CN1699155A - Preparation method for water soluble carbon nanotube - Google Patents
Preparation method for water soluble carbon nanotube Download PDFInfo
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- CN1699155A CN1699155A CN 200510018617 CN200510018617A CN1699155A CN 1699155 A CN1699155 A CN 1699155A CN 200510018617 CN200510018617 CN 200510018617 CN 200510018617 A CN200510018617 A CN 200510018617A CN 1699155 A CN1699155 A CN 1699155A
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Abstract
The invention relates to a preparation method for water soluble carbon nanotube, which is based on non-covalence surface finishing to the carbon nanotube by disazo dye molecule, a high water-solubility and effective detachment is realized for the carbon nano tubes. The method comprises using azo-dyes, carbon nano tube and water as raw material, purifying the commercial carbon nano tube and washing into neutral, drying and mixing the obtained purified carbon nano tube with excess azo-dyes, fully dissolving or dispersing the carbon nano tube through the conventional physical abrasion or supersonic dispersion.
Description
Technical field
The present invention relates to a kind ofly prepare the method for water-soluble carbon nanometer tube based on the disazo dye molecule non-covalent modification, be applicable to this carbon nanotube dissolving, purifying, separate, derive and follow-up practical application.
Background technology
Since being found in 1991, carbon nanotube is just with its particular structure, electricity, mechanics and optical characteristics and be subjected to numerous investigators' favor in field of nanometer technology potential wide application prospect.Almost each possible practical application all requires carbon nanotube to have good dissolving or dispersing property.Yet industrial extensive synthetic carbon nanotube often contains the various impurity that comprise catalyzer and various decolorizing carbon.And, owing to there is the bigger specific surface that Van der Waals force and carbon nanotube itself are had between extremely strong pipe between the carbon nanotube, the many pencil forms that form side by side with a large amount of single-root carbon nano-tubes of carbon nanotube exist, make carbon nanotube be dissolved in all solvents hardly, this has greatly limited the practical application of carbon nanotube.Therefore, the dissolving of carbon nanotube or dispersion technology are the popular domains of carbon nanotube basis research always.The method that disperses or dissolves of carbon nanotube has two big classes: a class is by various chemical covalent modification methods the sidewall of carbon nanotube or the port behind the open pipe to be carried out covalency to derive, realize that its dissolving disperses or effectively peels off, though this method solubleness is good, the charge stripping efficiency height, but thereby the perfect structure of meeting destroying carbon nanometer tube itself influences its various premium propertiess, and complex disposal process is difficult to control; Another kind of is with various non-covalent modification methods, by polymkeric substance or small molecules aggregate (as surfactant micelle) parcel of carbon nanotube is realized that its dissolving disperses and peels off, these class methods are little to the damage of carbon nanotube, basically keep its original performance, but often have that solubleness is little, poor stability and the low shortcoming of charge stripping efficiency, and some method needs expensive specific synthetic agent.All these unfavorable factors have all greatly limited the large-scale practical application of carbon nanotube.
Summary of the invention
For overcoming these problems that exist in the prior art, make carbon nanotube obtain better application, the invention provides a kind of brand-new preparation method who the non-covalent surface of carbon nanotube is modified the highly water-soluble of realizing carbon nanotube and the carbon nanotube of effectively peeling off based on disazo dye molecule, carbon nanotube with this method preparation not only has the characteristics of the highly water-soluble and the high charge stripping efficiency of covalent modification method, the low damage feature that also has the non-covalent modification method, and this method itself have with low cost, technology simple, be convenient to advantage such as large-scale industrial application.
The technical solution adopted for the present invention to solve the technical problems is: with azoic dyestuff, carbon nanotube and water is raw material, as follows preparation:
(1) with ordinary method with commercialization carbon nanotube purifying, be washed with water to neutral and oven dry, obtain purifying carbon nano-tube.
(2) purifying carbon nano-tube of gained and excessive azoic dyestuff are mixed, with conventional physical grinding or ultra-sonic dispersion method carbon nanotube is fully dissolved then or disperse.
(3) mixture that obtains is removed excessive free state dye molecule through washing, get water-soluble carbon nanometer tube.
Wherein azoic dyestuff is Congo red or has the disazo dyes of similar structures.
Aforesaid method is fit to preparation single wall, double-walled and multi-walled carbon nano-tubes.
Owing to can be peeled off into single-root carbon nano-tube effectively with the carbon nano-tube bundle of method for preparing, the good water solubility of carbon nanotube, so for chemical covalent modification method, have low abrasive advantage, and for existing non-covalent method, have better solvability and charge stripping efficiency.Again because of the selective dissolution of azoic dyestuff to carbon nanotube, the purifying that this method also can be used for carbon nanotube with separate, and azoic dyestuff low price, stability and Bc are good.Therefore this water-soluble carbon nanometer tube can be used widely at purifying, dissolving or dispersion, separation and the chemistry of carbon nanotube or physics aspect such as derive., mild condition simple from operation steps preparation technology of the present invention as can be seen, processing parameter are more easy to control, and these favourable conditions will promote greatly that also this water-soluble carbon nanometer tube can be by large-scale industrial application.
Description of drawings
Accompanying drawing is the solubility property comparison diagram of various carbon nanotubes.(a). carbon nanotube+water; (b). carbon nanotube+N, dinethylformamide (DMF); (c). carbon nanotube+Congo red+water; (d). carbon nanotube+Congo red+DMF; (e). it is Congo red (c) to remove free state through washing; (f). the dispersion again in water behind the water-soluble carbon nanometer tube complete drying (e); (g). carbon nanotube+sodium lauryl sulphate (SDS)+water
Embodiment
Embodiment 1
With the commercialization carbon nanotube through 48 hours backflow purifying of the rare nitric acid of 2.6mol/L, be washed with water to neutral and oven dry, again the purifying carbon nano-tube of gained and excessive disazo dyes are mixed back grinding 2 hours, the carbon nanotube of gained and the mixture of azoic dyestuff can be water-soluble fully, and wherein the azoic dyestuff of excessive free state can wash with water and remove and do not reduce the water-soluble of carbon nanotube.
Embodiment 2
With the commercialization carbon nanotube through 48 hours backflow purifying of the rare nitric acid of 2.6mol/L, be washed with water to neutral and oven dry, it is molten in right amount in water that the purifying carbon nano-tube of gained and excessive disazo dyes mix the back, and ultrasonic to there not being solid residue in the high-power ultrasonic instrument, wherein the azoic dyestuff of excessive free state can wash with water and remove and do not reduce the water-soluble of carbon nanotube.
Below in conjunction with the water-soluble carbon nanometer tube of description of drawings non-covalent modification provided by the present invention preparation good solubility property in water.From figure, can be clear that, though 48 hours backflow purification process of the rare nitric acid of process, carbon nanotube still insoluble fully in water (in the accompanying drawing (a)); When with this organic solvent dispersing Nano carbon tubes commonly used of DMF, most carbon nanotubes all settle down, and have only minute quantity to be dissolved in wherein (in the accompanying drawing (b)); Through carbon nanotube then dissolving fully in water of Congo red processing, and solubleness is up to 3.5mg/ml (in the accompanying drawing (c)); But the carbon nanotube of Congo red processing almost insoluble in DMF (in the accompanying drawing (d)); Meanwhile, when excessive free state Congo red after water washing is removed, the solubility property of carbon nanotube influenced hardly (in the accompanying drawing (e)); What is interesting is that no free state is Congo red when existing, be dissolved in and thoroughly lost that it is good water-soluble (in the accompanying drawing (f) behind the carbon nanotube complete drying in the water; As a comparison, this anion surfactant of the most widely used sodium lauryl sulphate (SDS) is used to disperse purified carbon nanotube in the world, but the carbon nanotube that still has only minute quantity be dissolved in the water (~0.1mg/ml), its solubleness is well below the prepared water-soluble carbon nanometer tube of the present invention (3.5mg/ml) (in the accompanying drawing (g)).
Claims (2)
1. the preparation method of a water-soluble carbon nanometer tube, it is characterized in that: with azoic dyestuff, carbon nanotube and water is raw material, as follows preparation:
(1) with ordinary method with commercialization carbon nanotube purifying, be washed with water to neutral and oven dry, obtain purifying carbon nano-tube.
(2) purifying carbon nano-tube of gained and excessive azoic dyestuff are mixed, with conventional physical grinding or ultra-sonic dispersion method carbon nanotube is fully dissolved then or disperse.
(3) mixture that obtains is removed excessive free state dye molecule through washing, get water-soluble carbon nanometer tube.
2. the preparation method of water-soluble carbon nanometer tube according to claim 1, it is characterized in that: azoic dyestuff is Congo red or has the disazo dyes of similar structures.
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CNB2005100186177A CN1331741C (en) | 2005-04-27 | 2005-04-27 | Preparation method for water soluble carbon nanotube |
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CNB2005100186177A CN1331741C (en) | 2005-04-27 | 2005-04-27 | Preparation method for water soluble carbon nanotube |
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CN1699155A true CN1699155A (en) | 2005-11-23 |
CN1331741C CN1331741C (en) | 2007-08-15 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102145885A (en) * | 2011-03-04 | 2011-08-10 | 南京师范大学 | Method for preparing surface phosphorylated water-soluble carbon nanotube and prepared carbon nanotube |
CN102516816A (en) * | 2011-12-08 | 2012-06-27 | 陕西科技大学 | Preparation method of acidic dye modified based on carbon nano-tubes, and dyeing method |
CN102535198A (en) * | 2011-12-08 | 2012-07-04 | 陕西科技大学 | Dyeing method of acid dyes assisted by functionalized carbon nanotubes |
CN110589806A (en) * | 2019-07-25 | 2019-12-20 | 武汉大学 | Efficient purification method of water-dispersible carbon nano material |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1436721A (en) * | 2002-02-08 | 2003-08-20 | 中国科学院化学研究所 | Prepn of water soluble carbon nanotube |
JP2005028560A (en) * | 2003-07-07 | 2005-02-03 | Naotoshi Nakajima | Method for manufacturing water-soluble carbon nanotube using dna and oligonucleotide |
CN1275853C (en) * | 2004-08-26 | 2006-09-20 | 复旦大学 | Process for preparing surface carboxyl modified carbon nano tube |
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2005
- 2005-04-27 CN CNB2005100186177A patent/CN1331741C/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102145885A (en) * | 2011-03-04 | 2011-08-10 | 南京师范大学 | Method for preparing surface phosphorylated water-soluble carbon nanotube and prepared carbon nanotube |
CN102516816A (en) * | 2011-12-08 | 2012-06-27 | 陕西科技大学 | Preparation method of acidic dye modified based on carbon nano-tubes, and dyeing method |
CN102535198A (en) * | 2011-12-08 | 2012-07-04 | 陕西科技大学 | Dyeing method of acid dyes assisted by functionalized carbon nanotubes |
CN102535198B (en) * | 2011-12-08 | 2014-01-29 | 陕西科技大学 | Dyeing method of acid dyes assisted by functionalized carbon nanotubes |
CN110589806A (en) * | 2019-07-25 | 2019-12-20 | 武汉大学 | Efficient purification method of water-dispersible carbon nano material |
CN110589806B (en) * | 2019-07-25 | 2022-08-05 | 武汉大学 | Efficient purification method of water-dispersible carbon nano material |
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CN1331741C (en) | 2007-08-15 |
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