CN101538032B - Method for preparing high-concentration stable carbon nano-tube aqueous solutions - Google Patents
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Abstract
The invention discloses a method for preparing high-concentration stable carbon nano-tube aqueous solution. The method comprises the steps of using an ultrasonic probe to oxidize carbon nano-tubes in a mixed strong-acid solution, filtering the solution, washing and drying filtered substances, using the ultrasonic probe to disperse the dried filtered substances in water and obtaining a uniform stable black solution. The method does not need to introduce surfactant, and the concentration of the carbon nano-tubes in the obtained aqueous solution reaches up to 0.5 mg/ml. Observation under a scanning electron microscope shows that most of the carbon nano-tubes in the solution are open in state and clear in tubular structure, and hollow tubular structures are maintained well. Dynamic light scattering test shows that the carbon nano-tubes are about 140 nanometers in mean effective diameter and 70 to 350 nanometers in distribution range. The stability of the carbon nano-tube aqueous solution prepared by the method can reach two weeks. The method provides guarantee for the further application of the carbon nano-tubes in the field of biological medicine.
Description
Technical field:
The present invention relates to a kind of preparation method and application that is used for the carbon nano-tube aqueous solutions of biomedical sector.
Background technology:
Carbon nanotube is one type of tubular carbon material with perfect graphite-structure, and diameter is generally from several nanometers to tens nanometer.Carbon nanotube has good electroconductibility, electromagnetic property and excellent mechanical property.There is wide application prospect in many aspects in the multiple excellent properties that itself has.But; The carbon nanotube of virgin state has strong-hydrophobicity, has simultaneously extremely strong agglomeration each other, therefore in water and organic solvent, macromolecule matrix, all is difficult to disperse; Be prone to assemble agglomerating; Generally be insoluble to any solvent, hindered it is carried out molecular level research and operational applications, also be difficult to it is applied to biomedical sector.
For the excellent properties with carbon nanotube is applied to biomedicine field, carbon nanotube is carried out surface treatment, it is disperseed in water, form the stable suspersion solution of carbon nanotube, have great importance for further biomedical applications.Adopt which kind of means that carbon nanotube is modified with functionalization and become the critical problem that carbon nanotube moves towards practicality.
The port of primary carbon nanotube seals.Under given conditions, there are some lattice imperfections in carbon nano tube surface.A lot of researchs adopt method for oxidation to make the port of carbon nanotube become open state by closed state, simultaneously in the oxidation of lattice imperfection place, introduce oxy radicals such as carboxyl with the surface at the carbon nanotube port, increase the wetting ability of carbon nanotube.
So far, carbon nanotube being carried out the many means of wetting ability modification application is covalent modification methods.General commonly used covalent modification method be with strong acid with carbon nanotube oxidation opening, and be cut into short tube, make its terminal or (with) carboxyl on the defect sites band of sidewall.For example, make carbon nanotube become open state, increase that it is water-soluble through long-time backflow the in hot salpeter solution; Also have through the mixing solutions long time treatment with the vitriol oil and nitric acid, ultrasonic down auxiliary, SWCN is prescinded to 100-300nm, carboxyl is introduced on the surface simultaneously; Increased solubleness (J.Liu, A.G.Rinzler, H.Dai, the J.H.Hafher of carbon nanotube in the aqueous solution; R.K.Bradley, P.J.Boul, A.Lu, T.Iverson; K.Shelimov, C.B.Huffman, F.Rodriguez-Macias, Y.-S.Shon and T.R.Lee D.T.Colbert; R.E.Smalley FullerenePipesscience 1998,280,1253-56).Mitra S study group utilizes microwave and mixed strong acids to disperse SWNT (Wang, Y, Iqbal; Z., Mitra, S.J.Rapidly Functionalized; Water-DispersedCarbon Nanotubes at High ConcentrationJ.Am.Chem.Soc.2006,128 (1), 95-99.); Introduce carboxyl and sulfonic group in carbon nano tube surface, obtained the carbon nano-tube aqueous solutions of high density.Find after the surface-element analysis, introduce a carboxyl on per 3 carbon atoms, introduce a sulfonic group on per 10 carbon atoms.Scanning electron microscopic observation diminishes to the diameter of carbon nanotube a little to some extent.The dynamic laser light scattering experimental analysis obtains particulate size in the solution at 3nm～800nm.
Except the method for oxidation, also there is research to adopt some other method that carbon nanotube is distributed in the aqueous solution, for example; Through water miscible macromole being wrapped in around the carbon nanotube, can make the carbon nanotube of complete length be distributed to (Zorbas V, Smith AL in the solution; Xie H, Ortiz-Acevedo A, Dalton AB; DieckmannGR; Draper RK, Baughman RH, Musselman IH Importance of Aromatic Content forPeptide/Single-Walled Carbon Nanotube Interactions J Am Chem Soc.2005 Sep7; 127 (35): 12323-8).Study group's report is also arranged; Under ultrasound condition, utilize BSA can obtain solution (the Karajanagi SS of stable SWCN as dispersion agent; Yang H, Asuri P, Sellitto E; Dordick JS, Kane RS Protein-assisted solubilization of single-walled carbonnanotubes Langmuir.2006Feb 14; 22 (4): 1392-5).Also having study group to utilize dna molecular to wait modifies and dispersing Nano carbon tubes.
So far, the overwhelming majority's the ultrasonic modifying method of concentrated acid (Nanotubes from Surface Modification JAm Chem Soc.2002 Oct 23; 124 (42): 12418-9; Lee GW, Kumar S Dispersion of NitricAcid-Treated SWNTs in Organic Solvents and Solvent Mixtures.Effect ofnicotinamide and urea on the solubility of riboflavin in various solvents.J Phys ChemB Condens Matter Mater Surf Interfaces Biophys.2005 Sep 15; 109 (36): 17128-33; LuQ, Keskar G, Ciocan R, Rao R, Mathur RB., Rao AM., Larcom LL.Determination ofCarbon Nanotube Density by Gradient Sedimentation J Phys Chem is Dec7 B.2006; 110 (48): the carbon nano-tube aqueous solutions concentration that 24371-6) obtains is still lower, generally at 0.01～0.2mg/ml, and needs the auxiliary of tensio-active agent or biomacromolecule usually.
Summary of the invention:
The objective of the invention is to remedy the blank of prior art, under the condition of not introducing tensio-active agent, a kind of method of the carbon nano-tube aqueous solutions for preparing high-concentration stable is provided and the carbon nano-tube aqueous solutions of the high-concentration stable for preparing with this method.
The present invention provides a kind of method for preparing high-concentration stable carbon nano-tube aqueous solutions, be with carbon nanotube in mixed strong acids solution with ultrasound probe carry out oxide treatment, filtration and washing leach thing and the oven dry leach thing after with its in water with obtaining uniform and stable dark solution after the ultrasound probe dispersion treatment.
Wherein, the volume proportion of the diameter of said ultrasound probe and mixing solutions is 1: 20～100.
Said mixed strong acids solution is prepared in 2: 1 ratio by the vitriol oil and concentrated nitric acid and is formed; The volume ratio scope of said carbon nanotube weight and mixing acid is 1: 5～2: 1 (mg: ml).
Said oven dry is meant and is dried to constant weight with leaching thing, and said drying temperature scope is room temperature～70 ℃.
Said washing leaches thing and is meant that water will leach thing washing to filtrating for neutral.
The working hour that said ultrasound probe carries out oxide treatment is 30s～12000s, and operating power is 500w～1200w; The working hour that said ultrasound probe carries out the dispersion treatment second time is 10s～15000s, and operating power is 200w～1200w.
Concrete, this method may further comprise the steps:
1) carbon nanotube is added in the mixed acid solution, carries out oxide treatment, obtain aterrimus solution with ultrasound probe;
2) dark solution is filtered, washing leaches thing to filtrating for neutral;
3) will leach thing dries to the constant weight powdered;
4) powder is added to the water, carries out dispersion treatment, obtain dark solution and be carbon nano-tube aqueous solutions with ultrasound probe.
Wherein, Said carbon nanotube and mixed acid solution ratio are 1: 0.8～1.5; The diameter of said ultrasound probe and the volume proportion of mixing solutions are 1: 20～30; Said drying temperature is 60～70 ℃, and the working hour that said ultrasound probe carries out oxide treatment is 30s～60s, and operating power is 1000w; The working hour that said ultrasound probe carries out the dispersion treatment second time is 10s～60s, and operating power is 1000w.
The present invention provides a kind of high-concentration stable carbon nano-tube aqueous solutions; Be to adopt above method to prepare; Said carbon nano-tube aqueous solutions meets the following conditions: concentration is between being less than or equal between the 0.5mg/ml greater than 0.2mg/ml, and at least 2 weeks of steady time of solution.
The present invention has adopted the oxidation of mixing concentrated acid to handle carbon nanotube with the ultrasonic method that combines; Under the condition of not introducing tensio-active agent; Can prepare high density, stable carbon nano-tube aqueous solutions; The inventive method is used in experimental verification, can obtain the aqueous solution of carbon nanotube concentration up to 0.5mg/ml; ESEM is observed down, and the how opening-like attitude of carbon nanotube wherein, the length of carbon nanotube become between 200～1000nm about by primary 50 μ m, and caliber is about 30nm, and tubular structure is clear, and hollow tubular structures is by maintenance well; The dynamic laser light scattering test shows the mean effective diameter of carbon nanotube about 140nm, and distribution range is 70～350nm; After the carbon nano normal temperature was placed 2 time-of-weeks, naked eyes were not observed tangible carbon nanotube aggregate and are occurred, and suspension-s does not change at the absorbance at ultraviolet 253nm place, and stability can reach for 2 weeks.
Description of drawings:
Fig. 1 is carbon nanotube dispersion state photo in water; A is the multi-walled carbon nano-tubes dispersive state in water with the ultrasonic tank supersound process among the wherein left figure; B is for using the multi-walled carbon nano-tubes aqueous solution that obtains after the probe supersound process.Right figure adopts the mixed strong acids oxidation to combine the carbon nano-tube aqueous solutions of the different concns of supersound process preparation; Wherein in No. 1 cup for concentration is the carbon nano-tube aqueous solutions of 0.5mg/ml, No. 2 cups are the carbon nano-tube aqueous solutions of 0.15mg/ml concentration, No. 3 cups are the carbon nano-tube aqueous solutions of 0.05mg/ml concentration.
Fig. 2 is the absorption spectrum of the multi-walled carbon nano-tubes aqueous solution of the present invention.
The multi-walled carbon nano-tubes electromicroscopic photograph of Fig. 3 for coming out from aqueous solution deposition.(a) dysoxidative multi-walled carbon nano-tubes electromicroscopic photograph wherein; (b) be the suitable multi-walled carbon nano-tubes electromicroscopic photograph of degree of oxidation; (c) be the multi-walled carbon nano-tubes photo of hyperoxidation.
Fig. 4 is the distribution of sizes (dynamic light scattering method mensuration) of multi-walled carbon nano-tubes in the carbon nano-tube aqueous solutions of the present invention.
Embodiment:
The preparation of high-concentration stable carbon nano-tube aqueous solutions of the present invention; Adopted the oxidation of mixing concentrated acid to handle carbon nanotube with the ultrasonic method that combines; Under the condition of not introducing tensio-active agent, the stable carbon nano-tube aqueous solutions of preparation high density (as being higher than 0.2mg/ml).Concrete steps are following:
1. the surface oxidation treatment of carbon nanotube:
The mixed strong acids solution of the preparation vitriol oil and concentrated nitric acid.Taking by weighing an amount of multi-walled carbon nano-tubes is added in the mixed acid solution.Behind the ultrasound probe processing certain hour with suitable diameter, obtain aterrimus solution.Thin up after-filtration (the filter membrane aperture is 2 μ m), drip washing leaches thing repeatedly, is neutral to filtrating.The carbon nanotube powder that leaches is dried to constant weight.
2. preparation carbon nano-tube aqueous solutions:
Take by weighing a certain amount of above-mentioned carbon nanotube and join in the pure water, handle certain hour, obtain uniform and stable dark solution with the ultrasound probe of suitable diameter.
Below in conjunction with the specific embodiment process in detail.
Embodiment one, preparation concentration are the carbon nano-tube solution of 0.5mg/ml
1) preparation of mixing acid: the vitriol oil and concentrated nitric acid are prepared formation mixed strong acids solution in 2: 1 ratio;
2) taking by weighing the 200mg multi-walled carbon nano-tubes and add in the mixed acid solution of 400ml, is that the ultrasound probe of 15mm extend in multi-walled carbon nano-tubes and the mixing acid with diameter, and 1000w power ultrasonic processing 2 minutes obtains aterrimus solution.
3) with aterrimus solution thin up after-filtration (the filter membrane aperture is 2 μ m), water washes repeatedly and leaches thing, is neutral to filtrating; With leach be deposited in 60 ℃ down the about 48h of oven dry obtain powder to constant weight.
4) take by weighing the above-mentioned powder of 5mg and join in the 10ml pure water, use diameter to handle once more 2 minutes, obtain the carbon nano-tube aqueous solutions that uniform and stable dark solution is concentration 0.5mg/ml as the ultrasound probe of 6mm.
Embodiment two, preparation concentration are the carbon nano-tube solution of 0.4mg/ml
1) adopt the step identical with embodiment one, wherein, the carbon nanotube of 100mg adds in the mixing acid of 200ml, and probe diameter is 10mm, and 800w power ultrasonic processing 2 minutes obtains aterrimus solution.
2) with aterrimus solution thin up after-filtration (the filter membrane aperture is 2 μ m), water washes repeatedly and leaches thing, is neutral to filtrating; With leach be deposited in 70 ℃ down oven dry 48h obtain powder to constant weight.
3) take by weighing the above-mentioned powder of 4mg and join in the 10ml pure water, use diameter to handle once more 2 minutes, obtain the carbon nano-tube aqueous solutions that uniform and stable dark solution is concentration 0.4mg/ml as the ultrasound probe of 6mm.
Embodiment three, preparation concentration are the carbon nano-tube solution of 0.3mg/ml
1) adopt the step identical with embodiment one, wherein, the carbon nanotube of 200mg adds in the mixing acid of 300ml, and probe diameter is 15mm, and 1000w power ultrasonic processing 2 minutes obtains aterrimus solution.
2) with aterrimus solution thin up after-filtration (the filter membrane aperture is 2 μ m), water washes repeatedly and leaches thing, is neutral to filtrating; The room temperature that is deposited in that leaches is dried to constant weight and obtained powder.
3) take by weighing the above-mentioned powder of 3mg and join in the 10ml pure water, use diameter to handle once more 2 minutes, obtain the carbon nano-tube aqueous solutions that uniform and stable dark solution is concentration 0.3mg/ml as the ultrasound probe of 6mm.
In above practical implementation, through set-up procedure 3) ratio of powder and water can obtain the carbon nano-tube aqueous solutions of different concns, and the carbon nano-tube aqueous solutions of low concentration such as 0.01mg/ml～0.2mg/ml can obtain too easily, does not therefore give an example one by one.
Carbon nano-tube aqueous solutions for the present invention's acquisition; Also analyze and confirm solution composition through spectral scan; Investigate the pattern of carbon nanotube in the solution through ESEM; And detect the distribution of sizes of carbon nanotube in the aqueous solution with dynamic light scattering, and monitor the stability of solution with the ultraviolet absorptivity value of solution, whether effective thereby overall approval prepares the method for carbon nano-tube aqueous solutions.
Concrete, the carbon nano-tube aqueous solutions with the aforesaid method preparation is carried out following analysis:
(1) use ultraviolet/visible/near infrared spectrophotometer carbon nano-tube aqueous solutions is carried out the spectral scan analysis, sweep limit is set at 190nm to 1400nm, scanning wavelength be spaced apart 0.5nm, before experiment is carried out, do reference with pure water, the balance timebase earlier.The carbon nano-tube aqueous solutions of suitably dilution is added in the sample pool and scans, and be about 30min each sweep time, obtains the wave spectrogram of carbon nanotube, if be presented at 253nm charateristic avsorption band arranged, and then can confirm to prepare product is carbon nano-tube aqueous solutions.
The result: the concentration of the present invention's preparation all has charateristic avsorption band at 253nm at the aqueous solution of 0.01～0.5mg/ml, can confirm as carbon nano-tube aqueous solutions.Its spectrogram scanning result is referring to Fig. 2.
(2) the carbon nanotube pattern after the application scanning electron microscopic observation is processed.Silicon chip earlier with behind the acetone immersion ultrasonic cleaning 2min, is used alcohol immersion ultrasonic cleaning 5min again, dry in the super clean bench.Draw the suitably carbon nano-tube aqueous solutions of dilution, drip to the silicon chip front, dry in the Bechtop.Pattern with ESEM direct viewing carbon nanotube.
Observations: referring to (b) picture among Fig. 3; The pattern of carbon nanotube in the carbon nano-tube aqueous solutions of demonstration 0.5mg/ml can see that carbon nanotube keeps single form to exist basically, a lot of opening-like attitudes of carbon nanotube; The length of carbon nanotube becomes between 200～1000nm about by primary 50 μ m; Caliber is about 30nm, and tubular structure is clear, and hollow tubular structures is kept well.
(3) dynamic dimension with carbon nanotube in the dynamic light scattering detection aqueous solution distributes.The carbon nano-tube aqueous solutions of suitably dilution is put into the dynamic laser light scattering experimental sample pool; Treat solution-stabilized after; With the laser continuous detecting of 690nm three minutes; (90Plus Particle Size software Ver.3.48) obtains the dynamic grain size distribution curve of carbon nanotube in the aqueous solution after analyzing through computer program with the size distribution of the particle that obtains in three minutes.
Experimental result: referring to Fig. 4, the mean effective diameter that shows carbon nanotube is about 140nm, and distribution range is 70～350nm.
(4) stability experiment
Carbon nano-tube solution has characteristic absorbance at the 253nm place, and the concentration linear dependence of carbon nanotube in the intensity of absorption peak and the solution, and promptly the OD value is big more, and the concentration of carbon nanotube is also high more in corresponding the solution.Utilizing this characteristics, is respectively the OD value of the carbon nano-tube aqueous solutions of 0.5mg/ml at the different time detectable level.After finding that room temperature placed for two weeks, the OD value of solution does not change, along with the prolongation of storage period; After one month, the OD value of solution can reduce to some extent, again with after the step 3) method is carried out supersound process among the embodiment like the room temperature placement; Carbon nanotubes in solution can be disperseed again, and the OD value increases.In addition, above-mentioned carbon nano-tube solution is after normal temperature is placed 2 time-of-weeks, and naked eyes are not observed tangible carbon nanotube aggregate and occurred.
Adopt the above preparation method and the method for inspection of describing; The present invention has carried out optimization Test to the process of the carbon nano-tube aqueous solutions of preparation; The result shows: in the preparation process; Selecting ultrasound probe rather than ultrasonic tank is crucial condition, in addition, the volume ratio of the diameter of ultrasound probe and the volume proportion of mixed acid solution, carbon nanotube weight and mixing acid, leaches the dryness of thing and ultrasonic the assisting when obtained aqueous solution also is the significant effects factor.
Optimization experiment one: when the using ultrasound technology is handled being dispersed in carbon nanotube in the mixing acid; The carbon nano-tube solution of mixing acid is placed in the ultrasonic tank handles; Be difficult to obtain the ideal oxidation effectiveness; When final obtained aqueous solution, can cause the concentration of carbon nanotube in the solution very low, concentration is usually below 0.01mg/ml.
And the present invention selects ultrasound probe, can make that the carbon nanotube maximum concentration reaches 0.5mg/ml in the aqueous solution.Referring to shown in Figure 1, A is the multi-walled carbon nano-tubes dispersive state in water with the ultrasonic tank supersound process among the left figure of Fig. 1; B is for using the multi-walled carbon nano-tubes aqueous solution that obtains after the probe supersound process.Right figure adopts the mixed strong acids oxidation to combine the carbon nano-tube aqueous solutions of the different concns of supersound process preparation; Solution is the carbon nano-tube aqueous solutions that concentration is 0.5mg/ml in No. 1 cup; And the carbon nano-tube solution that No. 2 cups are 0.15mg/ml concentration; No. 3 cups are the carbon nano-tube solution of 0.05mg/ml concentration, also can judge its concentration difference distance from the color intensity of solution.
Optimization experiment two: the diameter of ultrasound probe and the volume proportion of mixed acid solution are degree of oxidation, the dispersion effects that influences carbon nanotube and keep one of important factor of tubular structure.When the diameter of ultrasound probe with respect to liquor capacity less than 1: 100 (mm: in the time of ml); This moment, the ultrasound probe diameter was too small, from the pattern of scanning electron microscopic observation carbon nanotube, found that most of carbon nanotube does not all have oxidized prescinding; Assemble agglomerating distribution (referring to a picture among Fig. 3); Explain not reach the ideal degree of oxidation, and cause final carbon nanotube in water, not scatter, the concentration of carbon nanotube is usually below 0.01mg/ml in the aqueous solution; If greater than 1: 20 o'clock, this moment, the ultrasound probe diameter was excessive with respect to liquor capacity for the diameter of ultrasound probe, find that the carbon nanotube cast is destroyed; Becoming particulate state assembles agglomerating; (referring to c picture among Fig. 3) explains that degree of oxidation is too high, destroyed the tubular structure of carbon nanotube.
Optimization experiment three: the volume ratio of carbon nanotube weight and mixing acid is one of factor that influences the carbon nanotube degree of oxidation.Cross when low when the mixing acid volume, can cause the carbon nanotube degree of oxidation on the low side, the concentration of carbon nanotube is very low in the final aqueous solution; When the mixing acid volume is too high, can cause the carbon nanotube degree of oxidation too high, carbon nanotube is particulate state and assembles agglomerating.Optimization experiment confirms that finally effective proportional range is 1: 5～2: 1 (mg: ml) between carbon nanotube weight and mixing acid volume.
Optimization experiment four: the carbon nanotube through after the oxide treatment need keep dry.The carbon nanotube of same oxide treatment; Obtained aqueous solution after thorough drying; Can obtain the stable, aqueous solution of high density, not have the carbon nanotube of thorough drying then to be difficult to be distributed to once more in the water, the concentration of carbon nanotube is usually below 0.01mg/ml in the aqueous solution.The present invention to be being dried to the criterion of constant weight as thorough drying, and drying temperature is room temperature～70 ℃, and different drying temperatures can change its time of drying to some extent.
Optimization experiment five: when the preparation carbon nano-tube aqueous solutions,, adopt ultrasonic assisting, can carbon nanotube be distributed to rapidly in the aqueous solution once more, form the aqueous solution of stable high density for the carbon nanotube of same oxidation; And do not adopt ultrasonic supplementary means, carbon nanotube to be difficult to be distributed to fully in the water, can only obtain the very low and unsettled aqueous solution of concentration.
More than describe process and influence factor that the present invention prepares high-concentration stable carbon nano-tube aqueous solutions in detail; It is understandable that; Embodiment only is used to the preparation process is described, is not construed as limiting the invention, and other partial data, picture and text description all obtain according to real experiment in the specification sheets; Also be the result of practical implementation of the present invention, should constitute of the present invention open and the support of technical scheme of the present invention.
Claims (5)
1. method for preparing high-concentration stable carbon nano-tube aqueous solutions, be after carbon nanotube is carried out oxide treatment, filtration and washing and leaches thing and oven dry and leach thing with ultrasound probe in mixed strong acids solution with its in water with obtaining uniform and stable dark solution after the ultrasound probe dispersion treatment; The working hour that ultrasound probe carries out oxide treatment is 30s～12000s, and operating power is 500w～1200w, and the working hour that ultrasound probe carries out dispersion treatment is 10s～15000s, and operating power is 200w～1200w; Wherein:
Said mixed strong acids solution is prepared by 2: 1 volume ratio by the vitriol oil and concentrated nitric acid and is formed;
The volume ratio scope of said carbon nanotube weight and mixed strong acids is 1mg: 5ml～2mg: 1ml;
The concentration of said high-concentration stable carbon nano-tube aqueous solutions is between being less than or equal between the 0.5mg/ml more than or equal to 0.3mg/ml, and at least 2 weeks of steady time of solution.
2. according to the said method of claim 1, it is characterized in that said oven dry is meant and is dried to constant weight with leaching thing, said drying temperature scope is room temperature～70 ℃.
3. according to the said method of claim 1, it is characterized in that said washing leaches thing and is meant that water will leach thing washing to filtrating for neutral.
4. according to the said method of claim 1, it is characterized in that, specifically may further comprise the steps:
1) carbon nanotube is added in the mixed strong acids solution, carries out oxide treatment, obtain aterrimus solution with ultrasound probe;
2) aterrimus solution is filtered, washing leaches thing to filtrating for neutral;
3) will leach thing dries to the constant weight powdered;
4) powder is added to the water, carries out dispersion treatment, obtain dark solution and be carbon nano-tube aqueous solutions with ultrasound probe.
5. according to the said method of claim 4, it is characterized in that said carbon nanotube and mixed strong acids solution proportion are 1mg: 0.8～1.5ml, the working hour that said ultrasound probe carries out oxide treatment is 30s～60s, and operating power is 1000w; The working hour that said ultrasound probe carries out dispersion treatment is 10s～60s, and operating power is 1000w.
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