CN115108547A - Hydroxyl-rich core-shell structure carbon nanotube and preparation method thereof - Google Patents
Hydroxyl-rich core-shell structure carbon nanotube and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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Abstract
The invention relates to the technical field of nano materials, and discloses a hydroxyl-rich core-shell structure carbon nano tube and a preparation method thereof, wherein the preparation process comprises the following steps: step 1, performing high-sound intensity ultrasonic treatment on a carbon nano tube and a carbohydrate in a solvent to obtain a dispersed mixed solution; and 2, performing hydrothermal carbonization reaction on the dispersed mixed solution in a closed container, washing and drying a product to obtain the hydroxyl-rich core-shell structure carbon nano tube with the oxygen content of more than 12%. According to the invention, a large number of hydroxyl groups can be introduced without destroying the surface structure of the carbon nano tube, the hydroxyl content of the obtained hydroxyl-rich core-shell carbon material is high, the hydrophilicity can be effectively improved, and the finished product has good hydrophilicity and dispersibility. The preparation process is environment-friendly and green, the operation is simple, and the process production is easy.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a hydroxyl-rich core-shell structure carbon nano tube and a preparation method thereof.
Background
Carbon Nanotubes (CNTs) are a class of engineered nanomaterials with broad application prospects due to their unique physical, chemical and electronic properties. Although carbon nanotubes have many useful characteristics, they are not easily dispersed in an aqueous phase, hydrophobic interactions between individual carbon nanotubes are gathered by van der waals forces, applicability is reduced, and dispersibility and stability of carbon nanotubes can be effectively improved by introducing hydroxyl groups on the surface of carbon nanotubes through covalent and non-covalent modification.
The covalent modification method is to treat the carbon nano tube by means of strong acid, strong base, plasma and the like, but often destroys the graphitized structure of the carbon nano tube and grafts other groups on the surface, the oxygen content of the surface of the carbon nano tube can periodically cycle between high oxygen content and low oxygen content under the long-time action of a strong oxidant, because the graphitized structure on the surface of the carbon nano tube is destroyed and the exfoliation phenomenon occurs, the finally prepared hydroxylated carbon nano tube can cause performance reduction and less grafting group content. But also oxidation of the hydroxyl groups to other groups by the strong acid. For example, CN104085879A discloses a method for preparing a carbon nano-tube dispersion with high concentration by placing a carbon nano-tube into a strong oxidizing solution to obtain a carboxylated carbon nano-tube, and then performing amination. However, the method uses strong acid strong oxidant and toxic and harmful amine compounds, and secondary pollution emission is formed in the separation and purification process.
The non-covalent modification method is to treat the carbon nano tube by using protein, deoxyribonucleic acid, macromolecular polymer with enough hydrophobic part and the like, the method does not affect the internal structure of the carbon nano tube, does not damage the graphitized structure on the surface of the carbon nano tube, and the ideal electronic and mechanical properties of the carbon nano tube can be kept unchanged. For example, CN111499757A discloses a covalent bonding method using chitosan and phycocyanin, which is applied to biomedical materials, but the interaction force between carbon nanotubes and modifying molecules is very weak, and the process balance is influenced by the properties of solution concentration, ionic strength, temperature and solvent characteristics, which makes it difficult to apply the method widely.
Disclosure of Invention
Aiming at the problems of low hydroxyl group content, insufficient adsorption force, easy falling and the like existing in the method for hydroxylating the surface of the carbon nano tube in the prior art, the invention provides the method for preparing the carbon nano tube rich in the hydroxyl core-shell structure, which greatly enhances the hydrophilicity of the carbon nano tube, has the advantages of simple preparation method, mild reaction, stable dispersion product, low cost, industrialization suitability and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a carbon nano tube with a hydroxyl-rich core-shell structure comprises the following steps:
and 2, performing hydrothermal carbonization reaction on the dispersed mixed solution in a closed container, washing and drying a product to obtain the carbon nano tube with the hydroxyl-rich core-shell structure.
According to the invention, the mixed liquid is pretreated by using high-sound-intensity ultrasonic waves, and a treatment means of hydrothermal carbonization is utilized to perform caramelization reaction on the carbohydrate compound in a closed low-oxygen environment, so that a large number of hydroxyl groups in the carbohydrate compound can be reserved, the carbohydrate compound can generate caramel particles to be adsorbed on the surface of the carbon nano tube to generate a shell structure rich in hydroxyl, and finally the carbon nano tube with the core-shell structure rich in hydroxyl can be prepared. The method has the advantages of simple operation, low cost and the like, can modify a large number of hydroxyl groups on the surface of the carbon nanotube, and has good hydrophilic property.
The saccharide compound is water-soluble saccharide source, and comprises any one or more of glucose, fructose, maltol, maltose, pentamethyl furfural, cyclodextrin, starch and chitosan.
The carbon nanotube includes any one of a single-walled carbon nanotube, a multi-walled carbon nanotube and a carbon nanotube with a surface modified with other groups. including-OH, -COOH and-NH 2 The carbon nano tube modified by the groups can form a hydroxyl shell layer on the surface by adopting the method.
The mass ratio of the carbon nano tube to the carbohydrate is 1: 0.1-5. Too low a proportion of the saccharide compounds results in incomplete surface shell coverage of the final product, and too high a proportion of the saccharide compounds results in blocking of the final product.
Preferably, the mass ratio of the carbon nano tube to the carbohydrate is 1: 0.1-3; further preferably, the mass ratio of the two is 1: 0.2-2; further preferably in a mass ratio of 1:1 to 1.5. The product finally prepared in the proportion can completely cover the surface of the carbon nano tube, and has good dispersion performance.
The solvent in the step 1 comprises any one or more of water, ethanol, diethyl ether and propylene glycol. The solvent is selected to have good dissolving performance on the carbohydrate, and the carbon nano tube has weak adsorption force on the solvent, so that the carbohydrate can be effectively dissolved, and the influence on the carbon nano tube is avoided.
The sound intensity of the high sound intensity treatment is 1 multiplied by 10 5 The above. Because the agglomeration effect is easy to occur between the carbon nano tubes, the shearing action strength of the mechanical stirring is not enough to break the van der waals force between the carbon nano tubes, and the original carbon nano tubes are difficult to disperse efficiently. The invention can uniformly disperse the carbon nano tubes in the solvent through the ultrasonic action of high sound intensity, so that the carbon nano tubes and the solvent are changed into uniform mixed liquid, the liquidity of the formed mixed liquid is greatly reduced, the carbon nano tubes are fixed in the mixed liquid and can stably exist for a certain time, which is an effect which cannot be achieved by mechanical stirring, and therefore, the carbon nano tubes can be effectively and uniformly dispersed in the reaction container, and the caramelized compound can be efficiently adsorbed.
The sound intensity of the high-sound-intensity processing is calculated according to the working power/effective working area of the sound intensity generating source.
The treatment process of the dispersed mixed solution has great influence on the result, the carbon nano tubes cannot be effectively uniformly dispersed in the water due to too low sound intensity, the agglomeration phenomenon occurs, and preferably, the sound intensity of the high-sound-intensity treatment is 1 multiplied by 10 5 -2×10 8 W/m 2 。
The dispersed mixed solution after the high sound intensity treatment in the step 1 is very stable, no obvious layering condition occurs after standing for 36 hours, and the layering of the carbon nano tube and the liquid can occur only when the standing time exceeds more than 7 days, which is very favorable for the hydrothermal carbonization reaction in the step 2.
The temperature of the hydrothermal carbonization reaction is 100-350 ℃, and the reaction temperature is based on the caramelization reaction temperature of the saccharide compounds. The hydroxylated carbohydrate selected as the carbon source is subjected to caramelization reaction at high temperature to coat the surface of the carbon nano tube, so that a shell structure rich in hydroxyl is formed.
Preferably, the temperature of the hydrothermal carbonization reaction is 150-240 ℃, and particularly preferably 180-220 ℃.
The high sound intensity treatment time is 0.5-60 min; the hydrothermal carbonization reaction time is 6-36 h. The surface shell layer can not be completely covered when the hydrothermal reaction time is short.
Preferably, the high sound intensity treatment time is 2-30min, particularly preferably 5-10 min; the dispersion degree is not sufficient due to the short time, and the effect is more excellent in the range.
Preferably, the hydrothermal carbonization reaction time is 9 to 20h, particularly preferably 12 to 15 h.
Washing the product after the hydrothermal carbonization reaction by using water or solvents such as ethanol, ether and the like, drying at 70-90 ℃, and removing the solvents to obtain the black hydroxyl-rich core-shell structure carbon nano tube.
The hydroxyl-rich core-shell structure carbon nanotube obtained by the preparation method has the surface oxygen content of more than 12 percent by mass, contains rich hydroxyl groups, and can obviously enhance the hydrophilicity of the carbon nanotube.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention develops a new method for preparing the hydroxyl-rich carbon nano tube, a large number of hydroxyl groups can be introduced without destroying the surface structure of the carbon nano tube, the carbon nano tube can be effectively dispersed by high-sound strong ultrasound, the obtained mixed liquid with uniform solid-liquid dispersion can be stabilized for more than 36 hours, and a coated hydroxyl shell layer is formed on the surface of the carbon nano tube by hydrothermal carbonization reaction, so that the obtained hydroxyl-rich core-shell carbon material has high hydroxyl content, the hydrophilicity can be effectively improved, and the finished product has good hydrophilicity and dispersibility.
(2) Although the reaction system is in a high-temperature closed environment, a large amount of oxidant and reducer are not used in the system, the reaction process is mild, no residual gas is generated after the reaction, and the safety and reliability are high. And the saccharide compound selected by the hydroxylated carbon source can generate a great amount of substances harmful to the environment when the caramelization reaction is carried out at high temperature, and the product after the reaction is easy to treat, environment-friendly and pollution-free.
Therefore, the synthetic route of the hydroxyl-rich carbon nanotube prepared by the scheme is green and environment-friendly, the operation is simple, the equipment cost is low, a large amount of the hydroxyl-rich carbon nanotubes with the core-shell structures can be quickly prepared, the surface grafting hydroxyl content is high, and the prepared hydroxyl-rich carbon nanotube has good hydrophilicity and is easy to use.
Drawings
Figure 1 is a TEM image of untreated multi-walled carbon nanotube feedstock.
FIG. 2 is a TEM image of the hydroxyl-rich core-shell structure carbon nanotube CNT/C-OH prepared in example 1.
FIG. 3 shows the results of the characterization of the CNT/C-OH rich core-shell carbon nanotube prepared in example 1, wherein (a) is SEM, (b) is IR spectrum, (C) is XPS diagram, and (d) is fine C of XPS of CNT/C-OH 1s Spectrogram, (e) Fine O of XPS with CNT/C-OH 1s Spectra.
FIG. 4 shows the results of stability tests of the mixture of high-intensity treated carbon nanotubes and water, wherein (a) is a normal stirring for 2 hours, (b) is a high-intensity treatment for 5min, and (c) is a standing for 36 hours.
FIG. 5 is SEM images of stability test and carbon nanotubes after low intensity treatment of a mixture of carbon nanotubes and water in comparative example 1, wherein (a) is SEM image with 2h low intensity treatment, and (b) and (c) are SEM images with different magnifications.
FIG. 6 shows the CNT/C-OH and raw untreated carbon nanotubes hydrophilicity test results of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following embodiments are all commercially available. The sound intensity used for the high sound intensity ultrasonic treatment in the following examples was 5X 10 6 w/m 2 。
Example 1
Taking 1g of multi-walled carbon nanotube, 1g of glucose and 80mL of deionized water, putting the carbon nanotube, the glucose and the solvent deionized water into a reactor, performing high-sound strong ultrasonic treatment for 50min, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a 190 ℃ oven for 12 hours, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube CNT/C-OH.
Example 2
Taking 1g of single-walled carbon nanotube, 1.5g of pentamethyl furfural and 80mL of deionized water, putting the carbon nanotube, the pentamethyl furfural and a solvent into a reactor, carrying out high-sound intensity ultrasonic treatment for 0.5min, directly putting the reactor into a hydrothermal reaction kettle, heating the hydrothermal reaction kettle in a 200 ℃ oven for 12 hours, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solids to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 3
Taking 1g of multi-walled carbon nanotube, 1g of maltol and 80mL of ethanol, putting the carbon nanotube, the maltol and a solvent into a reactor, performing high-sound strong ultrasonic treatment for 40min, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a 190 ℃ oven for 12 hours, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 4
Taking 0.5g of multi-walled carbon nanotube, 1.5g of fructose and 80mL of ether, putting the carbon nanotube, the fructose and a solvent into a reactor, carrying out high-sound strong ultrasonic treatment for 5min, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a 350 ℃ oven for 6 hours, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 5
Taking 1g of hydroxylated carbon nanotube, 1g of cyclodextrin and 80mL of propylene glycol, putting the carbon nanotube, the cyclodextrin and a solvent into a reactor, carrying out high-sound strong ultrasonic treatment for 60min, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a 160 ℃ oven for 15 hours, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 6
Taking 1g of hydroxylated carbon nanotube, 0.1g of starch and 80mL of deionized water, putting the carbon nanotube, the starch and a solvent into a reactor, carrying out high-sound strong ultrasonic treatment for 10min, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a 100 ℃ oven for 36h, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 7
Taking 1g of multi-walled carbon nanotube, 0.2g of glucose and 80mL of deionized water, putting the carbon nanotube, the glucose and a solvent into a reactor, carrying out high-sound-intensity ultrasonic treatment for 2min, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a 230 ℃ oven for 9 hours, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 8
Taking 1g of carboxylated carbon nanotube, 2g of maltose and 80mL of ethanol, putting the carbon nanotube, the maltose and a solvent into a reactor, carrying out high-sound strong ultrasonic treatment for 30min, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a 150 ℃ oven for 20h, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 9
Taking 1g of multi-walled carbon nanotube, 1.5g of fructose and 80mL of deionized water, putting the carbon nanotube, the fructose and a solvent into a reactor, performing high-sound strong ultrasonic treatment for 20min, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a baking oven at 240 ℃ for 8 hours, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 10
Taking 1g of aminated carbon nanotube, 0.5g of starch and 80mL of propylene glycol, putting the carbon nanotube, the starch and a solvent into a reactor, carrying out high-sound strong ultrasonic treatment for 20min, directly putting into a hydrothermal reaction kettle, heating in a 100 ℃ oven for 30 h, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 11
Taking 1g of single-walled carbon nanotube, 0.1g of pentamethyl furfural and 80mL of deionized water, putting the carbon nanotube, the pentamethyl furfural and a solvent into a reactor, carrying out high-sound strong ultrasonic treatment for 5min, directly putting the reactor into a hydrothermal reaction kettle, heating the hydrothermal reaction kettle in a 190 ℃ oven for 13 h, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solids to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Example 12
Taking 1g of carboxylated carbon nanotube, 0.1g of glucose and 80mL of glucose, putting the carbon nanotube, the glucose and a solvent into a reactor, carrying out high-sound strong ultrasonic treatment for 10min, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a 170 ℃ oven for 24 h, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube.
Comparative example 1 Low Sound Strength treatment
Taking 1g of multi-walled carbon nanotube, 1g of glucose and 80mL of deionized water, putting the carbon nanotube, the glucose and the solvent deionized water into a reactor, and carrying out low-sound-intensity ultrasonic treatment for 120min, wherein the sound intensity is 4000w/m 2 Then go straight afterAnd putting the carbon nano tube into a hydrothermal reaction kettle, heating the carbon nano tube in an oven at 190 ℃ for 12 hours, taking out the inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nano tube CNT/C-OH.
Comparative example 2 mechanical agitation
Taking 1g of multi-walled carbon nanotube, 1g of pentamethyl furfural and 80mL of deionized water, putting the carbon nanotube, glucose and solvent deionized water into a reactor, mechanically stirring for 120min, directly putting into a hydrothermal reaction kettle, heating in a 190 ℃ oven for 12 hours, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube CNT/C-OH.
Comparative example 3 No agitation and No ultrasound
Taking 1g of multi-walled carbon nanotube, 0.5g of glucose and 80mL of deionized water, putting the carbon nanotube, the glucose and solvent deionized water into a reactor, directly putting the reactor into a hydrothermal reaction kettle, heating the reactor in a baking oven at 240 ℃ for 9 hours, taking out an inner container after the hydrothermal reaction kettle is completely and naturally cooled, and washing and drying the residual solid to obtain the prepared hydroxyl-rich core-shell structure carbon nanotube CNT/C-OH.
Performance testing
1. Carbon nanotube surface oxygen content
The hydroxyl-rich core-shell structure carbon nanotubes prepared in the examples and comparative examples were subjected to a surface oxygen content test by XPS for a test analysis of the mass fraction of surface oxygen elements of CNT/C-OH.
As shown in Table 1, it can be seen from the results that the mass fraction of oxygen content on the surface of CNT/C-OH can be 12% or more, the hydrophilicity can be effectively improved, and a large amount of hydroxyl groups can be retained under the reaction conditions in a closed low-oxygen environment. In the comparative example, the oxygen content mass fraction measured by XPS was high due to the presence of accompanying carbon spheres in the finally prepared CNT/C-OH by using ultrasonic dispersion with low sound intensity or mechanical stirring.
TABLE 1 mass fraction of oxygen content of CNT/C-OH surface under different examples
2. Characterization of
Microscopic morphology observation is carried out on the carbon nanotube prepared in example 1, a TEM is shown in fig. 1 and 2, a raw material carbon nanotube before being coated is shown in fig. 1, and a hydroxyl-rich core-shell structure carbon nanotube after being coated is shown in fig. 2, and it can be seen that the carbon nanotube in fig. 2 has a significant shell structure on the surface and a hydroxyl-based layer with a thickness of about 3 nm.
Other characterization of CNT/C-OH of example 1 is shown in FIG. 3, wherein (a) is SEM image, (b) is IR spectrum, (C) is XPS spectrum of CNT/C-OH, (d) is fine C of XPS of CNT/C-OH 1s Spectrogram, (e) Fine O of XPS with CNT/C-OH 1s Spectra. It can be seen from fig. 3(a) that the prepared CNT/C-OH agglomeration effect is reduced and the overall miscellany distribution is present. The CNT/C-OH hydroxyl stretching vibration absorption peak prepared from the infrared data of fig. 3(b) is significantly larger than that of the original carbon nanotube, indicating that the surface has a large amount of hydroxyl groups. The XPS spectrum of the CNT/C-OH in FIG. 3(C) shows the elemental composition and content of the surface, only the O and C elements, the mass ratio of the elements is obtained by calculating the peak area through software, and the result that the surface contains a large amount of oxygen elements can be obtained. Through the fine spectrograms of fig. 3(d) and (e) to analyze the valence compositions of the C and O elements, it can be analyzed that the oxygen-containing group whose surface is dominant is a hydroxyl group.
3. Stability test of Dispersion mixtures
The results of testing the stability of the dispersion mixture of carbon nanotubes subjected to high-intensity ultrasound treatment are shown in fig. 4, in which fig. 4(a) is a carbon nanotube aqueous solution after being stirred for 2 hours, the carbon nanotubes rapidly settle to the bottom after standing, and the mixture cannot be lifted by a glass rod after being stirred by the glass rod. In the step (b) of fig. 4, the mixed solution can stably exist after standing through high-sound-intensity ultrasonic treatment for 5min, and the mixed solution can be directly picked up through a glass rod. FIG. 4(c) shows that the mixed solution after the high intensity treatment was left to stand for 36 hours, and the mixed solution was still able to be picked up directly by the glass rod and was able to be stably dispersed in the container during the hydrothermal treatment.
The stability of the dispersion mixture of comparative example 1 is shown in fig. 5, and fig. 5(a) shows that the mixture was treated with low-intensity ultrasound for 2 hours, and we can clearly observe that only a small amount of carbon nanotubes entered the aqueous phase, which is significantly different from the treatment result of high-intensity ultrasound. SEM images of the CNT/C-OH prepared after hydrothermal treatment, as shown in FIG. 5(b) (C), the CNT/C-OH prepared contains a large amount of associated microspheres, which affects the quality of the final preparation.
4. Hydrophilicity test
The carbon nanotubes of example 1 were subjected to hydrophilicity test, and as a result, as shown in fig. 6, CNTs/C-OH and pristine untreated carbon nanotubes were uniformly shaken in an aqueous solution, and were respectively added dropwise to a petroleum ether solution using a dropper, the density of water was greater than that of petroleum ether, the water fell to the bottom, the CNTs/C-OH remained in the aqueous phase after slight shaking, and the pristine untreated carbon nanotubes were extracted into the petroleum ether phase, indicating that the prepared CNTs/C-OH had excellent hydrophilicity.
Claims (10)
1. A preparation method of a carbon nano tube with a hydroxyl-rich core-shell structure is characterized by comprising the following steps:
step 1, performing high-sound intensity ultrasonic treatment on a carbon nano tube and a carbohydrate in a solvent to obtain a dispersed mixed solution;
and 2, performing hydrothermal carbonization reaction on the dispersed mixed solution in a closed container, washing and drying a product to obtain the carbon nano tube with the hydroxyl-rich core-shell structure.
2. The method for preparing carbon nanotubes with hydroxyl-rich core-shell structures as claimed in claim 1, wherein the sugar compounds comprise any one or more of glucose, fructose, maltol, maltose, pentamethyl furfural, cyclodextrin, starch and chitosan.
3. The method for preparing carbon nanotubes with hydroxyl-rich core-shell structures as claimed in claim 1, wherein the carbon nanotubes include any one of single-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanotubes with surface modified with other groups.
4. The method for preparing carbon nanotubes with rich hydroxyl core-shell structures as claimed in claim 1, wherein the mass ratio of the carbon nanotubes to the carbohydrate compound is 1: 0.1-5.
5. The method for preparing carbon nanotube with rich hydroxyl core-shell structure in claim 1, wherein the solvent in step 1 comprises one or more of water, ethanol, ether and propylene glycol.
6. The method for preparing carbon nanotube with hydroxyl-rich core-shell structure according to claim 1, wherein the sound intensity of the high sound intensity treatment is 1 x 10 5 W/m 2 The above.
7. The method as claimed in claim 1, wherein the temperature of the hydrothermal carbonization reaction is 100-350 ℃.
8. The method for preparing carbon nanotube with hydroxyl-rich core-shell structure according to claim 1, wherein the high sound intensity treatment time is 0.5-60 min; the hydrothermal carbonization reaction time is 6-36 h.
9. The carbon nanotube with hydroxyl-rich core-shell structure obtained by the preparation method according to any one of claims 1 to 8.
10. The carbon nanotube of claim 9, wherein the mass fraction of oxygen content on the surface of the carbon nanotube is greater than 12%.
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