CN107814816A - A kind of azobenzene containing imidazole radicals/nitridation boron compound as New-type fuel and preparation method thereof - Google Patents
A kind of azobenzene containing imidazole radicals/nitridation boron compound as New-type fuel and preparation method thereof Download PDFInfo
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- CN107814816A CN107814816A CN201711009195.6A CN201711009195A CN107814816A CN 107814816 A CN107814816 A CN 107814816A CN 201711009195 A CN201711009195 A CN 201711009195A CN 107814816 A CN107814816 A CN 107814816A
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- azobenzene
- imidazole radicals
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- 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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Abstract
The present invention relates to a kind of azobenzene containing imidazole radicals/boron nitride hybrid fuel and preparation method.The azobenzene containing imidazole radicals by o-aminophenol and the reaction synthesis of 1 phenylimidazole, then it is using diazo-reaction that the azobenzene containing imidazole radicals and pretreated hexagonal boron nitride is compound, the obtained azobenzene containing imidazole radicals/nitridation boron compound, so as to form a kind of novel fuel.The fuel is easily prepared, and energy density is 60 Wh/kg, and energy value and half-life period compared with azobenzene small molecule are significantly improved, effectively to provide a kind of New-type fuel for being easy to energy storage and transhipment using solar energy.
Description
Technical field
The present invention designs a kind of azobenzene containing imidazole radicals/boron nitride hybrid fuel and preparation method, and it is in the following sun
There can be important application prospect in terms of storage, belong to composite functional material field.
Background technology
Fuel refers to the material by the release chemical energy that chemically reacts, and traditional fuel can be divided into 3 kinds by material type：Change
Stone fuel（Such as oil, coal, oil shale, methane, oil-sand, natural gas）；Bio-fuel（Such as ethanol, biodiesel）；Core fires
Material（Such as uranium 235, uranium 233, uranium 238, plutonium 239, thorium 232）.As pernicious gas caused by the burning of fossil fuel is to environment
Pollution and fossil fuel peter out, developing the new energy turns into the effective way for solving environmental degradation and energy crisis
（Chem Rev, 2010, 110:6474–6502）.It is the most green energy conversion process of people society directly using solar energy.But
It is directly to utilize two prominent technological deficiencies of presence of solar energy, in addition to transformation efficiency is low, be exactly difficult to store and turn
Fortune.Solar cell is a kind of energy storage mode, the finite energy of solar cell storage at present, preferable solar cell
Per kilogram stores the energy of 300 watt-hours, and is not easy to transport.And solar energy fuel is due to its adjustable storage（tunable
storage）With the release of solar thermal energy, 100% reversible occlusion circulation（revesible closed cycle）, do not discharge and appoint
What gas and chemical substance（Nat Chem, 2014, 6: 441–447）And cause extensive interest.Fuel molecule passes through
The absorption of light, in ground state（S0）Inferior stable state is reached by photoisomerization（S1）, store heat content Δ H, the energy then stored with
The form of heat discharges, and compound returns to ground state from inferior stable state（Energy Environ. Sci. 4, 4449–4472
(2011)）, can freely be discharged as one kind which results in solar heat fuel, a kind of reproducible resource, be adapted to modern society
Energy utilization pattern and facility.
Material using reversible chemical reaction release chemical energy is a kind of New-type fuel（Nano Lett., 2011, 11,
3156–3162）.Studying the more material using reversible chemical reaction release chemical energy at present has the ruthenium compound of fulvalene
（Angew Chem Int Ed, 2010, 49: 8926–8929 ；Phys Chem Chem Phys, 2013, 15: 7466–
7469 ；Energy Environ. Sci., 2012, 5, 8534–8537）, the cycloheptene of norbornadiene-four（Chem.
Commun., 2014, 50, 5330–5332； J. Org. Chem., 2017, 82, 1301–1315；Energy
Environ. Sci., 2017, 10, 728-734）, azobenzene（Angew. Chem., Int. Ed., 2015, 54,
1532–1536；J. Mater. Chem. A, 2015, 3, 11787–11795）.And because noble ruthenium is expensive, drop
Although the cycloheptene system enthalpy of borneol diene-four is larger but half-life period is shorter, so azobenzene is the emphasis studied at present.
Azobenzene is a kind of compound with cis-trans isomerism, illumination, temperature, humidity, mechanical force etc. change under he all
Cis-trans isomerism can occur, wherein illumination effect is maximum.It can become trans under ultraviolet light by cis, and be shone in visible ray
It can become cis by trans under penetrating, some physics and the change such as reversible isomerization reaction and adjoint possible hydrogen bond, dipole moment
Change is learned, cis-azobenzene releases energy as New-type fuel.And because the enthalpy of azobenzene is smaller, so we utilize nitridation
Boron is template, increases intermolecular active force and space resistance, the caused energy by cis-trans isomerism, increases enthalpy.Experiment
Prove, azobenzene/boron nitride composite containing imidazole radicals can produce good energy storage effect, can be as a kind of closure
Fuel uses.
The content of the invention
It is an object of the invention to study a kind of composite that can store solar energy, preparing a kind of new has high energy
Azobenzene/boron nitride composite containing imidazole radicals of metric density.
The present invention prepares a kind of azobenzene/nitrogen containing imidazole radicals that can be used as solar energy storage using following technical scheme
Change boron composite, its structure is as shown in formula：
By structural formula it will be seen that the azobenzene containing imidazole radicals prepared by experiment has been grafted on boron nitride.Using point
The cis-trans isomerism of active force and azobenzene between son is acted on to realize the storage and release of composite energy under illumination.
A kind of azobenzene containing imidazole radicals/boron nitride hybrid fuel of the present invention and preparation method.Methods described following 1）Nitrogen
Change the pretreatment of boron：The aqueous solution of 10-20 part boron nitride, ultrasonic disperse in 5 mol/L NaOH, and the N at 120 DEG C2Under atmosphere
Stirring 18 hours, filtering be washed to neutrality, dried in 80 DEG C of baking ovens, then by its again ultrasonic disperse in tetrahydrofuran.
2）The preparation of azobenzene/boron nitride composite containing imidazole radicals：Azobenzene containing imidazole radicals is added to step
1）Tetrahydrofuran solution in, add sulfuric acid reaction products therefrom water, ethanol and DMF and alternately clean, dried in 70 DEG C of baking ovens
It is dry, obtain azobenzene/boron nitride composite containing imidazole radicals.
Described 1）In, the quality parts ratio of boron nitride and sodium hydroxide is 10-30：100-300 parts.
Described 2）In, the quality parts ratio of material is as follows：Azobenzene of the 2-3 parts containing imidazole radicals：30-50 part tetrahydrochysene furans
Mutter：2-3 part sulfuric acid.
Described 2）In, the quality parts ratio of azobenzene and boron nitride containing imidazole radicals is 30-60 parts：80-100 parts.
The present invention includes diazol method and nucleophilic displacement of fluorine.O-aminophenol and the reaction synthesis of 1- phenylimidazoles are contained into miaow first
The azobenzene of oxazolyl, it is then compound with pretreated hexagonal boron nitride.What is obtained is multiple containing azobenzene/boron nitride containing imidazole radicals
Condensation material is greatly improved compared with azobenzene small molecule in energy value and half-life period, is advantageous to solar energy storage.
Detected by Dsc, the energy density for measuring azobenzene/boron nitride composite containing imidazole radicals of preparation is 60
Wh/kg。
Brief description of the drawings
Fig. 1 is the ultra-violet absorption spectrum of azobenzene/boron nitride composite of the example 1 containing imidazole radicals, as shown in the figure can be with
It is seen that there is the absworption peak of corresponding azo and imidazoles, the half-life period of composite.
Fig. 2 is the energy density analysis chart of azobenzene/boron nitride composite of the example 2 containing imidazole radicals, as shown in the figure may be used
To find out the energy density of composite.
Embodiment
Here is the further explanation to the present invention, rather than limits the scope of the present invention.
1）The preparation of azobenzene containing imidazole radicals：
1. the preparation of product (1)：The HCl of 5-20 parts o-aminophenol and 5-20 parts 36% is dissolved in 10-30 part deionized waters,
In 0-5 °C of lower stirring and dissolving, 6-25 part sodium nitrite solutions are slowly added dropwise, stir 30 min, adds 5-20 part urea liquids and removes
Unnecessary natrium nitrosum is removed, until the constant indigo plant of starch potassium iodide paper, then proceedes to stir 30 min, be filtrated to get target product
(1）.
2. the preparation of product (2)：1-3 part 1- phenylimidazoles and the HCl of 1-3 parts 36% is taken to be dissolved in 5-10 part deionized waters,
1-3 parts product (1 is slowly added dropwise）, 0-5 °C of stirring 4h is kept after being added dropwise, filtering, orange precipitation is obtained, is dried in vacuo, obtains
To target product (2）.
2）The pretreatment of boron nitride：The aqueous solution of 10-20 part boron nitride, ultrasonic disperse in 5 mol/L NaOH, and
N at 120 DEG C2Stirred 18 hours under atmosphere, filtering is washed to neutrality, is dried in 80 DEG C of baking ovens, and then by it, ultrasound is divided again
It is dispersed in tetrahydrofuran.
3）The preparation of azobenzene/boron nitride composite containing imidazole radicals：Azobenzene containing imidazole radicals is added to above-mentioned
Tetrahydrofuran solution in, add sulfuric acid reaction.Products therefrom water, ethanol and DMF alternately cleaning 3-5 times, in 70 DEG C of baking ovens
Middle drying, obtain azobenzene/boron nitride composite containing imidazole radicals.
Embodiment 1
1）The preparation of azobenzene containing imidazole radicals：
1. the preparation of product (1)：The HCl of 10 mmol o-aminophenols and 6 mL36% is dissolved in 15 mL part deionized waters,
0-5 °C of lower stirring and dissolving, 10 mL14% sodium nitrite solution is slowly added dropwise, stirs 30 min, add 5 mL10% urea liquids
Unnecessary natrium nitrosum is removed, until the constant indigo plant of starch potassium iodide paper, then proceedes to stir 30 min, is filtrated to get target production
Thing (1）.
2. the preparation of product (2)：10 mmol 1- phenylimidazoles and the HCl of 4 mL parts 36% is taken to be dissolved in 10 mL part deionizations
In water, by 10 mmol parts products (1）It is slowly dropped in reaction solution, 0-5 °C of stirring 4h is kept after being added dropwise, filtering, is obtained
Orange precipitation, vacuum drying, obtains target product (2）.
2）The pretreatment of boron nitride：The aqueous solution of boron nitride, ultrasonic disperse in the mol/L NaOH of 200 mL 5, and
N at 120 DEG C2Stirred 18 hours under atmosphere, filtering is washed to neutrality, is dried in 80 DEG C of baking ovens, and then by it, ultrasound is divided again
It is dispersed in tetrahydrofuran.
3）The preparation of azobenzene/boron nitride composite containing imidazole radicals：Azobenzenes of 0.5 g containing imidazole radicals is added
In the tetrahydrofuran solution above-mentioned to 100 mL, the h of 100 mL, 2 mol/L sulfuric acid reactions 3 is added.Products therefrom water, ethanol
With DMF alternately cleaning 3 times, dried in 70 DEG C of baking ovens, obtain azobenzene/boron nitride composite containing imidazole radicals.
Polymeric energy density produced by the present invention is 60 Wh/kg, and easily prepared, is carried for effective utilize of solar energy
New method and thinking are gone out.
Embodiment 2
1）The preparation of azobenzene containing imidazole radicals：
1. the preparation of product (1)：The HCl of 20 mmol o-aminophenols and 12 mL36% is dissolved in 25 mL part deionized waters,
In 0-5 °C of lower stirring and dissolving, 20 mL14% sodium nitrite solution is slowly added dropwise, stirs 30 min, adds 10 mL10% urea
Solution removes unnecessary natrium nitrosum, until the constant indigo plant of starch potassium iodide paper, then proceedes to stir 30 min, be filtrated to get mesh
Mark product (1）.
2. the preparation of product (2)：20 mmol 1- phenylimidazoles and the HCl of 8 mL parts 36% is taken to be dissolved in 20 mL part deionizations
In water, by 20 mmol parts products (1）It is slowly dropped in reaction solution, 0-5 °C of stirring 4h is kept after being added dropwise, filtering, is obtained
Orange precipitation, vacuum drying, obtains target product (2）.
2）The pretreatment of boron nitride：The aqueous solution of boron nitride, ultrasonic disperse in the mol/L NaOH of 300 mL 5, and
N at 120 DEG C2Stirred 18 hours under atmosphere, filtering is washed to neutrality, is dried in 80 DEG C of baking ovens, and then by it, ultrasound is divided again
It is dispersed in tetrahydrofuran.
3）The preparation of azobenzene/boron nitride composite containing imidazole radicals：Azobenzenes of 1 g containing imidazole radicals is added to
In tetrahydrofuran solution above-mentioned 200 mL, the h of 200 mL, 2 mol/L sulfuric acid reactions 3 is added.Products therefrom water, ethanol and
DMF alternately cleaning 5 times, dry in 70 DEG C of baking ovens, obtain azobenzene/boron nitride composite containing imidazole radicals.
Polymeric energy density produced by the present invention is 60 Wh/kg, and easily prepared, is carried for effective utilize of solar energy
New method and thinking are gone out.
Embodiment 3
1）The preparation of azobenzene containing imidazole radicals：
1. the preparation of product (1)：The HCl of 30 mmol o-aminophenols and 18 mL36% is dissolved in 40 mL part deionized waters,
In 0-5 °C of lower stirring and dissolving, 30 mL14% sodium nitrite solution is slowly added dropwise, stirs 30 min, adds 15 mL10% urea
Solution removes unnecessary natrium nitrosum, until the constant indigo plant of starch potassium iodide paper, then proceedes to stir 30 min, be filtrated to get mesh
Mark product (1）.
2. the preparation of product (2)：Take 30 mmol 1- phenylimidazoles and the HCl of 12 mL parts 36% be dissolved in 30 mL parts go from
In sub- water, by 30 mmol parts products (1）It is slowly dropped in reaction solution, 0-5 °C of stirring 4h is kept after being added dropwise, filtering, is obtained
To orange precipitation, vacuum drying, target product (2 is obtained）.
2）The pretreatment of boron nitride：The aqueous solution of boron nitride, ultrasonic disperse in the mol/L NaOH of 300 mL 5, and
N at 120 DEG C2Stirred 18 hours under atmosphere, filtering is washed to neutrality, is dried in 80 DEG C of baking ovens, and then by it, ultrasound is divided again
It is dispersed in tetrahydrofuran.
3）The preparation of azobenzene/boron nitride composite containing imidazole radicals：Azobenzenes of 1 g containing imidazole radicals is added to
In tetrahydrofuran solution above-mentioned 200 mL, the h of 200 mL, 2 mol/L sulfuric acid reactions 3 is added.Products therefrom water, ethanol and
DMF alternately cleaning 5 times, dry in 70 DEG C of baking ovens, obtain azobenzene/boron nitride composite containing imidazole radicals.
Polymeric energy density produced by the present invention is 60 Wh/kg, and easily prepared, is carried for effective utilize of solar energy
New method and thinking are gone out.
The method that the present invention is disclosed and proposed, those skilled in the art can suitably change condition by using for reference present disclosure
The links such as route are realized, although the method and technology of preparing of the present invention are described by preferred embodiment, related skill
Art personnel can substantially not depart from present invention, methods and techniques described herein route is being modified in spirit and scope
Or reconfigure, to realize final technology of preparing.In particular, all similar replacements and change are to ability
It is it will be apparent that they are considered as being included in spiritual, scope and content of the invention for field technique personnel.
Claims (6)
1. a kind of azobenzene/boron nitride composite containing imidazole radicals, it is characterized in that the azobenzene containing imidazole radicals is grafted on
On hexagonal boron nitride, structure such as formula is as follows：
。
2. the preparation method of azobenzene/boron nitride composite containing imidazole radicals of claim 1, it is characterized in that step is as follows：
1）The pretreatment of boron nitride：The aqueous solution of 10-20 part boron nitride, ultrasonic disperse in 5 mol/L NaOH, and at 120 DEG C
N2Stirred 18 hours under atmosphere, filtering be washed to neutrality, dried in 80 DEG C of baking ovens, then by its again ultrasonic disperse in tetrahydrochysene
In furans；
2）The preparation of azobenzene/boron nitride composite containing imidazole radicals：Azobenzene containing imidazole radicals is added to step 1）Institute
In the boron nitride tetrahydrofuran solution obtained, sulfuric acid reaction products therefrom is added, is alternately cleaned with water, ethanol and DMF, in 70 DEG C of bakings
Dried in case, obtain azobenzene/boron nitride composite containing imidazole radicals.
3. method as claimed in claim 2, it is characterized in that described 1）In, the quality parts ratio of boron nitride and sodium hydroxide is
10-30 ：100-300 parts.
4. method as claimed in claim 2, it is characterized in that described 2）In, the quality parts ratio of material is as follows：2-3 parts contain miaow
The azobenzene of oxazolyl：30-50 part tetrahydrofurans：2-3 part sulfuric acid.
5. method as claimed in claim 2, it is characterized in that described 2）In, the quality of azobenzene and boron nitride containing imidazole radicals
Portion rate is 30-60 parts：80-100 parts.
6. the method described in claim 2, it is characterized in that the azobenzene preparation method containing imidazole radicals is as follows：
1) HCl of 5-20 parts o-aminophenol and 5-20 parts 36% is dissolved in 10-30 part deionized waters, stirred under 0-5 °C
Dissolving, 6-25 part sodium nitrite solutions are slowly added dropwise, stir 30 min, add 5-20 parts urea and remove unnecessary natrium nitrosum,
Then proceed to stir 30 min, filtering；
2) take 1-3 part 1- phenylimidazoles and the HCl of 1-3 parts 36% to be dissolved in 5-10 part deionized waters, 1-3 part products are slowly added dropwise
(1）, 0-5 °C of stirring 4h is kept after being added dropwise, filtering, orange precipitation is obtained, is dried in vacuo, obtains the azo containing imidazole radicals
Benzene.
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| CN201711009195.6A CN107814816B (en) | 2017-10-25 | 2017-10-25 | Azobenzene/boron nitride compound containing imidazolyl as novel fuel and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1910260A (en) * | 2004-01-09 | 2007-02-07 | 香港大学 | Materials for electroluminescent devices |
| CN102265422A (en) * | 2008-12-26 | 2011-11-30 | 先锋株式会社 | Organic electroluminescent element |
| US20140088324A1 (en) * | 2011-03-18 | 2014-03-27 | Ucl Business Plc | Borazine derivatives |
| CN106047307A (en) * | 2016-05-24 | 2016-10-26 | 天津大学 | Tri-branched azobenzene/graphene composite energy storage material and preparation method thereof |
-
2017
- 2017-10-25 CN CN201711009195.6A patent/CN107814816B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1910260A (en) * | 2004-01-09 | 2007-02-07 | 香港大学 | Materials for electroluminescent devices |
| CN102265422A (en) * | 2008-12-26 | 2011-11-30 | 先锋株式会社 | Organic electroluminescent element |
| US20140088324A1 (en) * | 2011-03-18 | 2014-03-27 | Ucl Business Plc | Borazine derivatives |
| CN106047307A (en) * | 2016-05-24 | 2016-10-26 | 天津大学 | Tri-branched azobenzene/graphene composite energy storage material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 曹晨 等: "分子级光储热材料的研究进展", 《技术科学》 * |
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