CN102153071A - Large-scale single-walled carbon nanotube purification method based on supramolecular functionalization - Google Patents
Large-scale single-walled carbon nanotube purification method based on supramolecular functionalization Download PDFInfo
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Abstract
The invention relates to a large-scale single-walled carbon nanotube purification method based on supramolecular functionalization. The method comprises the following steps of: adding a single-walled carbon nanotube raw material and biological glycan into water so as to fully disperse single-walled carbon nanotubes contained in the raw material into the water solution, wherein the mass ratio of the biological glycan to the single-walled carbon nanotube raw material is jointly determined by the molecular weight and the concentration of chitosan, the acidity and the alkalinity of the solution as well as the purity of the single-walled carbon nanotube; removing precipitates in the water solution after dispersion to obtain a dispersion liquid of the single-walled carbon nanotubes; and removing biological glycan molecules adhered to the surfaces of the single-walled carbon nanotubes to obtain purified single-walled carbon nanotubes. Through the method provided by the invention, the efficient purification and the large-scale separation of the single-walled carbon nanotubes can be realized, and the surface structures of the single-walled carbon nanotubes can not be damaged. Meanwhile, the used physical method is mild, dispersion and purification are finished together, the treatment process is friendly to the environment, and no toxic and harmful matters are used or produced. The obtained carbon nanotube dispersion liquid is a high-concentration aqueous solution, can be produced in large scale, and is easy to preserve and use.
Description
Technical field
The present invention relates to a kind of purification process of Single Walled Carbon Nanotube, relate in particular to a kind of efficient, harmless, extensive Single Walled Carbon Nanotube and disperse purification treating method, belong to nano material and disperse the purification technique field based on the supramolecule functionalization.
Background technology:
Along with the development of carbon nanotube production technology, present hundred tonnes carbon nano tube growth technology has realized industrial application.Because the optics of carbon nanotube excellence, electricity, characteristics such as mechanics, it is at photoelectron, the semiconductor solar device, every field such as aerospace high performance material have broad application prospects.
But the application of carbon current nanotube mainly concentrates on the multi-wall carbon nano-tube tube material.And Single Walled Carbon Nanotube is because the condition harshness of its growth, the single wall carbon nano pipe purity of extensive growth is lower, can mix is difficult to the low density agraphitic carbon (for example, graphite granule etc.) removed in a large number, and the existence of these agraphitic carbons has had a strong impact on the performance of Single Walled Carbon Nanotube premium properties.Therefore, how low-cost, the purifying of realizing Single Walled Carbon Nanotube efficiently has very important meaning for the industrial application of Single Walled Carbon Nanotube.
The purification treating method of existing Single Walled Carbon Nanotube has a variety of, comprises the chemical solvents etch that is widely used at present, high-temperature heat treatment method, the combination of physical filtering method and these methods etc.But, these method complicated operations, cost height; efficient is low, can't obtain high-purity Single Walled Carbon Nanotube on a large scale, and the surface tissue of meeting havoc Single Walled Carbon Nanotube; reduce the various aspects of performance of Single Walled Carbon Nanotube, and organic efficiency is low, does not therefore have actual commercial value.
Summary of the invention
The object of the present invention is to provide a kind of efficient, harmless, large-scale Single Walled Carbon Nanotube purification process, thereby overcome deficiency of the prior art based on the supramolecule functionalization.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization is characterized in that this method is:
Get the Single Walled Carbon Nanotube raw material and biological glycan adds in the entry, make contained Single Walled Carbon Nanotube fully dispersion in the aqueous solution in the described raw material, wherein, the mass ratio of biological glycan and Single Walled Carbon Nanotube raw material is determined jointly by the molecular weight of chitosan and the purity of concentration, solution acid-basicity and Single Walled Carbon Nanotube, remove the precipitation in the aqueous solution after the dispersion, obtain the dispersion liquid of Single Walled Carbon Nanotube, remove the biological glycan molecule that is adsorbed on the Single Walled Carbon Nanotube surface again, make the Single Walled Carbon Nanotube of purifying.
Preferably, described pH value of aqueous solution is 2～13.
Further, if the biological glycan that adopts is a chitosan, then described pH value of aqueous solution is 2-7.
Further, described biological glycan is any one or two or more combination of polycation biological polyoses, polyanion biological polyoses and poly-nonionic biological polyoses.
It in this method at least a Single Walled Carbon Nanotube raw material abundant dispersive in the aqueous solution that makes that adopts in mechanical stirring, ball milling and the ultrasonic processing method.
The process that obtains the Single Walled Carbon Nanotube dispersion liquid in this method is specially: the aqueous solution that will be dispersed with the Single Walled Carbon Nanotube raw material leaves standstill under room temperature, and then this aqueous solution of centrifugal treating discards precipitation, and supernatant liquor is the Single Walled Carbon Nanotube dispersion liquid.
In this method be by filter repeatedly, centrifugal-biological glycan molecule of disperseing the mode of circulation or chemical oxidation treatment Single Walled Carbon Nanotube dispersion liquid to remove to be adsorbed on the Single Walled Carbon Nanotube surface.
The concentration of contained Single Walled Carbon Nanotube raw material is less than or equal to 0.1g/ml in the described aqueous solution.
As preferred embodiment a kind of, this method comprises the steps:
A. getting mass ratio and be 0.1～10 Single Walled Carbon Nanotube raw material and biological glycan adds in the entry, and accompany by mechanical stirring or ball milling or supersound process, make contained Single Walled Carbon Nanotube fully dispersion in the aqueous solution in the described raw material, the concentration≤0.1g/ml of contained Single Walled Carbon Nanotube raw material in this aqueous solution;
B. step a obtained aqueous solution is left standstill 15min～48h under room temperature, then with rotating speed centrifugal treating 5min～10h of 500～30000rpm, discard precipitation, supernatant liquor is the Single Walled Carbon Nanotube dispersion liquid;
C. adopt and filter repeatedly or centrifugal-dispersion round-robin mode treatment step b gained Single Walled Carbon Nanotube dispersion liquid, remove the biological glycan molecule that is adsorbed on the Single Walled Carbon Nanotube surface, make the Single Walled Carbon Nanotube of purifying.
This method also comprises following process: adjust Single Walled Carbon Nanotube raw material and biological glycan kind, and the mass ratio of adjustment Single Walled Carbon Nanotube raw material and biological glycan, make a series of Single Walled Carbon Nanotube dispersion liquids, should a series of Single Walled Carbon Nanotube dispersion liquids 30～150 ℃ respectively drying treatment get a series of solid samples, detect these a series of solid samples by Raman spectrum and/or electron microscope, thereby determine to produce the Single Walled Carbon Nanotube raw material-biological glycan combo of optimum purification effect and the mass ratio of Single Walled Carbon Nanotube raw material and biological glycan.
Compared with prior art, the invention has the advantages that: utilize in aqueous phase system Single Walled Carbon Nanotube surface the feature absorption of biological glycan molecule to be better than comprising the mechanism of the unformed impurity particle of graphite granule, by with the method for Single Walled Carbon Nanotube stable dispersion in the aqueous solution of biological glycan, thereby with Single Walled Carbon Nanotube and impurities in raw materials particle separation, realized the purifying of Single Walled Carbon Nanotube, isolating environment that this method adopted and operation are gentle, can not cause the destruction of surface tissue to Single Walled Carbon Nanotube, and do not use any hazardous and noxious substances, disperse purifying to finish in the lump, the process environmental protection, gained Single Walled Carbon Nanotube dispersion liquid is a high density water-based solution, can be mass-produced, and be easy to preserve and use.
Description of drawings
Fig. 1 be adopt mass ratio by 65: 35～35: 65 chitosan and Single Walled Carbon Nanotube raw material obtain the processing of Single Walled Carbon Nanotube dispersion liquid drying the Raman spectrogram of formation solid sample, after the mass ratio reduction with chitosan and Single Walled Carbon Nanotube, the Single Walled Carbon Nanotube of stable dispersion is at 1300cm
-1About Raman peaks reduce rapidly, and the intensity of this peak position is corresponding with foreign matter content, along with impurity is effectively separated, the intensity of its Raman peaks also reduces rapidly;
Fig. 2 a is the electromicroscopic photograph of purification process Single Walled Carbon Nanotube raw material not, and scale 500nm can be seen by this figure having the spherical impurity particle of small size in the raw material in a large number;
Fig. 2 b is the electromicroscopic photograph of Single Walled Carbon Nanotube after the purification process, and scale 500nm can see that by this figure purification process of the present invention can effectively remove the contained impurity particle of raw material;
Fig. 3 a is the transmission electron microscope photo that surface adsorption has the Single Walled Carbon Nanotube of biological glycan molecule;
Fig. 3 b is a transmission electron microscope photo of removing the biological glycan molecule Single Walled Carbon Nanotube afterwards that is adsorbed in the surface.
Embodiment
At deficiency of the prior art, this case contriver is through studying for a long period of time and putting into practice discovery, in aqueous phase system with gelling gum, chitosan, xanthan gum, hyaluronic acid, biological glycan such as agarose twines or the absorption of nano-micelle parcel is better than the agraphitic carbon of random pattern and the absorption on graphite granule surface the feature absorption of carbon nanotube at the supramolecule spiral of carbon nano tube surface, the strong and weak difference of this adsorptive power cause biological glycan to have the carbon nano tube surface of being preferentially adsorbed on and make its in the aqueous solution stable dispersion and with the isolating effect of impurity particle.The reason that produces above-mentioned phenomenon may be:
Single Walled Carbon Nanotube has 100% and is exposed to surperficial atom, and its solution has the general characteristic of polymer macromolecule, and simultaneously, the surface tissue of its similar graphite linings makes its surface have very strong hydrophobic property, and causes it to be difficult to disperse.In general, the dispersion of realization Single Walled Carbon Nanotube need obtain stable dispersion soln to its system's free energy of Single Walled Carbon Nanotube surface reduction by the molecular adsorption that contains non-polar group in the aqueous solution.Moreover because smooth surface and extra small diameter and overlength axial length that Single Walled Carbon Nanotube has approximate graphite linings structure, adsorbed molecules often can form specific ordered structure and obtain lower system's free energy on the Single Walled Carbon Nanotube surface.But, for the agraphitic carbon impurity particle, its geometric shape is unordered, the special surface structure that does not have Single Walled Carbon Nanotube, even graphite granule, because the atom proportion that its surface exposes is not as good as Single Walled Carbon Nanotube, and its geometry is also more orderly not as good as Single Walled Carbon Nanotube, its surface adsorption ability also is weaker than Single Walled Carbon Nanotube far away.
According to above-mentioned discovery, this case contriver has proposed by controlling biological glycan and the mass ratio that contains the Single Walled Carbon Nanotube raw material of impurity particle, reach the preferentially adsorbed of Single Walled Carbon Nanotube to biological glycan molecule, thereby in aqueous phase system, obtain stable existence, high-quality Single Walled Carbon Nanotube-biological glycan supramolecular structure, thereby impurity particle then can't stable dispersion not form precipitation owing to fully adsorb biological glycan molecule, so just realized efficient, harmless, extensive Single Walled Carbon Nanotube purifying.
Further; biological glycan molecule is at present in foodstuffs industry; biomedical sector uses in a large number; it is with low cost; environmental nonpollution is green sub powder and physiologically acceptable tissue engineering material efficiently, thereby therefore utilizes the singularity of biomolecules absorption configuration to realize Single Walled Carbon Nanotube is disperseed optionally to realize that its purifying has simply; harmless, the using value of large-scale production.
Method of the present invention can comprise following processing step:
Step 1, get the Single Walled Carbon Nanotube raw material and biological glycan adds in the entry, by regulating the mass ratio of Single Walled Carbon Nanotube raw material and biological glycan, make the biological glycan molecule of contained Single Walled Carbon Nanotube preferentially adsorbed in the described raw material, thereby in the aqueous solution, fully disperse, and impurity particle can't stable dispersion precipitation not occur owing to fully adsorb biological glycan molecule.
In this step, it should be noted that:
Need 10mL and just have enough volumes to realize dispersion treatment effectively that promptly, the concentration of aqueous solution of Single Walled Carbon Nanotube raw material should be below 0.1g/mL with the aqueous solution of upper volume for the 1g Single Walled Carbon Nanotube;
For Single Walled Carbon Nanotube is fully disperseed in the aqueous solution, also can accompany by stirring and/or ball milling and/or ultrasonic dispersing and handle operation;
Adopt biological glycan to disperse the purifying Single Walled Carbon Nanotube need realize in the scope of pH value 2～13 usually, especially for chitosan, its dispersion treatment Single Walled Carbon Nanotube should realize in acidity is the scope of pH value 2～7;
Because it is different that different production methods and manufacturer produce Single Walled Carbon Nanotube raw material impurity content, realize the essential corresponding adjustment raw materials quality ratio of purification effect of optimum Single Walled Carbon Nanotube, in general, the mass ratio of Single Walled Carbon Nanotube raw material and biological glycan can be preferably 0.1～1.
Step 2, the dispersion soln of the final gained Single Walled Carbon Nanotube of step 1 raw material is left standstill the back centrifugal treating, remove sedimentary impurity particle, obtain the Single Walled Carbon Nanotube dispersion liquid.
In this step, after preferably the dispersion soln of Single Walled Carbon Nanotube raw material at room temperature being left standstill 15min to 48h, handle 5min to 10h with the rotating speed high speed centrifugation of 500rpm to 30000rpm again, fully precipitate to impurity particle, then the gained supernatant liquor is the Single Walled Carbon Nanotube dispersion liquid.
Step 3, with the Single Walled Carbon Nanotube dispersion liquid by filter repeatedly or centrifugal-disperse circular treatment to remove the biological glycan molecule of surface adsorption, the final Single Walled Carbon Nanotube that obtains purifying, it is dispersed in the aqueous solution with higher concentration, is easy to preserve and use.
In addition, the inventive method also can further comprise following operation: adjust Single Walled Carbon Nanotube raw material and biological glycan kind, and the mass ratio of adjustment Single Walled Carbon Nanotube raw material and biological glycan, make a series of Single Walled Carbon Nanotube dispersion liquids, should a series of Single Walled Carbon Nanotube dispersion liquids 30～150 ℃ respectively drying treatment get a series of solid samples, detect these a series of solid samples by Raman spectrum and/or electron microscope, observe biological glycan molecule at the adsorption rate on Single Walled Carbon Nanotube surface and absorption shape etc., thereby determine to produce the Single Walled Carbon Nanotube raw material-biological glycan combo of optimum purification effect and the mass ratio of Single Walled Carbon Nanotube raw material and biological glycan.
Biological glycan of the present invention can be selected gelling gum for use, chitosan, xanthan gum, hyaluronic acid, polycations such as agarose, polyanion, poly-nonionic biological polyoses.
Need to prove that method of the present invention is also applicable to other inorganic simple substance (metal, nonmetal), compound (oxide compound, sulfide, selenide, telluride, the muriate etc.) monodimension nanometer material that forms, as the purifying of nano wire.
Below in conjunction with accompanying drawing and some preferred embodiments technical scheme of the present invention is elaborated.
Embodiment 1
With 0.35,0.40,0.55,0.60,0.65g chitosan (molecular weight 10,000 dalton) be dissolved in respectively in three parts of 10mL aqueous hydrochloric acids, the pH value is adjusted into 3, again with 0.65,0.60,0.45,0.40,0.35g the raw material Single Walled Carbon Nanotube adds respectively in above five parts of chitosan solutions, ultra-sonic dispersion 120 minutes, left standstill 5 hours, got under the dispersion liquid 20000rpm rotating speed centrifugal 1 hour, get supernatant liquor, dry, purity with Raman spectrum and the contained Single Walled Carbon Nanotube of each supernatant liquor of scanning electronic microscope comparative analysis, determine best proportion, prepared supernatant liquor cleans with the 10L water filtration, and cleaning finishes, carbon nano tube surface lifeless matter molecule, drying gets complete purifying carbon nano-tube sample.
Embodiment 2
With gelling gum and xanthan gum mixed by 10: 1, get mixture 0.4,0.3,0.2,0.1g add respectively in the 100mL water, the heated and stirred dissolving, cooling, in every part of solution, add 0.5g Single Walled Carbon Nanotube raw material then respectively, 1000rpm high-speed stirring 10 hours, left standstill 2 hours, and got dispersion liquid 3000rpm centrifugation 2 hours, get supernatant liquor, determine proper ratio in conjunction with Raman spectrum and sem observation, then supernatant liquor is caused no bubble with the 30% concentration hydrogen peroxide dipping of 500mL and discharge, filter and collect Single Walled Carbon Nanotube, filter the remaining ion in Single Walled Carbon Nanotube surface with the 1L deionized water, drying gets the purifying Single Walled Carbon Nanotube.
The inventive method can not cause any destruction to the surface tissue of Single Walled Carbon Nanotube, employed physical method gentleness, disperse purifying to finish in the lump, the treating processes environmental protection, do not use and produce any hazardous and noxious substances, gained carbon nanotube dispersion liquid is the aqueous solution of high density, can be mass-produced, and is easy to preserve and use.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization is characterized in that this method is:
Get the Single Walled Carbon Nanotube raw material and biological glycan adds in the entry, make contained Single Walled Carbon Nanotube fully dispersion in the aqueous solution in the described raw material, wherein, the mass ratio of biological glycan and Single Walled Carbon Nanotube raw material is determined jointly by the molecular weight of chitosan and the purity of concentration, solution acid-basicity and Single Walled Carbon Nanotube, remove the precipitation in the aqueous solution after the dispersion, obtain the dispersion liquid of Single Walled Carbon Nanotube, remove the biological glycan molecule that is adsorbed on the Single Walled Carbon Nanotube surface again, make the Single Walled Carbon Nanotube of purifying.
2. the extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization according to claim 1 is characterized in that described pH value of aqueous solution is 2～13.
3. the extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization according to claim 1 is characterized in that, if the biological glycan that adopts is a chitosan, then described pH value of aqueous solution is 2-7.
4. the extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization according to claim 1, it is characterized in that described biological glycan is any one or two or more combination of polycation biological polyoses, polyanion biological polyoses and poly-nonionic biological polyoses.
5. the extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization according to claim 1, it is characterized in that, be at least a Single Walled Carbon Nanotube raw material abundant dispersive in the aqueous solution that makes that adopts in mechanical stirring, ball milling and the ultrasonic processing method in this method.
6. the extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization according to claim 1, it is characterized in that, the process that obtains the Single Walled Carbon Nanotube dispersion liquid in this method is specially: the aqueous solution that will be dispersed with the Single Walled Carbon Nanotube raw material leaves standstill under room temperature, this aqueous solution of centrifugal treating then, discard precipitation, supernatant liquor is the Single Walled Carbon Nanotube dispersion liquid.
7. the extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization according to claim 1, it is characterized in that, in this method be by filter repeatedly, centrifugal-biological glycan molecule of disperseing the mode of circulation or chemical oxidation treatment Single Walled Carbon Nanotube dispersion liquid to remove to be adsorbed on the Single Walled Carbon Nanotube surface.
8. the extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization according to claim 1 is characterized in that the concentration of contained Single Walled Carbon Nanotube raw material is less than or equal to 0.1g/ml in the described aqueous solution.
9. the extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization according to claim 1 is characterized in that this method comprises the steps:
A. getting mass ratio and be 0.1～10 Single Walled Carbon Nanotube raw material and biological glycan adds in the entry, and accompany by mechanical stirring or ball milling or supersound process, make contained Single Walled Carbon Nanotube fully dispersion in the aqueous solution in the described raw material, the concentration≤0.1g/ml of contained Single Walled Carbon Nanotube raw material in this aqueous solution;
B. step a obtained aqueous solution is left standstill 15min～48h under room temperature, then with rotating speed centrifugal treating 5min～10h of 500～30000rpm, discard precipitation, supernatant liquor is the Single Walled Carbon Nanotube dispersion liquid;
C. adopt and filter repeatedly or centrifugal-dispersion round-robin mode treatment step b gained Single Walled Carbon Nanotube dispersion liquid, remove the biological glycan molecule that is adsorbed on the Single Walled Carbon Nanotube surface, make the Single Walled Carbon Nanotube of purifying.
10. according to claim 1 or 8 described extensive Single Walled Carbon Nanotube purification process based on the supramolecule functionalization, it is characterized in that, this method also comprises following process: adjust Single Walled Carbon Nanotube raw material and biological glycan kind, and the mass ratio of adjustment Single Walled Carbon Nanotube raw material and biological glycan, make a series of Single Walled Carbon Nanotube dispersion liquids, should a series of Single Walled Carbon Nanotube dispersion liquids 30～150 ℃ respectively drying treatment get a series of solid samples, detect these a series of solid samples by Raman spectrum and/or electron microscope, thereby determine to produce the Single Walled Carbon Nanotube raw material-biological glycan combo of optimum purification effect and the mass ratio of Single Walled Carbon Nanotube raw material and biological glycan.
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| CN103112848A (en) * | 2013-03-08 | 2013-05-22 | 厦门大学 | Method for preparing graphene |
| CN104211042B (en) * | 2014-08-07 | 2016-03-30 | 无锡东恒新能源科技有限公司 | A kind of method removing metallic impurity in carbon nanotube |
| CN111747400A (en) * | 2019-03-26 | 2020-10-09 | 中国科学院物理研究所 | Method for improving concentration of monodisperse carbon nanotube dispersion liquid |
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Application publication date: 20110817 |