CN107814816B - Azobenzene/boron nitride compound containing imidazolyl as novel fuel and preparation method thereof - Google Patents
Azobenzene/boron nitride compound containing imidazolyl as novel fuel and preparation method thereof Download PDFInfo
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- CN107814816B CN107814816B CN201711009195.6A CN201711009195A CN107814816B CN 107814816 B CN107814816 B CN 107814816B CN 201711009195 A CN201711009195 A CN 201711009195A CN 107814816 B CN107814816 B CN 107814816B
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- azobenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/16—Materials undergoing chemical reactions when used
Abstract
The invention relates to an imidazole-group-containing azobenzene/boron nitride composite fuel and a preparation method thereof. O-aminophenol and 1-phenylimidazole are reacted to synthesize azobenzene containing imidazolyl, and then the azobenzene containing imidazolyl and the pretreated hexagonal boron nitride are compounded through diazotization to obtain an azobenzene/boron nitride compound containing imidazolyl, so that the novel fuel is formed. The fuel is easy to prepare, has the energy density of 60 Wh/kg, is obviously improved compared with the energy value and half-life period of azobenzene micromolecules, and provides a novel fuel convenient for energy storage and transportation for effectively utilizing solar energy.
Description
Technical Field
The invention designs an imidazole-group-containing azobenzene/boron nitride composite fuel and a preparation method thereof, which have important application prospects in the aspect of future solar energy storage and belong to the field of composite functional materials.
Background
Fuel refers to a substance that releases chemical energy through a chemical reaction, and conventional fuels can be classified into 3 types by substance type: fossil fuels (e.g., petroleum, coal, oil shale, methane, oil sands, natural gas, etc.); biofuels (e.g., ethanol, biodiesel, etc.); nuclear fuels (e.g. uranium 235, uranium 233, uranium 238, plutonium 239, thorium 232, etc.). With the environmental pollution caused by harmful gases generated by the combustion of fossil fuels and the gradual depletion of fossil fuels, the development of new energy becomes an effective way to solve the environmental deterioration and energy crisis (Chem Rev, 2010, 110: 6474-. The direct utilization of solar energy is the greenest energy conversion process in human society. However, there are two significant technical drawbacks to direct solar energy utilization, in addition to low conversion efficiency, that is, difficulty in storage and transportation. The solar cell is an energy storage mode, the energy stored by the solar cell is limited at present, and the better solar cell stores 300 watt-hours per kilogram and is not easy to transfer. Solar fuels have attracted a great deal of interest due to their tunable storage (tunable storage) and release of solar thermal energy, 100% reversible closed cycle, without releasing any gases and chemicals (Nat Chem, 2014, 6: 441-. The fuel molecules are absorbed by light, undergo photoisomerization in a ground state (S0) to reach a metastable state (S1), the enthalpy of heat delta H is stored, then the stored Energy is released in the form of heat, and the compound returns to the ground state from the metastable state (Energy environ, Sci. 4, 4449 and 4472 (2011)), so that the solar thermal fuel becomes a freely releasable and renewable resource which is suitable for Energy utilization modes and facilities of modern society.
Substances which release chemical energy by means of reversible chemical reactions are a new class of fuels (Nano lett, 2011, 11, 3156-. Among the currently studied substances that release chemical Energy by reversible chemical reactions are the fullerene-rich ruthenium compounds (Angew Chem Int Ed 2010, 49: 8926-. However, the noble metal ruthenium is expensive, and the norbornadiene-tetracycloheptene system has a large enthalpy value but a short half life, so azobenzene is the focus of current research.
Azobenzene is a compound with cis-trans isomerism, and under the change of illumination, temperature, humidity, mechanical force and the like, the azobenzene can generate cis-trans isomerism, wherein the illumination influence is the largest. The cis-azobenzene can be changed from cis form to trans form under the irradiation of ultraviolet light, and can be changed from trans form to cis form under the irradiation of visible light, reversible isomerization reaction and possible physical and chemical changes such as hydrogen bonds, dipole moment and the like are carried out, and the cis-azobenzene releases energy to become a novel fuel. And because the enthalpy value of azobenzene is smaller, boron nitride is used as a template, intermolecular acting force and space resistance are increased, and the enthalpy value is increased by means of energy generated by cis-trans isomerization. Experiments prove that the azobenzene/boron nitride composite material containing the imidazolyl can generate a good energy storage effect and can be used as a closed fuel.
Disclosure of Invention
The invention aims to research a composite material capable of storing solar energy and prepare a novel imidazole-containing azobenzene/boron nitride composite material with high energy density.
The invention adopts the following technical scheme to prepare the azobenzene/boron nitride composite material containing the imidazolyl group, which can be used for solar energy storage, and the structure of the azobenzene/boron nitride composite material is shown as the formula:
as can be seen by the structural formula, the experimentally prepared azobenzene containing imidazolyl was grafted onto boron nitride. The storage and release of the energy of the composite material under illumination are realized by utilizing intermolecular acting force and cis-trans isomerization of azobenzene.
The invention relates to an imidazole-group-containing azobenzene/boron nitride composite fuel and a preparation method thereof. The method comprises the following steps of 1) pretreating boron nitride: 10 to 20 portions of aqueous solution of boron nitride, 5mol/L NaOH are ultrasonically dispersed, and N is carried out at 120 DEG C2Stirred under atmosphere for 18 hours, filtered and washed with water to neutrality, dried in an oven at 80 ℃ and then re-dispersed ultrasonically in tetrahydrofuran.
2) Preparation of azobenzene/boron nitride composite material containing imidazolyl: adding azobenzene containing imidazolyl into the tetrahydrofuran solution obtained in the step 1), adding sulfuric acid to react, alternately cleaning a product obtained by using water, ethanol and DMF, and drying in a 70 ℃ drying oven to obtain the azobenzene/boron nitride composite material containing imidazolyl.
In the step 1), the mass part ratio of boron nitride to sodium hydroxide is 10-30: 100 portions to 300 portions.
In the step 2), the mass parts of the substances are as follows: 2-3 parts of azobenzene containing imidazolyl: 30-50 parts of tetrahydrofuran: 2-3 parts of sulfuric acid.
In the step 2), the mass part ratio of azobenzene containing imidazolyl to boron nitride is 30-60: 80-100 parts.
The present invention includes diazonium salt methods and nucleophilic substitution. Firstly, o-aminophenol and 1-phenylimidazole react to synthesize azobenzene containing imidazolyl, and then the azobenzene is compounded with pretreated hexagonal boron nitride. Compared with azobenzene micromolecules, the obtained azobenzene/boron nitride composite material containing the imidazolyl has greatly improved energy value and half-life period, and is beneficial to solar energy storage.
The prepared azobenzene/boron nitride composite material containing the imidazolyl group is measured to have an energy density of 60 Wh/kg by Dsc detection.
Drawings
FIG. 1 is a UV absorption spectrum of an imidazole-containing azobenzene/boron nitride composite of example 1, showing that there are corresponding azo and imidazole absorption peaks, and the half-life of the composite.
FIG. 2 is an energy density analysis of an imidazole-containing azobenzene/boron nitride composite of example 2, as shown in the figure, the energy density of the composite can be seen.
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.
1) Preparation of imidazole group-containing azobenzene:
firstly, preparation of a product: dissolving 5-20 parts of o-aminophenol and 5-20 parts of 36% HCl in 10-30 parts of deionized water, stirring and dissolving at 0-5 ℃, slowly dropwise adding 6-25 parts of sodium nitrite solution, stirring for 30min, adding 5-20 parts of urea solution to remove redundant sodium nitrite until the starch potassium iodide test paper does not turn blue, then continuously stirring for 30min, and filtering to obtain the target product (1).
Secondly, preparing the product: dissolving 1-3 parts of 1-phenylimidazole and 1-3 parts of 36% HCl in 5-10 parts of deionized water, slowly dropwise adding 1-3 parts of the product (1), stirring for 4 hours at 0-5 ℃ after dropwise adding, filtering to obtain orange precipitate, and vacuum drying to obtain the target product (2).
2) Pretreatment of boron nitride: 10 to 20 portions of aqueous solution of boron nitride, 5mol/L NaOH are ultrasonically dispersed, and N is carried out at 120 DEG C2Stirred under atmosphere for 18 hours, filtered and washed with water to neutrality, dried in an oven at 80 ℃ and then re-dispersed ultrasonically in tetrahydrofuran.
3) Preparation of azobenzene/boron nitride composite material containing imidazolyl: adding azobenzene containing imidazolyl into the tetrahydrofuran solution, and adding sulfuric acid for reaction. And (3) alternately cleaning the obtained product with water, ethanol and DMF for 3-5 times, and drying in an oven at 70 ℃ to obtain the imidazole-containing azobenzene/boron nitride composite material.
Example 1
1) Preparation of imidazole group-containing azobenzene:
firstly, preparation of a product: dissolving 10 mmol of o-aminophenol and 6 mL of 36% HCl in 15 mL of deionized water, stirring and dissolving at 0-5 ℃, slowly dropwise adding 10 mL of 14% sodium nitrite solution, stirring for 30min, adding 5 mL of 10% urea solution to remove excessive sodium nitrite until starch potassium iodide paper does not turn blue, then continuing stirring for 30min, and filtering to obtain the target product (1).
Secondly, preparing the product: dissolving 10 mmol of 1-phenylimidazole and 4 mL of 36% HCl in 10 mL of deionized water, slowly dropwise adding 10 mmol of the product (1) into the reaction solution, stirring at 0-5 ℃ for 4h after dropwise adding, filtering to obtain orange precipitate, and vacuum drying to obtain the target product (2).
2) Pretreatment of boron nitride: an aqueous solution of boron nitride, 200 mL of 5mol/L NaOH, and N at 120 deg.C2Stirred under atmosphere for 18 hours, filtered and washed with water to neutrality, dried in an oven at 80 ℃ and then re-dispersed ultrasonically in tetrahydrofuran.
3) Preparation of azobenzene/boron nitride composite material containing imidazolyl: 0.5 g of azobenzene containing an imidazole group was added to 100 mL of the above tetrahydrofuran solution, and 100 mL of 2 mol/L sulfuric acid was added to react for 3 hours. And (3) alternately cleaning the obtained product with water, ethanol and DMF for 3 times, and drying in a 70 ℃ oven to obtain the imidazole-containing azobenzene/boron nitride composite material.
The polymer prepared by the invention has the energy density of 60 Wh/kg, is easy to prepare, and provides a new method and thought for the effective utilization of solar energy.
Example 2
1) Preparation of imidazole group-containing azobenzene:
firstly, preparation of a product: dissolving 20 mmol of o-aminophenol and 12 mL of 36% HCl in 25 mL of deionized water, stirring and dissolving at 0-5 ℃, slowly dropwise adding 20 mL of 14% sodium nitrite solution, stirring for 30min, adding 10 mL of 10% urea solution to remove excessive sodium nitrite until starch potassium iodide paper does not turn blue, then continuing stirring for 30min, and filtering to obtain the target product (1).
Secondly, preparing the product: and (3) dissolving 20 mmol of 1-phenylimidazole and 8 mL of 36% HCl in 20 mL of deionized water, slowly dropwise adding 20 mmol of the product (1) into the reaction solution, stirring at 0-5 ℃ for 4h after dropwise adding, filtering to obtain orange precipitate, and drying in vacuum to obtain the target product (2).
2) Pretreatment of boron nitride: an aqueous solution of boron nitride, 300 mL of 5mol/L NaOH, and N at 120 DEG C2Stirred under atmosphere for 18 hours, filtered and washed with water to neutrality, dried in an oven at 80 ℃ and then re-dispersed ultrasonically in tetrahydrofuran.
3) Preparation of azobenzene/boron nitride composite material containing imidazolyl: 1 g of azobenzene containing an imidazole group was added to 200 mL of the above tetrahydrofuran solution, and 200 mL of 2 mol/L sulfuric acid was added to the resulting solution to react for 3 hours. And (3) alternately cleaning the obtained product with water, ethanol and DMF for 5 times, and drying in an oven at 70 ℃ to obtain the imidazole-containing azobenzene/boron nitride composite material.
The polymer prepared by the invention has the energy density of 60 Wh/kg, is easy to prepare, and provides a new method and thought for the effective utilization of solar energy.
Example 3
1) Preparation of imidazole group-containing azobenzene:
firstly, preparation of a product: dissolving 30 mmol of o-aminophenol and 18 mL of 36% HCl in 40 mL of deionized water, stirring and dissolving at 0-5 ℃, slowly dropwise adding 30 mL of 14% sodium nitrite solution, stirring for 30min, adding 15 mL of 10% urea solution to remove excessive sodium nitrite until starch potassium iodide paper does not turn blue, then continuing stirring for 30min, and filtering to obtain the target product (1).
Secondly, preparing the product: and (3) dissolving 30 mmol of 1-phenylimidazole and 12 mL of 36% HCl in 30 mL of deionized water, slowly dropwise adding 30 mmol of the product (1) into the reaction solution, stirring at 0-5 ℃ for 4h after dropwise adding, filtering to obtain orange precipitate, and drying in vacuum to obtain the target product (2).
2) Pretreatment of boron nitride: an aqueous solution of boron nitride, 300 mL of 5mol/L NaOH, and N at 120 DEG C2Stirred under atmosphere for 18 hours, filtered and washed with water to neutrality, dried in an oven at 80 ℃ and then re-dispersed ultrasonically in tetrahydrofuran.
3) Preparation of azobenzene/boron nitride composite material containing imidazolyl: 1 g of azobenzene containing an imidazole group was added to 200 mL of the above tetrahydrofuran solution, and 200 mL of 2 mol/L sulfuric acid was added to the resulting solution to react for 3 hours. And (3) alternately cleaning the obtained product with water, ethanol and DMF for 5 times, and drying in an oven at 70 ℃ to obtain the imidazole-containing azobenzene/boron nitride composite material.
The polymer prepared by the invention has the energy density of 60 Wh/kg, is easy to prepare, and provides a new method and thought for the effective utilization of solar energy.
Although the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or rearrangements of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (4)
1. A preparation method of azobenzene/boron nitride composite material containing imidazolyl comprises the following steps:
the method is characterized by comprising the following steps:
1) pretreatment of boron nitride: 10-20 parts of aqueous solution of boron nitride, 5mol/LNaOH, and N at 120 DEG C2Stirring for 18 hours in the atmosphere, filtering, washing with water to be neutral, drying in an oven at 80 ℃, and then ultrasonically dispersing in tetrahydrofuran again;
2) preparation of azobenzene/boron nitride composite material containing imidazolyl: adding azobenzene containing imidazolyl into the boron nitride tetrahydrofuran solution obtained in the step 1), adding sulfuric acid to react to obtain a product, alternately cleaning with water, ethanol and DMF, and drying in a 70 ℃ drying oven to obtain the azobenzene/boron nitride composite material containing imidazolyl;
the preparation method of the azobenzene containing the imidazolyl comprises the following steps:
1) dissolving 5-20 parts of o-aminophenol and 5-20 parts of 36% HCl in 10-30 parts of deionized water, stirring and dissolving at 0-5 ℃, slowly dropwise adding 6-25 parts of sodium nitrite solution, stirring for 30min, adding 5-20 parts of urea to remove redundant sodium nitrite, then continuously stirring for 30min, and filtering;
2) dissolving 1-3 parts of 1-phenylimidazole and 1-3 parts of 36% HCl in 5-10 parts of deionized water, slowly dropwise adding 1-3 parts of the product (1), keeping the temperature of 0-5 ℃ after dropwise adding, stirring for 4 hours, filtering to obtain orange precipitate, and drying in vacuum to obtain the azobenzene containing the imidazolyl.
2. The method as set forth in claim 1), wherein the ratio of boron nitride to sodium hydroxide in 1) is 10-30 parts by weight: 100 portions to 300 portions.
3. The method as claimed in claim 1, wherein in 2), the mass parts of the substances are as follows: 2-3 parts of azobenzene containing imidazolyl: 30-50 parts of tetrahydrofuran: 2-3 parts of sulfuric acid.
4. The method as set forth in claim 1, wherein in 2), the mass part ratio of the azobenzene containing the imidazolyl group to the boron nitride is 30-60: 80-100 parts.
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| US7157155B2 (en) * | 2004-01-09 | 2007-01-02 | The University Of Hong Kong | Materials for electroluminescent devices |
| KR20110095891A (en) * | 2008-12-26 | 2011-08-25 | 파이오니아 가부시키가이샤 | Organic elelctroluminescent element |
| ES2530353T3 (en) * | 2011-03-18 | 2015-03-02 | Université De Namur | Borazeno derivatives |
| CN106047307B (en) * | 2016-05-24 | 2019-03-22 | 天津大学 | One kind three azobenzenes/graphene composite energy-storage material and preparation method |
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