CN111500001B - Preparation method and application of carbon nanotube nano composite material - Google Patents
Preparation method and application of carbon nanotube nano composite material Download PDFInfo
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Abstract
The invention discloses a method for preparing a carbon nano tube inorganic nano composite material by using a polymer. The method is characterized in that after covalent modification is carried out on the surface of the carbon nano tube, a polymer with a complexing group is introduced on the surface of the carbon nano tube through surface atom transfer radical polymerization reaction, a precursor grows in situ on a grafting site, and the carbon nano tube nano composite material with high load rate and excellent dispersion performance is synthesized. The method has the advantages of simple synthesis method, mild reaction conditions, simple and effective regulation and control of the morphology of the composite material and the like.
Description
Technical Field
The invention belongs to the field of nano composite materials, and particularly relates to a preparation method of a carbon nano tube nano particle composite material.
Background
Carbon nanotubes are a particular crystalline structure in the form of a hollow and closed tube, consisting of one or more rolled graphene. Since their discovery in 1991, carbon nanotubes have attracted extensive interest in the scientific community of physics, chemistry and materials all over the world. The carbon nanotube has the advantages of large specific surface area, high conductivity, excellent chemical and electrochemical stability, adjustable nanotube cavity structure, large length-diameter ratio, etc. and is widely applied to the aspects of hydrogen storage materials, field emission materials, battery materials, reinforced composite materials, sensor materials, catalyst carrier materials, etc. The nano particles have extremely large specific surface area and size effect, and the compound formed by loading the nano particles on the carbon nano tube has extremely excellent performance. Different loading of nanoparticles on carbon nanotubes can be applied in different directions. For example, the carbon nanotube surface loaded with noble metal nanoparticles can be applied to the fields of electrochemical cells, fuel cells, catalytic reactions, biomedicine and the like, and the composite formed by loading inorganic semiconductor nanoparticles on the carbon nanotube can be applied to the fields of thermoelectric materials, photoelectric materials, solar cells and the like. However, in general, carbon nanotubes have strong hydrophobicity and cannot be infiltrated by a liquid with a surface tension of more than 100 to 200mN/m, most of nanoparticles cannot be carried on the surface of the carbon nanotubes, and the nanoparticles are easy to fall off and agglomerate to grow during ultrasonic oscillation, stirring or heating, so that the surface of the carbon nanotubes is usually subjected to proper oxidation treatment, and functional groups such as hydroxyl, carboxyl, aldehyde and the like are introduced, and the functional groups can adsorb the nanoparticles and become active sites for the deposition of the nanoparticles. However, the number of such surface functional groups is limited and the distribution is not uniform. In addition, although the performance of the composite material can be improved by increasing the loading amount of the nanoparticles on the surface of the carbon nanotubes, the nanoparticles are easily agglomerated on the surface of the carbon nanotubes with the increase of the content of the nanoparticles, so that the dispersibility of the nanoparticles is reduced, thereby affecting the overall performance of the composite material. At present, the dispersibility and the load capacity of the carbon nano tube nano particle compound prepared by the prior art are difficult to meet the requirements at the same time, thereby influencing the performance and the application range of the carbon nano tube composite material. Therefore, the method for improving the loading of the nano particles on the surface of the carbon nano tube and uniformly dispersing the nano particles on the surface of the carbon nano tube becomes a research hotspot for preparing the carbon nano tube nano particle composite material.
Disclosure of Invention
Aiming at the defects of poor dispersity and low load of carbon nano tube loaded nano particles, the invention provides a preparation method of a carbon nano tube nano particle composite material. Compared with the prior art, the method is characterized in that the polymer with the complexing group is connected to the surface of the carbon nano tube through a covalent bond through free radical polymerization reaction to be used as an active site for nano particle deposition. The strong complexation effect exists between the complexation group on the polymer and the nano particle precursor, so that the nano particle precursor can be effectively adsorbed on the surface of the carbon nano tube, and can be dispersed and uniformly grown on the surface of the carbon nano tube in the subsequent nano crystal growth process. The method can effectively improve the loading capacity and the dispersity of the nano particles on the carbon nano tubes.
A preparation method of a carbon nano tube nano particle composite material is characterized by comprising the following steps:
in the first step, a reaction site which can initiate an atom transfer radical reaction on the surface modification of the carbon nano tube through a chemical reaction is used as a carbon nano tube macroinitiator.
Step 1, dispersing carbon nanotubes in a concentrated nitric acid solution by ultrasonic, heating to 100-120 ℃, carrying out reflux reaction for 6-12 h under magnetic stirring, cooling to room temperature, diluting with distilled water, carrying out vacuum filtration by using a filter funnel with an aperture G5, diluting a filtrate with distilled water, carrying out vacuum filtration, washing with deionized water to be neutral, and drying in a vacuum drying oven. After the reaction, the carbon tube surface has many reaction sites of carboxyl and hydroxyl for subsequent functionalization.
In an embodiment of the present invention, the carbon nanotube may be one or more of a single-walled carbon nanotube, a double-walled carbon nanotube, or a multi-walled carbon nanotube. The carbon nano tube can be prepared by methods such as an arc discharge method, a chemical vapor deposition method or a laser evaporation method, and the multi-walled carbon nano tube is prepared by the chemical vapor deposition method in the embodiment of the invention. The inner diameter of the multi-wall carbon nano tube is 10nm to 50nm, the outer diameter is 30nm to 80nm, and the length is 50 mu m to 100 mu m.
And 2, dispersing the acidified carbon nano tube in a thionyl chloride solution by ultrasonic, heating to 60 ℃, and reacting for 24 hours under magnetic stirring. After the reaction, the carboxyl group on the surface of the carbon nano tube is substituted by acyl, so that the acylated carbon nano tube (MWCNT-COCl) can be obtained. After removing the reaction liquid by centrifugation, the acylated carbon nano tube is washed by anhydrous THF for a plurality of times and is dried in a vacuum drying oven at 50 ℃ for 2h to obtain the acylated carbon nano tube.
And 3, dispersing the acylated carbon nano tube in a dihydric alcohol compound or a dihydric amine compound by ultrasonic, heating to 100-120 ℃, and reacting for 24 hours under magnetic stirring. And centrifuging the hydroxylated carbon nanotube to remove reaction liquid, washing with absolute ethyl alcohol for several times, and drying in a vacuum drying oven at 50 ℃ for 24 hours. In this step, the acyl group on the surface of the carbon nanotube is substituted with a hydroxyl group or an amino group to obtain a hydroxylated or aminated carbon nanotube (MWCNT-OH/MWCNT-NH)2)。
In the embodiment of the present invention, as specific examples thereof, the dihydric alcohol may be exemplified by, but not limited to, ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, tetraethylene glycol, neopentyl glycol, 1, 6-hexanediol, octanediol, nonanediol, decanediol, diethylene glycol, and the like.
In the embodiment of the present invention, specific examples of the diamine include, but are not limited to, methylenediamine, 1, 2-ethylenediamine, propylenediamine, 1, 2-diaminopropane, 1, 3-diaminopentane, hexamethylenediamine, diaminoheptane, diaminododecane, diethylaminopropylamine, and the like.
And 4, preparing the carbon nano tube macromolecular initiator. Ultrasonically dispersing the hydroxylated carbon nano tube in N-methyl pyrrolidone (NMP), adding 2-bromine isobutyryl bromide under the magnetic stirring of ice-water bath, and reacting for 24 hours at normal temperature. And centrifuging to remove reaction liquid, washing with dichloromethane and ethanol respectively, and drying in a vacuum drying oven at 50 ℃ for 24h to obtain the carbon nanotube macroinitiator (MWCNT-Br).
The carbon nano tube macromolecular initiator contains a structure shown in the following general formula,
wherein X is selected from O, NH; l is a divalent linking group;
the number of carbon atoms of L is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10.
The structure of L is not particularly limited and includes, but is not limited to, a single bond, a linear structure, a branched structure containing a pendant group. L is selected from C1-20Alkylene, divalent C1-20Heterohydrocarbyl, substituted C1-20Alkylene, substituted divalent C1-20Any divalent linking group or combination of divalent linking groups in the heterohydrocarbon group. The substituent atom or the substituent is not particularly limited, and is selected from a halogen atom, a hydrocarbon substituent, and a heteroatom-containing substituent.
Secondly, preparing a polymer-based carbon nanotube structure as a carrier by the carbon nanotube initiator through active atom transfer radical reaction;
and 5, adding a carbon nano tube macroinitiator, a polymer monomer, a catalyst for active polymerization and a solvent into a reaction bottle, uniformly mixing, introducing nitrogen for bubbling, reacting for 8-48 h at 25-120 ℃ in an oil bath, stopping, centrifuging the product, washing for several times by using dichloromethane, and drying for 24h at 30-50 ℃ in a vacuum oven.
In the embodiment of the present invention, specific examples of the polymer having a complexing group include, but are not limited to, polyacrylic acid, poly-2-vinylpyridine, poly-4-vinylpyridine, polyvinylpyrrolidone, polyacrylonitrile, polyvinylbenzenesulfonic acid, polyisopropenephosphonic acid, and the like.
The polymer containing a complexing group may be obtained by first polymerizing a precursor and then subjecting the precursor to a hydrolysis reaction, if necessary. For example, when preparing polyacrylic acid based carbon nanotube (MWCNT-PAA), tert-butyl acrylate (tBA) is used as a polymer monomer to react according to the steps to obtain polyacrylic acid tert-butyl ester based carbon nanotube (MWCNT-PtBA), and then hydrolysis is carried out to obtain polyacrylic acid based carbon nanotube. The specific hydrolysis step is that the carbon nanotube-based poly (tert-butyl acrylate) is dispersed in dichloromethane, excessive trifluoroacetic acid is added, and the reaction is carried out for 24 hours under magnetic stirring. And (3) centrifuging the product after the reaction is finished, washing the product for a plurality of times by using absolute ethyl alcohol, and drying the product in a vacuum oven at 50 ℃ for 24 hours to obtain the polyacrylic acid-based carbon nanotube.
In an embodiment of the invention, the living polymerization reaction is synergistically catalyzed by a monovalent copper compound in combination with an amine ligand. As specific examples thereof, the monovalent copper compound may be selected from Cu (I) salts such as CuCl, CuBr, CuI, CuCN, CuOAc, etc.; may also be selected from Cu (I) complexes, e.g. [ Cu (CH)3CN)4]PF6、[Cu(CH3CN)4]OTf、CuBr(PPh3)3Etc.; among them, the Cu (I) salt is preferably CuBr and CuI, and the Cu (I) complex is preferably CuBr (PPh)3)3. The amine ligand can be selected from Pentamethyldiethylenetriamine (PMDETA), and tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), tris [ (1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl]Amines (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), and the like; whereinThe amine ligand is preferably PMDETA and TBTA. The amount of the catalyst used is not particularly limited, but is usually 0.1 to 2% by weight.
In the embodiment of the present invention, the temperature and time of the living polymerization reaction are related to the kind of the polymer monomer, the temperature of the polymerization reaction may be 25 to 120 ℃, and the reaction time is preferably 8 to 48 hours.
And thirdly, reacting the carrier with an inorganic precursor through a chemical synthesis method to prepare the carbon nano tube nano particle composite material.
The chemical synthesis method comprises one or more of a colloid method, a solution reduction method, an impregnation method, an electrochemical deposition method and a supercritical fluid method. In the embodiment of the present invention, the solution reduction method is preferable.
The specific steps of the solution reduction method are that the carrier and the inorganic precursor are mixed and dispersed in a proper solvent, the polymer grafted on the carbon tube contains complexing groups such as carboxylic acid, amino, sulfydryl, sulfonic group and the like, the complexing group has good complexing effect on the inorganic precursor, and a reducing agent is added into the solution or the temperature is raised for reaction, so that the inorganic nano particles are uniformly deposited on the surface of the carbon nano tube.
The inorganic precursor comprises a metal ion precursor and a nonmetal precursor; wherein the metal ion precursor comprises acid or inorganic salt of gold, silver, platinum, copper, ruthenium, rhodium, palladium, lead, tin, iron, barium, cobalt, manganese, cesium, zirconium, and nickel, such as chloroauric acid (HAuCl)4) Gold chloride (AuCl)3) Silver nitrate (AgNO)3) Lead nitrate (PbNO)3) Chloroplatinic acid (H)2PtCl6) Ruthenium chloride (RuCl)3) Chlororhodic acid (H)3RhCl6) Palladium chloride (PdCl)2) Chloro osmic acid (H)2OsCl6) Chloro-iridic acid (H)2IrCl6) Copper sulfate (CuSO)4) Barium chloride (BaCl)2) Iron chloride (FeCl)3) And ferrous chloride (FeCl)2) Potassium permanganate (KMnO)4) Zirconium chloride (ZrCl)4) One or more of (a). The nonmetallic precursor comprises elemental or compound of oxygen, sulfur, selenium, tellurium, silicon, such asOxygen, ammonia, sodium sulfide (NaS), sodium hydroselenide (NaHSe), sodium tellurohydride (NaHTe), and Tetraethoxysilane (TEOS).
In an embodiment of the present invention, the solvent used for mixing the carrier and the inorganic precursor includes water, ethanol, ethylene glycol, DMF, NMP, dichloromethane, chloroform, acetone, tetrahydrofuran, and the like.
In an embodiment of the present invention, the carrier is mixed with the inorganic precursor and the mixture is ultrasonically dispersed for 0.5 to 24 hours.
In an embodiment of the present invention, the reducing agent used for the reaction of the support with the inorganic precursor includes ethylene glycol, sodium borohydride, ethanol, ascorbic acid, sodium citrate, borane-tert-butylamine, tri-n-octylphosphine, tributylphosphine, and the like.
In an embodiment of the present invention, the temperature used for the reaction of the support and the inorganic precursor may be 25 ℃ to 180 ℃
The metal nanoparticles comprise one or more of gold nanoparticles, silver nanoparticles, copper nanoparticles, platinum nanoparticles, palladium nanoparticles, ruthenium nanoparticles and rhodium nanoparticles.
The metal oxide nanoparticles comprise one or more of zinc oxide nanoparticles, nickel oxide nanoparticles, manganese dioxide nanoparticles, titanium dioxide nanoparticles, tin dioxide nanoparticles, ferric oxide nanoparticles, ferroferric oxide nanoparticles and cobaltosic oxide nanoparticles.
The inorganic semiconductor nanoparticles comprise one or more of cadmium selenide, cadmium sulfide, zinc sulfide, cadmium telluride, lead telluride, bismuth telluride and selenium sulfide nanoparticles
The perovskite nano particles comprise barium titanate nano particles, lead zirconate nano particles and lead cesium bromide (CsPbBr)3) Nanoparticles, cesium lead iodide (CsPbI)3) Nanoparticles, cesium lead iodobromide (CsPbI)xBr3-x) One or more of the nanoparticles.
In other aspects, the metal precursor or inorganic precursor can comprise other metal salts or solutions not specifically described herein, and the present invention is not intended to be limited to any particular inorganic precursor.
The carbon nano tube nano composite material comprises a carbon nano tube, a polymer coated on the surface of the carbon nano tube and nano particles adsorbed on the surface of the polymer. The nano particles are uniformly distributed on the surface of the polymer, the particle size of the nano particles is 1 nm-10 nm, and the particle size of the nano particles can be controllably adjusted through the reaction time and the type of the reducing agent. The mass ratio of the nano particles in the carbon nano tube nano particle compound is 20-60%.
Drawings
The invention will now be further described, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 is a Transmission Electron Microscope (TEM) image of the carbon nanotube-supported lead telluride nanoparticle composite material of the present invention.
Fig. 2 is a TEM of carbon nanotube-supported lead telluride nanoparticles without graft polymer.
It is shown that the carbon nanotube composite material prepared according to an embodiment of the present invention can greatly improve the nanoparticle dispersibility and loading amount.
FIG. 3 is a TEM image of the carbon nanotube supported ferroferric oxide nanoparticle composite material of the present invention.
Fig. 4 is a TEM image of the carbon nanotube-supported cadmium selenide nanoparticle composite material of the present invention.
Fig. 5 is a TEM image of the carbon nanotube-supported cesium lead bromide nanoparticle composite material of the present invention.
FIG. 6 is a TEM image of the carbon nanotube-supported titania nanoparticle composite of the present invention.
Fig. 7 is a TEM image of the carbon nanotube-supported palladium nanoparticle composite material of the present invention.
Fig. 8 is a TEM image of the carbon nanotube-supported barium titanate nanoparticle composite material of the present invention.
Fig. 9 is a TEM image of the carbon nanotube supported cobalt oxide nanoparticle composite material of the present invention.
Fig. 10 is a TEM image of the carbon nanotube silver-loaded nanoparticle composite material of the present invention.
Detailed Description
The present invention provides a method for preparing a carbon nanotube nanoparticle composite material, and for better understanding of the present invention, the present invention will be further described in detail with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the scope shown in the examples.
Example 1
This example describes the preparation of carbon nanotube-supported lead telluride nanocomposites by a simple chemical route.
(1) The method comprises the following steps: 1.0453g of crude MWCNT were added to 10.0mL of 60% HNO3In aqueous solution. The mixture was treated with ultrasound (40kHz) for 30 minutes and then stirred under reflux for 24 hours. Thereafter, the mixture was vacuum filtered through a 0.22 μm polycarbonate membrane and washed with distilled water until the filtrate had a pH of 7. The filtered solid was dried under vacuum at 60 ℃ for 12 hours to give 0.6104g of MWCNT-COOH.
(2) Step two: 0.6104g MWCNT-COOH were dispersed in 20mL thionyl chloride solution. The mixture was reacted at 65 ℃ for 24 h. The mixture was separated, the product was washed three times with anhydrous THF, and the solid was dried in a vacuum oven for 2h to give 0.5384g of MWCNT-COCl.
(3) Step three: 0.516g MWCNT-COCl was dispersed in 20mL of ethylene glycol solution. The mixture was reacted at 120 ℃ for 48 h. The mixture was vacuum filtered through a 0.22 μm polycarbonate membrane to collect the solid, the product was washed three times with anhydrous THF, and the solid was dried in a vacuum oven for 24h to give 0.4342g of MWCNT-OH.
(4) Step four: 0.4342g MWCNT-OH was dispersed in 20mL NMP, and 10mL 2-bromoisobutyryl bromide was added under magnetic stirring in an ice-water bath, followed by reaction at room temperature for 24 hours. After the reaction solution was removed by centrifugation, the reaction solution was washed with dichloromethane and ethanol, respectively, and dried in a vacuum oven at 50 ℃ for 24 hours to obtain 0.4203g of MWCNT-Br
(5) Step five: 0.0503g of MWCNT-Br (0.021mmol Br), 6.0mg (0.042mmol) of CuBr, 0.0073g (0.042mmol) of PMDETA and 0.25mL of DMF were placed in a 10mL flask. After evacuation and three nitrogen charges, 0.1006g (0.78mmol) of tBA were injected into the flask by syringe. The flask was immersed in an oil bath at 60 deg.CIn (1). The mixture was stirred for 4 hours, then diluted with CHCl3 and vacuum filtered using a 0.22 μm polycarbonate membrane. Dispersing the filtered material in CHCl3Then filtered and treated with CHCl3Washing, and drying the solid in a vacuum drying oven for 24h to obtain MWCNT-PtBA
(6) Step six: 0.0020g MWCNT-PtBA and 5mL CHCl3Placing the mixture into a 10mL round-bottom flask, ultrasonically dispersing the mixture, adding 0.5mL trifluoroacetic acid into the mixture, and stirring the mixture at normal temperature for 24 hours. And centrifuging, collecting the precipitate, washing the precipitate with ethanol for several times, and drying the solid in a vacuum drying oven for 24 hours to obtain MWCNT-PAA.
0.0200g MWCNT-PAA was ultrasonically dispersed in N, N-Dimethylformamide (DMF), and lead nitrate (PbNO) was added to a three-necked reaction flask3)0.0908g, adding the dispersed carbon nano tube polymer solution, and stirring vigorously for 1h under the nitrogen environment to completely dissolve the lead nitrate, so that the precursor can be tightly combined with the complexing group. And then heating the reaction to the reflux temperature, adding 0.0280g of tellurium powder (Te) dissolved by trioctylphosphine, and reacting for 1-3 h at the reflux temperature. After the reaction is finished, cooling the product to room temperature, centrifuging, washing with ethanol for 3 times, and collecting the MWCNT-PbTe nano composite material. The particle size of the lead telluride particles is 2-5 nm, and the mass percentage of the lead telluride particles in the compound is 40%.
Comparative example 1
The preparation process was the same as in example 1 except that the experiment was directly performed using carbon nanotubes, and a polymer was not grafted on the carbon nanotubes. Referring to fig. 1, fig. 2 is a transmission electron micrograph of the carbon nanotube nanoparticle composite prepared in comparative example 1.
As can be seen from the figure, the lead telluride particles are distributed on the surface of the carbon nanotube composite carrier. In fig. 2, the lead telluride particles are aggregated together on the surface of the carrier, while in fig. 1, a large amount of lead telluride particles are uniformly distributed on the surface of the carrier, and no agglomeration phenomenon occurs, which indicates that the addition of the polymer is favorable for inhibiting the agglomeration of the nanoparticles in the generated carbon nanotube nanocomposite.
The following example steps one to six correspond to example 1 and are not listed here.
Example 2
This example describes the preparation of a carbon nanotube-loaded gold nanocomposite by a simple chemical route. This synthesis method comprises ultrasonically dispersing 0.0200g MWCNT-PAA in N, N-Dimethylformamide (DMF), adding chloroauric acid (HAuCl)4)0.1000g, with vigorous stirring for 1h, to allow the precursor to bind tightly to the complexing groups. Then adding reducing agent, such as borane-tert-butylamine complex (TBAB), ethanol (CH)3CH2OH), sodium borohydride (NaBH)4) And Ascorbic Acid (AA), the product was centrifuged after the reaction and washed three times with ethanol, and the MWCNT-Au nanocomposite was collected. Wherein the grain diameter of the gold particles is 1 nm-3 nm, and the mass percentage of the gold nanoparticles in the compound is 35%.
Example 3
This example describes the preparation of a carbon nanotube-supported ferroferric oxide nanocomposite by a simple chemical route. The synthesis method comprises ultrasonically dispersing 0.0200g MWCNT-PAA in N, N-Dimethylformamide (DMF), and adding ferrous chloride tetrahydrate (FeCl) into a three-neck reaction bottle24H2O)0.0632g of iron chloride hexahydrate (FeCl)36H2O)0.0324g, transferring the carbon nanotube dispersion into a three-necked reaction flask under nitrogen atmosphere, vigorously stirring for 1H to allow the precursor to be tightly bound to the complexing group, and adding ammonia (NH)3·H2O)2mL, reacting at 50 ℃ for 0.5h, raising the reaction temperature to 80 ℃, and standing for 1 h. After the reaction is finished, the product is centrifugally collected, washed by ethanol for three times, and MWCNT-Fe is collected3O4A nanocomposite material. Wherein the particle size of the ferroferric oxide particles is 2-10 nm, and the ferroferric oxide nanoparticles in the compound account for 60 percent of the mass of the compound.
Example 4
This example describes the preparation of carbon nanotube cadmium selenide loaded nanocomposites by a simple chemical route. This synthesis method consisted of ultrasonically dispersing 0.0200g MWCNT-PAA in N, N-Dimethylformamide (DMF), adding chromium acetylacetonate (Cd (acac))2)0.1020g, the carbon nanotube dispersion was transferred to a three-necked reaction flask under nitrogen atmosphere with vigorous stirring for 1 hour to allow the precursor to be tightly bound to the complexing group. And then heating the reaction to a reflux temperature, injecting selenium powder (Se) dissolved in trioctylphosphine, and reacting for 1-3 h at the reflux temperature. After the reaction is finished, cooling the product to room temperature, centrifuging, washing with ethanol for 3 times, and collecting the MWCNT-CdSe nano composite material. Wherein the particle size of the cadmium selenide particles is 2-5 nm, and the mass percentage of the cadmium selenide particles in the compound accounts for 30 percent of the compound.
Example 5
This example describes the preparation of carbon nanotube-supported cesium lead bromide nanocomposites by a simple chemical route. This synthesis method comprises ultrasonically dispersing 0.0200g MWCNT-PAA in N, N-Dimethylformamide (DMF), adding lead bromide (PbBr) in a three-necked reaction flask2)0.0700g, the carbon nanotube dispersion was transferred to a three-necked reaction flask under nitrogen atmosphere, and cesium carbonate (CsCO) dissolved in benzyl alcohol was added3) And stirring vigorously for 1h to enable the precursor to be tightly combined with the complexing group. And then heating the reaction to a reflux temperature, and reacting for 1-3 h at the reflux temperature. After the reaction is finished, the product is cooled to room temperature, centrifuged, washed with ethanol for 3 times, and MWCNT-CsPbBr is collected3A nanocomposite material. Wherein the particle size of the cesium lead bromide nanoparticles is 1-5 nm, and the mass percentage of the inorganic lead halide perovskite particles in the compound is 50%.
Example 6
This example describes the preparation of carbon nanotube titanium dioxide nanocomposites by a simple chemical route. This synthesis method involved ultrasonically dispersing 0.0200g of MWCNT-PAA in a three-necked reaction flask containing N, N-Dimethylformamide (DMF). Under the condition of nitrogen, 0.5mL of isopropyl titanate (TTiP) is injected into a reaction bottle, and vigorous stirring is carried out for 1h, so that the precursor can be tightly combined with the complexing group. And then heating the reaction to a reflux temperature, and reacting for 1-3 h at the reflux temperature. After the reaction is finished, the product is cooled to room temperature and then centrifuged, and is washed 3 times by ethanol, and MWCNT-TiO is collected2Nano composite materialAnd (5) feeding. Wherein the particle size of the titanium dioxide particles is 2 nm-5 nm, and the mass percentage of the titanium dioxide particles in the composite is 45%.
Example 7
This example describes the preparation of carbon nanotube palladium nanoparticle composites by a simple chemical route. This synthesis method involved ultrasonic dispersion of 0.0200g of MWCNT-PAA in N, N-Dimethylformamide (DMF). Sodium chloropalladate (NaPdCl) was added4)0.1000g, with vigorous stirring for 1h, to allow the precursor to bind tightly to the complexing groups. Then adding reducing agent sodium borohydride (NaBH)4) After the reaction, the product was centrifuged and washed with ethanol three times, and the MWCNT-Pd nanocomposite was collected. Wherein the particle diameter of the palladium particles is 1 nm-5 nm, and the mass percent of the gold nanoparticles in the composite is 55%.
Example 8
This example describes the preparation of carbon nanotube/barium titanate nanoparticle composites by a simple chemical route. This synthesis method comprises ultrasonically dispersing 0.0200g MWCNT-PAA in N, N-Dimethylformamide (DMF), adding barium chloride (BaCl) in a three-necked reaction flask2)0.1623g of titanium tetrachloride (TiCl)4)0.1316g and 0.0278g of sodium hydroxide (NaOH), the carbon nanotube dispersion was transferred to a three-necked reaction flask under nitrogen atmosphere with vigorous stirring for 1 hour to allow the precursor to be tightly bound to the complexing group. And then heating the reaction to a reflux temperature, reacting for 1-3 h at the reflux temperature, transferring the product to a 20mL polytetrafluoroethylene high-pressure reaction kettle, and reacting for 2h at 200 ℃. After the reaction is finished, cooling to room temperature, centrifuging, washing with ethanol for 3 times, and collecting MWCNT-BaTiO3A nanocomposite material. Wherein the particle size of the barium titanate particles is 2 nm-8 nm, and the barium titanate particles in the composite account for 35% of the mass of the composite.
Example 9
This example describes the preparation of a carbon nanotube supported cobalt oxide nanocomposite by a simple chemical route. This synthesis method included mixing 0.0200g MWCNT-PAA and 0.5000g cobalt acetate (Co (CH)3COO)2·4H2O) ultrasonic dispersion in 25mL of ethanol and 2.5mL of ammonia water, and stirring the mixed solution for 10min to enable the precursor to be tightly combined with the complexing group. The product was transferred to a 50mL Teflon autoclave and reacted at 150 ℃ for 3 h. After the reaction is finished, the mixture is cooled to room temperature, centrifuged, washed with ethanol for 3 times, and MWCNT-Co is collected3O4A nanocomposite material. Wherein the particle size of the cobalt oxide particles is 2-8 nm, and the cobalt oxide particles in the compound account for 20% of the compound by mass.
Example 10
This example describes the preparation of a carbon nanotube silver-loaded nanocomposite by a simple chemical route. This synthesis method involved ultrasonic dispersion of 0.0200g of MWCNT-PAA in N, N-Dimethylformamide (DMF). Silver chloride (AgCl)0.1000g is added with vigorous stirring for 1h to allow the precursor to bind tightly to the complexing groups. Then adding reducing agent sodium borohydride (NaBH)4) And centrifuging the product after reaction, washing the product with ethanol for three times, and collecting the silver nanotube nano composite material. Wherein the particle size of the silver particles is 1 nm-5 nm, and the mass percentage of the gold nanoparticles in the compound is 25%.
The above is only a specific application example of the present invention, and the protection scope of the present invention is not limited in any way. In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by using equivalent substitutions or equivalent transformations fall within the scope of the present invention.
Claims (10)
1. A preparation method of a carbon nano tube nano particle composite material is characterized by comprising the following preparation steps:
(1) the method comprises the following steps: 1.0453g of crude carbon nanotube MWCNT were added to 10.0mL of 60% HNO3In an aqueous solution; the mixture was treated with ultrasound at 40kHz for 30 minutes and then stirred under reflux for 24 hours; thereafter, the mixture was vacuum filtered through a 0.22 μm polycarbonate membrane and washed with distilled water until the pH of the filtrate was 7; the filtered solid was dried under vacuum at 60 ℃ for 12 hours to give 0.6104g MWCNT-COOH;
(2) step two: 0.6104g MWCNT-COOH were dispersed in 20mL thionyl chloride solution; reacting the mixture at 65 ℃ for 24 h; the mixture was separated, the product was washed three times with anhydrous THF, and the solid was dried in a vacuum oven for 2h to give 0.5384g of MWCNT-COCl;
(3) step three: 0.516g MWCNT-COCl was dispersed in 20mL of ethylene glycol solution; reacting the mixture at 120 ℃ for 48 h; the mixture was vacuum filtered through 0.22 μm polycarbonate membrane to collect the solid, the product was washed three times with anhydrous THF, and the solid was dried in a vacuum oven for 24h to give 0.4342g MWCNT-OH;
(4) step four: 0.4342g MWCNT-OH is dispersed in 20mL NMP, 10mL 2-bromine isobutyryl bromide is added under magnetic stirring in ice water bath, and the reaction is carried out for 24h at normal temperature; centrifuging to remove reaction liquid, washing with dichloromethane and ethanol respectively, and drying in a vacuum drying oven at 50 deg.C for 24h to obtain 0.4203g MWCNT-Br;
(5) step five: 0.0503g MWCNT-Br 0.021mmol Br, 6.0mg 0.042mmol CuBr, 0.0073g 0.042mmol PMDETA and 0.25mL DMF were placed in a 10mL flask; after evacuation and three nitrogen charges, 0.1006g of 0.78mmol of tert-butyl acrylate tBA were injected into the flask by means of a syringe; immersing the flask in an oil bath at 60 ℃; the mixture was stirred for 4 hours, then diluted with CHCl3 and vacuum filtered using a 0.22 μm polycarbonate membrane; dispersing the filtered material in CHCl3Then filtered and treated with CHCl3Washing, and drying the solid in a vacuum drying oven for 24h to obtain a poly (tert-butyl acrylate) -based carbon nanotube MWCNT-PtBA;
(6) step six: 0.0020g MWCNT-PtBA and 5mL CHCl3Placing the mixture into a 10mL round-bottom flask, adding 0.5mL trifluoroacetic acid into the ultrasonic-dispersed image mixed solution, and stirring for 24 hours at normal temperature; centrifuging, collecting the precipitate, washing with ethanol for several times, and drying the solid in a vacuum drying oven for 24h to obtain polyacrylic acid-based carbon nanotube MWCNT-PAA;
(7) step seven: and mixing the polyacrylic acid-based carbon nanotube MWCNT-PAA obtained in the sixth step with an inorganic precursor of lead telluride, gold, ferroferric oxide, cadmium selenide, perovskite, titanium dioxide, palladium, barium titanate, cobalt oxide or silver, and reacting by a chemical synthesis method to obtain the carbon nanotube nano particle composite material.
2. The method for preparing a carbon nanotube nanoparticle composite material according to claim 1, wherein 0.0200g of MWCNT-PAA obtained in the sixth step is ultrasonically dispersed in N, N-dimethylformamide DMF, and lead nitrate PbNO is added to a three-necked reaction flask3 0.0908g, adding the dispersed carbon nanotube polymer solution, and stirring vigorously for 1h under a nitrogen environment to completely dissolve lead nitrate, wherein the precursor can be tightly combined with a complexing group; then heating the reaction to a reflux temperature, adding 0.0280g of tellurium powder dissolved by trioctylphosphine, and reacting for 1-3 h at the reflux temperature; after the reaction is finished, cooling the product to room temperature, centrifuging, washing with ethanol for 3 times, and collecting the MWCNT-PbTe nano composite material.
3. The method for preparing carbon nanotube nanoparticle composite material according to claim 1, wherein 0.0200g of MWCNT-PAA obtained in the sixth step is ultrasonically dispersed in N, N-dimethylformamide DMF, and HAuCl chloroauric acid is added40.1000g, with vigorous stirring for 1h to allow the precursor to bind tightly to the complexing group, and then adding a reducing agent such as borane-tert-butylamine complex TBAB, ethanol CH3CH2OH, sodium borohydride NaBH4And Ascorbic Acid (AA), the product was centrifuged after the reaction and washed three times with ethanol, and the MWCNT-Au nanocomposite was collected.
4. The method for preparing a carbon nanotube nanoparticle composite material according to claim 1, wherein 0.0200g of MWCNT-PAA obtained in the sixth step is ultrasonically dispersed in N, N-dimethylformamide DMF, and ferrous chloride tetrahydrate FeCl is added into a three-necked reaction flask2·4H2O0.0632 g, FeCl iron chloride hexahydrate3·6H2O0.0324 g, transferring the carbon nano tube dispersion liquid into a three-neck reaction bottle under the nitrogen environment, stirring vigorously for 1h to ensure that the precursor can be tightly combined with the complexing group, and then adding ammonia NH3·H2O2 mL, reacting at 50 ℃ for 0.5h, increasing the reaction temperature to 80 ℃, and standingStanding for 1 h; after the reaction is finished, the product is centrifugally collected, washed by ethanol for three times, and MWCNT-Fe is collected3O4A nanocomposite material.
5. The method for preparing carbon nanotube nanoparticle composite material according to claim 1, wherein 0.0200g of MWCNT-PAA obtained in the sixth step is ultrasonically dispersed in N, N-dimethylformamide DMF, and chromium acetylacetonate Cd (acac) is added into a three-necked reaction flask20.1020g, transferring the carbon nanotube dispersion liquid into a three-neck reaction bottle under the nitrogen environment, and stirring vigorously for 1h to enable the precursor to be tightly combined with the complexing group; then heating the reaction to a reflux temperature, injecting selenium powder dissolved by trioctylphosphine, and reacting for 1-3 h at the reflux temperature; after the reaction is finished, cooling the product to room temperature, centrifuging, washing with ethanol for 3 times, and collecting the MWCNT-CdSe nano composite material.
6. The method for preparing a carbon nanotube nanoparticle composite material according to claim 1, wherein 0.0200g of MWCNT-PAA obtained in the sixth step is ultrasonically dispersed in N, N-dimethylformamide DMF, and lead bromide PbBr is added to a three-necked reaction flask20.0700g, transferring the carbon nanotube dispersion liquid into a three-neck reaction flask under nitrogen atmosphere, and adding benzyl alcohol-dissolved cesium carbonate CsCO3Stirring vigorously for 1h to enable the precursor to be tightly combined with the complexing group; then heating the reaction to a reflux temperature, and reacting for 1-3 h at the reflux temperature; after the reaction is finished, the product is cooled to room temperature, centrifuged, washed with ethanol for 3 times, and MWCNT-CsPbBr is collected3A nanocomposite material.
7. The method for preparing a carbon nanotube nanoparticle composite material according to claim 1, wherein 0.0200g of MWCNT-PAA obtained in the sixth step is ultrasonically dispersed in a three-necked reaction flask containing N, N-dimethylformamide DMF; under the condition of nitrogen, 0.5mL of isopropyl titanate TTiP is injected into a reaction bottle, and is stirred vigorously for 1h, so that the precursor can be tightly combined with the complexing group; the reaction was then warmed to reflux temperature,and reacting for 1-3 h at the reflux temperature; after the reaction is finished, the product is cooled to room temperature and then centrifuged, and is washed 3 times by ethanol, and MWCNT-TiO is collected2A nanocomposite material.
8. The method for preparing a carbon nanotube nanoparticle composite material according to claim 1, wherein 0.0200g of MWCNT-PAA obtained in the sixth step is ultrasonically dispersed in N, N-dimethylformamide DMF; adding sodium chloropalladate NaPdCl40.1000g, and vigorously stirring for 1h to ensure that the precursor can be tightly combined with the complexing group; then adding reducing agent sodium borohydride NaBH4After the reaction, the product was centrifuged and washed with ethanol three times, and the MWCNT-Pd nanocomposite was collected.
9. The method for preparing carbon nanotube nanoparticle composite material according to claim 1, wherein 0.0200g of MWCNT-PAA and 0.5000g of Co (CH) acetate obtained in the sixth step are mixed with each other3COO)2·4H2Ultrasonically dispersing O in 25mL of ethanol and 2.5mL of ammonia water, and stirring the mixed solution for 10min to enable the precursor to be tightly combined with the complexing group; transferring the product to a 50mL polytetrafluoroethylene high-pressure reaction kettle, and reacting for 3h at 150 ℃; after the reaction is finished, the mixture is cooled to room temperature, centrifuged, washed with ethanol for 3 times, and MWCNT-Co is collected3O4A nanocomposite material.
10. The method for preparing a carbon nanotube nanoparticle composite material according to claim 1, wherein 0.0200g of MWCNT-PAA obtained in the sixth step is ultrasonically dispersed in N, N-dimethylformamide DMF; adding 0.1000g of silver chloride AgCl, and stirring vigorously for 1h to ensure that the precursor can be tightly combined with the complexing group; then adding reducing agent sodium borohydride NaBH4And centrifuging the product after reaction, washing the product with ethanol for three times, and collecting the silver nanotube nano composite material.
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