CN110734410A - double-grafted heterocyclic azobenzene graphene energy storage material and preparation method thereof - Google Patents
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Abstract
The invention discloses double-grafted heterocyclic azobenzene graphene energy storage materials and a preparation method thereof, wherein two azo molecules of a main material are grafted to the surface of graphene in a covalent bond mode, azo molecules are grafted to every 20-50 carbon atoms, the two azo molecules are prepared firstly, then graphene reduction and oxidation are pretreated, and finally the double-grafted heterocyclic azobenzene graphene composite material is prepared.
Description
Technical Field
The invention belongs to the field of functional composite materials, and particularly relates to dual-grafted heterocyclic azobenzene graphene composite energy storage materials and a preparation method thereof, which have important application prospects in the aspect of solar energy storage in the future.
Background
Along with the rapid development of modern society, the demand of people on energy is continuously increased, the energy crisis in the global scope is increasingly prominent, the traditional fossil energy such as coal, oil and the like is exhausted, the energy crisis is caused, the global environmental problem is caused, such as global warming, coal burning can emit a large amount of chemical toxic heavy metals, radioactive substances and the like through coal cinder and smoke, meanwhile, along with the reduction of the fossil energy, the price is correspondingly improved, the production and living level of people are seriously restricted to be improved, so that the clean eating resources such as solar energy which is more and more developed for renewable energy are carried along with the reduction of the fossil energy, the solar energy has the advantages of (1) being the most abundant energy which can be utilized by human beings, the estimation shows that the sun only consumes 2% of the energy in the past ten hundred million years, the sun can not obviously change in the future, the solar energy can not generate a large amount of harmful gas in the future, the south of the world, the environment can not be exploited, the environment is not polluted by the natural gas, the natural gas can not be extracted, the natural gas can not be used in the ten hundred of hundred years, the south of the south, the south of the south, the north, the south of the south, the south of the south, the north, the south of the south, the north, the south of the south, the.
The azobenzene molecule has cis-trans configuration, which is good photoresponse materials, under the irradiation of ultraviolet light, the trans configuration can be converted into cis configuration after absorbing energy, and under the irradiation of heating or visible light, the cis configuration can be converted back into the trans configuration, thereby releasing energy and achieving the energy storage effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides double-grafted heterocyclic azobenzene graphene energy storage materials and a preparation method thereof, wherein the preparation of two azo molecules is firstly carried out, then graphene reduction and oxidation pretreatment is carried out, and finally the preparation of the double-grafted heterocyclic azobenzene graphene composite material is carried out, through the characterization of DSC, the composite energy storage material has extremely high energy density which is as high as 145 Wh/kg., the highest isomerization rate is 90 percent, and the improvement is 30 percent compared with a monomer molecule.
The technical purpose of the invention is realized by the following technical scheme:
kinds of double-grafted heterocyclic azobenzene graphene energy storage material has a structure shown in the following chemical formula.
Namely, two azobenzene molecules are grafted to the surface of the graphene in a covalent bond mode.
Further, the graphene is a reduced graphene oxide (i.e., a reduced graphene oxide).
Moreover, the two azobenzene molecules have the structures shown in the following molecular formulas.
And the two azo molecules are grafted to the surface of the graphene in a covalent bond mode, azobenzene molecules are grafted to every 20-50 carbon atoms, and azobenzene molecules are preferably grafted to 20-30 carbon atoms.
In the double-grafted heterocyclic azobenzene graphene structure, solar energy can be efficiently stored, the double-grafted heterocyclic azobenzene graphene structure has the characteristics of high energy density and controllable heat release, and cis-trans isomerism is adopted for energy storage and release, and the method is as follows:
in the technical scheme of the invention, graphene can be reduced by graphene oxide to obtain graphene (namely, reduced graphene oxide), so that a benzene ring structure of the graphene is damaged, a compact six-membered ring (benzene ring) structure has a certain carbon atom loss to form a vacancy, a reaction site is provided for grafting of heterocyclic azobenzene, heterocyclic azobenzene molecules are grafted per 20-50 carbon atoms, azobenzene molecules are preferably grafted per 20-30 carbon atoms, after the two azobenzene molecules are grafted by the graphene, sulfur atoms, nitrogen atoms and hydroxyl groups of the two azobenzene molecules interact with each other to form a multiple hydrogen bond interaction structure, namely, hydrogen bond interactions are formed on two sides of the graphene.
Two preparation methods of azobenzene molecules; the reaction process is shown as the following chemical formula:
the preparation method of the 2-aminothiazole azobenzene comprises the following steps: uniformly dispersing 2-aminothiazole and sodium nitrite in deionized water, adding a mixed solution of hydrochloric acid and acetone, stirring and dispersing the system under an ice bath condition, adding a sodium hydroxide aqueous solution dispersed with aniline into the system, continuously stirring under the ice bath condition and the pH of 8-9 for reaction, neutralizing by using hydrochloric acid after the reaction is finished, and performing suction filtration, drying and crystallization to obtain the target heterocyclic azo monomer 2-aminothiazole azobenzene. Specifically, the method comprises the following steps:
the amount of the 2-aminothiazole is 20-50 mol parts, and each mol parts is 1 mmol.
The molar ratio of the 2-aminothiazole azobenzene to the sodium nitrite is 1: (1-1.5), preferably 1: (1.2-1.5).
The molar ratio of the 2-aminothiazole azobenzene to the aniline is 1: 1.
in the mixed liquid of hydrochloric acid and acetone, the volume ratio of the hydrochloric acid to the acetone is 2:1, and the hydrochloric acid concentration is 1 mol/L.
In an aqueous solution of sodium hydroxide in which aniline was dispersed, the concentration of sodium hydroxide was 1 mol/L.
The volume ratio of the mixed solution of deionized water, hydrochloric acid and acetone to the aqueous solution of sodium hydroxide in which aniline is dispersed is (50-60): (25-55): (20-30).
The stirring speed is 100-300 revolutions per minute and the reaction time is 1-5 hours, preferably 3-5 hours.
The preparation method of the 3, 5' -dihydroxyaminoazobenzene comprises the following steps: dispersing 3, 5-dihydroxyaniline in deionized water, adding hydrochloric acid, stirring and dispersing uniformly under an ice bath condition, adding a sodium nitrite aqueous solution, and stirring and reacting to form a diazonium salt solution; dropwise adding the diazonium salt solution into hydrochloric acid with uniformly dispersed aniline, adjusting the pH to 6-7 by using a saturated sodium bicarbonate aqueous solution, continuously stirring and reacting under the inert protective gas atmosphere, and carrying out suction filtration, washing and crystallization to obtain the 3, 5' -dihydroxyaminoazobenzene as the hydroxy azo monomer. Specifically, the method comprises the following steps:
the using amount of the 3, 5-dihydroxyaniline is 20-50 mol parts, and each mol parts is 1 mmol.
The molar ratio of the 3, 5-dihydroxyaniline to the sodium nitrite is 1: (1-1.5).
The molar ratio of 3, 5-dihydroxyaniline to aniline is 1: 1.
the stirring speed is 100-300 r/min, and the inert protective gas is nitrogen, helium or argon.
The diazonium salt solution is dropwise added to hydrochloric acid for uniformly dispersing aniline, the reaction time is 20-30 min, and the reaction is continuously stirred for 1-5 hours, preferably 3-5 hours under the inert protective gas atmosphere.
After the reaction is finished, a crude product is obtained by suction filtration, and is washed by distilled water for a plurality of times, and then is recrystallized in a mixed solution of ethanol and acetone (the volume ratio of the ethanol to the acetone is 1:1), so that the target hydroxy azo monomer is obtained.
Reduced Graphene Oxide (RGO) treatment: and adjusting the pH value of the aqueous solution of the uniformly dispersed graphene oxide to 8-9 by using sodium hydroxide, adding sodium borohydride, and reducing the graphene oxide by using the sodium borohydride under inert protective gas to obtain reduced graphene oxide. Centrifuging, filtering and washing the product for multiple times to obtain the prepared product; finally, the mixture is dispersed in water by using ultrasound. Specifically, the method comprises the following steps:
stirring is adopted in the reaction process to ensure that the mixture is uniformly dispersed and reacted, the stirring speed is 100-300 revolutions per minute, and the inert protective gas is nitrogen, helium or argon.
The reaction is carried out at 80 to 90 ℃ for 1 to 5 hours, preferably 2 to 3 hours.
The concentration of sodium borohydride is 10-30mg/ml (mass of sodium borohydride, mg/volume of water, ml), and the amount of sodium borohydride is excessive relative to graphene oxide, so that graphene oxide is fully reduced.
The preparation method of the double-grafted heterocyclic azobenzene graphene energy storage material comprises the following steps: uniformly dispersing 2-aminothiazole azobenzene, 3, 5' -dihydroxyaminoazobenzene, sodium hydroxide and sodium nitrate in deionized water, adding the deionized water into hydrochloric acid, and reacting under an ice bath condition; and dropwise adding an aqueous solution of uniformly dispersed reduced graphene oxide into the graphene oxide for reaction under an ice bath condition, and then continuously reacting at the room temperature of 20-25 ℃ to graft the 2-aminothiazole azobenzene and the 3, 5' -dihydroxyaminoazobenzene to the surface of the graphene in a covalent bond mode. Specifically, the method comprises the following steps:
2-aminothiazole azobenzene, 3, 5' -dihydroxy aminoazobenzene, sodium hydroxide and sodium nitrate in equal molar ratio.
The dosage of the 2-aminothiazole azobenzene is 1 to 5mol portions, and each mol portions is 1 mmol.
Adding into hydrochloric acid, reacting for 1-5 hours, preferably 1-2 hours under ice bath condition, the concentration of hydrochloric acid is 1mol/L, and the dosage of hydrochloric acid and deionized water is equal volume ratio.
Dropwise adding an aqueous solution of uniformly dispersed reduced graphene oxide, reacting for 1-5 hours, preferably 3-4 hours under ice bath conditions, and then continuing to react for 5-10 hours, preferably 8-10 hours at room temperature of 20-25 ℃ to graft the 2-aminothiazole azobenzene and the 3, 5' -dihydroxyaminoazobenzene to the surface of the graphene in a covalent bond manner.
Washing the reaction product with deionized water and acetone for 3-6 times, and performing suction filtration to obtain the target product, namely the multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material.
In the aqueous solution in which the reduced graphene oxide is uniformly dispersed, the amount of the reduced graphene oxide is 5 to 20 parts by mass, 1mg per parts by mass, preferably 10 to 20 parts by mass, and the amount of the aqueous solution in which the reduced graphene oxide is uniformly dispersed is 50 to 100 parts by volume, 1ml per parts by volume, preferably 60 to 80 parts by volume.
According to the dual-grafted heterocyclic azobenzene graphene composite energy storage material (namely the multiple hydrogen bond dual-grafted heterocyclic azobenzene graphene composite material) and the preparation method, two azo molecules of a main material are grafted to the surface of graphene in a covalent bond mode, azobenzene molecules are grafted every 20-50 carbon atoms (XPS test and verification).
Drawings
Fig. 1 is an ultraviolet absorption spectrum diagram of a multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material.
Fig. 2 is a DSC heat flow graph of a multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite.
Fig. 3 is a scanning electron microscope picture of a multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material.
Fig. 4 is an infrared spectrum of the multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material.
Detailed description of the preferred embodiments
The following is a further description of the invention and is not intended to limit the scope of the invention.
Example 1
1) Preparation of 2-aminothiazole azobenzene (1.5 equivalents based on moles of 2-aminothiazole: 1.5 times the moles of 2-aminothiazole): 50mmol of 2-aminothiazole and 1.5 equivalents of sodium nitrite are dissolved in 60ml of deionized water; then adding 30ml of a mixed solution of 1mol/L hydrochloric acid and acetone (the volume ratio of the hydrochloric acid to the acetone is 2:1), and stirring the system for 30 minutes under the ice bath condition; dissolving equivalent aniline into 30ml of 1mol/L sodium hydroxide solution, and adding the solution into the system; the reaction mixture was stirred at pH9 for 5 hours under ice-bath conditions; neutralizing with 40ml of 1.5mol/L hydrochloric acid solution (aqueous hydrogen chloride solution), filtering, vacuum drying the obtained crude product, and recrystallizing in ethanol for purification to obtain the target heterocyclic azo monomer.
2) Preparation of 3,5 ' -dihydroxyazobenzene (1.5 equivalents based on moles of 3,5 ' -dihydroxyazobenzene is 1.5 times the moles of 3,5 ' -dihydroxyazobenzene): dissolving 50mmol of 3, 5-dihydroxyaniline in deionized water; then adding 25ml of 1mol/L hydrochloric acid (aqueous hydrogen chloride solution), and stirring under the ice bath condition to dissolve the hydrochloric acid; then, 1.5 equivalents of an aqueous solution of sodium nitrite was added dropwise to the system, and stirred for 30 minutes to obtain a diazonium salt solution. Adding equivalent aniline into 20ml of 1mol/L hydrochloric acid, and stirring and dissolving under an ice bath condition; the diazonium salt solution was then slowly added dropwise to the above solution (30 min in use) and the pH was adjusted to 7 with 50ml of saturated sodium bicarbonate solution; continuously stirring for 5 hours under the protection of argon, and performing suction filtration to obtain a crude product; after washing with distilled water for several times, recrystallization was carried out in a mixed solution of ethanol and acetone to obtain the objective hydroxyazo monomer.
3) Reduced Graphene Oxide (RGO) treatment: adjusting the pH value of 80ml of graphene oxide solution to 8 by using a sodium hydroxide solution; then 0.3g of sodium borohydride is added and stirred to be dispersed evenly; reacting for 5 hours at 90 ℃ under the protection of argon, centrifuging, filtering and washing the product for multiple times to obtain the prepared reduced graphene oxide; finally, the mixture is dispersed in water by using ultrasound.
4) Preparing a multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material: 2mmol of azobenzene prepared in the step 1)2), equimolar sodium hydroxide and sodium nitrate are added into 20ml of deionized water; stirring evenly at room temperature, and slowly adding into 30ml of 1mol/L hydrochloric acid solution; reacting for 2 hours under ice bath condition; then dropwise adding the mixture into 60ml of RGO solution (aqueous solution of dispersed RGO, the mass of RGO is 10ng), reacting for 3 hours under ice bath condition, and then reacting for 10 hours at room temperature; and washing the product with deionized water and acetone for 5 times, and performing suction filtration to obtain the target product, namely the multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material. The energy density of the composite material can reach 130 Wh/kg.
Example 2
1) Preparation of 2-aminothiazolazobenzene (equivalent 1 time of the mole of 2-aminothiazole): 20mmol of 2-aminothiazole and 1.2 equivalents of sodium nitrite were dissolved in 50ml of deionized water; then adding 55ml of a mixed solution of 1mol/L hydrochloric acid and acetone (the volume ratio of the hydrochloric acid to the acetone is 2:1), and stirring the system for 15 minutes under the ice bath condition; dissolving equivalent aniline into 20ml of 1mol/L sodium hydroxide solution, and adding the solution into the system; the reaction mixture was stirred at pH8 for 3 hours under ice-bath conditions; neutralizing with 30ml of 1.5mol/L hydrochloric acid solution, filtering, vacuum drying the obtained crude product, and recrystallizing in ethanol for purification to obtain the target heterocyclic azo monomer.
2) Preparation of 3,5 ' -dihydroxyazobenzene (1.5 equivalents based on moles of 3,5 ' -dihydroxyazobenzene is 1.5 times the moles of 3,5 ' -dihydroxyazobenzene): dissolving 20mmol of 3, 5-dihydroxyaniline in deionized water; then adding 55ml of 1mol/L hydrochloric acid, and stirring under the ice bath condition to dissolve the hydrochloric acid; then, 1.4 equivalents of sodium nitrite solution was added dropwise to the system, and stirred for 25 minutes to obtain a diazonium salt solution. Adding equivalent aniline into 30ml of 1mol/L hydrochloric acid solution, and stirring and dissolving under an ice bath condition; the diazonium salt solution was then slowly added dropwise to the above solution (30 min in use) and the pH was adjusted to 7 with 50ml of saturated sodium bicarbonate solution; continuously stirring for 4 hours under the protection of argon, and performing suction filtration to obtain a crude product; after washing with distilled water for several times, recrystallization was carried out in a mixed solution of ethanol and acetone to obtain the objective hydroxyazo monomer.
3) Reduced Graphene Oxide (RGO) treatment: adjusting the pH of 50ml of graphene oxide solution to 8 by using a sodium hydroxide solution; then 0.2g of sodium borohydride is added and stirred to be dispersed evenly; reacting for 3 hours under the condition of low argon protection and 80 ℃, centrifuging, filtering and washing the product for multiple times to obtain the prepared reduced graphene oxide; finally, the mixture is dispersed in water by using ultrasound.
4) Preparing a multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material: 3mmol of azobenzene prepared in the step 1)2), equimolar sodium hydroxide and sodium nitrate are added into 30ml of deionized water; stirring evenly at room temperature, and slowly adding into 20ml of 1mol/L hydrochloric acid solution; reacting for 1 hour under ice bath condition; then dropwise adding the mixture into 70ml of RGO solution (aqueous solution of dispersed RGO, the mass of RGO is 10ng), reacting for 4 hours under ice bath condition, and then reacting for 8 hours at room temperature; and washing the product with deionized water and acetone for 5 times, and performing suction filtration to obtain the target product, namely the multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material. The energy density of the composite material can reach 145 Wh/kg.
Example 3
1) Preparation of 2-aminothiazolazobenzene (equivalent 1 time of the mole of 2-aminothiazole): 30mmol of 2-aminothiazole and 1.2 equivalents of sodium nitrite were dissolved in 60ml of deionized water; then adding 40ml of a mixed solution of 1mol/L hydrochloric acid and acetone (the volume ratio of the hydrochloric acid to the acetone is 2:1), and stirring the system for 20 minutes under the ice bath condition; dissolving equivalent aniline into 30ml of 1mol/L sodium hydroxide solution, and adding the solution into the system; the reaction mixture was stirred at pH8 for 4 hours under ice-bath conditions; neutralizing with 40ml of 1.5mol/L hydrochloric acid solution, filtering, vacuum drying the obtained crude product, and recrystallizing in ethanol for purification to obtain the target heterocyclic azo monomer.
2) Preparation of 3,5 ' -dihydroxyazobenzene (1.5 equivalents based on moles of 3,5 ' -dihydroxyazobenzene is 1.5 times the moles of 3,5 ' -dihydroxyazobenzene): dissolving 30mmol of 3, 5-dihydroxyaniline in deionized water; then adding 40ml of 1mol/L hydrochloric acid (aqueous hydrogen chloride solution), and stirring under the ice bath condition to dissolve the hydrochloric acid; then, 1.1 equivalents of an aqueous solution of sodium nitrite was added dropwise to the system, and stirred for 20 minutes to obtain a diazonium salt solution. Adding equivalent aniline into 20ml of 1mol/L hydrochloric acid, and stirring and dissolving under an ice bath condition; the diazonium salt solution was then slowly added dropwise to the above solution (20 min in use) and the pH was adjusted to 6 with 30ml of saturated sodium bicarbonate solution; continuously stirring for 3 hours under the protection of argon, and performing suction filtration to obtain a crude product; after washing with distilled water for several times, recrystallization was carried out in a mixed solution of ethanol and acetone to obtain the objective hydroxyazo monomer.
3) Reduced Graphene Oxide (RGO) treatment: adjusting the pH of 60ml of graphene oxide solution to 9 by using a sodium hydroxide solution; then 0.3g of sodium borohydride is added and stirred to be dispersed evenly; reacting for 2 hours under the condition of low argon protection and 90 ℃, centrifuging, filtering and washing the product for multiple times to obtain the prepared reduced graphene oxide; finally, the mixture is dispersed in water by using ultrasound.
4) Preparing a multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material: 3mmol of azobenzene prepared in the step 1)2), equimolar sodium hydroxide and sodium nitrate are added into 20ml of deionized water; stirring evenly at room temperature, and slowly adding into 25ml of 1mol/L hydrochloric acid solution; reacting for 2 hours under ice bath condition; then dropwise adding the mixture into 80ml of RGO solution (aqueous solution of dispersed RGO, the mass of RGO is 10ng), reacting for 3 hours under ice bath condition, and then reacting for 9 hours at room temperature; and washing the product with deionized water and acetone for 5 times, and performing suction filtration to obtain the target product, namely the multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material. The energy density of the composite material can reach 135 Wh/kg.
The prepared multiple hydrogen bond double-grafted heterocyclic azobenzene graphene composite material is characterized as shown in attached figures 1-4. 696cm in IR spectrum analysis-1The absorption peak of (a) is an absorption peak of a-C-S-bond of 1479cm-1The absorption peak of (A) is the characteristic absorption peak of benzene ring, 1572cm-1Absorption peak of C ═ C bond, absorption peak of-N ═ N-bond, 16120 cm-1An absorption peak of-C ═ N-bond, 3315 to 3476 absorption peaks of intermolecular hydrogen bond, 3741cm-1As a result of the above analysis, two azobenzene monomers were successfully synthesized and joined together as a free-OH absorption peakAccording to the method, the surface of the RGO is obviously wrinkled as shown by a scanning electron microscope picture, the situation that azobenzene molecules are grafted to the surface of the RGO is shown, the wrinkles are mutually interpenetrated and stacked to be beneficial to the interaction between the RGO and the formation of an interpenetration structure between the RGO, the energy density and the half life of the RGO are improved, the azobenzene monomer can generate cis-trans isomerism under the irradiation of an ultraviolet lamp, as shown by an ultraviolet absorption spectrum, when the azobenzene graphene energy storage material is not irradiated with ultraviolet light, as the two grafted azobenzene molecules belong to an aminoazobenzene type and a push-pull azobenzene type respectively, a pi-pi absorption band can generate fixed red shift and is positioned near 350-370 nm, after the ultraviolet lamp is irradiated for 45 minutes, the pi-pi absorption band is reduced, the trans structure is proved to be converted into a cis structure, the n-pi absorption band and the pi-pi absorption band generate fixed coincidence, a DSC (differential scanning calorimetry) is utilized to scan an exothermic peak of the material, and then a Wh-pi absorption band is used for calculating the corresponding exothermic energy, so that the corresponding mass is calculated, and the corresponding mass is obtained.
The invention has been described by way of example only and it is to be understood that any simple modification, adaptation or equivalent substitution by a person skilled in the art, without having to resort to the inventive measures, is within the scope of protection of the present invention.
Claims (10)
- The dual-grafted heterocyclic azobenzene graphene energy storage material is characterized by having a structure shown in the following chemical formula, wherein two azobenzene molecules, namely 2-aminothiazole azobenzene and 3, 5' -dihydroxy aminoazobenzene, are grafted to the surface of graphene in a covalent bond mode, and after the graphene is grafted with the two azobenzene molecules, sulfur atoms, nitrogen atoms and hydroxyl groups of the two azobenzene molecules interact with each other to form an interaction structure of multiple hydrogen bonds.
- 2. The kinds of dual-grafted heterocyclic azobenzene graphene energy storage material of claim 1, wherein graphene is redox graphene.
- 3. The kinds of dual-grafted heterocyclic azobenzene graphene energy storage material according to claim 1 or 2, wherein azobenzene molecules are grafted per 20-50 carbon atoms, preferably azobenzene molecules are grafted per 20-30 carbon atoms.
- 4, preparation method of double-grafted heterocyclic azobenzene graphene energy storage material, which is characterized in that 2-aminothiazole azobenzene, 3,5 '-dihydroxy aminoazobenzene, sodium hydroxide and sodium nitrate are uniformly dispersed in deionized water and added into hydrochloric acid to react under ice bath condition, then aqueous solution of uniformly dispersed reduced graphene oxide is added dropwise to react under ice bath condition, and then the reaction is continued at room temperature of 20-25 ℃ to graft the 2-aminothiazole azobenzene and the 3, 5' -dihydroxy aminoazobenzene on the surface of graphene in a covalent bond mode.
- 5. The method for preparing dual-grafted heterocyclic azobenzene graphene energy storage materials according to claim 4, wherein 2-aminothiazole azobenzene, 3, 5' -dihydroxy aminoazobenzene, sodium hydroxide and sodium nitrate are in equimolar ratio, and the amount of 2-aminothiazole azobenzene is 1-5 mol parts, and 1mmol is used in each mol parts.
- 6. The preparation method of kinds of dual-grafted heterocyclic azobenzene graphene energy storage materials according to claim 4, wherein the aqueous solution of uniformly dispersed reduced graphene oxide is added dropwise, reacted under ice bath conditions for 1-5 hours, preferably 3-4 hours, and then the reaction is continued at room temperature of 20-25 ℃ for 5-10 hours, preferably 8-10 hours.
- 7. The method for preparing dual-grafted heterocyclic azobenzene graphene energy storage materials according to claim 4, wherein in the aqueous solution of uniformly dispersed reduced graphene oxide, the amount of reduced graphene oxide is 5-20 parts by mass, each parts by mass is 1mg, preferably 10-20 parts by mass, and the amount of the aqueous solution of uniformly dispersed reduced graphene oxide is 50-100 parts by volume, each parts by volume is 1ml, preferably 60-80 parts by volume.
- 8. The preparation method of kinds of dual-grafted heterocyclic azobenzene graphene energy storage materials according to claim 4, wherein the pH value of an aqueous solution in which graphene oxide is uniformly dispersed is adjusted to 8-9 by using sodium hydroxide, sodium borohydride is added, and the graphene oxide is subjected to reduction treatment by using the sodium borohydride under inert protective gas, so that reduced graphene oxide is obtained.
- 9. The preparation method of double-grafted heterocyclic azobenzene graphene energy storage materials according to claim 4, wherein the preparation method comprises the steps of uniformly dispersing 2-aminothiazole and sodium nitrite in deionized water, adding a mixed solution of hydrochloric acid and acetone, stirring and dispersing the system under an ice bath condition, adding a sodium hydroxide aqueous solution dispersed with aniline into the system, continuously stirring in an ice bath at a pH of 8-9 for reaction, neutralizing with hydrochloric acid after the reaction is finished, and performing suction filtration, drying and crystallization to obtain the target heterocyclic azo monomer 2-aminothiazole azobenzene.
- 10. The preparation method of double-grafted heterocyclic azobenzene graphene energy storage materials according to claim 4, wherein the preparation method comprises the steps of dispersing 3, 5-dihydroxyaniline in deionized water, adding hydrochloric acid, uniformly stirring and dispersing under an ice bath condition, adding a sodium nitrite aqueous solution, stirring and reacting to form a diazonium salt solution, dropwise adding the diazonium salt solution into hydrochloric acid uniformly dispersing aniline, adjusting the pH to 6-7 by using a saturated sodium bicarbonate aqueous solution, continuously stirring and reacting under an inert protective gas atmosphere, and performing suction filtration, washing and crystallization to obtain the 3, 5' -dihydroxyaminoazobenzene monomer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113264521A (en) * | 2021-05-31 | 2021-08-17 | 广东工业大学 | Azobenzene-three-dimensional carbon nano hybrid film and preparation method and application thereof |
| CN115206689A (en) * | 2022-07-07 | 2022-10-18 | 浙江理工大学 | Graphene modified material and preparation method thereof |
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| CN113173864B (en) * | 2020-10-30 | 2023-06-30 | 山西大同大学 | Graphene synergistic photo-thermal energy storage composite material and preparation method and application thereof |
| CN113264521A (en) * | 2021-05-31 | 2021-08-17 | 广东工业大学 | Azobenzene-three-dimensional carbon nano hybrid film and preparation method and application thereof |
| CN115206689A (en) * | 2022-07-07 | 2022-10-18 | 浙江理工大学 | Graphene modified material and preparation method thereof |
| CN115206689B (en) * | 2022-07-07 | 2024-02-09 | 浙江理工大学 | Graphene modified material and preparation method thereof |
| CN116041210A (en) * | 2022-12-07 | 2023-05-02 | 南京工业大学 | Chiral nano material and preparation method thereof |
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