CN108636363B - Glutamic acid modified carbon nanotube composite material and preparation method and application thereof - Google Patents

Glutamic acid modified carbon nanotube composite material and preparation method and application thereof Download PDF

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CN108636363B
CN108636363B CN201810545851.2A CN201810545851A CN108636363B CN 108636363 B CN108636363 B CN 108636363B CN 201810545851 A CN201810545851 A CN 201810545851A CN 108636363 B CN108636363 B CN 108636363B
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glutamic acid
carbon nanotube
composite material
nano tube
solution
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CN108636363A (en
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晏铭
宋彪
曾光明
龚继来
谭婷院
张鹏
曹伟成
李娟�
唐旺旺
冯浩鹏
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Hunan University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a glutamic acid modified carbon nanotube composite material, a preparation method and application thereof, wherein the composite material comprises a carbon nanotube, glutamic acid is modified on the surface of the carbon nanotube, and the mass content of carboxyl in the composite material is 2-3%. The preparation method comprises the following steps: carrying out oxidation treatment on the carbon nano tube; preparing an activated carbon nanotube intermediate; and mixing the activated carbon nanotube intermediate with a glutamic acid solution for reaction to prepare the glutamic acid modified carbon nanotube composite material. The composite material has the advantages of stable structure, strong adsorption capacity, good biocompatibility, high practical application value and the like, and the preparation method has the advantages of simple process, easiness in operation, mild and controllable reaction conditions, low cost, low energy consumption, short time consumption and the like. The composite material can be used for adsorbing dye and heavy metal in water, has obvious adsorption and removal effects, has higher application value in the aspect of treating polluted water, and has wide application prospect.

Description

Glutamic acid modified carbon nanotube composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of environment nano new functional materials, and relates to a glutamic acid modified carbon nano tube composite material, and a preparation method and application thereof.
Background
With the development of industry and agriculture and the enlargement of urban construction scale, a large amount of domestic sewage, industrial wastewater, industrial waste residues, construction waste, chemical fertilizers and pesticides and the like are discharged into lake and river wetland systems, so that the serious pollution problem of wetland environment is caused. Therefore, proper treatment measures are urgently needed to be taken to effectively treat the polluted wetland water body and bottom mud, and a novel functional nano material with high-efficiency adsorption capacity and low ecological toxicity risk for pollutants is developed, so that the method has important value and significance for treating wetland pollution.
The carbon nanotube material has great application prospect in the aspects of environmental protection and pollution control as a typical one-dimensional functional nano material. The unique hollow tube body structure and the huge specific surface area of the carbon nano tube enable the carbon nano tube to have good adsorption performance on a plurality of pollutants, especially hydrophobic organic pollutants (such as polycyclic aromatic hydrocarbon, polychlorinated biphenyl, organic chlorine pesticide and the like), and the potential environmental risk and the ecological toxicity of the carbon nano tube material are one of the main bottlenecks which limit the application of the carbon nano tube in the aspect of environmental pollution control at present. In addition, the carbon nano tube has weak adsorption capacity to heavy metals, and the wide use of the carbon nano tube in the aspect of environmental pollution treatment is also limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a glutamic acid modified carbon nanotube composite material with stable structure, strong adsorption capacity, good biocompatibility and high practical application value, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a glutamic acid modified carbon nanotube composite material comprises a carbon nanotube, wherein glutamic acid is modified on the surface of the carbon nanotube; the mass content of carboxyl in the glutamic acid modified carbon nano tube composite material is 2-3%.
As a general technical concept, the present invention also provides a method for preparing the glutamic acid modified carbon nanotube composite material, comprising the following steps:
s1, carrying out oxidation treatment on the carbon nano tube;
s2, activating the carbon nano tube subjected to oxidation treatment in the step S1 by adopting a 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide solution, and adding an N-hydroxysuccinimide solution for reaction to obtain an activated carbon nano tube intermediate;
and S3, mixing the activated carbon nanotube intermediate obtained in the step S2 with a glutamic acid solution for reaction to obtain the glutamic acid modified carbon nanotube composite material.
In the above preparation method, further improvement is provided, in the step S2, the activation is that the carbon nanotubes subjected to oxidation treatment in the step S1 are mixed with a 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide solution and stirred uniformly; the reaction is carried out at the temperature of 60-80 ℃ and the rotating speed of 120-200 rpm for 1-2 h.
In the above preparation method, further improved, in the step S2, the mass-to-volume ratio of the oxidized carbon nanotube, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide solution and the N-hydroxysuccinimide solution is 0.5 g-1 g: 10 mL; the concentration of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide solution is 0.05-0.10M; the concentration of the N-hydroxysuccinimide solution is 0.05M-0.10M.
In the above preparation method, further improvement is provided, in step S3, the volume ratio of the activated carbon nanotube intermediate to the glutamic acid solution is 1.2: 1; the concentration of the glutamic acid solution is 5 g/L-10 g/L.
In the above preparation method, further improvement is that in the step S3, the reaction is carried out at 60 ℃ to 80 ℃ and the rotation speed is 120rpm to 200rpm, and the stirring is carried out for 4h to 6 h.
In the above preparation method, further improvement is that, in step S1, the oxidation treatment is: mixing the carbon nano tube with mixed acid liquor of concentrated sulfuric acid and concentrated nitric acid, carrying out ultrasonic treatment, heating to boil, filtering, washing and drying; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid liquid of the concentrated sulfuric acid and the concentrated nitric acid is 3: 1; the ultrasonic treatment time is 30-60 min; keeping for 4-6 h after heating and boiling; ultrapure water is adopted for washing; the washing times are 3-5 times; the drying is vacuum drying; the vacuum drying time is 12-18 h.
As a general technical concept, the invention also provides an application of the glutamic acid modified carbon nano tube composite material or the glutamic acid modified carbon nano tube composite material prepared by the preparation method in adsorbing dye and/or heavy metal in water.
The application is further improved, and comprises the following steps: mixing the carbon nano tube composite material modified by the glutamic acid with a water body containing dye and/or heavy metal for oscillation treatment to complete the adsorption treatment of the dye and the heavy metal in the water body; the mass volume ratio of the glutamic acid modified carbon nano tube composite material to the water containing dye and/or heavy metal is 0.05 g-0.5 g: 1L.
In the above application, further improvement is that in the water body containing the dye and/or the heavy metal, the dye is methylene blue, and the heavy metal is lead; the initial concentration of the dye in the water body containing the dye is 1 mg/L-10 mg/L; the initial concentration of lead in the water body containing heavy metals is 25 mg/L-200 mg/L; the temperature of the oscillation treatment is 20-30 ℃; the rotation speed of the oscillation treatment is 150 rpm-240 rpm; the time of the oscillation treatment is 24-48 h.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a glutamic acid modified carbon nanotube composite material which comprises a carbon nanotube, wherein glutamic acid is modified on the surface of the carbon nanotube. In the present invention, glutamic acid is one of amino acids constituting a protein, plays an important role in the protein metabolism of an organism, and participates in many important chemical reactions in the organism. From the molecular structure, the glutamic acid molecule has two carboxyl groups, is an acidic amino acid, and has good water solubility, degradability and biocompatibility. Glutamic acid is modified on the surface of the carbon nano tube through covalent grafting, so that the adsorption capacity of the carbon nano tube on organic dye and heavy metal ions is improved, and the biocompatibility of the carbon nano tube material is enhanced; meanwhile, the carbon nano tube is connected with the glutamic acid through a stable amide bond, so that the structure is stable. According to the invention, glutamic acid is used for modifying the carbon nano tube, so that the hydrophilicity, adsorption capacity, biocompatibility and stability of the adsorption material are improved, and the application of the carbon nano tube material in the aspect of treating polluted water is expanded. The glutamic acid modified carbon nanotube composite material has the advantages of stable structure, strong adsorption capacity, good biocompatibility, high practical application value and the like, can be used for adsorbing organic dyes (such as methylene blue) and heavy metals (such as lead) in water, and is a novel carbon nanotube material with great prospect.
(2) In the glutamic acid modified carbon nano tube composite material, 2 carboxyl groups exist in one glutamic acid molecule, the glutamic acid is modified on the surface of the carbon nano tube, so that the content of the carboxyl groups on the surface of the material is increased, and the higher the content of the carboxyl groups is, the stronger the adsorption removal capacity on metal ions and cationic organic matters is, so that the mass content of the carboxyl groups in the glutamic acid modified carbon nano tube composite material is 2-3%, and the composite material can be ensured to have stronger adsorption removal capacity.
(3) The invention also provides a preparation method of the glutamic acid modified carbon nanotube composite material, which takes the carbon nanotube as a raw material and generates carboxyl on the surface of the carbon nanotube through oxidation treatment; the carbon nano tube after oxidation treatment is subjected to carboxyl activation by adopting a 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide solution to generate a substance with a high-activity ortho-acylisourea structure, the substance can rapidly generate hydrolysis reaction in the solution, then an N-hydroxysuccinimide solution is added for reaction to generate more stable succinimide ester, hydrolysis is inhibited, and an activated carbon nano tube intermediate is obtained. On the basis, the invention adopts a covalent grafting method to modify glutamic acid on the surface of the carbon nano tube, which specifically comprises the following steps: mixing the activated carbon nanotube intermediate with a glutamic acid solution, and introducing glutamic acid on the surface of the carbon nanotube through reaction; meanwhile, the succinimide ester in the activated carbon nanotube intermediate and the amino group in the glutamic acid are subjected to an affinity substitution reaction to form a stable amido bond, and the carbon nanotube and the glutamic acid are connected by the stable amido bond, so that the glutamic acid can be more stably modified on the surface of the carbon nanotube and cannot fall off from the carbon nanotube in the using process, and the problem that the modified carbon nanotube material is unstable is solved; in addition, the invention reduces the damage to the carbon nano tube material body by strictly controlling the reaction conditions, such as controlling the temperature in the preparation process, thereby ensuring that the glutamic acid modified carbon nano tube composite material keeps better adsorption removal capability. Therefore, the modified carbon nanotube material prepared by the method has the advantages of stable structure, strong adsorption capacity, good stabilizing effect and the like; meanwhile, the preparation method has the advantages of simple process, easiness in operation, mild and easily-controlled reaction conditions, low cost, low energy consumption, short consumed time and the like, is suitable for continuous large-scale batch production, and is convenient for industrial utilization.
(4) The invention also provides application of the glutamic acid modified carbon nano tube composite material in adsorption of dyes and heavy metals in water, and the adsorption treatment of the dyes and the heavy metals in the water can be realized by mixing the glutamic acid modified carbon nano tube composite material with the water containing the dyes and/or the heavy metals for oscillation treatment. Taking a water body containing methylene blue as an example, the glutamic acid modified carbon nano tube composite material has stronger adsorption capacity to the methylene blue in the water body, when the initial concentration of the methylene blue in the water body is 5mg/L, the adsorption amount is up to 89.38mg/g, and is increased by 69mg/g compared with the original carbon nano tube; meanwhile, the glutamic acid modified carbon nanotube composite material has stronger adsorption capacity to lead in a water body, when the initial concentration of lead ions in the water body is 75mg/L, the adsorption capacity is up to 31.34mg/g, and the adsorption capacity is improved by 28.252mg/g compared with that of the original carbon nanotube. The glutamic acid modified carbon nano tube composite material has good adsorption capacity on dye (such as methylene blue), also has good adsorption capacity on heavy metal (such as lead), has obvious adsorption and removal effects on dye and heavy metal in water, is suitable for repairing polluted water, can realize effective treatment on dye and heavy metal polluted water, has high application value in the aspect of treating polluted water, and has wide application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is an SEM image of the glutamic acid-modified carbon nanotube composite material prepared in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the processes used were conventional processes, the equipment used were conventional equipment, and the data obtained were average values of three or more experiments.
Example 1:
a glutamic acid modified carbon nanotube composite material comprises a carbon nanotube, wherein glutamic acid is modified on the surface of the carbon nanotube, and the glutamic acid is modified on the surface of the carbon nanotube through covalent grafting. The mass content of carboxyl in the glutamic acid modified carbon nanotube composite material is 2.26% (w/w).
The preparation method of the glutamic acid modified carbon nanotube composite material in the embodiment comprises the following steps:
(1) carrying out oxidation treatment on the carbon nano tube: putting 1g of multi-walled carbon nanotubes (commercially available, the multi-walled carbon nanotubes have the outer diameter of 10-20 nm and the length of 5-20 microns) into a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid (the mixed solution is formed by mixing 150mL of concentrated sulfuric acid and 50mL of concentrated nitric acid), performing ultrasonic treatment for 30 minutes, heating and boiling, keeping for 6 hours, cooling, performing suction filtration to remove the acid solution, filtering to obtain solid matters, washing the solid matters with ultrapure water for 5 times, and performing vacuum drying on the washed solid matters for 18 hours to obtain the carbon nanotubes subjected to oxidation treatment.
(2) Dispersing 1g of the carbon nanotube subjected to oxidation treatment obtained in the step (1) in 100mL of ultrapure water, adding 10mL of a 0.05M 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide solution, uniformly stirring, activating the carbon nanotube subjected to oxidation treatment, adding 10mL of a 0.05M N-hydroxysuccinimide solution, and continuously stirring at a rotation speed of 150rpm at 60 ℃ for 2 hours (even if the activated carbon nanotube reacts with the N-hydroxysuccinimide solution to generate more stable succinimide ester), thereby obtaining an activated carbon nanotube intermediate.
(3) Dispersing 1g of glutamic acid in 100mL of ultrapure water, heating, stirring and dissolving to obtain a glutamic acid solution; and (3) mixing a glutamic acid solution with the activated carbon nanotube intermediate in the step (2), continuously stirring at a constant temperature of 60 ℃ and a rotation speed of 200rpm for 6 hours (namely, succinimide ester in the activated carbon nanotube intermediate and amino in glutamic acid are subjected to an affinity substitution reaction to form a stable amido bond), cooling to room temperature, filtering, drying a solid, and grinding to obtain the glutamic acid modified carbon nanotube composite material.
The appearance of the glutamic acid modified carbon nanotube composite material prepared in the embodiment 1 of the invention is black powder. The glutamic acid-modified carbon nanotube composite material prepared in example 1 of the present invention was observed under a scanning electron microscope, and the result is shown in fig. 1. Fig. 1 is an SEM image of the glutamic acid-modified carbon nanotube composite material prepared in example 1 of the present invention. As can be seen from FIG. 1, the glutamic acid modified carbon nanotube composite material still has a large number of elongated tubular structures, and has no obvious difference from the common carbon nanotubes in appearance.
Example 2:
an application of a glutamic acid modified carbon nanotube composite material in adsorbing dye in water, in particular to an application in adsorbing methylene blue in water, which comprises the following steps:
weighing two parts of the glutamic acid modified carbon nanotube composite material prepared in the example 1 according to the mass-to-volume ratio of the glutamic acid modified carbon nanotube composite material to a water body (methylene blue aqueous solution) of 0.05 g: 1L, respectively adding the two parts into methylene blue aqueous solutions with the concentrations of 3mg/L and 5mg/L (the volume of the solution is 100mL), uniformly mixing, and carrying out constant-temperature oscillation treatment for 24 hours at the rotation speed of 180rpm and the temperature of 25 ℃ in a dark condition to complete the treatment of the methylene blue aqueous solution. After the oscillation treatment, the mixture was allowed to stand for precipitation, the supernatant was taken and the concentration of methylene blue was measured with an ultraviolet-visible spectrophotometer, and the adsorption amount of the glutamic acid-modified carbon nanotube composite material to methylene blue was calculated, and the results are shown in table 1.
The unmodified original carbon nanotube is used as a control and is used for adsorbing methylene blue in a water body under the same condition. The results of the adsorption of methylene blue by the pristine carbon nanotubes are shown in Table 1.
TABLE 1 adsorption of various materials on methylene blue in water
Initial concentration of methylene blue (mg/L) 3 5
Original carbon nanotube (mg/g) 17.44 20.38
Glutamic acid modified carbon nano-tube (mg/g) 55.86 89.38
As can be seen from the results in table 1, compared with the original carbon nanotube, the adsorption capacity of the glutamic acid-modified carbon nanotube composite material prepared in example 1 of the present invention to methylene blue in an aqueous solution is significantly increased, wherein when the initial concentration of methylene blue is 5mg/L, the adsorption capacity of the glutamic acid-modified carbon nanotube composite material to methylene blue in a water body is up to 89.38mg/g, which is increased by 69mg/g compared with the original carbon nanotube, which indicates that the modification of glutamic acid on the surface of the carbon nanotube in the present invention has a significant enhancing effect on the improvement of the adsorption capacity of the carbon nanotube to organic dye molecules.
Example 3:
an application of a glutamic acid modified carbon nanotube composite material in adsorbing heavy metals in a water body, in particular to an application in adsorbing lead in the water body, which comprises the following steps:
weighing two parts of the glutamic acid modified carbon nanotube composite material prepared in the example 1 according to the mass-to-volume ratio of the glutamic acid modified carbon nanotube composite material to a water body (lead ion aqueous solution) of 0.05 g: 1L, respectively adding the two parts into 25mg/L and 75mg/L lead ion aqueous solutions (the volume of the solutions is 100mL), uniformly mixing, and carrying out constant-temperature oscillation treatment at the rotating speed of 180rpm and the temperature of 25 ℃ for 24 hours to finish the treatment of the lead ion aqueous solution. After the completion of the shaking treatment, the mixture was allowed to stand for precipitation, and the supernatant was taken to measure the lead concentration by atomic absorption spectrophotometry, whereby the adsorption amount of the glutamic acid-modified carbon nanotube composite material to lead was calculated, and the results are shown in table 2.
The unmodified original carbon nanotube is used as a control and is used for adsorbing the lead in the water body under the same condition. The adsorption amount of lead to the pristine carbon nanotubes was as shown in Table 2.
TABLE 2 adsorption of lead in water by different materials
Initial concentration of lead (mg/L) 25 75
Original carbon nanotube (mg/g) 2.098 3.088
Glutamic acid modified carbon nano-tube (mg/g) 24.08 31.34
As can be seen from the results in table 2, the adsorption capacity of the glutamic acid-modified carbon nanotube composite material prepared in example 1 of the present invention to lead in an aqueous solution is significantly increased as compared to the original carbon nanotube. When the initial concentration of lead ions is 75mg/L, the adsorption capacity of the carbon nanotube composite material modified by glutamic acid on lead in a water body is up to 31.34mg/g, which is improved by 28.252mg/g compared with the original carbon nanotube, and the glutamic acid modified on the surface of the carbon nanotube has obvious enhancement effect on the capacity of the carbon nanotube for adsorbing heavy metals.
The glutamic acid is used for modifying the carbon nano tube, so that the hydrophilicity, the adsorption capacity, the biocompatibility and the stability of the adsorption material are improved, and the application of the carbon nano tube material in polluted water is expanded. The glutamic acid modified carbon nanotube composite material has the advantages of stable structure, strong adsorption capacity, good biocompatibility, high practical application value and the like, and is a novel carbon nanotube material with great prospect. The glutamic acid modified carbon nano tube composite material has good adsorption capacity on dye (such as methylene blue), also has good adsorption capacity on heavy metal (such as lead), has obvious adsorption and removal effects on dye and heavy metal in water, is suitable for repairing polluted water, can realize effective treatment on dye and heavy metal composite polluted water, has high application value in the aspect of treating polluted water, and has wide application prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.

Claims (9)

1. A preparation method of a glutamic acid modified carbon nanotube composite material is characterized by comprising the following steps:
s1, carrying out oxidation treatment on the carbon nano tube;
s2, activating the carbon nano tube subjected to oxidation treatment in the step S1 by adopting a 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide solution, and adding an N-hydroxysuccinimide solution for reaction to obtain an activated carbon nano tube intermediate;
s3, mixing the activated carbon nanotube intermediate obtained in the step S2 with a glutamic acid solution for reaction to obtain a glutamic acid modified carbon nanotube composite material;
the glutamic acid modified carbon nanotube composite material comprises a carbon nanotube, wherein glutamic acid is modified on the surface of the carbon nanotube; the mass content of carboxyl in the glutamic acid modified carbon nano tube composite material is 2-3%.
2. The method according to claim 1, wherein in step S2, the activation is performed by mixing the carbon nanotubes subjected to oxidation treatment in step S1 with a solution of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, and stirring the mixture uniformly; the reaction is carried out at the temperature of 60-80 ℃ and the rotating speed of 120-200 rpm for 1-2 h.
3. The method according to claim 2, wherein in step S2, the mass-to-volume ratio of the oxidized carbon nanotube, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide solution and the N-hydroxysuccinimide solution is 0.5g to 1 g: 10 mL; the concentration of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide solution is 0.05-0.10M; the concentration of the N-hydroxysuccinimide solution is 0.05M-0.10M.
4. The method according to claim 1, wherein in step S3, the volume ratio of the activated carbon nanotube intermediate to the glutamic acid solution is 1.2: 1; the concentration of the glutamic acid solution is 5 g/L-10 g/L.
5. The method according to claim 1, wherein the reaction is carried out at 60 ℃ to 80 ℃ for 4 to 6 hours by stirring at a rotation speed of 120rpm to 200rpm in the step S3.
6. The production method according to any one of claims 1 to 5, wherein in the step S1, the oxidation treatment is: mixing the carbon nano tube with mixed acid liquor of concentrated sulfuric acid and concentrated nitric acid, carrying out ultrasonic treatment, heating to boil, filtering, washing and drying; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid liquid of the concentrated sulfuric acid and the concentrated nitric acid is 3: 1; the ultrasonic treatment time is 30-60 min; keeping for 4-6 h after heating and boiling; ultrapure water is adopted for washing; the washing times are 3-5 times; the drying is vacuum drying; the vacuum drying time is 12-18 h.
7. The application of the glutamic acid modified carbon nanotube composite material prepared by the preparation method of any one of claims 1-6 in adsorption of dyes and/or heavy metals in water.
8. Use according to claim 7, characterized in that it comprises the following steps: mixing the carbon nano tube composite material modified by the glutamic acid with a water body containing dye and/or heavy metal for oscillation treatment to complete the adsorption treatment of the dye and/or heavy metal in the water body; the mass volume ratio of the glutamic acid modified carbon nano tube composite material to the water containing dye and/or heavy metal is 0.05 g-0.5 g: 1L.
9. The use according to claim 8, wherein in the water body containing the dye and/or the heavy metal, the dye is methylene blue, and the heavy metal is lead; the initial concentration of the dye in the water body containing the dye is 1 mg/L-10 mg/L; the initial concentration of lead in the water body containing heavy metals is 25 mg/L-200 mg/L; the temperature of the oscillation treatment is 20-30 ℃; the rotation speed of the oscillation treatment is 150 rpm-240 rpm; the time of the oscillation treatment is 24-48 h.
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