CN113264521A - Azobenzene-three-dimensional carbon nano hybrid film and preparation method and application thereof - Google Patents

Azobenzene-three-dimensional carbon nano hybrid film and preparation method and application thereof Download PDF

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CN113264521A
CN113264521A CN202110604474.7A CN202110604474A CN113264521A CN 113264521 A CN113264521 A CN 113264521A CN 202110604474 A CN202110604474 A CN 202110604474A CN 113264521 A CN113264521 A CN 113264521A
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carbon nano
azobenzene
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罗文�
刘家兴
黎汉江
刘包平
夏浩涛
黄金
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Guangdong University of Technology
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    • C01B2202/00—Structure or properties of carbon nanotubes
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Abstract

The invention relates to the technical field of energy materials, in particular to an azobenzene-three-dimensional carbon nano hybrid film and a preparation method and application thereof. The application provides a preparation method of an azobenzene-three-dimensional carbon nano hybrid film, which comprises the steps of firstly carrying out solution self-assembly reaction on a graphene oxide dispersion solution and a short carbon nano tube dispersion solution, then reducing an oxygen-containing group part to obtain a three-dimensional carbon nano material, carrying out ice-bath reaction on the three-dimensional carbon nano material and azobenzene for 3-6 hours, heating to room temperature for reaction overnight, and carrying out suction filtration and drying to obtain the azobenzene-three-dimensional carbon nano hybrid film; compared with the low-dimensional carbon nano material, the three-dimensional carbon nano material has good dispersibility and large surface area, can graft active sites and is fully exposed, and the grafting rate and the steric hindrance of azobenzene are improved. The azobenzene-three-dimensional carbon nano hybrid film and the preparation method and the application thereof provided by the invention are at least used for solving the technical problems of low azobenzene energy density and short half-life period, and are beneficial to the application of the azobenzene-three-dimensional carbon nano hybrid film in the field of solar fuels.

Description

Azobenzene-three-dimensional carbon nano hybrid film and preparation method and application thereof
Technical Field
The invention relates to the technical field of energy materials, in particular to an azobenzene-three-dimensional carbon nano hybrid film and a preparation method and application thereof.
Background
The solar energy has the excellent characteristics of environmental protection, cleanness, wide source range, inexhaustibility and the like. However, the annual availability of solar energy is scarce and scarce due to the lack of high-energy long-lasting storage methods. Therefore, the storage of solar energy has become a key issue for the research of new energy field in the world nowadays.
Azobenzene has cis-form and trans-form configuration, and can generate cis-trans isomerization process under external stimulation conditions of light, heat and the like. Through a cis-trans isomerization process, azobenzene can realize the storage and release of solar energy.
The carbon nanotube is a one-dimensional carbon material, can be regarded as being formed by curling graphite sheets and is divided into a single-wall carbon nanotube and a multi-wall carbon nanotube, the tube wall is formed by hexagons formed by carbon atoms, and the end cover is formed by pentagons and hexagons. The carbon nano tube has excellent mechanical, electrical and thermal properties.
Graphene is a two-dimensional carbon material with a honeycomb lattice structure, carbon atoms are connected in sp2 hybridization, pz orbitals perpendicular to the layer plane of each carbon atom can form a large pi bond of multiple atoms throughout the layer, and the surface is slightly wrinkled. Graphene also has excellent mechanical, electrical and thermal properties.
In the prior art, azobenzene is grafted by taking one-dimensional or two-dimensional carbon materials such as carbon nanotubes or graphene as a template, so that the energy density and the thermal stability of azobenzene are improved, and the half-life period of azobenzene is prolonged. However, low-dimensional carbon nanomaterials such as carbon nanotubes and graphene are easy to agglomerate, the surface area is small, exposed graftable active sites are few, the grafting rate of azobenzene on the low-dimensional carbon nanomaterial templates such as the carbon nanotubes or the graphene is low, the steric hindrance is small, and therefore the capacity of improving the energy density of azobenzene and prolonging the half-life period of azobenzene is very limited.
Disclosure of Invention
In view of the above, the application provides an azobenzene-three-dimensional carbon nano hybrid film, and a preparation method and an application thereof, which are at least used for solving the technical problems of low azobenzene energy density and short half-life period, and are beneficial to the application of the azobenzene in the field of solar fuels.
According to a first aspect of the application, an azobenzene-three-dimensional carbon nano hybrid film is provided, and comprises azobenzene and a three-dimensional carbon nano material, wherein one end of the azobenzene contains an amino group, and the three-dimensional carbon nano material is grafted with the azobenzene through a covalent bond.
Preferably, the structural formula of the azobenzene containing amino at one end is shown as formula I;
Figure BDA0003093713420000021
wherein X is methyl or methoxy, Y1Is a carboxyl group, a hydroxyl group or a sulfonic acid group, Y2Is carboxyl, hydroxyl or sulfonic group.
It should be noted that in the azobenzene-three-dimensional carbon nano hybrid film, the adjacent azobenzene with a plurality of substituents can form intermolecular hydrogen bonds through amino groups and carboxyl groups, hydroxyl groups or sulfonic groups, thereby improving the energy density of the azobenzene-three-dimensional carbon nano hybrid film.
Preferably, the three-dimensional carbon nanomaterial comprises reduced graphene oxide and reduced short carbon nanotubes.
Preferably, the reduced graphene oxide comprises a single-layer or few-layer reduced graphene oxide, and the reduced short carbon nanotubes comprise reduced short multi-walled carbon nanotubes.
It should be noted that the acting force of the multi-walled carbon nanotube is greater than that of the single-walled carbon nanotube, so that the multi-walled carbon nanotube can form a good three-dimensional carbon nanomaterial with graphene oxide, thereby providing a grafting template for azobenzene.
The second aspect of the application provides a preparation method of an azobenzene-three-dimensional carbon nano hybrid film, which comprises the steps of adding azobenzene diazonium salt solution with one end containing amino into three-dimensional carbon nano material dispersion liquid for carrying out a first reaction to obtain the azobenzene-three-dimensional carbon nano hybrid film;
the first reaction is specifically ice-bath reaction for 3-6h, and then heating to room temperature for reaction overnight.
It should be noted that the diazonium salt is easily decomposed when the temperature is too high, so that the diazonium salt can be prevented from being decomposed when the temperature is raised to room temperature after the ice bath reaction is carried out for 3 to 6 hours, and the azobenzene-three-dimensional carbon nano hybrid film is prepared.
The preparation method of the three-dimensional carbon nano-material dispersion liquid comprises the following steps: and ultrasonically mixing the graphene oxide dispersion liquid and the short carbon nanotube dispersion liquid to perform solution self-assembly reaction, and then performing reduction reaction to obtain the three-dimensional carbon nano-material dispersion liquid.
Preferably, the solution self-assembly is carried out by mixing the following components in a volume ratio of (2-4): 1, mixing the graphene oxide dispersion liquid and the short carbon nanotube dispersion liquid, and performing ultrasonic treatment for 0.5-1.5 h.
Preferably, the reduction reaction comprises partial reduction of the oxygen-containing group.
Preferably, the reduction reaction is specifically that after the solution is self-assembled, 0.8-1.5 g of NaBH is added4Adjusting the pH value to 9-11 and the temperature to 65-85 ℃, and reacting for 1-2 h.
It is noted that the reduction reaction is carried out after the solution self-assembly, so that more graftable sites are provided, and the grafting rate is improved; meanwhile, the reduction reaction is carried out after the assembly, rather than the reduction reaction of the two components independently, so that the reduction of the dispersibility of the two components is avoided, the two components are easy to agglomerate together, and the uniform mixing effect cannot be achieved in the ultrasonic treatment, so that the two components are difficult to be well lapped to form the three-dimensional carbon material.
Preferably, the method for preparing the short carbon nanotube comprises the following steps: and purifying the carbon nano tubes in sequence, oxidizing and cutting to obtain the short carbon nano tubes.
Preferably, the purification reaction is specifically to put the carbon nanotube into an acid solution, stir and then carry out centrifugal treatment to obtain a purified carbon nanotube;
the carbon nanotube has a diameter of 20 to 30nm and a length of 10 to 30 μm.
And the acid solution in the purification reaction is a hydrochloric acid solution, and the stirring time is 4-6 h.
Preferably, the oxidation cutting comprises placing the purified carbon nano tube in mixed acid, stirring and performing ultrasonic treatment to obtain a short carbon nano tube;
the stirring comprises stirring for 8-10 h at 35-75 ℃;
the ultrasonic treatment comprises ultrasonic treatment at 35-45 ℃ for 3-5 h;
the mixed acid comprises concentrated H with the volume ratio of 3:12SO4And concentrated HNO3The mixed acid of (1).
It should be noted that the purified carbon nanotube dispersion liquid is stirred with the mixed acid solution, and the purified carbon nanotube can be cut into a plurality of short carbon nanotubes with relatively uniform lengths by ultrasonic treatment, so that the number of graftable active sites is increased, the steric hindrance of the three-dimensional carbon nanomaterial is increased, and the grafting rate is increased.
The preparation method of the single-layer or few-layer graphene oxide comprises the steps of carrying out ultrasonic treatment for 1-1.5 hours, centrifuging at a centrifugal rotating speed of 1000-5000 r/min, centrifuging at a centrifugal rotating speed of 10000-12000 r/min, and repeatedly centrifuging for 3-6 times to obtain the single-layer or few-layer graphene oxide dispersion liquid.
The third aspect of the application provides an application of the azobenzene-three-dimensional carbon nano hybrid film in the field of solar fuel.
In summary, the application provides an azobenzene-three-dimensional carbon nano hybrid film and a preparation method and application thereof, the method comprises the steps of carrying out solution self-assembly reaction on graphene oxide dispersion liquid and carbon nano tube dispersion liquid, then reducing oxygen-containing groups to obtain a three-dimensional carbon nano material, carrying out ice-bath reaction on the three-dimensional carbon nano material and azobenzene for 3-6 hours, heating to room temperature for reaction overnight, carrying out suction filtration and drying to obtain the azobenzene-three-dimensional carbon nano hybrid film; compared with the low-dimensional carbon nano material, the three-dimensional carbon nano material has good dispersibility, is not easy to agglomerate, has large surface area, can fully expose graftable active sites, can improve the grafting rate and steric hindrance of azobenzene, further improves the energy density of azobenzene, prolongs the half-life period, and can solve the technical problems of low energy density and short half-life period of the existing azobenzene.
Drawings
FIG. 1 is a graph showing an ultraviolet-visible light absorption spectrum of 4-amino-2, 6-dimethoxy-4' -carboxyazobenzene prepared in example 1 of the present application;
FIG. 2 is an SEM image of short multi-walled carbon nanotubes prepared in example 1 of the present application;
fig. 3 is an SEM image of graphene oxide prepared in example 1 of the present application;
fig. 4 is an SEM image of a three-dimensional carbon nanomaterial prepared in example 1 of the present application;
FIG. 5 is a schematic representation of the azobenzene-three-dimensional carbon nano-hybrid film prepared in example 1 of the present application;
fig. 6 is a structural view of a three-dimensional carbon nanomaterial prepared by the present application.
The specific implementation mode is as follows:
the application provides an azobenzene-three-dimensional carbon nano hybrid film, and a preparation method and application thereof, which are at least used for solving the technical problems of low azobenzene energy density and short half-life period.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The reagents or raw materials used in the following examples are commercially available or self-made.
Example 1
The embodiment 1 of the application provides an azobenzene-three-dimensional carbon nano hybrid film, and the preparation method comprises the following steps:
step 1, preparing 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene,
step 101, weighing 10mmol of 4-aminobenzoic acid and 10mmol of NaOH, dissolving in a beaker containing 40mL of deionized water, stirring uniformly in an ice bath, and then weighing NaNO of slightly more than 10mmol2DissolutionAfter uniformly stirring in an ice bath in a beaker containing 20mL of deionized water, slowly dropwise adding the solution into the solution, continuously stirring in the ice bath during dropwise adding, and slowly dropwise adding the solution into 60mL of 25mmol of HCl solution after uniformly stirring to generate a diazonium salt solution;
step 102, weighing 5mmol of 3, 5-dimethoxyaniline and dissolving in 40mL of solution containing 10mmol of HCl, slowly dropwise adding the diazonium salt solution, and after dropwise adding, using saturated NaHCO3And regulating the pH value of the solution to 6, stirring for 1.5h in an ice bath, washing for multiple times, filtering, and then drying for 48h in vacuum to obtain the 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene.
Step 2, preparing graphene oxide dispersion liquid,
step 201, weighing 3g of crystalline flake graphite, and dissolving in 400mL of mixed acid (concentrated H)2SO4: concentrated H3PO4To 9:1), 18g KMnO was slowly added under ice-bath4Stirring the mixture evenly, continuing stirring the mixture for 12 hours at 50 ℃, then cooling the mixture to room temperature, and slowly pouring the mixture in 5mL of 30% H2O2Mixing with 400mL of water to prepare ice blocks;
step 202, filtering and removing concentrated acid liquid, then repeatedly washing with deionized water until the pH value of the solution is 6-7, centrifuging for 4 times, performing ultrasonic dispersion for 1h before each centrifugation, performing centrifugation at the rotating speeds of 1000r/min, 2000r/min and 3000r/min for the first 3 times and taking supernatant, performing centrifugation at the rotating speed of 12000r/min for the last time and taking down the precipitate, and performing suction filtration and drying to prepare the graphene oxide dispersion liquid.
Step 3, preparing a short multi-walled carbon nanotube dispersion liquid,
step 301, weighing 0.3g of multi-walled carbon nanotubes, putting the multi-walled carbon nanotubes into a conical flask containing 60mL of 36% HCl solution, stirring for 4 hours, performing centrifugal separation, and washing the multi-walled carbon nanotubes to be neutral by deionized water;
step 302, add it to 160mL of mixed acid (concentrated H)2SO4: concentrated H3PO4Stirring at 70 ℃ for 9h, then performing ultrasonic treatment at 40 ℃ for 4h, diluting to neutrality by using deionized water, performing suction filtration and drying, and then preparing into a short multi-walled carbon nanotube dispersion liquid with the concentration of 1 mg/mL.
Step 4, preparing three-dimensional carbon nano material dispersion liquid,
step 401, weighing 100mL of the short multi-walled carbon nanotube dispersion liquid prepared in step 3 and 300mL of the graphene oxide dispersion liquid prepared in step 2, mixing according to a volume ratio of 1:3, performing ultrasonic treatment for 1h, and performing self-assembly reaction;
step 402, after the self-assembly reaction, 1.5g of NaBH is added4Then NaOH is used for adjusting the pH value of the solution to 9, and the solution is stirred for 2 hours at the temperature of 75 ℃ for reduction reaction;
and step 403, after the reduction reaction, cooling to room temperature, washing to be neutral by using deionized water, performing suction filtration for many times, drying, and preparing into a three-dimensional carbon nano material dispersion liquid with the concentration of 1 mg/mL.
Step 5, preparing the azobenzene-three-dimensional carbon nano hybrid film,
step 501, 3mmol of 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene and 5mmol of NaOH are weighed and dissolved in a beaker containing 20mL of deionized water, the mixture is stirred evenly in ice bath, and then NaNO which is slightly more than 5mmol is weighed2Dissolving the mixture in a beaker containing 10mL of deionized water, slowly dripping the mixture into the solution after uniformly stirring in an ice bath, continuously stirring in the ice bath during dripping, and slowly dripping the mixture into 60mL of 25mmol of HCl solution after uniformly stirring to generate a diazonium salt solution;
step 502, slowly adding the diazonium salt solution obtained in the step 501 into the three-dimensional carbon nano material dispersion liquid prepared in the step 4, reacting for 4 hours in ice bath, and then heating to room temperature for reacting overnight to obtain an azobenzene-three-dimensional carbon nano hybrid film initial product;
step 503, washing the initial product of the azobenzene-three-dimensional carbon nano hybrid film with deionized water, acetone and DMF in sequence to obtain an initial product for three times or more, and obtaining an intermediate product of the azobenzene-three-dimensional carbon nano hybrid film;
and 504, repeatedly reacting and purifying the intermediate product of the azobenzene-three-dimensional carbon nano hybrid film for 2 times by using the functional method, and performing suction filtration and vacuum drying for 48 hours to obtain the azobenzene-three-dimensional carbon nano hybrid film.
Example 2
The embodiment 2 of the application provides an azobenzene-three-dimensional carbon nano hybrid film, and the preparation method comprises the following steps:
step 1, preparing 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene,
step 101, weighing 10mmol of 4-aminobenzoic acid and 10mmol of NaOH, dissolving in a beaker containing 40mL of deionized water, stirring uniformly in an ice bath, and then weighing NaNO of slightly more than 10mmol2Dissolving the mixture in a beaker containing 20mL of deionized water, slowly dripping the mixture into the solution after uniformly stirring in an ice bath, and continuously stirring in the ice bath during dripping. After stirring uniformly, slowly dripping the mixture into 60mL of solution containing 25mmol of HCl to generate a diazonium salt solution;
step 102, weighing 5mmol of 3, 5-dimethoxyaniline and dissolving in 40mL of solution containing 10mmol of HCl, slowly dropwise adding the diazonium salt solution, and after dropwise adding, using saturated NaHCO3And regulating the pH value of the solution to 6, stirring for 2h in an ice bath, washing for multiple times, carrying out suction filtration, and then carrying out vacuum drying for 48h to obtain the 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene.
Step 2, preparing graphene oxide dispersion liquid,
step 201, weighing 3g of crystalline flake graphite, and dissolving in 400mL of mixed acid (concentrated H)2SO4: concentrated H3PO4To 9:1), 18g kmno was slowly added under ice-bath4Stirring the mixture evenly, continuing stirring the mixture for 12 hours at 50 ℃, then cooling the mixture to room temperature, and slowly pouring the mixture in 5mL of 30% H2O2Reacting in ice blocks prepared by mixing with 400mL of water;
202, after the reaction is finished, filtering and removing concentrated acid solution, repeatedly washing with deionized water until the pH value of the solution is 6-7, centrifuging for 3 times, performing ultrasonic dispersion for 1h before each centrifugation, centrifuging at the rotating speeds of 1000r/min and 2000r/min and taking supernatant for the first 2 times, centrifuging at the rotating speed of 12000r/min and taking down the precipitate for the last time, performing suction filtration and drying, and then preparing graphene oxide dispersion liquid with the concentration of 1 mg/mL.
Step 3, preparing a short multi-walled carbon nanotube dispersion liquid,
step 301, weighing 0.3g of multi-walled carbon nanotubes, putting the multi-walled carbon nanotubes into a conical flask containing 60mL of 36% HCl solution, stirring for 4 hours, performing centrifugal separation, and washing the multi-walled carbon nanotubes to be neutral by deionized water;
step 302, add it to 160mL of mixed acid (concentrated H)2SO4Concentrated HNO3Stirring at 70 ℃ for 9h, then performing ultrasonic treatment at 45 ℃ for 5h, diluting to neutrality by using deionized water, performing suction filtration and drying, and then preparing into a short multi-walled carbon nanotube dispersion liquid with the concentration of 1 mg/mL.
Step 4, preparing three-dimensional carbon nano material dispersion liquid,
step 401, weighing 100mL of short multi-walled carbon nanotube dispersion liquid and 300mL of graphene oxide dispersion liquid, mixing according to a volume ratio of 1:3, performing ultrasonic treatment for 1 hour, performing self-assembly reaction,
step 402, after the self-assembly reaction, add 1.2g NaBH4Then NaOH is used for adjusting the pH value of the solution to 9, the solution is stirred for 2 hours at the temperature of 80 ℃ for reduction reaction,
and step 403, after the reduction reaction, cooling to room temperature, washing to neutrality by using deionized water, performing suction filtration for many times, drying, and preparing into the three-dimensional carbon composite dispersion liquid with the concentration of 1 mg/mL.
Step 5, preparing the azobenzene-three-dimensional carbon nano hybrid film,
step 501, 3mmol of 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene and 5mmol of NaOH are weighed and dissolved in a beaker containing 20mL of deionized water, the mixture is stirred evenly in ice bath, and then NaNO which is slightly larger than 5mmol is weighed2Dissolving the mixture in a beaker containing 10mL of deionized water, slowly dripping the mixture into the solution after uniformly stirring in an ice bath, continuously stirring in the ice bath during dripping, and slowly dripping the mixture into 60mL of 25mmol of HCl solution after uniformly stirring to generate a diazonium salt solution;
step 502, slowly adding the diazonium salt solution prepared in the step 501 into 100mL of three-dimensional carbon nano material dispersion liquid, carrying out ice-bath reaction for 5 hours, and then heating to room temperature for reaction overnight to obtain an azobenzene-three-dimensional carbon nano hybrid film initial product;
step 503, washing the azobenzene-three-dimensional carbon nano hybrid film with deionized water, acetone and DMF in sequence to obtain a primary product more than three times, and obtaining an azobenzene-three-dimensional carbon nano hybrid film intermediate product;
and 504, repeatedly reacting and purifying the intermediate product of the azobenzene-three-dimensional carbon nano hybrid film for 2 times by using the functional method, and performing suction filtration and vacuum drying for 48 hours to obtain the azobenzene-three-dimensional carbon nano hybrid film.
Example 3
The application embodiment 3 provides an azobenzene-three-dimensional carbon nano hybrid film, and the preparation method comprises the following steps:
step 1, preparing 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene,
step 101, weighing 10mmol of 4-aminobenzoic acid and 10mmol of NaOH, dissolving in a beaker containing 40mL of deionized water, stirring uniformly in an ice bath, and then weighing NaNO of slightly more than 10mmol2Dissolving the mixture in a beaker containing 20mL of deionized water, slowly dripping the mixture into the solution after uniformly stirring in an ice bath, and continuously stirring in the ice bath during dripping. After stirring uniformly, slowly dripping the mixture into 60mL of solution containing 25mmol of HCl to generate a diazonium salt solution;
step 102, weighing 5mmol of 3, 5-dimethoxyaniline and dissolving in 40mL of solution containing 10mmol of HCl, slowly dropwise adding the diazonium salt solution, and after dropwise adding, using saturated NaHCO3And regulating the pH value of the solution to 6, stirring for 2h in an ice bath, washing for multiple times, carrying out suction filtration, and then carrying out vacuum drying for 48h to obtain the 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene.
Step 2, preparing graphene oxide dispersion liquid,
step 201, weighing 3g of crystalline flake graphite, and dissolving in 400mL of mixed acid (concentrated H)2SO4: concentrated H3PO4To 9:1), 18g kmno was slowly added under ice-bath4Stirring the mixture evenly, continuing stirring the mixture for 10 hours at 50 ℃, then cooling the mixture to room temperature, and slowly pouring the mixture in 5mL of 30% H2O2Reacting in ice blocks prepared by mixing with 400mL of water,
step 202, after the reaction is finished, filtering and removing concentrated acid solution, then repeatedly washing with deionized water until the pH value of the solution is 6-7, centrifuging for 4 times, performing ultrasonic dispersion for 1h before each centrifugation, centrifuging for the first 3 times at the rotating speeds of 1000r/min, 2000r/min and 4000r/min respectively, taking supernatant, centrifuging at the rotating speed of 11000r/min for the last time, taking down precipitate, performing suction filtration and drying, and then preparing graphene oxide dispersion liquid with the concentration of 1 mg/mL.
Step 3, preparing a short multi-walled carbon nanotube dispersion liquid,
step 301, weighing 0.3g of multi-walled carbon nanotubes, putting the multi-walled carbon nanotubes into a conical flask containing 60mL of 36% HCl solution, stirring for 4 hours, performing centrifugal separation, and washing the multi-walled carbon nanotubes to be neutral by deionized water;
step 302, add it to 160mL of mixed acid (concentrated H)2SO4Concentrated HNO3Stirring at 70 ℃ for 10h, then performing ultrasonic treatment at 40 ℃ for 3h, diluting to neutrality by using deionized water, performing suction filtration and drying, and then preparing into a short multi-walled carbon nanotube dispersion liquid with the concentration of 1 mg/mL.
Step 4, preparing three-dimensional carbon nano material dispersion liquid,
step 401, measuring 100mL of short multi-walled carbon nanotube dispersion liquid and 300mL of graphene oxide dispersion liquid, mixing according to a volume ratio of 1:3, performing ultrasonic treatment for 1h, and performing self-assembly reaction;
step 402, after the self-assembly reaction, add 1.2g NaBH4Then NaOH is used for adjusting the pH value of the solution to 9, and the solution is stirred for 1.5h at the temperature of 80 ℃ for reduction reaction;
and step 403, after the reduction reaction, cooling to room temperature, washing to neutrality by using deionized water, performing suction filtration for many times, drying, and preparing into the three-dimensional carbon nano-material dispersion liquid with the concentration of 1 mg/mL.
Step 5, preparing the azobenzene-three-dimensional carbon nano hybrid film,
step 501, weighing 3mmol of 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene, and performing diazotization reaction to generate diazonium salt;
step 502, slowly adding the diazonium salt prepared in step 502 into 100mL of three-dimensional carbon composite dispersion liquid, reacting for 4 hours in an ice bath, heating to room temperature, reacting overnight, and obtaining an initial product of the azobenzene-three-dimensional carbon nano hybrid film;
step 503, washing the initial product of the azobenzene-three-dimensional carbon nano hybrid film with deionized water, acetone and DMF in sequence to obtain an intermediate product of the azobenzene-three-dimensional carbon nano hybrid film;
and 504, repeatedly reacting and purifying the intermediate product of the azobenzene-three-dimensional carbon nano hybrid film for 2 times by using the functional method, and performing suction filtration and vacuum drying for 48 hours to obtain the azobenzene-three-dimensional carbon nano hybrid film.
Example 4
The embodiment 4 of the application provides an azobenzene-three-dimensional carbon nano hybrid film, and the preparation method comprises the following steps:
step 1, preparing 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene,
step 101, weighing 10mmol of 4-aminobenzoic acid and 10mmol of NaOH, dissolving in a beaker containing 40mL of deionized water, stirring uniformly in an ice bath, and then weighing NaNO of slightly more than 10mmol2Dissolving the mixture in a beaker containing 20mL of deionized water, slowly dripping the mixture into the solution after uniformly stirring in an ice bath, and continuously stirring in the ice bath during dripping. After stirring uniformly, slowly dripping the mixture into 60mL of solution containing 25mmol of HCl to generate a diazonium salt solution;
step 102, weighing 5mmol of 3, 5-dimethoxyaniline and dissolving in 40mL of solution containing 10mmol of HCl, slowly dropwise adding the diazonium salt solution, and after dropwise adding, using saturated NaHCO3And regulating the pH value of the solution to 6, stirring for 1h in an ice bath, washing for multiple times, carrying out suction filtration, and then carrying out vacuum drying for 48h to obtain the 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene.
Step 2, preparing graphene oxide dispersion liquid,
step 201, weighing 3g of crystalline flake graphite, and dissolving in 400mL of mixed acid (concentrated H)2SO4: concentrated H3PO4To 9:1), slowly add 20g kmno under ice bath4Stirring the mixture evenly, continuing stirring the mixture for 12 hours at 50 ℃, then cooling the mixture to room temperature, and slowly pouring the mixture in 5mL of 30% H2O2Reacting in ice blocks prepared by mixing with 400mL of water;
step 202, after the reaction is finished, filtering and removing concentrated acid solution, then repeatedly washing with deionized water until the pH value of the solution is 6-7, centrifuging for 4 times, performing ultrasonic dispersion for 1h before each centrifugation, centrifuging for the first 3 times at the rotating speeds of 1000r/min, 2000r/min and 3000r/min respectively, taking supernatant, centrifuging for the last time at the rotating speed of 12000r/min, taking down the precipitate, performing suction filtration and drying, and then preparing the graphene oxide dispersion liquid with the concentration of 1 mg/mL.
Step 3, preparing a short multi-walled carbon nanotube dispersion liquid,
step 301, weighing 0.3g of multi-walled carbon nanotubes, putting the multi-walled carbon nanotubes into a conical flask containing 60mL of 36% HCl solution, stirring for 4 hours, performing centrifugal separation, and washing the multi-walled carbon nanotubes to be neutral by deionized water;
step 302, add it to 160mL of mixed acid (concentrated H)2SO4Concentrated HNO3Stirring at 70 ℃ for 9h, then performing ultrasonic treatment at 40 ℃ for 4h, diluting to neutrality by using deionized water, performing suction filtration and drying, and then preparing into a short multi-walled carbon nanotube dispersion liquid with the concentration of 1 mg/mL.
Step 4, preparing three-dimensional carbon nano material dispersion liquid,
step 401, measuring 100mL of short multi-walled carbon nanotube dispersion liquid and 300mL of graphene oxide dispersion liquid, mixing according to a volume ratio of 1:4, and performing ultrasonic treatment for 1 hour to perform self-assembly reaction;
step 402, after the self-assembly reaction, 1.5g of NaBH is added4Then NaOH is used for adjusting the pH value of the solution to 9, and the solution is stirred for 2 hours at the temperature of 80 ℃ for reduction reaction;
and step 403, after the reduction reaction, cooling to room temperature, washing to neutrality by using deionized water, performing suction filtration for many times, drying, and preparing into the three-dimensional carbon nano-material dispersion liquid with the concentration of 1 mg/mL.
Step 5, preparing the azobenzene-three-dimensional carbon nano hybrid film,
step 501, weighing 3mmol of 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene, and performing diazotization reaction to generate diazonium salt;
step 502, slowly adding the azobenzene-azobenzene nano-hybrid film into 100mL of three-dimensional carbon nano-material dispersion liquid, reacting for 4 hours in an ice bath, and heating to room temperature for reacting overnight to obtain an initial product of the azobenzene-three-dimensional carbon nano-hybrid film;
step 503, washing the azobenzene-three-dimensional carbon nano hybrid film primary product with deionized water, acetone and DMF (dimethyl formamide) for two to three times in sequence to obtain an azobenzene-three-dimensional carbon nano hybrid film intermediate product;
and step 504, repeating the reaction and purification for 3 times by using the functionalization method, and performing suction filtration and vacuum drying for 48 hours to obtain the azobenzene-three-dimensional carbon nano hybrid film.
Example 5
Embodiment 5 of the present application provides an azobenzene-three-dimensional carbon nano hybrid film, and a preparation method thereof includes the following steps:
step 1, preparing 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene,
step 101, weighing 10mmol of 4-aminobenzoic acid and 10mmol of NaOH, dissolving in a beaker containing 40mL of deionized water, stirring uniformly in an ice bath, and then weighing NaNO of slightly more than 10mmol2Dissolving the mixture in a beaker containing 20mL of deionized water, slowly dripping the mixture into the solution after uniformly stirring in an ice bath, and continuously stirring in the ice bath during dripping. After stirring uniformly, slowly dripping the mixture into 60mL of solution containing 25mmol of HCl to generate a diazonium salt solution;
step 102, weighing 5mmol of 3, 5-dimethoxyaniline and dissolving in 40mL of solution containing 10mmol of HCl, slowly dropwise adding the diazonium salt solution, and after dropwise adding, using saturated NaHCO3And regulating the pH value of the solution to 5, stirring for 2 hours in an ice bath, washing for multiple times, filtering, and then drying for 48 hours in vacuum to obtain the 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene.
Step 2, preparing graphene oxide dispersion liquid,
step 201, weighing 3g of crystalline flake graphite, and dissolving in 400mL of mixed acid (concentrated H)2SO4: concentrated H3PO4To 9:1), 18g kmno was slowly added under ice-bath4Stirring the mixture evenly, continuing stirring the mixture for 12 hours at 50 ℃, then cooling the mixture to room temperature, and slowly pouring the mixture in 5mL of 30% H2O2Reacting in ice blocks prepared by mixing with 400mL of water;
step 201, after the reaction is finished, filtering and removing concentrated acid solution, then repeatedly washing with deionized water until the pH value of the solution is 6-7, then centrifuging for 4 times, performing ultrasonic dispersion for 1 hour before each centrifugation, centrifuging for the first 5 times at the rotating speeds of 1000r/min, 2000r/min, 3000r/min and 4000r/min respectively, taking supernatant, centrifuging for the last time at the rotating speed of 12000r/min, taking down the precipitate, performing suction filtration and drying, and then preparing the graphene oxide dispersion liquid with the concentration of 1 mg/mL.
Step 3, preparing a short multi-walled carbon nanotube dispersion liquid,
step 301, weighing 0.3g of multi-walled carbon nanotubes, putting the multi-walled carbon nanotubes into a conical flask containing 60mL of 36% HCl solution, stirring for 4 hours, performing centrifugal separation, and washing the multi-walled carbon nanotubes to be neutral by deionized water;
step 302, add it to 160mL of mixed acid (concentrated H)2SO4Concentrated HNO3Stirring at 70 ℃ for 9h, then performing ultrasonic treatment at 40 ℃ for 4h, diluting to neutrality by using deionized water, performing suction filtration and drying, and then preparing into a short multi-walled carbon nanotube dispersion liquid with the concentration of 1 mg/mL.
Step 4, preparing three-dimensional carbon nano material dispersion liquid,
step 401, mixing 100mL of short multi-walled carbon nanotube dispersion liquid and 300mL of graphene oxide dispersion liquid according to a volume ratio of 1:2, performing ultrasonic treatment for 1h, and performing self-assembly reaction;
step 402, after the self-assembly reaction, 1g of NaBH is added4Then NaOH is used for adjusting the pH value of the solution to 9, and the solution is stirred for 1 hour at the temperature of 85 ℃ for reduction reaction;
and step 403, after the reduction reaction, cooling to room temperature, washing to neutrality by using deionized water, performing suction filtration for many times, drying, and preparing into the three-dimensional carbon nano-material dispersion liquid with the concentration of 1 mg/mL.
Step 5, preparing the azobenzene-three-dimensional carbon nano hybrid film,
step 501, weighing 3mmol of 4-amino-2, 6-dimethoxy-4' -carboxyl azobenzene, and performing diazotization reaction to generate diazonium salt;
step 502, slowly adding the diazonium salt obtained in the step 501 into 100mL of three-dimensional carbon composite dispersion liquid, reacting for 5 hours in an ice bath, and then heating to room temperature for reacting overnight to obtain an initial product of the azobenzene-three-dimensional carbon nano hybrid film;
step 503, washing the initial product of the azobenzene-three-dimensional carbon nano hybrid film with deionized water, acetone and DMF in sequence to obtain an intermediate product of the azobenzene-three-dimensional carbon nano hybrid film;
and 504, repeatedly reacting and purifying the intermediate product of the azobenzene-three-dimensional carbon nano hybrid film for 4 times by the functional method, and performing suction filtration and vacuum drying for 48 hours to obtain the azobenzene-three-dimensional carbon nano hybrid film.
The foregoing is only a preferred embodiment of the present application and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the present application and these modifications should also be considered as the protection scope of the present application.

Claims (10)

1. The azobenzene-three-dimensional carbon nano hybrid film is characterized by comprising azobenzene and a three-dimensional carbon nano material, wherein one end of the azobenzene contains an amino group, and the three-dimensional carbon nano material is grafted with the azobenzene through a covalent bond.
2. The azobenzene-three-dimensional carbon nano hybrid film as claimed in claim 1, wherein the structural formula of the azobenzene containing amino at one end is as formula I;
Figure FDA0003093713410000011
wherein X is methyl or methoxy, Y1Is a carboxyl group, a hydroxyl group or a sulfonic acid group, Y2Is carboxyl, hydroxyl or sulfonic group.
3. The azobenzene-three-dimensional carbon nano hybrid film as claimed in claim 1, wherein the three-dimensional carbon nano material comprises reduced graphene oxide and reduced short carbon nanotubes.
4. The azobenzene-three-dimensional carbon nano hybrid film as claimed in claim 1, wherein the reduced graphene oxide comprises single-layer or few-layer reduced graphene oxide, and the reduced short carbon nanotubes comprise short multi-walled carbon nanotubes.
5. The preparation method of the azobenzene-three-dimensional carbon nano hybrid film is characterized by comprising the following steps: adding azobenzene diazonium salt solution with amino at one end into three-dimensional carbon nano material dispersion liquid for carrying out first reaction, and carrying out suction filtration and drying to obtain an azobenzene-three-dimensional carbon nano hybrid film;
the first reaction is specifically carried out for 3-6h in ice bath, and then the temperature is raised to room temperature for reaction overnight.
6. The method for preparing azobenzene-three-dimensional carbon nano hybrid film according to claim 5, wherein the method for preparing the three-dimensional carbon nano material dispersion liquid comprises the following steps: and ultrasonically mixing the graphene oxide dispersion liquid and the short carbon nanotube dispersion liquid to perform solution self-assembly reaction, and then performing reduction reaction to obtain the three-dimensional carbon nano-material dispersion liquid.
7. The method of claim 6, wherein the reduction reaction comprises partial reduction of oxygen-containing groups.
8. The method for preparing azobenzene-three-dimensional carbon nano hybrid film according to claim 5, wherein the method for preparing the short carbon nano tube comprises the following steps: and purifying and oxidizing and cutting the carbon nano tube in sequence to obtain the short carbon nano tube.
9. The method for preparing azobenzene-three-dimensional carbon nano hybrid film according to claim 8, wherein the oxidative cutting comprises placing the purified carbon nano tube in mixed acid, stirring, and performing ultrasonic treatment to obtain short carbon nano tube;
the stirring comprises stirring for 8-10 h at 35-75 ℃;
the ultrasonic treatment comprises ultrasonic treatment at 35-45 ℃ for 3-5 h;
the mixed acid comprises concentrated H with the volume ratio of 3:12SO4And concentrated HNO3The mixed acid of (1).
10. Use of the azobenzene-three-dimensional carbon nano hybrid film as defined in any one of claims 1 to 4 or prepared by the preparation method as defined in claims 5 to 9 in the field of solar fuel.
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