that the chirality of carbon nanotubes is (8,4).
The Analysis on Mechanism of embodiment 3, the catalyst preparation of (2m, m) single-walled carbon nanotube horizontal array；
1st, the Analysis on Mechanism verification that prepared by the catalyst monodisperse of (2m, m) single-walled carbon nanotube horizontal array；
Gained crystal growth substrate carries out AFM surface analyses after spin coating in embodiment 1 is carried ammonium molybdate annealing, such as Fig. 8 institutes
Show, Fig. 8 a) scheme for the AFM of the ammonium molybdate presoma of initial spin coating, after annealing, all disappear, be dispersed in single crystal substrates
Surface, such as Fig. 8 b) shown in, almost without any catalyst granules on substrate surface after AFM display annealing.
Further to prove the monodisperse process of catalyst precursor, the ammonium molybdate of various concentration is spin-coated on single crystal substrates
On, such as Fig. 9 a), 9b) and 9c) shown in, it can be seen that with the increase of molybdic acid ammonium concentration, the Mo/Al that XPS displays obtain is than dimension
It holds on a similar order of magnitude, this further demonstrates the monodisperses of catalyst precursor.
2) the reduction releasing mechanism of the catalyst of (2m, m) single-walled carbon nanotube horizontal array；
By monodisperse crosses the crystal growth substrate of catalyst precursor and is put into chemical vapor deposition system in embodiment 1
Middle carry out hydrogen reducing, reduction temperature are 450 DEG C, hydrogen flowing quantity 200sccm, recovery time 10min.As shown in Figure 10, it is right
Compare Fig. 8, it can be seen that occurring substantial amounts of nano particle after reduction without the substrate surface of any particle originally, i.e.,
The nucleating point of carbon nanotubes.
2) analysis of the reduction temperature of the catalyst of (2m, m) single-walled carbon nanotube horizontal array；
By monodisperse crosses the crystal growth substrate of catalyst precursor and is put into chemical vapor deposition system in embodiment 1
Middle carry out hydrogen reducing, hydrogen flowing quantity 200sccm, recovery time 10min choose different reduction temperatures, 450 DEG C and
800℃.Such as Figure 11 a) and 11b) shown in, AFM show reduces obtained catalyst with narrower distribution and homogeneous by 450 DEG C
Size, relatively low reduction temperature is conducive to obtain more uniform catalyst.
Claims (10)
1. a kind of preparation method of (2m, m) carbon nanotubes horizontal array, includes the following steps：
1) ammonium salt is transferred in substrate, is then made annealing treatment；
2) ammonium salt is reduced using hydrogen；
3) after the reduction step, carbon source gas is passed through into reaction vessel and is grown to get (2m, m) the carbon nanometer
Pipe horizontal array.
2. preparation method according to claim 1, it is characterised in that：In step 1), the ammonium salt is ammonium molybdate or wolframic acid
It presses.
3. preparation method according to claim 1 or 2, it is characterised in that：In step 1), the mode of the ammonium salt is shifted
For：
The alcoholic solution of ammonium salt is spun in the substrate；
The molar concentration of the alcoholic solution of the ammonium salt is 0.01~0.1mM；
The rate of the spin coating is 2300~2800r/min.
4. preparation method according to any one of claim 1-3, it is characterised in that：In step 1), the substrate is single
Brilliant substrate.
5. according to the preparation method any one of claim 1-4, it is characterised in that：In step 1), the annealing
Condition it is as follows：
Temperature is 800~1200 DEG C；
When time is 6~10 small.
6. according to the preparation method any one of claim 1-5, it is characterised in that：In step 2), the item of the reduction
Part is as follows：
The flow velocity of hydrogen is 100~200sccm；
Temperature is 400~800 DEG C；
Time is 5~20 minutes.
7. according to the preparation method any one of claim 1-6, it is characterised in that：In step 3), the carbon source gas is
Ethylene, acetylene or alcohol vapor；
The carbon source gas be passed through mode for it is following 1) or 2)：
1) when the carbon source gas be ethylene or acetylene, by the way of being introduced directly into；
2) when the carbon source gas be alcohol vapor, using argon gas introducing by the way of.
8. preparation method according to claim 7, it is characterised in that：In step 3), the rate that is passed through of the carbon source gas is
50~150sccm.
9. according to the preparation method any one of claim 1-8, it is characterised in that：In step 3), the item of the growth
Part is as follows：
Temperature is 800~900 DEG C；
Time is 15~30 minutes.
10. (2m, m) carbon nanotubes horizontal array prepared by method any one of claim 1-9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1868867A (en) * | 2005-05-28 | 2006-11-29 | 鸿富锦精密工业（深圳）有限公司 | Preparation method of carbon nanometer pipe |
| US20090208403A1 (en) * | 2008-02-17 | 2009-08-20 | Quaid-E-Azam University | Novel catalyst to manufacture carbon nanotubes and hydrogen gas |
| CN105565292A (en) * | 2014-10-29 | 2016-05-11 | 北京大学 | Ultra-high-density single-walled carbon nanotube horizontal array and controllable preparation method thereof |
| CN106145082A (en) * | 2015-03-30 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Narrow chirality distribution SWCN horizontal array and preparation method thereof |
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- 2016-11-22 CN CN201611040477.8A patent/CN108085655B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1868867A (en) * | 2005-05-28 | 2006-11-29 | 鸿富锦精密工业（深圳）有限公司 | Preparation method of carbon nanometer pipe |
| US20090208403A1 (en) * | 2008-02-17 | 2009-08-20 | Quaid-E-Azam University | Novel catalyst to manufacture carbon nanotubes and hydrogen gas |
| CN105565292A (en) * | 2014-10-29 | 2016-05-11 | 北京大学 | Ultra-high-density single-walled carbon nanotube horizontal array and controllable preparation method thereof |
| CN106145082A (en) * | 2015-03-30 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Narrow chirality distribution SWCN horizontal array and preparation method thereof |
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