CN102145885A - Method for preparing surface phosphorylated water-soluble carbon nanotube and prepared carbon nanotube - Google Patents
Method for preparing surface phosphorylated water-soluble carbon nanotube and prepared carbon nanotube Download PDFInfo
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- CN102145885A CN102145885A CN2011100517353A CN201110051735A CN102145885A CN 102145885 A CN102145885 A CN 102145885A CN 2011100517353 A CN2011100517353 A CN 2011100517353A CN 201110051735 A CN201110051735 A CN 201110051735A CN 102145885 A CN102145885 A CN 102145885A
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Abstract
The invention discloses a method for preparing a surface phosphorylated water-soluble carbon nanotube and the prepared carbon nanotube. The method comprises the following steps of: purifying a carbon nanotube, performing calcination treatment on the purified carbon nanotube, and putting into aqueous solution of a phosphonic acid derivative of an aromatic compound; performing ultrasonic dispersion for 3 to 10 hours; filtering and repeatedly washing; and drying at the temperature of between 25 and 40 DEG C to obtain the surface phosphorylated water-soluble carbon nanotube. In the invention, a -PO3H2 functional group is modified on the surface of the carbon nanotube through nonconvalent binding under the action of pi-pi accumulation conjugation, so that the unique property of the carbon nanotube is maintained and the dispersion stability of the carbon nanotube in water is improved on the basis of high water solubility of the phosphonic acid functional group. The preparation method has definite and reliable mechanisms, is simple and practicable and is low in price; and the prepared carbon nanotube has high dissolution dispersibility in the water and has a wide application prospect in the field of material science and biomedicine.
Description
Technical field
The present invention relates to a kind of preparation method of water-soluble carbon nanometer tube and the carbon nanotube that makes, relate in particular to a kind of preparation method of water-soluble carbon nanometer tube of finishing phosphonyl group and the carbon nanotube that makes.
Background technology
Carbon nanotube (Carbon Nanotubes, be called for short CNTs), be the hollow tube that is rolled into by the Graphene lamella that carbon atom forms, be divided into Single Walled Carbon Nanotube (Single-wall Nanotubes, SWNT) and multi-walled carbon nano-tubes (Multi-wall Nanotubes, MWNT).Japanese scientist Lijima found carbon nanotube since 1991, because advantages such as the carbon nanotube caliber is little, length-to-diameter ratio is big, make it have performances such as good mechanics, calorifics, electricity, optics, be subjected to area research persons' such as Materials science, chemistry and physics favor, be a kind of nano material with unique texture and wide application prospect always.
Have and interact strongly between the CNTs of one dimension Nano structure, therefore the bunchy of easily reuniting is difficult to by most of polarity or non-polar solvent dissolving.Simultaneously because carbon nanotube lacks active group, be insoluble in organic solvent and water, this has greatly limited the application of CNTs in a plurality of fields such as blend polymer, miniature electrical equipment element, electroluminescent device, chemistry and biosensors, and the research of its chemical property also is difficult to deeply carry out.
From 1998, the surface treatment of carbon nanotube and the research work of functionalization are launched gradually.By the surface-functionalized dispersiveness that strengthens in the solvability of carbon nanotube in solvent and other substrate materials of carbon nanotube, thus the actual use value of raising carbon nanotube.
Surface chemical modification to CNTs mainly is to pass through dual mode at present: the one, by non covalent bond functional molecular is adsorbed on the CNTs surface; Another kind of is chemical group to be connected on the graphite-structure of CNTs by covalent linkage, and its purpose all is to form an amphiphilic or water-wetted surface outside the CNTs pipe.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and water-soluble carbon nanometer tube of water-soluble carbon nanometer tube of finishing phosphonyl group,, satisfy the requirement that use the carbon nanotube research and development in relevant field to overcome the defective of carbon nanotube poorly water-soluble.
The present invention utilizes the phosphonate derivative of aromatics and the pi-pi accumulation conjugation between the CNTs, and phosphonyl group is modified at the CNTs surface.The planar conjugate molecule that forms is similar to a kind of " bifunctional linking agent ", and the conjugate planes structure closely acts on the CNTs, and hydrophilic structure then stretches in the solvent, has strengthened the water-soluble of CNTs.
The preparation method of surperficial phosphine acidifying water-soluble carbon nanometer tube of the present invention is as follows:
Carbon nanotube after purifying and the calcination processing is put in the aqueous solution of phosphonate derivative of aromatics, ultra-sonic dispersion 3 ~ 10 hours filters and repetitive scrubbing, and 25 ~ 40 ℃ of following dryings obtain surperficial phosphine acidifying water-soluble carbon nanometer tube.
Described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
Described aromatics is benzene, naphthalene, pyrene or anthracene, or their derivative.The phosphonate derivative of aromatics is for not only containing phenyl ring but also containing the aromatics of phosphonyl group, include but not limited to phenyl-phosphonic acid, the substituted-phenyl phosphonic acids, phenylalkyl phosphonic acids or substituted-phenyl alkyl phosphonic acid, the naphthyl phosphonic acids, the substituted naphthyl phosphonic acids, naphthyl alkyl phosphonic acid or substituted naphthyl alkyl phosphonic acid, the pyrenyl phosphonic acids, replace the pyrenyl phosphonic acids, pyrenyl alkyl phosphonic acid or replacement pyrenyl alkyl phosphonic acid, the anthryl phosphonic acids, replace the anthryl phosphonic acids, anthryl alkyl phosphonic acid or replacement anthryl alkyl phosphonic acid etc., for example Ben Yajiaji phosphonic acids, the styroyl phosphonic acids, the aminophenyl phosphonic acids, naphthalene-1-methylene phosphonic acid, naphthalene-5-methylene phosphonic acid, pyrene-1-methylene phosphonic acid, pyrene-4-methylene phosphonic acid, anthracene-1-methylene phosphonic acid, anthracene-10-methylene phosphonic acid etc.
Described carbon nanotube with the quality of material ratio that the phosphonate derivative of aromatics is thrown in preparation process is: 1:10 ~ 10:1.
The present invention removes the foreign metal granules of catalyst that exists in the carbon nanotube with the carbon nanotube purification process, removes the oxy radical of carbon nano tube surface again by high-temperature calcination.The carbon nanotube after handling and the phosphonate derivative of aromatics are piled up effect by π-π, phosphonyl group is modified at the CNTs surface, utilize the phosphonic acids negatively charged ion that has good aqueous solubility on the phosphonate derivative of benzene, naphthalene, pyrene, anthracene to improve the dispersion stabilization of carbon nanotube in water, thereby obtain the water-soluble CNTs of surperficial phosphine acidifying.
The purifying of carbon nanotube, calcining processing method are:
(1) in being housed, the three-necked flask of reflux condensate device adds carbon nanotube and concentrated hydrochloric acid, reflux down at 50 ℃, magnetic agitation simultaneously, react 5 h after, be cooled to room temperature, the adding distil water dilution, leave standstill to carbon nanotube precipitation fully, outwell supernatant liquid, lower floor's suspension liquid filtering with microporous membrane, water washing obtains the black filter cake of the carbon nanotube of black to the filtrate pH=7 that drips.Drying obtains product A under the room temperature.
(2) product A and the concentrated nitric acid in the adding step 1 in the three-necked flask of reflux condensate device is housed, reflux down at 50 ℃, magnetic agitation simultaneously, react 3 h after, be cooled to room temperature, adding distil water dilution, leave standstill to the carbon nanotube precipitation fully, outwell supernatant liquid, lower floor's suspension liquid filtering with microporous membrane, water washing obtains the black filter cake of the carbon nanotube of black to the filtrate pH=7 that drips, and drying obtains product B under the room temperature;
(3) with the carbon nanotube of product B after 500 ℃ of calcining 2 h obtain handling under the nitrogen protection condition that obtains in the step (2).
The invention still further relates to a kind of by the prepared surperficial phosphine acidifying water-soluble carbon nanometer tube of aforesaid method.
Described surperficial phosphine acidifying water-soluble carbon nanometer tube, in carbon nano tube surface, the phosphonate derivative of aromatics and carbon nanotube are modified at carbon nano tube surface by the pi-pi accumulation conjugation with phosphonyl group.
Described carbon nanotube is 1:10 ~ 10:1 with the quality of material ratio that the phosphonate derivative of aromatics is thrown in preparation process.
The present invention utilizes the pi-pi accumulation conjugation, with phosphonate group (PO
3H
2) functional group is modified at carbon nano tube surface by non-covalent combination, not only kept the peculiar property of carbon nanotube self, and improved the dispersion stabilization of carbon nanotube in water by the phosphonic acid functional groups good water-solubility.Mechanism of the present invention is clear and definite, reliable, simple, the low price of preparation method, and the carbon nanotube that obtains shows good dissolution dispersity in water.And because-PO
3H
2Advantages such as functional group's possess hydrophilic property is good, coordination ability strong, good biocompatibility, phosphine acidifying water-soluble carbon nanometer tube of the present invention can be applicable to the load of extraordinary aqueous additive, precious metal, the fields, forward position such as structure of bionical film, and in Materials science such as nano-device, fuel cell, biosimulation Enzyme sensor and biomedicine field wide application prospect is arranged.
Below by specific embodiment the present invention is described in further detail, protection scope of the present invention is not subjected to the restriction of specific embodiment, but be defined by the claims.
Description of drawings
The MWNTs(right side of Fig. 1 a unmodified) and naphthalene-and a CNTs(left side that the 1-methylene phosphonic acid is modified) photo in water behind ultrasonic 30 min;
The MWNTs(right side of Fig. 1 b unmodified) and naphthalene-a CNTs(left side that the 1-methylene phosphonic acid is modified) ultrasonic 30 min in water, leave standstill the photo behind 1 h;
The TEM collection of illustrative plates of the MWNTs of Fig. 2 a unmodified;
The TEM collection of illustrative plates of the MWNTs that Fig. 2 b naphthalene-1-methylene phosphonic acid is modified;
Fig. 3 carbon nanotube is corresponding Raman collection of illustrative plates before and after naphthalene-1-methylene phosphonic acid is modified, and curve a is the Raman collection of illustrative plates of the MWNTs of unmodified among the figure, and curve b is the Raman collection of illustrative plates of the MWNTs of naphthalene-1-methylene phosphonic acid modification;
Fig. 4 carbon nanotube is corresponding Fourier's infared spectrum before and after naphthalene-1-methylene phosphonic acid is modified, and curve a is Fourier's infared spectrum of the MWNTs of unmodified among the figure, and curve b is Fourier's infared spectrum of the MWNTs of naphthalene-1-methylene phosphonic acid modification.
Embodiment:
The inventive method is at first carried out the acidifying purification process with carbon nanotube, removes the foreign metal granules of catalyst that exists in the carbon nanotube, removes the oxy radical of carbon nano tube surface again by high-temperature calcination.With the phosphonate derivative of the carbon nanotube handled well and benzene, naphthalene, pyrene, anthracene householder method by ultra-sonic dispersion, phosphonyl group is modified at the CNTs surface, by the pi-pi accumulation conjugation, phosphonyl group is modified at carbon nano tube surface by non-covalent combination, utilize the phosphonic acids negatively charged ion that has good aqueous solubility on the phosphonate derivative to improve the dispersion stabilization of carbon nanotube in water, thereby obtain the water-soluble CNTs of surperficial phosphine acidifying.
By the following method carbon nanotube carried out purifying, calcination processing:
(1) in being housed, 50 ml three-necked flasks of reflux condensate device add 100 ~ 500 mg MWNTs carbon nanotubes and 10 ~ 35 ml concentrated hydrochloric acids (36-38%), reflux down at 50 ℃, magnetic agitation simultaneously, react 5 h after, be cooled to room temperature, add 100 ml distilled water dilutings, leave standstill to carbon nanotube precipitation fully, outwell supernatant liquid, lower floor's suspension liquid filtering with microporous membrane, water washing obtains the black filter cake of the carbon nanotube of black to the filtrate pH=7 that drips.Drying obtains product A under the room temperature.
(2) in being housed, 50 ml three-necked flasks of reflux condensate device add exsiccant product A and 10 ~ 35 ml concentrated nitric acids (65-68%) in the step 1, reflux down at 50 ℃, magnetic agitation simultaneously, react 3 h after, be cooled to room temperature, add 100 ml distilled water dilutings, leave standstill to carbon nanotube precipitation fully, outwell supernatant liquid, lower floor's suspension liquid filtering with microporous membrane, water washing obtains the black filter cake of the carbon nanotube of black to the filtrate pH=7 that drips.Drying obtains product B under the room temperature.
(3) product B that obtains in the step (2) is placed in the tube furnace carbon nanotube that behind calcining 2 h under 500 ℃ of conditions of nitrogen protection, obtains handling well.
Get the MWNTs that 60 mg handle well and be dissolved in 30 ml distilled water, add the Ben Yajiaji phosphonic acids of 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 10 h, fully reaction back filtering with microporous membrane, water washing is to clean, and drying obtains the water-soluble MWNTs of phosphine acidifying under the room temperature.
Embodiment 2
Get SWNTs(treatment process that 6.66 mg handle well with embodiment 1) be dissolved in 30 ml distilled water, the Ben Yajiaji phosphonic acids that adds 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 10 h, fully use filtering with microporous membrane after the reaction, water washing is to clean, and drying obtains the water-soluble SWNTs of phosphine acidifying under the room temperature.
Embodiment 3
Get MWNTs(treatment process that 666 mg handle well with embodiment 1) be dissolved in 300 ml distilled water, naphthalene-1-the methylene phosphonic acid that adds 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 10 h, fully use filtering with microporous membrane after the reaction, water washing is to clean, and drying obtains the water-soluble MWNTs of phosphine acidifying under the room temperature.
Embodiment 4
Get SWNTs(treatment process that 333 mg handle well with embodiment 1) be dissolved in 150 ml distilled water, naphthalene-1-the methylene phosphonic acid that adds 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 10 h, fully use filtering with microporous membrane after the reaction, water washing is to clean, and drying obtains the water-soluble SWNTs of phosphine acidifying under the room temperature.
Embodiment 5
Get SWNTs(treatment process that 60 mg handle well with embodiment 1) be dissolved in 30 ml distilled water, the aminophenylphosphoniacid acid that adds 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 3 h, fully use filtering with microporous membrane after the reaction, water washing is to clean, and drying obtains the water-soluble SWNTs of phosphine acidifying under the room temperature.
Embodiment 6
Get MWNTs(treatment process that 60 mg handle well with embodiment 1) be dissolved in 30 ml distilled water, the aminophenylphosphoniacid acid that adds 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 5 h, fully use filtering with microporous membrane after the reaction, water washing is to clean, and drying obtains the water-soluble MWNTs of phosphine acidifying under the room temperature.
Embodiment 7
Get SWNTs(treatment process that 60 mg handle well with embodiment 1) be dissolved in 30 ml distilled water, pyrene-1-the methylene phosphonic acid that adds 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 7 h, fully use filtering with microporous membrane after the reaction, water washing is to clean, and drying obtains the water-soluble SWNTs of phosphine acidifying under the room temperature.
Embodiment 8
Get MWNTs(treatment process that 60 mg handle well with embodiment 1) be dissolved in 30 ml distilled water, pyrene-1-the methylene phosphonic acid that adds 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 10 h, fully use filtering with microporous membrane after the reaction, water washing is to clean, and drying obtains the water-soluble MWNTs of phosphine acidifying under the room temperature.
Embodiment 9
Get SWNTs(treatment process that 60 mg handle well with embodiment 1) be dissolved in 30 ml distilled water, anthracene-1-the methylene phosphonic acid that adds 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 10 h, fully use filtering with microporous membrane after the reaction, water washing is to clean, and drying obtains the water-soluble SWNTs of phosphine acidifying under the room temperature.
Embodiment 10
Get MWNTs(treatment process that 60 mg handle well with embodiment 1) be dissolved in 30 ml distilled water, anthracene-1-the methylene phosphonic acid that adds 30 ml, 10 mM pH=7 after ultrasonic half an hour, mixture carries out ultrasonic 10 h, fully use filtering with microporous membrane after the reaction, water washing is to clean, and drying obtains the water-soluble MWNTs of phosphine acidifying under the room temperature.
The carbon nanotube that makes according to the inventive method shows good dissolution dispersity in water, the phosphonate derivative of aromatics is modified by non-covalent combination phosphonyl group by the pi-pi accumulation conjugation to its surface:
Fig. 1 a and Fig. 1 b are that carbon nanotube is modified front and back dispersion stabilization contrast photo in the aqueous solution through naphthalene-1-methylene phosphonic acid.Fig. 1 a is the MWNTs(right side of unmodified) the MWNTs(left side modified of and naphthalene-1-methylene phosphonic acid) photo in water behind ultrasonic 30 min; Fig. 1 b is the MWNTs(right side of unmodified) the MWNTs(left side modified of and naphthalene-1-methylene phosphonic acid) ultrasonic 30 min in water, leave standstill the photo behind 1 h.As can be seen from the figure, after one hour the MWNTs(right side of unmodified) sedimentation fully, and the MWNTs(left side that naphthalene-1-methylene phosphonic acid is modified) still present good dispersion stabilization.What this illustrated the success of naphthalene-1-methylene phosphonic acid on the one hand is modified at the MWNTs surface; The modification that phosphonyl group also is described on the other hand effectively raises the dispersion stabilization of MWNTs in the aqueous solution.
Fig. 2 a and Fig. 2 b are carbon nanotube corresponding TEM collection of illustrative plates before and after naphthalene-1-methylene phosphonic acid is modified.Fig. 2 a is the TEM collection of illustrative plates of the MWNTs of unmodified; Fig. 2 b is the TEM collection of illustrative plates of the MWNTs of naphthalene-1-methylene phosphonic acid modification.As can be seen, the structure of carbon nanotube does not have destroyedly before and after modifying from the transmission electron microscope picture, and carbon nanotube still keeps its original height length-to-diameter ratio.
Fig. 3 is carbon nanotube corresponding Raman collection of illustrative plates before and after naphthalene-1-methylene phosphonic acid is modified.Curve a represents the Raman collection of illustrative plates of the MWNTs of unmodified among the figure; Curve b represents the Raman collection of illustrative plates of the MWNTs of naphthalene-1-methylene phosphonic acid modification.D mould and the G mould of the MWNTs of unmodified appear at 1347 cm respectively
-1With 1573 cm
-1The place.D mould and the G mould of MWNTs appeared at 1360 cm respectively after naphthalene-1-methylene phosphonic acid was modified
-1With 1590 cm
-1The place.This shows that tangible red shift has all taken place two characteristic peaks of phosphine acidifying MWNTs in Raman spectrum, show to have certain effect between MWNTs and naphthalene-1-methylene phosphonic acid.
Fig. 4 is carbon nanotube corresponding Fourier's infared spectrum before and after naphthalene-1-methylene phosphonic acid is modified.Curve a represents Fourier's infared spectrum of the MWNTs of unmodified among the figure; Curve b represents Fourier's infared spectrum of the MWNTs of naphthalene-1-methylene phosphonic acid modification.Modify in the infared spectrum of back MWNTs 1072 cm at naphthalene-1-methylene phosphonic acid
-1The PO of place
3The appearance of characteristic peak, what confirmed on the one hand phosphonyl group success is modified at the MWNTs surface; The skew that has also confirmed characteristic peak in the phosphonic acids MWNTs Raman collection of illustrative plates on the other hand is because the influence of phosphonyl group.
Claims (10)
1. the preparation method of a surperficial phosphine acidifying water-soluble carbon nanometer tube, it is characterized in that, carbon nanotube after purifying and the calcination processing is put in the aqueous solution of phosphonate derivative of aromatics, ultra-sonic dispersion 3 ~ 10 hours, filter and repetitive scrubbing, 25 ~ 40 ℃ of following dryings obtain surperficial phosphine acidifying water-soluble carbon nanometer tube.
2. the preparation method of surperficial phosphine acidifying water-soluble carbon nanometer tube according to claim 1 is characterized in that described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
3. the preparation method of surperficial phosphine acidifying water-soluble carbon nanometer tube according to claim 1 is characterized in that described aromatics is benzene, naphthalene, pyrene or anthracene, or their derivative.
4. the preparation method of surperficial phosphine acidifying water-soluble carbon nanometer tube according to claim 1, the phosphonate derivative that it is characterized in that described aromatics is phenyl-phosphonic acid, substituted-phenyl phosphonic acids, phenylalkyl phosphonic acids or substituted-phenyl alkyl phosphonic acid, naphthyl phosphonic acids, substituted naphthyl phosphonic acids, naphthyl alkyl phosphonic acid or substituted naphthyl alkyl phosphonic acid, pyrenyl phosphonic acids, replacement pyrenyl phosphonic acids, pyrenyl alkyl phosphonic acid or replacement pyrenyl alkyl phosphonic acid, anthryl phosphonic acids, replacement anthryl phosphonic acids, anthryl alkyl phosphonic acid or replacement anthryl alkyl phosphonic acid.
5. the preparation method of surperficial phosphine acidifying water-soluble carbon nanometer tube according to claim 4, the phosphonate derivative that it is characterized in that described aromatics is Ben Yajiaji phosphonic acids, styroyl phosphonic acids, aminophenyl phosphonic acids, naphthalene-1-methylene phosphonic acid, naphthalene-5-methylene phosphonic acid, pyrene-1-methylene phosphonic acid, pyrene-4-methylene phosphonic acid, anthracene-1-methylene phosphonic acid or anthracene-10-methylene phosphonic acid.
6. the preparation method of surperficial phosphine acidifying water-soluble carbon nanometer tube according to claim 1 is characterized in that the mass ratio of the phosphonate derivative of described carbon nanotube and aromatics is: 1:10 ~ 10:1.
7. the preparation method of surperficial phosphine acidifying water-soluble carbon nanometer tube according to claim 1 is characterized in that described carbon nanotube purifying, calcining processing method are:
(1) in being housed, the three-necked flask of reflux condensate device adds carbon nanotube and concentrated hydrochloric acid, reflux down at 50 ℃, magnetic agitation simultaneously, react 5 h after, be cooled to room temperature, adding distil water dilution, leave standstill to the carbon nanotube precipitation fully, outwell supernatant liquid, lower floor's suspension liquid filtering with microporous membrane, water washing obtains the black filter cake of the carbon nanotube of black to the filtrate pH=7 that drips, and drying obtains product A under the room temperature;
(2) product A and the concentrated nitric acid in the adding step 1 in the three-necked flask of reflux condensate device is housed, reflux down at 50 ℃, magnetic agitation simultaneously, react 3 h after, be cooled to room temperature, adding distil water dilution, leave standstill to the carbon nanotube precipitation fully, outwell supernatant liquid, lower floor's suspension liquid filtering with microporous membrane, water washing obtains the black filter cake of the carbon nanotube of black to the filtrate pH=7 that drips, and drying obtains product B under the room temperature;
(3) with the carbon nanotube of product B after 500 ℃ of calcining 2 h obtain handling under the nitrogen protection condition that obtains in the step (2).
8. the surperficial phosphine acidifying water-soluble carbon nanometer tube of a method according to claim 1 preparation.
9. surperficial phosphine acidifying water-soluble carbon nanometer tube according to claim 8, it is characterized in that described carbon nano tube surface, the phosphonate derivative of aromatics and carbon nanotube are modified at carbon nano tube surface by the pi-pi accumulation conjugation with phosphonyl group.
10. surperficial phosphine acidifying water-soluble carbon nanometer tube according to claim 8 is characterized in that the quality of material ratio that the described carbon nanotube and the phosphonate derivative of aromatics are thrown in is 1:10 ~ 10:1 in preparation process.
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| CN113675387A (en) * | 2021-07-15 | 2021-11-19 | 南京信息工程大学 | Sulfur-carbon composite material, preparation method and application thereof |
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Application publication date: 20110810 |