CN104445151A - Method for preparing water-soluble multi-walled carbon nanotube - Google Patents
Method for preparing water-soluble multi-walled carbon nanotube Download PDFInfo
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- CN104445151A CN104445151A CN201410716865.8A CN201410716865A CN104445151A CN 104445151 A CN104445151 A CN 104445151A CN 201410716865 A CN201410716865 A CN 201410716865A CN 104445151 A CN104445151 A CN 104445151A
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- walled carbon
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- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 67
- 230000035484 reaction time Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000002041 carbon nanotube Substances 0.000 claims description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 9
- 230000033444 hydroxylation Effects 0.000 claims description 7
- 238000005805 hydroxylation reaction Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000012047 saturated solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 11
- 238000010141 design making Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002620 method output Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing a water-soluble multi-walled carbon nanotube. The method is characterized by comprising the important factors as follows: the NaOH concentration is 1-5mol/L; the adding amount of a catalyst H2O2 is 0-2ml; and the reaction time is 3-12 hours. MWC-NTols are wrapped by PVP, so as to prepare a hydroxylated multi-walled carbon nanotube (PVP-MWCNTols) wrapped by PVP. The dissolving property of the multi-walled carbon nanotube in water is further enhanced after non-covalent package action. The method is simple, relatively mild in reaction condition and stable in dispersion product, and has the advantages of low cost, industrialization and the like.
Description
Technical field
The present invention relates to a kind of preparation method, refer in particular to a kind of preparation method of water-soluble multi-wall carbon nanotube.
Background technology
Multi-walled carbon nano-tubes (Multi-walled carbon nanotubes, MWCNTs) and Single Walled Carbon Nanotube (Single-walled carbon nanotubes is found respectively from 1991 and 1993.SWC-NTs) since, the character such as electricity, optics, mechanics, thermodynamics due to its uniqueness receives the extensive concern of each subject, but dispersiveness limited in all kinds of SOLVENTS and solvability limit its investigation and application to a certain extent.Therefore, one of important content in carbon nanotube research field is become to the exploration of carbon nanotube dispersed performance.By covalency and non-covalent method, it is modified, effectively can improve the dispersing property of carbon nanotube.Be introduce carboxyl on carbon nanotube port and sidewall rhythm defect covalent approach (as strong acid oxidation style), the reactions such as recycling neutralization, acidylate, addition connect various group (as: alkyl chain, organic amine etc.) thereon.Not only can be improved the solvability of carbon nanotube by covalent modification, and its chemical property and range of application are also enriched in the introducing of various functionalization group.Carbon nanotube is being carried out in the research of chemically modified, mostly be adopt to generate carboxylated carbon nanotube under the effect of the strong oxidizer such as strong acid, nitration mixture, this method acutely easily causes the damage of carbon nanotube because of reaction conditions, and carbon nanotube is ruptured, long than reducing.Adopt pulse discharge method to prepare hydroxylated carbon nanotube, the introducing of hydroxyl changes the polarity of carbon nano tube surface, and what reduce between tube and tube is towering. and towering effect, enhances its wetting ability.The method reaction conditions is gentleer, and the structure of carbon nanotube can not be destroyed.But this method output is lower, is unsuitable for suitability for industrialized production.Non-covalent approach is then do not changing on the basis of carbon nanotube structure, utilizes towering. towering accumulation, electronics supply. by effect, hydrophilic-hydrophobic effect etc., solubility organic macromolecule, superpolymer are wrapped in the surface of carbon nanotube, to reach the object of solubilising.In non-covalent approach, utilize high molecular polymer polyvinylpyrrolidone (Polyvinylpyrrolidone, PVP) to wrap up SWCNTs, effectively can strengthen that it is water-soluble.The method has the advantages such as simple to operate, with low cost.Covalent modification and non-covalent modification respectively have its feature, change in the research of flight of steps leading to a palace hall solubilising play respective advantage at carbon nanotube.
So the research of low cost, functionalization capable of being industrialized and solubilizing method receives to be paid close attention to widely.
Summary of the invention
The present invention adopts PVP to wrap up MWC-NTols, the obtained hydroxylation multi-walled carbon nano-tubes (PVP-MWCNTols) through PVP parcel.After non-covalent package action, further enhancing the solubility property of multi-walled carbon nano-tubes in water.This method is simple, reaction conditions is gentleer, and dispersion product is stablized, have low cost, can the advantage such as industrialization.
The object of this invention is to provide a kind of preparation method of water-soluble multi-wall carbon nanotube.
For achieving the above object, the present invention adopts following technical scheme:
NaOH concentration: 1 mol/L ~ 5mol/L;
Catalyzer H
2o
2add-on: 0ml ~ 2ml;
Reaction times: 3h ~ 12h.
Preferably, each influence factor of the present invention is respectively: NaOH concentration: 10mol/L; Catalyzer H
2o
2add-on: 2ml; Reaction times: 12h.
Preparation method of the present invention comprises the following steps:
(1) preparation of hydroxylation multi-walled carbon nano-tubes (MWCNTols)
Claim 500 mg MWCNTs ultrasonic disperse 30 min in 200mL NaOH solution, room temperature reaction under magnetic agitation.The H of 30% is slowly added after reaction starts
20
2solution is as the catalyzer of reaction.After question response terminates with the speed of 8000 r/min by reaction solution centrifugation 5 min, discard upper strata alkali lye, solid second distillation water washing, with identical speed and time centrifugation, abandoning supernatant.Repeated washing is until the pH ≈ 7 of supernatant liquor.Gained solid is dried at 90 DEG C and can obtain hydroxylated multi-walled carbon nano-tubes (MWCNTols).Be dissolved in redistilled water by excessive MWCNTols, ultrasonic 30 min centrifugations can obtain its saturated solution.
(2) PVP wraps up the preparation of hydroxylation multi-walled carbon nano-tubes (PVP-MWC-NTols)
Joined in the massfraction 1%SDS aqueous solution by multi-walled carbon nano-tubes (MWCNTols) after hydroxyl modified, add PVP after ultrasonic disperse, 50 DEG C of lower magnetic forces stir and wrap up MWCNTols.Solution centrifugal after parcel is separated, and will be deposited in bottom centrifuge tube by the MWCNTols that PVP wraps up, and still be resided in solution by the MWCNTols that PVP wraps up.Solid-liquid separation, a certain amount of dehydrated alcohol is added in solution, stir and leave standstill in a moment, after disperseing sample in the solution to reassemble, centrifugation, remove upper solution, repeat this operation with the SDS removing carbon nano tube surface and remain and the PVP combined loosely, the 90 DEG C of oven dry of gained solid can be obtained product---the hydroxylation multi-walled carbon nano-tubes (PVP-MWCNTols) after PVP parcel.
Wherein, concentration, the catalyzer H of NaOH
20
2the factor such as add-on, reaction times have material impact to reaction result.Utilize the preparation process of orthogonal experiment method to MWCNTols to investigate, optimize experiment condition.The factor that orthogonal experiment is chosen and level as shown in table 1.L is chosen according to level of factor table
9(3
4) orthogonal table experiment arrangement scheme.With the absorbancy of product MWCNTols saturated solution for evaluation index.Specific practice is: take a certain amount of product, centrifugation after ultrasonic disperse, gets upper strata MWCNTols saturated solution, and measure the absorbance A at its certain wavelength place after being diluted to certain multiple, experimental result is in table 2.
Table 1 factor and level
Table 2 orthogonal experiments
As shown in Table 2, (1), from extreme difference R, the impact of each factor on experimental result is followed successively by from big to small: the concentration of NaOH, H
20
2volume and the reaction times, wherein, the concentration of NaOH is major influence factors; (2) optimum level is combined as A
3b
3c
3, namely NaOH concentration is 5 mol/L, H
20
2volume be 2 mL, the reaction times is 12 h.The optimum level of three factors is cut off value, need expand span and compare experiment.Because of H
20
2volume and the reaction times little on experimental result impact, so fixing H
20
2volume be 2 mL, the reaction times is 12 h, and continue to increase the concentration of NaOH and do further control experiment, result is as shown in table 3.
Table 3 controlled trial result
According to the result of table 2 and table 3, finally determine that preparation condition be NaOH concentration is 10 mol/L, H
20
2volume be 2 mL, the reaction times is 12h.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail, but the present invention is not limited to these embodiments.
Embodiment one:
By following schematic design making: NaOH concentration: 1 mol/L; Catalyzer H
2o
2add-on: 1ml; Reaction times: 3h.
Embodiment two:
By following schematic design making: NaOH concentration: 2 mol/L; Catalyzer H
2o
2add-on: 0ml; Reaction times: 5h.
Embodiment three:
By following schematic design making: NaOH concentration: 5mol/L; Catalyzer H
2o
2add-on: 2ml; Reaction times: 12h.
Embodiment four:
By following schematic design making: NaOH concentration: 10mol/L; Catalyzer H
2o
2add-on: 2ml; Reaction times: 12h.
Embodiment five:
By following schematic design making: NaOH concentration: 20mol/L; Catalyzer H
2o
2add-on: 2ml; Reaction times: 12h.
Embodiment six:
By following schematic design making: NaOH concentration: 4mol/L; Catalyzer H
2o
2add-on: 2ml; Reaction times: 8h.
Embodiment seven:
By following schematic design making: NaOH concentration: 5mol/L; Catalyzer H
2o
2add-on: 0ml; Reaction times: 6h.
Embodiment eight:
By following schematic design making: NaOH concentration: 1mol/L; Catalyzer H
2o
2add-on: 1ml; Reaction times: 3h.
Claims (4)
1. a preparation method for water-soluble multi-wall carbon nanotube, is characterized in that: comprise the following steps:
(1) preparation of hydroxylation multi-walled carbon nano-tubes (MWCNTols):
Claim 500 mg MWCNTs ultrasonic disperse 30 min in 200mL NaOH solution, room temperature reaction under magnetic agitation; The H of 30% is slowly added after reaction starts
20
2solution is as the catalyzer of reaction; After question response terminates with the speed of 8000 r/min by reaction solution centrifugation 5 min, discard upper strata alkali lye, solid second distillation water washing, with identical speed and time centrifugation, abandoning supernatant; Repeated washing is until the pH ≈ 7 of supernatant liquor; Gained solid is dried at 90 DEG C and can obtain hydroxylated multi-walled carbon nano-tubes (MWCNTols); Be dissolved in redistilled water by excessive MWCNTols, ultrasonic 30 min centrifugations can obtain its saturated solution;
(2) PVP wraps up the preparation of hydroxylation multi-walled carbon nano-tubes (PVP-MWC-NTols): join in the massfraction 1%SDS aqueous solution by the multi-walled carbon nano-tubes (MWCNTols) after hydroxyl modified, add PVP after ultrasonic disperse, 50 DEG C of lower magnetic forces stir and wrap up MWCNTols; Solution centrifugal after parcel is separated, and will be deposited in bottom centrifuge tube by the MWCNTols that PVP wraps up, and still be resided in solution by the MWCNTols that PVP wraps up; Solid-liquid separation, a certain amount of dehydrated alcohol is added in solution, stir and leave standstill in a moment, after disperseing sample in the solution to reassemble, centrifugation, remove upper solution, repeat this operation with the SDS removing carbon nano tube surface and remain and the PVP combined loosely, the 90 DEG C of oven dry of gained solid can be obtained product---the hydroxylation multi-walled carbon nano-tubes (PVP-MWCNTols) after PVP parcel.
2. the preparation method of a kind of water-soluble multi-wall carbon nanotube according to claim 1, is characterized in that: MWCNTs purity is greater than 90%, caliber 30 ~ 50 nm, pipe range 50 μm.
3. the preparation method of a kind of water-soluble multi-wall carbon nanotube according to claim 1, is characterized in that: be made up of following important factor:
NaOH concentration: 1 mol/L ~ 5mol/L;
Catalyzer H
2o
2add-on: 0ml ~ 2ml;
Reaction times: 3h ~ 12h.
4. a kind of preparation method of water-soluble multi-wall carbon nanotube according to claim 1 or 2, is characterized in that: be made up of following important factor:
NaOH concentration: 10mol/L;
Catalyzer H
2o
2add-on: 2ml;
Reaction times: 12h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517152A (en) * | 2016-11-02 | 2017-03-22 | 山东科技大学 | Method for uniform dispersion of single-walled carbon nanotubes in water solvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557011A (en) * | 2012-03-09 | 2012-07-11 | 桂林理工大学 | Method for performing functionalization treatment to surface of multi-walled carbon nanotube by utilizing hydrogen peroxide |
| CN104118862A (en) * | 2014-07-24 | 2014-10-29 | 成都工业学院 | Surface modification method of carbon nanotubes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557011A (en) * | 2012-03-09 | 2012-07-11 | 桂林理工大学 | Method for performing functionalization treatment to surface of multi-walled carbon nanotube by utilizing hydrogen peroxide |
| CN104118862A (en) * | 2014-07-24 | 2014-10-29 | 成都工业学院 | Surface modification method of carbon nanotubes |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517152A (en) * | 2016-11-02 | 2017-03-22 | 山东科技大学 | Method for uniform dispersion of single-walled carbon nanotubes in water solvent |
| CN106517152B (en) * | 2016-11-02 | 2018-08-31 | 山东科技大学 | Single-walled carbon nanotube method evenly dispersed in aqueous solvent |
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| CN104445151B (en) | 2016-12-07 |
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