CN109592668A - A method of control carbon nanotube diameter - Google Patents
A method of control carbon nanotube diameter Download PDFInfo
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- CN109592668A CN109592668A CN201910072490.9A CN201910072490A CN109592668A CN 109592668 A CN109592668 A CN 109592668A CN 201910072490 A CN201910072490 A CN 201910072490A CN 109592668 A CN109592668 A CN 109592668A
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- 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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- 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
- C01B32/176—Cutting
Abstract
The invention belongs to field of carbon nanotubes, disclose a kind of method for controlling carbon nanotube diameter, method includes the following steps: carbon nanotube is dispersed to take a small amount of supernatant liquor drop in heating core on piece and heating, drying so that solvent volatilization in the clear liquid and carbon nanotube under remaining in a solvent by (1)；(2) under vacuum conditions, carbon nanotube is heated to 800 DEG C or more using the heating chip, carbon nanotube is irradiated using electron beam later, reduced by the lossless controllable continuous of carbon nanotube diameter, carbon nanotube is made to reach expected diameter.The carbon nanotube of any specific diameter (being less than initial diameter) can be prepared using method provided by the invention, single-root carbon nano-tube can not only be handled, acceptable more carbon nanotubes of mass disposal simultaneously obtain the special diameter even carbon nanotube of minimum diameter.
Description
Technical field
The invention belongs to field of carbon nanotubes, and in particular to a method of control carbon nanotube diameter.
Background technique
Since 1991 by since finding for the first time, carbon nanotube is due to its unique structure and peculiar physical chemistry
Matter causes extensive concern in the whole world.Studies have shown that the physics and chemical property of carbon nanotube largely depend on
In its size and chirality, the slight change of chiral index can greatly change the band structure and electrical property of carbon nanotube
Energy.Therefore, diameter and chiral controllable carbon nanotube are prepared for developing various electronics and photoelectron device based on carbon nanotube
Part is extremely crucial.In addition, strong curvature effect can be such that σ and π orbital hybridization aggravates when carbon nanotube diameter becomes minimum,
It is distributed to change electronic state and increases Electron-phonon coupling, so that carbon nanotube shows some unconventional characteristics, such as superconduction
Behavior.Meanwhile with the reduction of carbon nanotube diameter, mechanics, calorifics and magnetics etc. may also can show with it is big straight
The completely different property of the carbon nanotube of diameter.
In recent years, the minimum that many researchers are dedicated to exploring carbon nanotube using various experiments and theoretical method is straight
Diameter, and achieve a series of impressive progresses.Smaller 0.4nm is gradually decrease to from the 0.7nm single-walled carbon nanotube of early detection
The single-walled carbon nanotube of left and right, or even under the conditions of few number space confinement, carbon nanotube can be smaller, such as multi-walled carbon nanotube
The diameter observed of most crucial place be 0.3nm single-walled carbon nanotube.For simple multi-walled carbon nanotube, i.e. double-walled carbon is received
For mitron, also there is the theoretical prediction to its minimum diameter.However, how to prepare the smallest double-walled carbon nano-tube and other are few
Wall carbon nano tube but lacks relevant experimental study.People also naturally can be curious, the diameter of minimum double-walled or few-wall carbon nanotube
It is how many actually? under its minimum diameter, which physics and chemical property that these carbon nanotubes can have unusual again? therefore,
Urgent need develops that a kind of can simply and effectively to control the method for carbon nanotube diameter important and have practical application to solve these
The problem of value.
Summary of the invention
The present invention is intended to provide a kind of method of new control carbon nanotube diameter.
It is provided by the invention control carbon nanotube diameter method the following steps are included:
(1) in a solvent by carbon nanotube dispersion, take a small amount of supernatant liquor drop in heating core on piece and heating, drying so that
It obtains the solvent volatilization in the clear liquid and remains lower carbon nanotube；
(2) under vacuum conditions, carbon nanotube is heated to 800 DEG C or more using the heating chip, recycles electronics
Beam irradiates carbon nanotube, is reduced by the lossless controllable continuous of carbon nanotube diameter, and carbon nanotube is made to reach expected straight
Diameter.
Preferably, the carbon nanotube is selected from single-walled carbon nanotube, double-walled carbon nano-tube, three wall carbon nano tubes and four wall carbon
At least one of nanotube.
Preferably, the solvent is selected from least one of ethyl alcohol, ethylene glycol and acetone.Wherein, the condition of the dispersion
As long as enabling to carbon nanotube fully dispersed in a solvent, that is, exist by dispersed rather than in the form of state of aggregation.
Preferably, the temperature of the heating, drying is 60~100 DEG C.
Preferably, when the diameter of the carbon nanotube no longer reduces, stop electron beam irradiation immediately.
Preferably, in step (2), the temperature of the heating is 1000~1200 DEG C.
Preferably, in step (2), the intensity of the electron beam irradiation is 10~100A/cm2。
Preferably, in step (2), the heating method is that the heating chip after drying is installed on add in-place hot rod,
Then add in-place hot rod is transferred in transmission electron microscope, starts temperature control software matched with add in-place hot rod, to heating
Chip is heated, make to heat chip be rapidly heated to 800 DEG C or more, be preferably heated to 1000~1200 DEG C, keep perseverance
Temperature.
Preferably, in step (2), the mode of the electron beam irradiation is calibration transmission electron microscope optical path, chooses institute
Single or more carbon nanotube of heating core on piece is stated as irradiation object, adjusts different amplification and electronics beam intensity
Degree carries out electron beam irradiation to selected carbon nanotube, and records carbon nanotube diameter change procedure, when carbon nanotube reaches
It is expected that stopping electron beam irradiation when diameter or diameter no longer reduce.
The present invention irradiates carbon nanotube by using electron beam under the high temperature conditions, make carbon nanotube occur diameter is lossless can
Control is continuously reduced to expected diameter even minimum diameter, to realize the purpose of accurate control carbon nanotube diameter size, fills up
The blank of existing minimum diameter carbon nanotube preparation means.
Advantages of the present invention and technical effect are as follows:
(1) operation of the present invention is simple, can prepare single wall, double-walled, three walls and four wall carbon nano tubes of minimum diameter.
(2) present invention can be prepared any specific diameter and (be less than initial straight by the diameter reduction rate of control carbon nanotube
Diameter) carbon nanotube.
(3) present invention can not only be handled single-root carbon nano-tube, can also be carried out simultaneously to more carbon nanotubes
Mass disposal obtains the carbon nanotube of special diameter or minimum diameter.
Detailed description of the invention
Fig. 1 is the process schematic of control carbon nanotube diameter provided by the invention；
Fig. 2 is the electron microscope for any one initial double-walled carbon nano-tube chosen；
Fig. 3 is to carry out 10 minutes electron microscopes obtained after heating-radiation treatment to double-walled carbon nano-tube selected by Fig. 2；
Fig. 4 is the electron microscope of inner tube fracture and axial shrinkage after double-walled carbon nano-tube diameter reduction to the limit；
Fig. 5 is the electron microscope of the minimum diameter double-walled carbon nano-tube obtained after long-time heating-radiation treatment；
Fig. 6 is the electron microscope of the minimum diameter single-walled carbon nanotube obtained after long-time heating-radiation treatment；
Fig. 7 is the electron microscope of three wall carbon nano tube of minimum diameter obtained after long-time heating-radiation treatment；
Fig. 8 is the electron microscope of four wall carbon nano tube of minimum diameter obtained after long-time heating-radiation treatment；
Fig. 9 is the carbon nanotube reduced outer diameter rate diagram that electron beam irradiation condition is identical but heating temperature is different；
Figure 10 is the carbon nanotube reduced outer diameter rate diagram that heating temperature is identical but electron beam irradiation intensity is different；
Figure 11 is the electron microscope for a wide range of carbon nanotube chosen；
Figure 12 is the electron microscope for the carbon nanotube amplified in black dotted lines box in Figure 11；
Figure 13 is the electron microscope carried out after 60 minutes heating-radiation treatments to the carbon nanotube within the scope of Figure 12；
Figure 14 is the carbon nanotube electron microscope of electron beam irradiation after ten minutes under 600 DEG C of heating conditions.
Specific embodiment
The embodiment of the present invention is described below in detail, the examples of the embodiments are intended to be used to explain the present invention, and cannot
It is interpreted as limitation of the present invention.In the examples where no specific technique or condition is specified, described according to the literature in the art
Technology or conditions or carried out according to product description.Reagents or instruments used without specified manufacturer is that can lead to
Cross the conventional products of commercially available acquisition.
Embodiment 1
The method that the embodiment is used to illustrate control carbon nanotube diameter provided by the invention.
Carbon nanotube used in the embodiment is the double-walled carbon nano-tube prepared by arc discharge method, wherein also containing few
The single-walled carbon nanotube of amount, three wall carbon nano tubes and four wall carbon nano tubes.
(1) it takes a small amount of carbon nanotube-sample (1mg) to be put into the centrifuge tube of 1ml first, then instills the ethylene glycol of 0.5ml
Solvent, then centrifuge tube is put into ultrasonic cleaning instrument ultrasound 30 minutes, tube stand a few minutes are taken out, take 1.5 μ with pipettor
L supernatant liquor instills in the hole slot of heating chip, the heating chip for being mounted with carbon nanotube-sample is finally put into vacuum drying
Case, it is 30 minutes dry at 80 DEG C.
(2) as shown in Figure 1, the heating chip after drying is installed on add in-place hot rod, high-temperature heating is to pass through original position
What heating pole was realized, bar heating chip in situ can be with accurate temperature controlling at ± 0.1 DEG C, and maximum heating rate can reach 10 DEG C/s, add
Hot temperature is up to 1200 DEG C.Add in-place hot rod is transferred in transmission electron microscope later, starting is matched with add in-place hot rod
The temperature control software of set, heats carbon nanotube, and heating chip is made to be rapidly heated with the speed of 10 DEG C/s to 1200 DEG C, and
Keep constant temperature.After temperature is stablized, sample stage height is adjusted, starts to observe using transmitted electron Electronic Speculum, found one and individually hang
Empty double-walled carbon nano-tube, records its position and takes pictures, acquired results are as shown in Figure 2.Figure it is seen that being obtained by measurement
Initial double-walled carbon nano-tube diameter to selection is 4.32nm.
Transmission electron microscope optical path is calibrated, suitable spot size (generally using 1~3) is chosen, in higher amplification
Under multiple herein (amplification factor selected is 1,000,000 times), electron beam speed spot is moved on into white space, and hot spot is scattered to whole
A fluorescent screen, adjusting electron beam irradiation intensity, (choosing electron beam irradiation intensity herein is 20A/cm2).Finally by the initial of selection
Double-walled carbon nano-tube moves to fluorescent screen center, carries out electron beam irradiation processing, double with video software record in irradiation process
The dynamic evolution process of wall carbon nano tube structure.As shown in figure 3, after 10 minutes heating-radiation treatments, double-walled carbon nano-tube
2.36nm, about 45% or so are reduced to by initial diameter 4.32nm, the rate of diameter reduction is 0.20nm/min.When continuing long
Between irradiate, double-walled carbon nano-tube diameter will constantly become smaller, until double-walled carbon nano-tube inner tube occurs being broken and axially contract (such as
Shown in Fig. 4), stop electron beam irradiation immediately to get the double-walled carbon nano-tube (as shown in Figure 5) of minimum diameter is arrived.From Fig. 4 and figure
5 inner tubes that can be seen that double-walled carbon nano-tube have been broken and have occurred axial shrinkage, and it is the smallest to illustrate that its diameter has been reduced to
Limiting value is 1.04nm, internal diameter 0.32nm by the outer diameter that measurement obtains minimum diameter double-walled carbon nano-tube.
Embodiment 2
The method that the embodiment is used to illustrate control carbon nanotube diameter provided by the invention.
Carbon nanotube used in the embodiment is the single-walled carbon nanotube prepared by arc discharge method, wherein also containing few
The double-walled carbon nano-tube of amount, three wall carbon nano tubes and four wall carbon nano tubes.
(1) it takes a small amount of carbon nanotube-sample (1mg) to be put into the centrifuge tube of 1ml first, then instills the ethylene glycol of 0.5ml
Solvent, then centrifuge tube is put into ultrasonic cleaning instrument ultrasound 30 minutes, tube stand a few minutes are taken out, take 1.5 μ with pipettor
L supernatant liquor instills in the hole slot of heating chip, the heating chip for being mounted with carbon nanotube-sample is finally put into vacuum drying
Case, it is 30 minutes dry at 80 DEG C.
(2) as shown in Figure 1, the heating chip after drying is installed on add in-place hot rod, high-temperature heating is to pass through original position
What heating pole was realized, bar heating chip in situ can be with accurate temperature controlling at ± 0.1 DEG C, and maximum heating rate can reach 10 DEG C/s, add
Hot temperature is up to 1200 DEG C.Add in-place hot rod is transferred in transmission electron microscope later, starting is matched with add in-place hot rod
The temperature control software of set, heats carbon nanotube, and heating chip is made to be rapidly heated with the rate of 10 DEG C/s to 1000 DEG C,
And keep constant temperature.After temperature is stablized, sample stage height is adjusted, starts to observe using transmitted electron Electronic Speculum, finds one individually
Hanging single-walled carbon nanotube records its position and takes pictures.By measurement, the initial diameter of single-wall carbon nano tube chosen is
1.74nm。
Transmission electron microscope optical path is calibrated, suitable spot size (generally using 1~3) is chosen, in higher amplification
Under multiple herein (amplification factor selected is 1,000,000 times), electron beam speed spot is moved on into white space, and hot spot is scattered to whole
A fluorescent screen, adjusting electron beam irradiation intensity, (choosing electron beam irradiation intensity herein is 30A/cm2).Finally by the initial of selection
Single-walled carbon nanotube moves to fluorescent screen center, carries out electron beam irradiation processing, and video software record is used in irradiation process
The dynamic evolution process of wall carbon nano tube structure.After 2 minutes heating-radiation treatments, single-walled carbon nanotube is by initial diameter
1.74nm has been reduced to 0.70nm, about 60% or so, and the rate of diameter reduction is 0.52nm/min.Continue Long-Duration Exposure, it is single
Wall carbon nano-tube pipe diameter will constantly become smaller, until single-walled carbon nanotube no longer reduces, stop electron beam irradiation immediately to get to most
The single-walled carbon nanotube (as shown in Figure 6) of minor diameter.From fig. 6, it can be seen that the minimum single-walled carbon nanotube obtained by the present invention
Diameter be 0.43nm, coincide with minimum diameter of single-wall carbon nano tube reported at present, illustrate control carbon provided by the invention
The reliability of nanometer diameter method.
Embodiment 3
The method that the embodiment is used to illustrate control carbon nanotube diameter provided by the invention.
Carbon nanotube used in the embodiment is three wall carbon nano tubes prepared by arc discharge method, wherein also containing few
Single-walled carbon nanotube, double-walled carbon nano-tube and four wall carbon nano tubes of amount.
(1) it takes a small amount of carbon nanotube-sample (1mg) to be put into the centrifuge tube of 1ml first, then instills the ethylene glycol of 0.5ml
Solvent, then centrifuge tube is put into ultrasonic cleaning instrument ultrasound 30 minutes, tube stand a few minutes are taken out, take 1.5 μ with pipettor
L supernatant liquor instills in the hole slot of heating chip, the heating chip for being mounted with carbon nanotube-sample is finally put into vacuum drying
Case, it is 30 minutes dry at 80 DEG C.
(2) as shown in Figure 1, the heating chip after drying is installed on add in-place hot rod, high-temperature heating is to pass through original position
What heating pole was realized, bar heating chip in situ can be with accurate temperature controlling at ± 0.1 DEG C, and maximum heating rate can reach 10 DEG C/s, add
Hot temperature is up to 1200 DEG C.Add in-place hot rod is transferred in transmission electron microscope later, starting is matched with add in-place hot rod
The temperature control software of set, heats carbon nanotube, and heating chip is made to be rapidly heated with the rate of 10 DEG C/s to 1100 DEG C,
And keep permanent.After temperature is stablized, sample stage height is adjusted, starts to observe using transmitted electron Electronic Speculum, found one and individually hang
Three empty wall carbon nano tubes, record its position and take pictures.By measurement, the initial three wall carbon nano-tubes pipe diameter chosen is
3.37nm。
Transmission electron microscope optical path is calibrated, suitable spot size (generally using 1~3) is chosen, in higher amplification
Under multiple herein (amplification factor selected is 1,000,000 times), electron beam speed spot is moved on into white space, and hot spot is scattered to whole
A fluorescent screen, adjusting electron beam irradiation intensity, (choosing electron beam irradiation intensity herein is 35A/cm2).Finally by the initial of selection
Three wall carbon nano tubes move to fluorescent screen center, carry out electron beam irradiation processing, with video software record three in irradiation process
The dynamic evolution process of wall carbon nano tube structure.After 5 minutes heating-radiation treatments, three wall carbon nano tubes are by initial diameter
3.37nm has been reduced to 1.93nm, about 43% or so, and the rate of diameter reduction is 0.29nm/min.Continuation Long-Duration Exposure, three
Wall carbon nano-tube pipe diameter will constantly become smaller, until three wall carbon nano tube inner tubes occur being broken and axially contract, stop electricity immediately
Beamlet irradiation is to get three wall carbon nano tubes (as shown in Figure 7) for arriving minimum diameter.From figure 7 it can be seen that obtained by the present invention
The outer diameter of minimum three wall carbon nano tubes is 1.66nm, internal diameter 0.32nm.
Embodiment 4
The method that the embodiment is used to illustrate control carbon nanotube diameter provided by the invention.
Carbon nanotube used in the embodiment is four wall carbon nano tubes prepared by arc discharge method, wherein also containing few
Single-walled carbon nanotube, double-walled carbon nano-tube and three wall carbon nano tubes of amount.
(1) it takes a small amount of carbon nanotube-sample (1mg) to be put into the centrifuge tube of 1ml first, then instills the ethylene glycol of 0.5ml
Solvent, then centrifuge tube is put into ultrasonic cleaning instrument ultrasound 30 minutes, tube stand a few minutes are taken out, take 1.5 μ with pipettor
L supernatant liquor instills in the hole slot of heating chip, the heating chip for being mounted with carbon nanotube-sample is finally put into vacuum drying
Case, it is 30 minutes dry at 80 DEG C.
(2) as shown in Figure 1, the heating chip after drying is installed on add in-place hot rod, high-temperature heating is to pass through original position
What heating pole was realized, bar heating chip in situ can be with accurate temperature controlling at ± 0.1 DEG C, and maximum heating rate can reach 10 DEG C/s, add
Hot temperature is up to 1200 DEG C.Add in-place hot rod is transferred in transmission electron microscope later, starting is matched with add in-place hot rod
The temperature control software of set, heats carbon nanotube, and heating chip is made to be rapidly heated with the rate of 10 DEG C/s to 1100 DEG C,
And keep constant temperature.After temperature is stablized, sample stage height is adjusted, starts to observe using transmitted electron Electronic Speculum, finds one individually
Four hanging wall carbon nano tubes record its position and take pictures.By measurement, the initial four wall carbon nano-tubes pipe diameter chosen is
5.73nm。
Transmission electron microscope optical path is calibrated, suitable spot size (generally using 1~3) is chosen, in higher amplification
Under multiple herein (amplification factor selected is 1,000,000 times), electron beam speed spot is moved on into white space, and hot spot is scattered to whole
A fluorescent screen, adjusting electron beam irradiation intensity, (choosing electron beam irradiation intensity herein is 50A/cm2).Finally by the initial of selection
Four wall carbon nano tubes move to fluorescent screen center, carry out electron beam irradiation processing, with video software record four in irradiation process
The dynamic evolution process of wall carbon nano tube structure.After 5 minutes heating-radiation treatments, four wall carbon nano tubes are by initial diameter
5.73nm has been reduced to 4.23nm, about 26% or so, and the rate of diameter reduction is 0.3nm/min.Continue Long-Duration Exposure, four walls
Carbon nanotube diameter will constantly become smaller, until four wall carbon nano tube inner tubes occur being broken and axially contract, stop electronics immediately
Beam irradiation is to get four wall carbon nano tubes (as shown in Figure 8) for arriving minimum diameter.From figure 8, it is seen that being obtained most by the present invention
The outer diameter of small four wall carbon nano tube is 2.41nm, internal diameter 0.32nm.
As can be seen from the above results, method provided by the invention can not only prepare minimum diameter double-walled carbon nano-tube, and
And the single-walled carbon nanotube of minimum diameter, three wall carbon nano tubes and four wall carbon nano tubes can also be prepared, that is, be less than or equal to wall number
4 minimum diameter carbon nanotube is applicable in.In addition, heating temperature and electron beam irradiation intensity are that influence carbon nanotube is lossless continuous
Reduce two big factors of rate: under identical electronic beam irradiation intensity, heating temperature is higher, and the lossless reduction rate of carbon nanotube is got over
Fastly；Under identical heating temperature, electron beam irradiation intensity is bigger, and the lossless reduction rate of carbon nanotube is faster.Therefore, tune can be passed through
Prepare any specific diameter (special diameter is less than initial diameter) carbon with saving heating temperature and electron beam irradiation intensity controlled is received
Mitron.
Embodiment 5
The method that the embodiment is used to illustrate control carbon nanotube diameter provided by the invention.
Carbon nanotube diameter is controlled according to the method for embodiment 1, unlike, bar in situ heating chip is heated to 1000
DEG C, remaining condition is the same as embodiment 1.The result shows that double-walled carbon nano-tube diameter will be continuous with the extension of electron beam irradiation time
Become smaller, until double-walled carbon nano-tube inner tube occurs being broken and axially contract, stops electron beam irradiation immediately to get straight to minimum
The double-walled carbon nano-tube of diameter.
Embodiment 6
The method that the embodiment is used to illustrate control carbon nanotube diameter provided by the invention.
Carbon nanotube diameter is controlled according to the method for embodiment 1, unlike, bar in situ heating chip is heated to 800
DEG C, remaining condition is the same as embodiment 1.The result shows that double-walled carbon nano-tube diameter will be continuous with the extension of electron beam irradiation time
Become smaller, until double-walled carbon nano-tube inner tube occurs being broken and axially contract, stops electron beam irradiation immediately to get straight to minimum
The double-walled carbon nano-tube of diameter.In addition, when carbon nanotube diameter is with electron beam irradiation in embodiment 1, embodiment 5 and embodiment 6
Between extended result of variations it is as shown in Figure 9.From fig. 9, it can be seen that double-walled carbon nano-tube exists under identical electronic beam irradiation intensity
The rate reduced at 800 DEG C, 1000 DEG C, 1200 DEG C is 0.07nm/min, 0.13nm/min, 0.20nm/min, this explanation respectively
Under identical electronic beam irradiation intensity, heating temperature is higher, and the lossless reduction rate of carbon nanotube is faster.
Embodiment 7- embodiment 9
The method that embodiment 7- embodiment 9 is used to illustrate control carbon nanotube diameter provided by the invention.
Carbon nanotube diameter is controlled according to the method for embodiment 1, unlike, the intensity of electron beam irradiation is replaced respectively
For 75A/cm2、45A/cm2And 15A/cm2, for remaining condition with embodiment 1, acquired results are as shown in Figure 10.It can from Figure 10
Out, under identical heating temperature, double-walled carbon nano-tube is in 15A/cm2、45A/cm2、75A/cm2Reduce under electron beam irradiation intensity
Rate is 0.11nm/min, 0.42nm/min, 0.67nm/min respectively, this explanation is when heating temperature is identical, electron beam irradiation
Intensity is bigger, and the lossless reduction rate of carbon nanotube is faster.
Embodiment 10
The method that the embodiment is used to illustrate control carbon nanotube diameter provided by the invention.
Carbon nanotube diameter is controlled according to the method for embodiment 1, unlike, by the amplification factor of transmission electron microscope
It adjusts to 1.1 ten thousand times, and electron beam irradiation intensity is adjusted to 12A/cm2, remaining is the same as embodiment 1, acquired results such as Figure 11-13
It is shown.Wherein, Figure 11 is the electron microscope for a wide range of carbon nanotube chosen, and Figure 12 is to amplify in black dotted lines box in Figure 11
The electron microscope of carbon nanotube, Figure 13 are the Electronic Speculum carried out after 60 minutes heating-radiation treatments to the carbon nanotube within the scope of Figure 12
Figure.It can be seen that from the result of Figure 11-13 and handled by heating for a long time with electron beam irradiation, whole double-walleds in the visual field
Carbon nanotube reduces and becomes smaller, this explanation can also more carbon nanotube (> of batch processing using method provided by the invention
1000).
Comparative example 1
The method that the comparative example is used to illustrate the control carbon nanotube diameter of reference.
Carbon nanotube diameter is controlled according to the method for embodiment 1, unlike, bar in situ heating chip is heated to 600
DEG C, for remaining condition with embodiment 1, acquired results are as shown in figure 14.It is seen from figure 14 that prolonging with the electron beam irradiation time
It is long, it is not nondestructively to reduce although double-walled carbon nano-tube diameter can also reduce.Since heating temperature is lower, electron beam
Irradiation can make carbon nanotube generate defect, such as be distorted.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (9)
1. a kind of method for controlling carbon nanotube diameter, which is characterized in that method includes the following steps:
(1) in a solvent by carbon nanotube dispersion, a small amount of supernatant liquor drop is taken in heating core on piece and heating, drying is so that institute
It states the solvent volatilization in clear liquid and remains lower carbon nanotube；
(2) under vacuum conditions, carbon nanotube is heated to 800 DEG C or more using the heating chip, recycles electron beam pair
Carbon nanotube is irradiated, and is reduced by the lossless controllable continuous of carbon nanotube diameter, carbon nanotube is made to reach expected diameter.
2. the method for control carbon nanotube diameter according to claim 1, which is characterized in that the carbon nanotube is selected from single
At least one of wall carbon nano tube, double-walled carbon nano-tube, three wall carbon nano tubes and four wall carbon nano tubes.
3. it is according to claim 1 control carbon nanotube diameter method, which is characterized in that the solvent be selected from ethyl alcohol,
At least one of ethylene glycol and acetone.
4. the method for control carbon nanotube diameter according to claim 1, which is characterized in that the temperature of the heating, drying
It is 60~100 DEG C.
5. the method for carbon nanotube diameter is controlled described in any one of -4 according to claim 1, which is characterized in that when described
When the diameter of carbon nanotube no longer reduces, stop electron beam irradiation immediately.
6. the method for carbon nanotube diameter is controlled described in any one of -4 according to claim 1, which is characterized in that step
(2) in, the temperature of the heating is 1000~1200 DEG C.
7. the method for carbon nanotube diameter is controlled described in any one of -4 according to claim 1, which is characterized in that step
(2) in, the intensity of the electron beam irradiation is 10~100A/cm2。
8. the method for carbon nanotube diameter is controlled described in any one of -4 according to claim 1, which is characterized in that step
(2) in, the heating method is that the heating chip after drying is installed on add in-place hot rod, then shifts add in-place hot rod
Into transmission electron microscope, start temperature control software matched with add in-place hot rod, heating chip is heated, makes to add
Hot chip is rapidly heated to 800 DEG C or more, and keeps constant temperature.
9. the method for control carbon nanotube diameter according to claim 8, which is characterized in that in step (2), the electronics
The mode of beam irradiation is calibration transmission electron microscope optical path, chooses single or more carbon nanotube of the heating core on piece
As irradiation object, different amplification and electron beam intensity are adjusted, electron beam irradiation is carried out to selected carbon nanotube,
And carbon nanotube diameter change procedure is recorded, when carbon nanotube reaches expected diameter or diameter no longer reduces, stop electronics
Beam irradiation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115562A (en) * | 2019-12-13 | 2020-05-08 | 华东师范大学 | Method for in-situ processing of hollow nanometer cavity |
| CN111470489A (en) * | 2019-11-05 | 2020-07-31 | 中山大学 | Conversion method for converting single-wall carbon nanotube into double-wall carbon nanotube |
| CN114195129A (en) * | 2021-12-10 | 2022-03-18 | 湖南金博氢能科技有限公司 | Carbon nano elastomer material and preparation method thereof, gas diffusion membrane and battery |
| WO2023173357A1 (en) * | 2022-03-14 | 2023-09-21 | 无锡东恒新能源科技有限公司 | Method for synthesizing thin-walled carbon nanotube |
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| US20100284898A1 (en) * | 2006-05-05 | 2010-11-11 | William Marsh Rice University | Bulk cutting of carbon nanotubes using electron beam irradiation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111470489A (en) * | 2019-11-05 | 2020-07-31 | 中山大学 | Conversion method for converting single-wall carbon nanotube into double-wall carbon nanotube |
| CN111115562A (en) * | 2019-12-13 | 2020-05-08 | 华东师范大学 | Method for in-situ processing of hollow nanometer cavity |
| CN111115562B (en) * | 2019-12-13 | 2023-03-10 | 华东师范大学 | Method for in-situ processing of hollow nanometer cavity |
| CN114195129A (en) * | 2021-12-10 | 2022-03-18 | 湖南金博氢能科技有限公司 | Carbon nano elastomer material and preparation method thereof, gas diffusion membrane and battery |
| WO2023173357A1 (en) * | 2022-03-14 | 2023-09-21 | 无锡东恒新能源科技有限公司 | Method for synthesizing thin-walled carbon nanotube |
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