CN113713637B - Densified carbon nanotube film and preparation method thereof - Google Patents
Densified carbon nanotube film and preparation method thereof Download PDFInfo
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- 239000002238 carbon nanotube film Substances 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title abstract description 9
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- 239000002041 carbon nanotube Substances 0.000 claims abstract description 50
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 239000011261 inert gas Substances 0.000 claims abstract description 28
- 238000010306 acid treatment Methods 0.000 claims abstract description 17
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- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 21
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 14
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a densified carbon nanotube film and a preparation method thereof, and relates to the technical field of nano materials. The preparation method of the invention comprises the following steps: mixing a carbon source, a catalyst and a promoter to obtain a precursor solution; under the protection of inert gas, injecting the precursor solution into a reactor, and obtaining gaseous carbon nano tube aerogel through high-temperature pyrolysis; preparing the gaseous carbon nano tube aerogel into an initial carbon nano tube film; under the protection of inert gas, heating the initial carbon nano tube film at high temperature, and then performing acid treatment to obtain an activated carbon nano tube film; immersing the activated carbon nanotube film in a sulfonating agent to obtain a densified carbon nanotube film. The preparation process is simple, the densification degree of the membrane material is improved, the hydrophilicity of the membrane material is improved, the tensile property of the membrane material is enhanced, the screening performance of the dye and the composite dye is improved, and the carbon nano tube membrane is expected to play a larger role in the related field by immersing the carbon nano tube membrane in the sulfonating reagent.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a densified carbon nano tube film and a preparation method thereof.
Background
At present, with the sustainable development of global economy, various organic and inorganic pollutants in wastewater discharged by industries such as industry, agriculture and the like are gradually increased, and the pollution to environmental water bodies is aggravated. In these waste waters, dyes, drugs, proteins and petroleum compounds are often detected. In addition, natural water contains high molecular organic matters such as humic acid, sodium alginate and the like. During water treatment, if the treatment is incomplete, some organic contaminants may be converted into highly toxic disinfection byproducts through chlorine substitution or addition reactions during disinfection, resulting in acute or chronic illness in humans or animals. Therefore, it is of great importance to develop advanced treatment technologies that can effectively remove organic contaminants.
To reduce organic contaminants in water, various techniques have been applied such as flocculation/precipitation, adsorption, advanced oxidation and membrane separation. Among these methods, membrane separation is receiving more and more attention and research because of its advantages of high efficiency, simple operation, continuous process, less running requirements, modularization, small occupied area, and the like. According to the requirements of different separation conditions, the membrane can be divided into microfiltration (0.1-10 microns), ultrafiltration (0.01-0.1 microns), nanofiltration (0.001-0.01 microns) and reverse osmosis (0.0001-0.001 microns) according to the pore size of the membrane. In addition, the technology such as membrane distillation, forward osmosis and the like has a wide application range.
Membrane materials such as nanofiltration membranes that are capable of removing organic contaminants are typically very dense and require high pressures, which results in high energy consumption during operation. The membranes can foul during long term operation, resulting in temporary or permanent flux drops and increased energy consumption. The membrane pollution is mainly in three stages, namely, the membrane holes are blocked, which is the initial stage of the membrane pollution, and the flux begins to drop; then a gel layer is formed on the surface of the membrane, which is the middle stage of membrane pollution, and the flux is obviously reduced; later on of membrane fouling, a cake layer forms on the surface, where flux will stabilize. Most of the membranes used in the prior art are made of high polymer materials, and besides the defects of unstable structure, easiness in pollution by organic pollutants in water body and the like, the membranes are difficult to remove after pollution, and serious damage to the membrane structure caused by chemical cleaning is an important factor for restricting the greater development of membrane separation technology.
Currently, commercial chemical cleaning resistant membranes are mainly ceramic membranes. Ceramic membranes, which are inorganic membranes, have been increasingly used in water treatment due to their properties of being structurally strong, acid and alkali resistant, resistant to chemical cleaning, etc. However, because of its inherent physical properties, such as high mechanical strength, it is brittle and difficult to withstand high pressures; the density is high, so that the weight is high, and the transportation cost is high; and the internal structure of the film is very stable after sintering, and the microstructure of the film is difficult to regulate and control. This is also a limiting factor that hinders the further development of ceramic membranes.
As a novel inorganic material, carbon nanotubes with nanoscale diameters and smooth surfaces are expected to meet the requirement of reducing energy consumption. Although carbon nanotubes are hydrophobic materials, related studies have demonstrated that water can occupy the hydrophobic channels of carbon nanotubes. A great deal of research into water passing through carbon nanotubes has shown that not only do water occupy these channels, but rapid molecular transport occurs. Molecular dynamics modeling attribute this enhancement to the atomic level smoothness of the carbon nanotube surface, as well as molecular ordering phenomena that may occur in a limited range of 1 to 2 nm. Therefore, the carbon nanotube film can maintain high flux under the condition of lower pressure, which is beneficial to reducing energy consumption. In view of the fact that carbon nanotubes themselves are hydrophobic and have a high specific surface area, studies have been made to give their strong adsorption properties for hydrophobic organic substances. In addition, electron polarization of aromatic rings on the surface of carbon nanotubes may greatly enhance adsorption of organic substances. Carbon nanotubes are therefore a promising material for water purification.
Disclosure of Invention
Based on this, the present invention aims to overcome the above-mentioned shortcomings of the prior art and provide a densified carbon nanotube film and a method for preparing the same.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a densified carbon nano tube film, which comprises the following steps:
(1) Mixing a carbon source, a catalyst and a promoter to obtain a precursor solution;
(2) Under the protection of inert gas, continuously injecting the precursor solution into a tube furnace tube, and obtaining gaseous carbon nanotube aerogel through high-temperature pyrolysis;
(3) Continuously collecting the gaseous carbon nanotube aerogel through a rolling shaft to obtain an initial carbon nanotube film;
(4) Under the protection of inert gas, heating the initial carbon nano tube film at high temperature, and then performing acid treatment to obtain an activated carbon nano tube film;
(5) And cleaning and drying the activated carbon nanotube film, and then soaking the activated carbon nanotube film in a sulfonating reagent to obtain the densified carbon nanotube film.
The inventor finds that organic matters such as carbon sources, catalysts, accelerators and the like which are uniformly mixed are volatilized and cracked into a gaseous mixture at high temperature, and elements such as carbon, iron, sulfur and the like are cracked; under the assistance of sulfur, carbon atoms form carbon nanotubes under the catalysis of iron, and a large number of carbon nanotubes are subjected to electrostatic adsorption due to charges of self structures to self-assemble into gaseous carbon nanotube aerogel. The charge property of the carbon nano tube can be changed by heating at high temperature, and hydroxyl is generated on the surface of the carbon nano tube by reaction, so that the subsequent reaction on the carbon nano tube is facilitated. The invention can then react on the surface of the carbon nano tube to generate carboxyl groups by acid treatment, which is beneficial to the subsequent reaction on the carbon nano tube. In addition, the acid treatment can dissolve impurity metal elements mixed in the carbon nano tube, so that the purity of the carbon nano tube is improved. Sulfonation of the carbon nanotubes can promote charge separation and protonation processes of the carbon nanotubes, thereby enhancing interaction force among the carbon nanotubes and increasing density of the carbon nanotube film.
Preferably, in the step (1), the volume ratio of the carbon source to the accelerator is 100:1-10:1, wherein the concentration of the catalyst in the precursor solution is 1-10mg/mL.
Preferably, the carbon source in the step (1) is methanol, ethanol or acetone, the catalyst is ferrocene, and the promoter is thiophene.
Methanol, ethanol or acetone are carbon sources for synthesizing carbon nanotubes. The liquid organic carbon compound can be used for dissolving and fully mixing the catalyst and the accelerator, so that the reaction after the precursor solution is facilitated. Ferrocene is a catalyst for synthesizing carbon nanotubes. Ferrocene is an organic transition metal compound with high thermal stability and chemical stability and aromatic property, and is suitable for long-time catalytic reaction at high temperature. Thiophene is an accelerator for synthesizing carbon nanotubes. Thiophene has aromaticity, is easier to generate electrophilic substitution reaction compared with benzene, plays a certain catalysis assisting effect by providing sulfur atoms, and can assist in controlling the shape parameters such as pipe diameter, wall number, helicity and the like of the prepared carbon nano-tube.
Preferably, the inert gas in the step (2) is argon or helium, and the gas flow rate is 2000-5000sccm; the pyrolysis temperature is 600-1500 ℃. Preferably, in the step (2), the precursor solution is injected at a rate of 0.1-0.2mL/min.
Preferably, the inert gas in the step (4) is argon or helium, and the gas flow rate is 100-500sccm; the high-temperature heating temperature is 600-1500 ℃ and the heating time is 10-15 hours.
The inventors found through research that the charge property of the carbon nanotubes can be changed by heating at a high temperature, and hydroxyl groups are generated by reaction on the surfaces of the carbon nanotubes, which is beneficial to subsequent reactions on the carbon nanotubes.
Preferably, in the step (4), the acid treatment adopts a reagent of concentrated sulfuric acid or concentrated nitric acid, and the treatment time is 6-24 hours.
Preferably, in the step (5), the sulfonating agent is chlorosulfonic acid, and the soaking time is 5-30 minutes.
In addition, the application provides the densified carbon nanotube film prepared by the preparation method.
Further, the application provides application of the densified carbon nanotube film in the field of water treatment.
Compared with the prior art, the invention has the beneficial effects that:
The invention provides a densified carbon nanotube film and a preparation method thereof.
The invention has simple process, improves the compactness of the membrane material, improves the hydrophilicity of the membrane material, enhances the tensile property of the membrane material, improves the sieving performance of the dye and the composite dye, and is expected to play a larger role in the related fields.
Drawings
FIG. 1 is a scanning electron microscope image of an initial carbon nanotube film prepared in example 1, a densified carbon nanotube film prepared in example 2, and a densified carbon nanotube film prepared in example 3;
FIG. 2 is a cross-sectional view of the densified carbon nanotube film prepared in example 3;
FIG. 3 is a graph showing nuclear magnetic resonance and contact angle measurements of the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, and the densified carbon nanotube film prepared in example 3;
FIG. 4 is a graph showing tensile strength of the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, and the densified carbon nanotube film prepared in example 3;
FIG. 5 is a graph showing the removal effect of rhodamine B dye solutions of the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, the densified carbon nanotube film prepared in example 3, the densified carbon nanotube film prepared in example 4, and the densified carbon nanotube film prepared in example 5;
FIG. 6 is a graph showing the removal effect of acid orange G dye solutions of the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, the densified carbon nanotube film prepared in example 3, the densified carbon nanotube film prepared in example 4, and the densified carbon nanotube film prepared in example 5;
Fig. 7 is a graph showing sieving effects of rhodamine B and acid orange G mixed dye solutions of the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, and the densified carbon nanotube film prepared in example 3.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
An embodiment of the present application provides a method for preparing a densified carbon nanotube film, including the following steps:
(1) Mixing 50mL of ethanol, 50mg of ferrocene and 1mL of thiophene to obtain a precursor solution;
(2) Continuously injecting the precursor solution obtained in the step (1) into a tube furnace tube in an inert gas atmosphere, and performing high-temperature pyrolysis on the precursor solution to obtain gaseous carbon nanotube aerogel, wherein the precursor solution is injected at a speed of 0.15mL per minute, the high-temperature pyrolysis temperature is 1000 ℃, the inert gas is argon, and the gas flow rate is 4000sccm;
(3) Continuously collecting the gaseous carbon nanotube aerogel obtained in the step (2) through a rolling shaft to obtain an initial carbon nanotube film.
Example 2
An embodiment of the present application provides a method for preparing a densified carbon nanotube film, including the following steps:
(1) Mixing 50mL of ethanol, 50mg of ferrocene and 1mL of thiophene to obtain a precursor solution;
(2) Continuously injecting the precursor solution obtained in the step (1) into a tube furnace tube in an inert gas atmosphere, and performing high-temperature pyrolysis on the precursor solution to obtain gaseous carbon nanotube aerogel, wherein the precursor solution is injected at a speed of 0.15mL per minute, the high-temperature pyrolysis temperature is 1000 ℃, the inert gas is argon, and the gas flow rate is 4000sccm;
(3) Continuously collecting the gaseous carbon nanotube aerogel obtained in the step (2) through a rolling shaft to obtain an initial carbon nanotube film;
(4) Heating the initial carbon nanotube film obtained in the step (3) in inert gas at a high temperature, and then soaking the film in acid to perform acid treatment to obtain an activated carbon nanotube film, wherein the inert gas is argon, the gas flow rate is 400sccm, the high-temperature heating temperature is 800 ℃, the duration is 12 hours, the reagent adopted in the acid treatment is concentrated sulfuric acid, and the treatment time is 12 hours;
(5) And (3) cleaning and drying the activated carbon nanotube film obtained in the step (4), and then soaking the activated carbon nanotube film in a sulfonating reagent to obtain the densified carbon nanotube film, wherein the sulfonating reagent is chlorosulfonic acid, and the soaking time is 10 minutes.
Example 3
An embodiment of the present application provides a method for preparing a densified carbon nanotube film, including the following steps:
(1) Mixing 50mL of ethanol, 50mg of ferrocene and 1mL of thiophene to obtain a precursor solution;
(2) Continuously injecting the precursor solution obtained in the step (1) into a tube furnace tube in an inert gas atmosphere, and performing high-temperature pyrolysis on the precursor solution to obtain gaseous carbon nanotube aerogel, wherein the precursor solution is injected at a speed of 0.15mL per minute, the high-temperature pyrolysis temperature is 1000 ℃, the inert gas is argon, and the gas flow rate is 4000sccm;
(3) Continuously collecting the gaseous carbon nanotube aerogel obtained in the step (2) through a rolling shaft to obtain an initial carbon nanotube film;
(4) Heating the initial carbon nanotube film obtained in the step (3) in inert gas at a high temperature, and then soaking the film in acid to perform acid treatment to obtain an activated carbon nanotube film, wherein the inert gas is argon, the gas flow rate is 400sccm, the high-temperature heating temperature is 800 ℃, the duration is 12 hours, the reagent adopted in the acid treatment is concentrated sulfuric acid, and the treatment time is 12 hours;
(5) And (3) cleaning and drying the activated carbon nanotube film obtained in the step (4), and then soaking the activated carbon nanotube film in a sulfonating reagent to obtain the densified carbon nanotube film, wherein the sulfonating reagent is chlorosulfonic acid, and the soaking time is 20 minutes.
Example 4
An embodiment of the present application provides a method for preparing a densified carbon nanotube film, including the following steps:
(1) Mixing 10mL of methanol, 10mg of ferrocene and 1mL of thiophene to obtain a precursor solution;
(2) Continuously injecting the precursor solution obtained in the step (1) into a tube furnace tube in an inert gas atmosphere, and performing high-temperature pyrolysis on the precursor solution to obtain gaseous carbon nanotube aerogel, wherein the precursor solution is injected at a speed of 0.15mL per minute, the high-temperature pyrolysis temperature is 1000 ℃, the inert gas is argon, and the gas flow rate is 4000sccm;
(3) Continuously collecting the gaseous carbon nanotube aerogel obtained in the step (2) through a rolling shaft to obtain an initial carbon nanotube film;
(4) Heating the initial carbon nanotube film obtained in the step (3) in inert gas at a high temperature, and then soaking the film in acid to perform acid treatment to obtain an activated carbon nanotube film, wherein the inert gas is argon, the gas flow rate is 400sccm, the high-temperature heating temperature is 800 ℃, the duration time is 12 hours, the reagent adopted in the acid treatment is concentrated nitric acid, and the treatment time is 12 hours;
(5) And (3) cleaning and drying the activated carbon nanotube film obtained in the step (4), and then soaking the activated carbon nanotube film in a sulfonating reagent to obtain the densified carbon nanotube film, wherein the sulfonating reagent is chlorosulfonic acid, and the soaking time is 10 minutes.
Example 5
An embodiment of the present application provides a method for preparing a densified carbon nanotube film, including the following steps:
(1) Mixing 100mL of acetone, 10mg of ferrocene and 1mL of thiophene to obtain a precursor solution;
(2) Continuously injecting the precursor solution obtained in the step (1) into a tube furnace tube in an inert gas atmosphere, and performing high-temperature pyrolysis on the precursor solution to obtain gaseous carbon nanotube aerogel, wherein the precursor solution is injected at a speed of 0.15mL per minute, the high-temperature pyrolysis temperature is 1000 ℃, the inert gas is argon, and the gas flow rate is 4000sccm;
(3) Continuously collecting the gaseous carbon nanotube aerogel obtained in the step (2) through a rolling shaft to obtain an initial carbon nanotube film;
(4) Heating the initial carbon nanotube film obtained in the step (3) in inert gas at a high temperature, and then soaking the film in acid to perform acid treatment to obtain an activated carbon nanotube film, wherein the inert gas is argon, the gas flow rate is 400sccm, the high-temperature heating temperature is 800 ℃, the duration is 12 hours, the reagent adopted in the acid treatment is concentrated sulfuric acid, and the treatment time is 12 hours;
(5) And (3) cleaning and drying the activated carbon nanotube film obtained in the step (4), and then soaking the activated carbon nanotube film in a sulfonating reagent to obtain the densified carbon nanotube film, wherein the sulfonating reagent is chlorosulfonic acid, and the soaking time is 10 minutes.
Test example 1 scanning electron microscope test
Scanning electron microscope testing was performed on the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, and the densified carbon nanotube film prepared in example 3. The results are shown in FIG. 1, and FIGS. 1a and 1b are scanning electron microscope images of the initial carbon nanotube film prepared in example 1; fig. 1c and 1d are sem images of the densified carbon nanotube film prepared in example 2, and fig. 1e, 1f and 2 are sem images of the densified carbon nanotube film prepared in example 3.
The comparison shows that compared with the macropores and finer carbon nanotubes on the surface of the initial carbon nanotube film (P-CNT-M), the pore diameter of the surface of the densified carbon nanotube film (Tr-P-CNT-M-1) prepared by the method in the embodiment 2 is obviously reduced, and the carbon nanotubes are thickened. With the increase of the time for soaking chlorosulfonic acid, the densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3 has a denser surface, the degree of carbon nanotube enrichment is increased, and more obvious carbon nanotube stacked micro-nano structures appear.
Test example 2 Nuclear magnetic resonance and contact Angle test
Nuclear magnetic resonance testing was performed on the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, and the densified carbon nanotube film prepared in example 3. As a result, as shown in the bar graph of fig. 3 (the corresponding axis is left), it can be found that the relaxation times of water of the initial carbon nanotube film (P-CNT-M) prepared in example 1, the densified carbon nanotube film (Tr-P-CNT-M-1) prepared in example 2, and the densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3 gradually decrease, which indicates that the water retention times of the three films decrease, reflecting the enhancement of hydrophilicity of the films.
Contact angle tests were performed on the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, and the densified carbon nanotube film prepared in example 3. As a result, as shown in the line graph in fig. 3 (the corresponding coordinate axis is the right axis), it can be found that the contact angles of the initial carbon nanotube film (P-CNT-M) prepared in example 1, the densified carbon nanotube film (Tr-P-CNT-M-1) prepared in example 2, and the densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3 gradually decrease, which indicates that the adhesiveness of the three films to water gradually increases, reflecting the enhancement of hydrophilicity of the films.
Test example 3 tensile Strength test
Tensile strength tests were performed on the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, and the densified carbon nanotube film prepared in example 3. As a result, as shown in fig. 4, it was found that the initial carbon nanotube film (P-CNT-M) prepared in example 1 was substantially identical to the densified carbon nanotube film (Tr-P-CNT-M-1) prepared in example 2 in terms of tensile strength before 75Mpa pull force, but the densified carbon nanotube film prepared in example 2 could continue to stretch after exceeding 75Mpa, but the densified carbon nanotube film prepared in example 2 had been destroyed, showing that the initial densification could enhance the tensile properties of the film. While the densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3 exhibited approximately 2 times the tensile pressure of the densified carbon nanotube film prepared in example 2 at the same tensile length, indicating that densification can effectively increase the ability of the carbon nanotube film to withstand high tensile strength.
Test example 4 dye removal and dye sieving test
The test process comprises the following steps: dye removal and dye screening tests were performed at 0.1MPa using 1L 100mg/L rhodamine B solution, 1L 100mg/L acid orange G solution, and 1L mixed dye solution containing 50mg/L rhodamine B and 50mg/L acid orange G as test solutions, the initial carbon nanotube film prepared in example 1, the densified carbon nanotube film prepared in example 2, the densified carbon nanotube film prepared in example 3, the densified carbon nanotube film prepared in example 4, and the densified carbon nanotube film prepared in example 5, including three test procedures: the first part was rhodamine B solution filtration for 60 minutes (30 minutes rhodamine B solution filtration for the initial carbon nanotube film prepared in example 1), the second part was acid orange G solution filtration for 10 minutes, and the third part was mixed dye solution filtration for 30 minutes (60 minutes mixed dye solution filtration for the densified carbon nanotube film prepared in example 3).
Test results:
The results of the rhodamine B solution filtration are shown in fig. 5, and it was found by comparison that the initial carbon nanotube film (P-CNT-M) prepared in example 1 had significantly poorer and faster removal of rhodamine B, and thus was subjected to only 30 minutes of filtration. The densified carbon nanotube film (Tr-P-CNT-M-1) prepared in example 2 has improved removal of rhodamine B and decreased more slowly. The densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3 has excellent removal of rhodamine B and still maintains a removal rate of approximately 70% at 60 minutes. In contrast, the removal rates of the densified carbon nanotube film (Tr-P-CNT-M-3) prepared in example 4 and the densified carbon nanotube film (Tr-P-CNT-M-4) prepared in example 5 were relatively close, and were maintained at about 55% between the densified carbon nanotube film (Tr-P-CNT-M-1) prepared in example 2 and the densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3 for 60 minutes.
As shown in fig. 6, the results of the acid orange G solution filtration show that the initial carbon nanotube film (P-CNT-M) prepared in example 1 had significantly poorer acid orange G removal, while the densified carbon nanotube film (Tr-P-CNT-M-1) prepared in example 2 had improved acid orange G removal, but both had less than 20%. Whereas the densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3 has a better removal effect on acid orange G, exceeding 30%. The increased soaking time thus allows smaller membrane pores after densification to facilitate removal of the acid orange G dye. In contrast, the removal rates of the densified carbon nanotube film (Tr-P-CNT-M-3) prepared in example 4 and the densified carbon nanotube film (Tr-P-CNT-M-4) prepared in example 5 were relatively close, at about 25%, and were between the densified carbon nanotube film (Tr-P-CNT-M-1) prepared in example 2 and the densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3. Combining the separation effect of rhodamine B and acid orange G dye solutions, it can be seen that the densified carbon nanotube film (Tr-P-CNT-M-3) prepared in example 4 and the densified carbon nanotube film (Tr-P-CNT-M-4) prepared in example 5 have no significant advantage over the densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3. Therefore, the test of the densified carbon nanotube film (Tr-P-CNT-M-3) prepared in example 4 and the densified carbon nanotube film (Tr-P-CNT-M-4) prepared in example 5 was not performed during the separation of the mixed dye solution.
As shown in fig. 7, the results of the mixed dye solution filtration show that the initial carbon nanotube film (P-CNT-M) prepared in example 1 had significantly worst removal effect on rhodamine B, the first point removal rate was about 70% and decreased rapidly, and the first point removal rate was 40% or more for acid orange G, which failed to show screening performance for two different fuels, and thus filtration was performed for only 30 minutes. The densified carbon nanotube film (Tr-P-CNT-M-1) prepared in example 2 had an improved removal effect on rhodamine B of more than 80% and was relatively stable, but it also had an effect on acid orange G of more than 40%, and could not exhibit sieving performance for two different fuels, so that only 30 minutes of filtration was performed. The densified carbon nanotube film (Tr-P-CNT-M-2) prepared in example 3 has excellent removal effect on rhodamine B, can be stabilized to be more than 90%, can maintain the removal rate of acid orange G to be less than 10% except the first two points, and shows remarkably excellent dye screening performance.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing a densified carbon nanotube film, comprising the steps of:
(1) Mixing a carbon source, a catalyst and a promoter to obtain a precursor solution;
(2) Under the protection of inert gas, injecting the precursor solution into a reactor, and obtaining gaseous carbon nano tube aerogel through high-temperature pyrolysis;
(3) Preparing the gaseous carbon nano tube aerogel into an initial carbon nano tube film;
(4) Under the protection of inert gas, heating the initial carbon nano tube film at high temperature, and then performing acid treatment to obtain an activated carbon nano tube film; the acid treatment is carried out by soaking in an acid treatment reagent for 6-24 hours;
(5) Immersing the activated carbon nanotube film in a sulfonating agent to obtain a densified carbon nanotube film; the soaking time is 5-30 minutes.
2. The method of producing a densified carbon nanotube film of claim 1 wherein in step (1), the volume ratio of carbon source to promoter is 100:1-10:1, wherein the concentration of the catalyst in the precursor solution is 1-10mg/mL.
3. The method of claim 1, wherein the carbon source in step (1) is methanol, ethanol or acetone, the catalyst is ferrocene, and the promoter is thiophene.
4. The method of producing a densified carbon nanotube film of claim 1, wherein the inert gas in step (2) is argon or helium at a gas flow rate of 2000-5000sccm; the pyrolysis temperature is 600-1500 ℃.
5. The method of producing a densified carbon nanotube film of claim 1 wherein the precursor solution in step (2) is injected into the reactor at a rate of 0.1-0.2mL/min.
6. The method of producing a densified carbon nanotube film of claim 1, wherein the inert gas in step (4) is argon or helium at a gas flow rate of 100-500sccm; the high-temperature heating temperature is 600-1500 ℃ and the heating time is 10-15 hours.
7. The method of claim 1, wherein in step (4), the acid treatment agent is concentrated sulfuric acid or concentrated nitric acid.
8. The method of preparing a densified carbon nanotube film of claim 1 wherein in step (5), the sulfonating agent is chlorosulfonic acid.
9. A densified carbon nanotube film prepared by the method of any one of claims 1-8.
10. Use of the densified carbon nanotube film of claim 9 in the field of water treatment.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803594A (en) * | 2005-11-25 | 2006-07-19 | 清华大学 | Large-area ultra-thin carbon nanotube film and its preparation process |
| CN101665247A (en) * | 2009-09-25 | 2010-03-10 | 天津大学 | Method and device for preparing carbon nanotube film |
| CN101830455A (en) * | 2010-04-30 | 2010-09-15 | 北京航空航天大学 | Method for synthesizing continuous carbon nanometer tube film |
| CN102557012A (en) * | 2012-03-12 | 2012-07-11 | 天津大学 | Chemical vapor deposition method for continuously preparing carbon nanotubes with a few walls under condition of no carrier gas |
| CN112174114A (en) * | 2020-10-29 | 2021-01-05 | 南京源昌新材料有限公司 | Mixed carbon nanotube film and preparation method thereof |
| CN112279238A (en) * | 2020-10-29 | 2021-01-29 | 南京源昌新材料有限公司 | Preparation method of high-conductivity double-wall carbon nanotube film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150298164A1 (en) * | 2011-09-13 | 2015-10-22 | William Marsh Rice University | Carbon nanotube films processed from strong acid solutions and methods for production thereof |
| US11873222B2 (en) * | 2019-07-29 | 2024-01-16 | 4th Phase Technologies, Inc. | Highly metallic, hydrophilic, polymer-free carbon nanotube (CNT) thin sheet and uses thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803594A (en) * | 2005-11-25 | 2006-07-19 | 清华大学 | Large-area ultra-thin carbon nanotube film and its preparation process |
| CN101665247A (en) * | 2009-09-25 | 2010-03-10 | 天津大学 | Method and device for preparing carbon nanotube film |
| CN101830455A (en) * | 2010-04-30 | 2010-09-15 | 北京航空航天大学 | Method for synthesizing continuous carbon nanometer tube film |
| CN102557012A (en) * | 2012-03-12 | 2012-07-11 | 天津大学 | Chemical vapor deposition method for continuously preparing carbon nanotubes with a few walls under condition of no carrier gas |
| CN112174114A (en) * | 2020-10-29 | 2021-01-05 | 南京源昌新材料有限公司 | Mixed carbon nanotube film and preparation method thereof |
| CN112279238A (en) * | 2020-10-29 | 2021-01-29 | 南京源昌新材料有限公司 | Preparation method of high-conductivity double-wall carbon nanotube film |
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