CN111229182A - Double-functional group modified carbon nanotube composite material and preparation method thereof - Google Patents
Double-functional group modified carbon nanotube composite material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000000034 method Methods 0.000 claims abstract description 11
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- 238000005406 washing Methods 0.000 claims description 28
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- 239000007822 coupling agent Substances 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
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- 239000000203 mixture Substances 0.000 claims description 10
- 230000002431 foraging effect Effects 0.000 claims description 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 7
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000012024 dehydrating agents Substances 0.000 claims description 6
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- XYWBBDSPFGNYOJ-UHFFFAOYSA-N 3-[diethoxy(methoxy)silyl]propan-1-amine Chemical compound CCO[Si](OCC)(OC)CCCN XYWBBDSPFGNYOJ-UHFFFAOYSA-N 0.000 claims description 4
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
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- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
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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
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- B01J20/26—Synthetic macromolecular compounds
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Abstract
The invention belongs to the technical field of nano adsorption materials, and particularly relates to a bifunctional group modified carbon nanotube composite material and a preparation method thereof. The invention modifies the carboxylated carbon nanotube by a chemical method in a chemical bonding mode, successfully bonds amino and sulfydryl on the surface of the carboxylated carbon nanotube, avoids the problem of internal crosslinking of silicon-oxygen bonds of polysilsesquioxane, has simple and easily operated synthesis process, and has the advantages of good dispersibility, high strength, good adsorption performance and the like.
Description
Technical Field
The invention belongs to the technical field of nano adsorption materials, and particularly relates to a bifunctional group modified carbon nanotube composite material and a preparation method thereof.
Background
The carbon nanotube is a seamless and hollow tube body carbon nanotube rolled by a graphene sheet layer formed by carbon atoms, and due to the unique one-dimensional structure, the carbon nanotube has the performances of high elastic modulus, high strength, high toughness and the like, and the good mechanical properties are proved by experiments and have very wide application prospects, so the carbon nanotube becomes a research hotspot in the field of carbon nanotubes. However, while carbon nanotubes have excellent properties, they also have some disadvantages, such as: 1) the agglomeration phenomenon of the multi-wall carbon nano tube is serious, the multi-wall carbon nano tube is difficult to disperse, and the application range of the multi-wall carbon nano tube is directly influenced by the dispersion performance of the carbon nano tube; 2) the carbon nano tube has strong chemical inertness, so that the carbon nano tube cannot form effective chemical infiltration with a polymer material when being used as a high-strength reinforcing filler, and cannot well adsorb heavy metal ions when being used as an adsorbing material.
In view of the above disadvantages, in order to better utilize the excellent performance of the carbon nanotube itself, the surface of the carbon nanotube needs to be modified, and the methods for modifying the surface of the carbon nanotube mainly include two main types: (1) physical modification method, also called non-covalent modification method, mainly utilizes aromatic compound, surfactant and polymer to make functionalization, or introduces pi-pi bond to make stacking; (2) the chemical modification method is mainly to graft reaction group onto the surface of carbon nanotube via covalent bond, and the reaction may be performed in the head and tail end or defective side wall of carbon nanotube.
The polysilsesquioxane is an organic-inorganic hybrid material because the organic functional group R is connected to the outside of the structure of the polysilsesquioxane and the Si-O inorganic bond is arranged inside the polysilsesquioxane, so that the polysilsesquioxane has unique advantages: 1) the group has high reactivity, and the internal organic group can be connected with various functional groups through chemical reaction, so that the material is endowed with specific physicochemical properties; 2) corrosion resistance, oxidation resistance, good heat resistance and stable mechanical property. In a word, polysilsesquioxane has many excellent performances as an organic-inorganic hybrid material, and can be used in the fields of semiconductor materials, catalysis, adsorption, liquid crystal and the like. However, polysilsesquioxane is difficult to recycle after adsorbing heavy metals, and internal crosslinking of silicon-oxygen bonds occurs in polysilsesquioxane itself, which causes an agglomeration phenomenon and cannot fully exert the function of a functional group.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a bifunctional group modified carbon nanotube composite material and a preparation method thereof.
The technical scheme for solving the technical problems is as follows: a preparation method of a modified carbon nanotube composite material modified by double functional groups comprises the following steps:
(1) taking a carboxylated carbon nanotube, ultrasonically dispersing the carboxylated carbon nanotube in absolute ethyl alcohol until the carboxylated carbon nanotube is uniformly dispersed, carrying out suction filtration, washing the carbon nanotube with the absolute ethyl alcohol, and drying the carbon nanotube in a 60 ℃ drying oven;
(2) taking the carboxylated carbon nanotube solid powder obtained in the step (1), and ultrasonically dispersing in tetrahydrofuran until the powder is uniformly dispersed; continuously adding a dehydrating agent, and performing ultrasonic dispersion for 0.5-1 h;
(3) continuously adding an aminosilane coupling agent into the step (2), reacting for 4-6h under the conditions of magnetic stirring at 15-25 ℃, carrying out suction filtration, washing with tetrahydrofuran and washing with absolute ethyl alcohol, and then placing in a 60 ℃ drying oven for drying to obtain a modified carboxyl carbon nano tube connected with the aminosilane coupling agent;
(4) taking the modified carboxyl carbon nano tube connected with the aminosilane coupling agent in the step (3), and ultrasonically dispersing in a DMSO solution until the modified carboxyl carbon nano tube is uniformly dispersed; then adding an aminosilane coupling agent and a mercaptosilane coupling agent with a molar ratio of 1:1, and stirring and reacting the obtained mixed solution for 12 hours at the temperature of 60 ℃;
(5) after the mixed solution in the step (4) is cooled to 10-25 ℃, adding the gelling agent under the stirring condition, and continuing stirring for 24 hours;
(6) adding the mixed solution obtained in the step (5) into a white plastic bottle, placing the white plastic bottle in an oven for aging, cooling, filtering, washing with absolute ethyl alcohol, wrapping the obtained solid with two layers of filter paper, placing the wrapped solid in a Soxhlet extractor, and performing reflux extraction for 48 hours with absolute ethyl alcohol;
(7) and (4) putting the product obtained in the step (6) into an oven, and drying at 60 ℃ to obtain the amino sulfydryl polysilsesquioxane modified bifunctional-based carbon nanotube composite material.
Further, in the step (1), the carboxyl content in the carboxylated carbon nanotube is 1 to 10 weight percent.
Further, in the step (2), the dehydrating agent is dicyclohexylcarbodiimide; the weight ratio of the carboxylated carbon nanotube solid powder to the dehydrating agent is (5-20) to 1.
Furthermore, the dosage ratio of the carboxylated carbon nanotube solid powder in the step (2) to the aminosilane coupling agent in the step (3) is 1g (3-0.4) mL.
Furthermore, in the step (4), the dosage ratio of the modified carboxyl carbon nano-tube connected with the amino silane coupling agent to the amino silane coupling agent is 1g (3-0.4) mL.
Further, in the step (5), the gelling agent is ammonium fluoride NH4F; the weight ratio of the modified carboxyl carbon nano tubes connected with the amino silane coupling agent in the step (4) to the gelling agent in the step (5) is (1-20): 1.
Further, in the step (6), the white plastic bottle is tetrafluoroethylene or high density polyethylene (0.941-0.96 g/cm)3) Material quality; the specific operation of aging is to place the mixture in an oven at 60-80 ℃ for aging for 7-12 days.
Further, the aminosilane coupling agent in the steps (3) and (4) is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or 3-aminopropylmethoxydiethoxysilane.
Further, the mercaptosilane coupling agent in the step (4) is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.
The second purpose of the invention is to provide the modified carbon nano tube composite material modified by the bifunctional group obtained by the preparation method.
The invention has the characteristics and beneficial effects that:
the invention modifies the carboxylated carbon nanotube by a chemical method in a chemical bonding mode, successfully bonds amino and sulfydryl on the surface of the carboxylated carbon nanotube, avoids the problem of internal crosslinking of silicon-oxygen bonds of polysilsesquioxane, has simple and easily operated synthesis process, and has the advantages of good dispersibility, high strength, good adsorption performance and the like.
Drawings
FIG. 1 is a scanning electron microscope image of raw material carboxylated carbon nanotube CNTs-COOH, the end product of example 1 amino mercapto polysilsesquioxane modified bifunctional base carbon nanotube CNTs-AM, the end product of comparative example 1 amino polysilsesquioxane modified monofunctional base carbon nanotube CNTs-A, the end product of comparative example 2 mercapto polysilsesquioxane modified monofunctional base carbon nanotube CNTs-M and amino silane coupling agent bonded carbon nanotube CNTs-APTMS;
FIG. 2 is an infrared spectrum of the raw material carboxylated carbon nanotube CNTs-COOH in example 1, the end product amino mercapto polysilsesquioxane modified bifunctional base carbon nanotube CNTs-AM in example 1, the end product amino polysilsesquioxane modified monofunctional base carbon nanotube CNTs-A in comparative example 1, the end product mercapto polysilsesquioxane modified monofunctional base carbon nanotube CNTs-M in comparative example 2, and amino silane coupling agent bonded carbon nanotube CNTs-APTMS;
FIG. 3 shows the static saturation adsorption capacity of metal ions by the raw material carboxylated carbon nanotube CNTs-COOH in example 1, the end product amino mercapto polysilsesquioxane modified bifunctional carbon nanotube CNTs-AM in example 1, the end product amino polysilsesquioxane modified monofunctional carbon nanotube CNTs-A in comparative example 1, and the end product mercapto polysilsesquioxane modified monofunctional carbon nanotube CNTs-M in comparative example 2.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
In the embodiment of the invention, CNTs-COOH represents a carboxylated carbon nanotube, CNTs-A represents a monofunctional carbon nanotube modified by amino polysilsesquioxane, CNTs-M represents a monofunctional carbon nanotube modified by mercapto polysilsesquioxane, CNTs-AM represents a bifunctional carbon nanotube modified by amino mercapto polysilsesquioxane, and CNTs-APTMS represents a modified carbon nanotube modified by 3-aminopropyltrimethoxysilane.
Example 1
A preparation method of a modified carbon nanotube composite material modified by double functional groups comprises the following steps:
(1) taking carboxylated carbon nanotube CNTs-COOH with the carboxyl content of 3.86 wt%, ultrasonically dispersing in absolute ethyl alcohol until the dispersion is uniform, carrying out suction filtration, washing with absolute ethyl alcohol, and drying in an oven at 60 ℃;
(2) taking 5g of the carboxylated carbon nanotube solid powder cleaned in the step (1), and ultrasonically dispersing in tetrahydrofuran until the powder is uniformly dispersed; continuously adding 0.5g of dicyclohexylcarbodiimide, and ultrasonically dispersing for 0.5 h;
(3) continuously adding 10mL of 3-aminopropyltrimethoxysilane into the step (2), reacting for 4 hours at 23 ℃ under the condition of magnetic stirring, performing suction filtration, washing twice with tetrahydrofuran and washing twice with absolute ethyl alcohol, and drying in an oven at 60 ℃ to obtain a modified carboxyl carbon nanotube (CNTs-APTMS) connected with an aminosilane coupling agent;
(4) taking 4g of CNTs-APTMS obtained in the step (3), and ultrasonically dispersing in a DMSO solution until the dispersion is uniform; then 10mL of 3-aminopropyltrimethoxysilane and 12mL of 3-mercaptopropyltrimethoxysilane with the molar ratio of 1:1 are added, and the obtained mixed solution is stirred and reacts for 12 hours at the temperature of 60 ℃;
(5) after the mixture of step (4) was cooled to room temperature, 0.6g of ammonium fluoride (NH) was added with stirring4F) Continuously stirring the solid for 24 hours;
(6) adding the mixed solution obtained in the step (5) into a white plastic bottle, placing the white plastic bottle in an oven at 80 ℃ for aging for 7 days, cooling, filtering, washing with absolute ethyl alcohol, wrapping the obtained solid with two layers of filter paper, placing the wrapped solid in a Soxhlet extractor, and performing reflux extraction for 48 hours with absolute ethyl alcohol;
(7) and (4) putting the product obtained in the step (6) into an oven, and drying at 60 ℃ to obtain the CNTs-AM modified by the amino sulfydryl polysilsesquioxane.
Example 2
A preparation method of a modified carbon nanotube composite material modified by double functional groups comprises the following steps:
(1) taking a carboxylated carbon nano tube with the carboxyl content of 3.86 wt%, carrying out ultrasonic dispersion in absolute ethyl alcohol until the carboxyl content is uniformly dispersed, carrying out suction filtration, washing with absolute ethyl alcohol, and drying in a 60 ℃ oven;
(2) taking 3g of the carboxylated carbon nanotube solid powder cleaned in the step (1), and ultrasonically dispersing in tetrahydrofuran until the powder is uniformly dispersed; continuously adding 0.4g of dicyclohexylcarbodiimide, and ultrasonically dispersing for 0.5 h;
(3) continuously adding 8mL of 3-aminopropyltriethoxysilane into the step (2), reacting for 4 hours under the conditions of 23 ℃ and magnetic stirring, performing suction filtration, washing twice with tetrahydrofuran and washing twice with absolute ethyl alcohol, and drying in a 60 ℃ drying oven to obtain the modified carboxyl carbon nanotube connected with the aminosilane coupling agent;
(4) taking 2g of the modified carboxyl carbon nano tubes connected with the aminosilane coupling agent in the step (3), and ultrasonically dispersing in a DMSO solution until the modified carboxyl carbon nano tubes are uniformly dispersed; then 6mL of 3-aminopropyltriethoxysilane and 7mL of 3-mercaptopropyltriethoxysilane with a molar ratio of 1:1 are added, and the obtained mixed solution is stirred and reacts for 12 hours at the temperature of 60 ℃;
(5) after the mixture of step (4) is cooled to room temperature, 0.4g of ammonium fluoride (NH) is added with stirring4F) Continuously stirring the solid for 24 hours;
(6) adding the mixed solution obtained in the step (5) into a white plastic bottle, placing the white plastic bottle in an oven at 80 ℃ for aging for 7 days, cooling, filtering, washing with absolute ethyl alcohol, wrapping the obtained solid with two layers of filter paper, placing the wrapped solid in a Soxhlet extractor, and performing reflux extraction for 48 hours with absolute ethyl alcohol;
(7) and (4) putting the product obtained in the step (6) into an oven, and drying at 60 ℃ to obtain the amino sulfydryl polysilsesquioxane modified bifunctional-based carbon nanotube composite material.
Example 3
A preparation method of a modified carbon nanotube composite material modified by double functional groups comprises the following steps:
(1) taking a carboxylated carbon nano tube with the carboxyl content of 3.86 wt%, carrying out ultrasonic dispersion in absolute ethyl alcohol until the carboxyl content is uniformly dispersed, carrying out suction filtration, washing with absolute ethyl alcohol, and drying in a 60 ℃ oven;
(2) taking 8g of the carboxylated carbon nanotube solid powder cleaned in the step (1), and ultrasonically dispersing in tetrahydrofuran until the powder is uniformly dispersed; continuously adding 0.6g of dicyclohexylcarbodiimide, and ultrasonically dispersing for 0.5 h;
(3) continuously adding 20mL of 3-aminopropyl methoxy diethoxysilane into the step (2), reacting for 4 hours at 23 ℃ under the condition of magnetic stirring, performing suction filtration, washing twice with tetrahydrofuran and washing twice with absolute ethyl alcohol, and then placing the mixture into a drying oven at 60 ℃ for drying to obtain the modified carboxyl carbon nanotube connected with the aminosilane coupling agent;
(4) taking 6g of the modified carboxyl carbon nano tubes connected with the aminosilane coupling agent in the step (3), and ultrasonically dispersing in a DMSO solution until the modified carboxyl carbon nano tubes are uniformly dispersed; then adding 15mL of 3-aminopropyl methoxy diethoxy silane and 18mL of 3-mercaptopropyl triethoxy silane in a molar ratio of 1:1, and stirring the obtained mixed solution at the temperature of 60 ℃ for reaction for 12 hours;
(5) after the mixture of step (4) was cooled to room temperature, 0.8g of ammonium fluoride (NH) was added with stirring4F) Continuously stirring the solid for 24 hours;
(6) adding the mixed solution obtained in the step (5) into a white plastic bottle, placing the white plastic bottle in an oven at 80 ℃ for aging for 7 days, cooling, filtering, washing with absolute ethyl alcohol, wrapping the obtained solid with two layers of filter paper, placing the wrapped solid in a Soxhlet extractor, and performing reflux extraction for 48 hours with absolute ethyl alcohol;
(7) and (4) putting the product obtained in the step (6) into an oven, and drying at 60 ℃ to obtain the amino sulfydryl polysilsesquioxane modified bifunctional-based carbon nanotube composite material.
Comparative example 1
A preparation method of a modified carbon nanotube composite material modified by a single functional group comprises the following steps:
(1) taking a carboxylated carbon nano tube with the carboxyl content of 3.86 wt%, carrying out ultrasonic dispersion in absolute ethyl alcohol until the carboxyl content is uniformly dispersed, carrying out suction filtration, washing with absolute ethyl alcohol, and drying in a 60 ℃ oven;
(2) taking 5g of the carboxylated carbon nanotube solid powder cleaned in the step (1), and ultrasonically dispersing in tetrahydrofuran until the powder is uniformly dispersed; continuously adding 0.5g of dicyclohexylcarbodiimide, and ultrasonically dispersing for 0.5 h;
(3) continuously adding 10mL of 3-aminopropyltrimethoxysilane into the step (2), reacting for 4h under the condition of magnetic stirring at 23 ℃, carrying out suction filtration, washing twice with tetrahydrofuran and washing twice with absolute ethyl alcohol, and then placing the mixture in a drying oven at 60 ℃ for drying to obtain a modified carboxyl carbon nanotube connected with an aminosilane coupling agent, so as to obtain a modified carbon nanotube composite material with amino on the surface, namely CNTs-APTMS;
(4) taking 4g of CNTs-APTMS obtained in the step (3), and ultrasonically dispersing in a DMSO solution until the dispersion is uniform; then adding 18mL of 3-aminopropyltrimethoxysilane, and stirring the obtained mixed solution at the temperature of 60 ℃ to react for 12 hours;
(5) after the mixture of step (4) was cooled to room temperature, 0.6g of ammonium fluoride (NH) was added with stirring4F) Continuously stirring the solid for 24 hours;
(6) adding the mixed solution obtained in the step (5) into a white plastic bottle, placing the white plastic bottle in an oven at 80 ℃ for aging for 7 days, cooling, filtering, washing with absolute ethyl alcohol, wrapping the obtained solid with two layers of filter paper, placing the wrapped solid in a Soxhlet extractor, and performing reflux extraction for 48 hours with absolute ethyl alcohol;
(7) and (4) putting the product obtained in the step (6) into an oven, and drying at 60 ℃ to obtain the amino polysilsesquioxane modified single-functional-group carbon nanotube composite material CNTs-A.
Comparative example 2
A preparation method of a modified carbon nanotube composite material modified by a single functional group comprises the following steps:
(1) taking a carboxylated carbon nano tube with the carboxyl content of 3.86 wt%, carrying out ultrasonic dispersion in absolute ethyl alcohol until the carboxyl content is uniformly dispersed, carrying out suction filtration, washing with absolute ethyl alcohol, and drying in a 60 ℃ oven;
(2) taking 5g of the carboxylated carbon nanotube solid powder cleaned in the step (1), and ultrasonically dispersing in tetrahydrofuran until the powder is uniformly dispersed; continuously adding 0.5g of dicyclohexylcarbodiimide, and ultrasonically dispersing for 0.5 h;
(3) continuously adding 12mL of 3-mercaptopropyltrimethoxysilane into the step (2), reacting for 4 hours under the condition of magnetic stirring at 23 ℃, carrying out suction filtration, washing twice with tetrahydrofuran and washing twice with absolute ethyl alcohol, and then placing the mixture in a drying oven at 60 ℃ for drying to obtain a modified carboxyl carbon nanotube connected with a mercaptosilane coupling agent, thereby obtaining a modified carbon nanotube composite material with mercapto on the surface;
(4) taking 4g of the modified carbon nanotube composite material with the surface provided with the sulfydryl in the step (3), and ultrasonically dispersing in a DMSO solution until the dispersion is uniform; then adding 20mL of 3-mercaptopropyltrimethoxysilane, and stirring the obtained mixed solution at the temperature of 60 ℃ for reaction for 12 hours;
(5) after the mixture of step (4) was cooled to room temperature, 0.6g of ammonium fluoride (NH) was added with stirring4F) Continuously stirring the solid for 24 hours;
(6) adding the mixed solution obtained in the step (5) into a white plastic bottle, placing the white plastic bottle in an oven at 80 ℃ for aging for 7 days, cooling, filtering, washing with absolute ethyl alcohol, wrapping the obtained solid with two layers of filter paper, placing the wrapped solid in a Soxhlet extractor, and performing reflux extraction for 48 hours with absolute ethyl alcohol;
(7) and (4) putting the product obtained in the step (6) into an oven, and drying at 60 ℃ to obtain the single-functional-group carbon nanotube composite material CNTs-M modified by the sulfydryl polysilsesquioxane.
The modified carbon nanotubes obtained in example 1, comparative example 1 and comparative example 2 were used for comparison.
As shown in FIG. 1, CNTs-APTMS has a slightly coarser carbon nanotube surface and a slightly rougher surface compared to the original carboxylated carbon nanotube CNTs-COOH, because the surface is bonded with an aminosilane coupling agent; and the surfaces of the CNTs-AM, the CNTs-A and the CNTs-M are rough, because the surface of the carbon nano tube is coated with a layer of polysilsesquioxane, the feasibility of the preparation method is proved in the aspect of morphology.
As shown in FIG. 2, CNTs-APTMS, CNTs-AM and CNTs-A, CNTs-M are 2928cm higher than that of original carboxylated carbon nanotube CNTs-COOH-1Is the CH connected with Si2The infrared absorption peak of (a) indicates that the first step of bonding the silane coupling agent is successful; CNTs-AM, CNTs-A and CNTs-M at 1000--1An infrared absorption peak of a Si-O-Si structure appears, which indicates that the polysilsesquioxane is successfully loaded.
As shown in FIG. 3, the original carboxylated carbon nanotube CNTs-COOH has very small and almost negligible adsorption performance on metal ions, while the modified carbon nanotube CNTs-AM has a better adsorption effect on metal ions, especially has a better adsorption performance on two metal ions, namely Au (III) and Hg (II), and has a better adsorption selectivity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a bifunctional group modified carbon nanotube composite material is characterized by comprising the following steps:
(1) taking a carboxylated carbon nanotube, ultrasonically dispersing the carboxylated carbon nanotube in absolute ethyl alcohol until the carboxylated carbon nanotube is uniformly dispersed, carrying out suction filtration, washing the carbon nanotube with the absolute ethyl alcohol, and drying the carbon nanotube in a 60 ℃ drying oven;
(2) taking the carboxylated carbon nanotube solid powder obtained in the step (1), and ultrasonically dispersing in tetrahydrofuran until the powder is uniformly dispersed; continuously adding a dehydrating agent, and performing ultrasonic dispersion for 0.5-1 h;
(3) continuously adding an aminosilane coupling agent into the step (2), reacting for 4-6h under the conditions of magnetic stirring at 15-25 ℃, carrying out suction filtration, washing with tetrahydrofuran and washing with absolute ethyl alcohol, and then placing in a 60 ℃ drying oven for drying to obtain a modified carboxyl carbon nano tube connected with the aminosilane coupling agent;
(4) taking the modified carboxyl carbon nano tube connected with the aminosilane coupling agent in the step (3), and ultrasonically dispersing in a DMSO solution until the modified carboxyl carbon nano tube is uniformly dispersed; then adding an aminosilane coupling agent and a mercaptosilane coupling agent with a molar ratio of 1:1, and stirring and reacting the obtained mixed solution for 12 hours at the temperature of 60 ℃;
(5) after the mixed solution in the step (4) is cooled to 10-25 ℃, adding the gelling agent under the stirring condition, and continuing stirring for 24 hours;
(6) adding the mixed solution obtained in the step (5) into a white plastic bottle, placing the white plastic bottle in an oven for aging, cooling, filtering, washing with absolute ethyl alcohol, wrapping the obtained solid with two layers of filter paper, placing the wrapped solid in a Soxhlet extractor, and performing reflux extraction for 48 hours with absolute ethyl alcohol;
(7) and (4) putting the product obtained in the step (6) into an oven, and drying at 60 ℃ to obtain the amino sulfydryl polysilsesquioxane modified bifunctional-based carbon nanotube composite material.
2. The method according to claim 1, wherein in the step (1), the carboxyl group content in the carboxylated carbon nanotube is 1 to 10 wt%.
3. The production method according to claim 1, wherein in the step (2), the dehydrating agent is dicyclohexylcarbodiimide; the weight ratio of the carboxylated carbon nanotube solid powder to the dehydrating agent is (5-20) to 1.
4. The preparation method of claim 1, wherein the ratio of the amount of the carboxylated carbon nanotube solid powder in the step (2) to the amount of the aminosilane coupling agent in the step (3) is 1g (3-0.4) mL.
5. The preparation method according to claim 1, wherein in the step (4), the dosage ratio of the modified carboxyl carbon nanotubes grafted with the aminosilane coupling agent to the aminosilane coupling agent is 1g (3-0.4) mL.
6. The method according to claim 1, wherein in the step (5), the gelling agent is ammonium fluoride (NH)4F; the weight ratio of the modified carboxyl carbon nano tubes connected with the amino silane coupling agent in the step (4) to the gelling agent in the step (5) is (1-20): 1.
7. The method according to claim 1, wherein in the step (6), the white plastic bottle is made of tetrafluoroethylene or high-density polyethylene; the specific operation of aging is to place the mixture in an oven at 60-80 ℃ for aging for 7-12 days.
8. The method according to claim 1, wherein the aminosilane coupling agent used in step (3) (4) is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, or 3-aminopropylmethoxydiethoxysilane.
9. The method according to claim 1, wherein the mercaptosilane coupling agent in the step (4) is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.
10. A bifunctional group modified carbon nanotube composite obtained by the preparation method of any one of claims 1 to 9.
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