CN106744817B - A method of by single-walled carbon nanotube tube bank removing at single single-walled carbon nanotube - Google Patents
A method of by single-walled carbon nanotube tube bank removing at single single-walled carbon nanotube Download PDFInfo
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- CN106744817B CN106744817B CN201611096459.1A CN201611096459A CN106744817B CN 106744817 B CN106744817 B CN 106744817B CN 201611096459 A CN201611096459 A CN 201611096459A CN 106744817 B CN106744817 B CN 106744817B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The present invention provides a kind of method for removing single-walled carbon nanotube tube bank at single discrete single-walled carbon nanotube, is related to technical field of nanometer material preparation science.The present invention carries out intercalation stripping using potassium permanganate and concentrated sulfuric acid intercalation oxidation, to carbon nanotube bundles, has obtained having water-soluble single discrete single-walled carbon nanotube.The single-walled carbon nanotube not instead of tube bank type, with existing for single form, caliber 1-2nm.
Description
Technical field
The present invention relates to technical field of nanometer material preparation science, especially by single-walled carbon nanotube tube bank removing at single
The method of discrete single-walled carbon nanotube.
Background technique
Single-walled carbon nanotube (single-walled carbon nanotubes, SWCNTs) is a kind of with single layer tube wall
One-dimensional tubular structure carbon nanomaterial.Single-walled carbon nanotube has excellent Wuli-Shili-Renli system approach, in mechanics, electricity, light
It learns and the fields such as electronics has broad application prospects.Currently our single-walled carbon nanotubes obtained are not with single
Existing for discrete form, but between Guan Yuguan hexagonal Mi Dui formed tube bank by way of existing for.It is managed in these tube banks
There is strong van der Waals interaction between pipe, be difficult to be removed, while being also very difficult to be dispersed in water.This state
Some excellent properties (such as optical characteristics) of some excellent properties of single itself itself cannot be not only given full play to, and
And also will limit the application in some fields of carbon nanotube, such as application as drug delivery carrier.Therefore, it is necessary to by single wall
The single-walled carbon nanotube at single discrete type is removed in carbon nanotube tube bank, and makes it have preferable water solubility.Currently, by single wall
Carbon nanotube tube bank is dispersed into the ultrasonic dispersion that single single-walled carbon nanotube most popular method is ultracentrifugation auxiliary.It is this
Method generally requires large-scale centrifugation apparatus device, operates more complicated and deal with also than relatively time-consuming.And this side
Method must be introduced into some surfactants, polymer etc. to disperse single wall carbon carbon nanotube in sonication stage, this is often
It is difficult to the subsequent processing of carbon nanotube and application bring.Meanwhile this method is needed with ultracentrifugation (usually
50000 turns or more) sample is extracted, amount per treatment also very lacks (usually in microgram magnitude), in practical applications
Also it is difficult to promote.Therefore, a kind of method by single-walled carbon nanotube tube bank removing at single discrete single-walled carbon nanotube is invented
It has important practical significance.
Summary of the invention
The purpose of the present invention is to some shortcomings of the prior art, provide a kind of restrain single-walled carbon nanotube and remove
At the method for single discrete single-walled carbon nanotube.
The present invention is achieved by the following technical solutions, and the present invention is made using potassium permanganate and the oxidation of concentrated sulfuric acid intercalation
With, to carbon nanotube bundles carry out intercalation stripping, obtained have water-soluble single discrete single-walled carbon nanotube.
The method of the present invention includes following steps:
Initial single-walled carbon nanotube solid and potassium permanganate solid are added separately to certain proportion excessive dense
In sulfuric acid solution, obtained reaction mixture is placed in 40-70 DEG C of water-bath and is persistently stirred to react 1-6h, by reacted mixing
Liquid is diluted with deionized water, is added excessive hydrogen peroxide solution reduction and is removed the manganese dioxide solid generated, by miillpore filter
After filtering and the washing of dilute hydrochloric acid solution, obtained solid is washed by high speed centrifugation to supernatant liquor with deionized water again is
Neutral (PH=6-7) after then taking lower layer's solid that deionized water is added to be sufficiently stirred, further after centrifugation, takes upper layer uniform, stable
Solution to get to polymolecularity single single-walled carbon nanotube aqueous solution.The black that will be collected into after solution filtering
Solid is single (non-tube bank type) single-walled carbon nanotube.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of original single-walled carbon nanotube.
Fig. 2 is the high-resolution-ration transmission electric-lens photo of original single-walled carbon nanotube tube bank
Fig. 3 is single discrete single-walled carbon nanotube scanning probe microscopy photo.
Fig. 4 is the single-walled carbon nanotube stereoscan photograph of single non-tube bank type.
Fig. 5 is the single-walled carbon nanotube transmission electron microscope photo of single non-tube bank type.
Fig. 6 is single discrete single-walled carbon nanotube scanning probe microscopy photo.
Fig. 7 is single discrete single-walled carbon nanotube scanning probe microscopy photo.
Specific embodiment
Example 1:
0.1 gram and 0.2 gram of single-walled carbon nanotube (Fig. 1 and Fig. 2) initial of potassium permanganate solid is added sequentially to
It fills in the beaker of the concentrated sulfuric acid (98%) of 10ml, after stirring, is placed in stir process 3 in 40 DEG C of thermostat water bath
Hour, after being cooled to room temperature, is diluted with the deionized water of about 100ml, and be stirred continuously, add 30% dioxygen of about 10ml
Aqueous solution uses filtering with microporous membrane after being stirred to react 15 minutes.Obtained black solid directly pours into dilute salt of the 4% of 100ml
Agitator treating in acid, then with filtering with microporous membrane, and with deionized water filtration washing, obtained black solid is poured into again
After being sufficiently stirred in the deionized water of 200ml, it is centrifuged 30 minutes under 14000 turns with centrifuge, after layering, it is clear outwells upper layer
Liquid, and continue to be added suitable deionized water into centrifuge tube and washing is sufficiently stirred and then is centrifuged again, it is layered, it is clear to outwell upper layer
Obtained centrifugal deposition is finally collected and is added the deionized water of about 200ml, stirs by liquid, repeatedly centrifuge washing 4-6 times
After mixing 30 minutes, after obtained dispersion liquid centrifuge is centrifuged 30 minutes under 14000 turns, it is molten that upper layer dispersion is collected in careful extraction
Liquid is collected into the single single-walled carbon nanotube aqueous solution that dispersion solution is high dispersive.The single-walled carbon nanotube dispersed in solution
Be it is single discrete, caliber is 1-2nm (Fig. 3).The black solid being collected into after solution filtering with microporous membrane is put
The single-walled carbon nanotube (Fig. 4) obtained by drying to single non-tube bank type in drying box.
Embodiment 2:
It is added sequentially to 0.1 gram and 0.1 gram of single-walled carbon nanotube initial of potassium permanganate solid to fill 10ml's
In the beaker of the concentrated sulfuric acid (98%), after stirring, stir process 6 hours in 50 DEG C of thermostat water bath are placed in, to cold
But it to after room temperature, is diluted with the deionized water of about 100ml, and be stirred continuously, adds 30% hydrogen peroxide solution of about 10ml, stir
After mixing reaction 15 minutes, filtering with microporous membrane is used.Obtained black solid is directly poured into 4% dilute hydrochloric acid of 100ml and is stirred
Washing, then with filtering with microporous membrane, and with deionized water filtration washing, obtained black solid be poured into again 200ml go from
After being sufficiently stirred in sub- water, be centrifuged 30 minutes under 14000 turns with centrifuge, after layering, outwell supernatant liquor, and continue toward from
Be added in heart pipe suitable deionized water be sufficiently stirred washing then be centrifuged again, be layered, outwell supernatant liquor, repeatedly from
The heart washs 4-6 times, and obtained centrifugal deposition is finally collected to and is added the deionized water of about 200ml and is obtained after stirring 30 minutes
After the dispersion liquid centrifuge arrived is centrifuged 30 minutes under 14000 turns, careful extract collects upper layer dispersion solution, is collected into dispersion
Solution is the single single-walled carbon nanotube aqueous solution of high dispersive.The single-walled carbon nanotube dispersed in solution is single discrete
's.The black solid being collected into after solution filtering with microporous membrane is placed on obtained by drying to single in drying box by (Fig. 5)
The single-walled carbon nanotube of non-tube bank type.
Embodiment 3:
It is added sequentially to 0.1 gram and 0.4 gram of single-walled carbon nanotube initial of potassium permanganate solid to fill 10ml's
In the beaker of the concentrated sulfuric acid (98%), after stirring, it is placed in stir process 1 hour in 40 DEG C of thermostat water bath, to cold
But it to after room temperature, is diluted with the deionized water of about 100ml, and be stirred continuously, adds 30% hydrogen peroxide solution of about 10ml, stir
After mixing reaction 15 minutes, filtering with microporous membrane is used.Obtained black solid is directly poured into 4% dilute hydrochloric acid of 100ml and is stirred
Washing, then with filtering with microporous membrane, and with deionized water filtration washing, obtained black solid be poured into again 200ml go from
After being sufficiently stirred in sub- water, be centrifuged 30 minutes under 14000 turns with centrifuge, after layering, outwell supernatant liquor, and continue toward from
Be added in heart pipe suitable deionized water be sufficiently stirred washing then be centrifuged again, be layered, outwell supernatant liquor, repeatedly from
The heart washs 4-6 times, and obtained centrifugal deposition is finally collected to and is added the deionized water of about 200ml and is obtained after stirring 30 minutes
After the dispersion liquid centrifuge arrived is centrifuged 30 minutes under 4000 turns, careful extract collects upper layer dispersion solution, is collected into dispersion
Solution is the single single-walled carbon nanotube aqueous solution of high dispersive.The single-walled carbon nanotube dispersed in solution is single discrete
's.The black solid being collected into after solution filtering with microporous membrane is placed on obtained by drying to single in drying box by (Fig. 6)
The single-walled carbon nanotube of non-tube bank type.
Embodiment 4:
It is added sequentially to 0.1 gram and 0.1 gram of single-walled carbon nanotube initial of potassium permanganate solid to fill 10ml's
In the beaker of the concentrated sulfuric acid (98%), after stirring, it is placed in stir process 1 hour in 70 DEG C of thermostat water bath, to cold
But it to after room temperature, is diluted with the deionized water of about 100ml, and be stirred continuously, adds 30% hydrogen peroxide solution of about 10ml, stir
After mixing reaction 15 minutes, filtering with microporous membrane is used.Obtained black solid is directly poured into 4% dilute hydrochloric acid of 100ml and is stirred
Washing, then with filtering with microporous membrane, and with deionized water filtration washing, obtained black solid be poured into again 200ml go from
After being sufficiently stirred in sub- water, be centrifuged 30 minutes under 14000 turns with centrifuge, after layering, outwell supernatant liquor, and continue toward from
Be added in heart pipe suitable deionized water be sufficiently stirred washing then be centrifuged again, be layered, outwell supernatant liquor, repeatedly from
The heart washs 4-6 times, and obtained centrifugal deposition is finally collected to and is added the deionized water of about 200ml and is obtained after stirring 30 minutes
After the dispersion liquid centrifuge arrived is centrifuged 30 minutes under 14000 turns, careful extract collects upper layer dispersion solution, is collected into dispersion
Solution is the single single-walled carbon nanotube aqueous solution of high dispersive.The single-walled carbon nanotube dispersed in solution is single discrete
's.The black solid being collected into after solution filtering with microporous membrane is placed on obtained by drying to single in drying box by (Fig. 7)
The single-walled carbon nanotube of non-tube bank type.
Claims (2)
1. a kind of method for removing single-walled carbon nanotube tube bank at single discrete single-walled carbon nanotube, which is characterized in that packet
Include following steps: by original single-walled carbon nanotube solid and potassium permanganate solid with mass ratio 1:(1~4) proportion be added to
In the concentrated sulfuric acid solution of amount, after being reacted 1~6 hour at 40~70 DEG C, successively through water dilution, hydrogen peroxide reduction except dereaction life
At manganese dioxide solid, refilter, after the solid that centrifuge washing obtains adds water and stirs, pass through 4000~14000 turns of centrifuging and takings
Upper layer dispersion solution obtains the single single-walled carbon nanotube aqueous solution of polymolecularity, the black which is collected by filtration
Solid is the single single-walled carbon nanotube of non-tube bank type.
2. according to the method described in claim 1, it is characterized by: the single single-walled carbon nanotube of the polymolecularity is water-soluble
Liquid has the characteristics that the single single-walled carbon nanotube caliber of uniform, stable, described non-tube bank type is 1-2nm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328276A (en) * | 2008-07-24 | 2008-12-24 | 同济大学 | Preparation of single wall carbon nanotube-polymer conductive composite film |
| CN102791617A (en) * | 2010-01-25 | 2012-11-21 | 得克萨斯A&M大学体系 | Dispersion and retrieval of de-bundled nanotubes |
| CN104724691A (en) * | 2013-12-23 | 2015-06-24 | 北京阿格蕾雅科技发展有限公司 | Method for raising dispersibility of single-walled carbon nanotubes |
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| TWI552956B (en) * | 2015-05-29 | 2016-10-11 | 國立臺灣科技大學 | Producing method of graphene and applications thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328276A (en) * | 2008-07-24 | 2008-12-24 | 同济大学 | Preparation of single wall carbon nanotube-polymer conductive composite film |
| CN102791617A (en) * | 2010-01-25 | 2012-11-21 | 得克萨斯A&M大学体系 | Dispersion and retrieval of de-bundled nanotubes |
| CN104724691A (en) * | 2013-12-23 | 2015-06-24 | 北京阿格蕾雅科技发展有限公司 | Method for raising dispersibility of single-walled carbon nanotubes |
Non-Patent Citations (1)
| Title |
|---|
| Individual Single-Walled Nanotubes and Hydrogels Made by Oxidative Exfoliation of Carbon Nanotube Ropes;Nina I. Kovtyukhova et al.，;《Journal of American Chemistry Society》;20030717;第125卷;第9761-9769页 * |
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