CN109293552A - A kind of indoles azobenzene/graphene composite solar heat accumulating and preparation method thereof - Google Patents
A kind of indoles azobenzene/graphene composite solar heat accumulating and preparation method thereof Download PDFInfo
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- CN109293552A CN109293552A CN201811071506.6A CN201811071506A CN109293552A CN 109293552 A CN109293552 A CN 109293552A CN 201811071506 A CN201811071506 A CN 201811071506A CN 109293552 A CN109293552 A CN 109293552A
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- azobenzene
- indoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/40—Nitrogen atoms, not forming part of a nitro radical, e.g. isatin semicarbazone
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Abstract
The present invention relates to a kind of indoles azobenzene/graphene composite solar heat accumulatings, the indoles azo molecules of monomer are covalently grafted to graphene surface, every 30~50 carbon atoms are grafted an azo molecules, the preparation method is as follows: the preparation of azo molecules；Graphene oxide is subjected to partial reduction: the aqueous solution of graphene oxide being adjusted into pH to 7-9 with the sodium carbonate that mass fraction is 20%-30%, the aqueous solution for the graphene oxide that pH is mixed up is added in sodium borohydride solution, and it is placed under 75-90 degrees Celsius, the graphene oxide Jing Guo partial reduction is obtained after centrifugal filtration, is then dispersed in water again by ultrasound；Azobenzene graft grapheme: the sodium nitrite of indoles type azobenzene and equimolar amounts is added in deionized water, hydrochloric acid is slowly added dropwise under condition of ice bath, diazonium salt is made, the diazonium salt of acquisition is slowly added dropwise into the previously obtained graphene oxide by partial reduction, is reacted one day in ice bath.
Description
Technical field
The present invention is a kind of indoles azobenzene/graphene composite solar heat accumulating and preparation method thereof, which exists
Future can be used in the high-new application of photo-thermal storage and Solar use etc., belong to field of compound material.
Background technique
With the continuous development of society, environmental pollution has become each country and requires the problem of facing, to show in life
It is extremely serious in destruction of the common petroleum-based energy to environment.In order to solve environmental problem, it would be desirable to develop a kind of novel green
The color energy is used to replace used high pollution now and the petroleum resources that will be used up.
Solar energy is the energy the most abundant on a kind of earth, per hour provided by energy be more than the mankind 2001 complete
Ball energy consumption summation, although the mankind rely on the photosynthesis of plant to can be carried out utilization to the sun always, now to too
The utilization of positive energy is still seldom.Photovoltaic or solar battery mostly used to the utilization of solar energy now, however these sides
Method energy conversion times are excessive, and energy conversion efficiency is low.Energy can be converted if directly storing energy using optothermal material
Efficiency greatly improves.
A kind of dyestuff of the azobenzene as photoisomerization is a kind of photo-thermal energy storage material having good prospects.Azobenzene is steady
Fixed transconfiguration can become cis-azobenzene under action of ultraviolet light, and store energy in chemical bond, centainly pierce
Swash lower and energy can be discharged, and returns to rock-steady structure.However the shortcomings that tradition azobenzene, is that its filming performance is poor, energy
Metric density is low and half-life short.In order to increase the energy difference of azobenzene Cis-trans structures, need to carry out molecule and knot to azobenzene
Structure design improves intermolecular force, increases steric effect, azobenzene can be improved by the way that condensed cyclic structure is added in azobenzene
Thermal storage performance.By the way that azobenzene grafting on the surface of graphene, can be further improved the thermal storage performance of azobenzene, and mention
The high filming performance of material.
Summary of the invention
The purpose of the present invention is to provide one kind can store solar energy, has high-energy density, the indoles of long half-lift
Type azobenzene/graphene composite material and preparation method thereof.The invention adopts the following technical scheme:
1. a kind of indoles azobenzene/graphene composite solar heat accumulating, the indoles azo molecules of monomer are with covalent
Key mode is grafted to graphene surface, and every 30~50 carbon atoms are grafted an azo molecules, and structural formula is as follows:
2. indoles azobenzene described in claim 1/graphene composite solar heat accumulating preparation method, step is such as
Under:
1) preparation of azo molecules: by -5 chloro-indole of 3- amino be added the beaker with distilled water in, hydrochloric acid by its
Sodium nitrite solution is added in dissolution under condition of ice bath after dissolution, ice bath reacts 1-3 hours, and diazonium salt is made, and 1-2 is added and works as
3,5 dimethoxyanilines of amount simultaneously react in argon atmosphere, obtain indoles type azo benzene monomer, wherein -5 chlorine Yin of 3- amino
The molar ratio of diindyl, hydrochloric acid and sodium nitrite is 1:(3-4): (1.05-1.2)；
2) graphene oxide is carried out partial reduction: the sodium carbonate for being 20%-30% with mass fraction is by graphene oxide
Aqueous solution adjust pH to 7-9, the aqueous solution of graphene oxide that addition pH is mixed up in sodium borohydride solution, and in 75-90
It is placed 6-8 hours under degree Celsius, by centrifugation, filter operation finally obtains the graphene oxide Jing Guo partial reduction, then leads to
Ultrasound is crossed to be dispersed in water again；
3) azobenzene graft grapheme: the sodium nitrite of indoles type azobenzene and equimolar amounts is added in deionized water,
Diazonium salt is made in the hydrochloric acid that 1mol/L is slowly added dropwise under condition of ice bath, and wherein the molar ratio of azobenzene and hydrochloric acid is 1:(3-
4), the diazonium salt of acquisition is slowly added dropwise into the previously obtained graphene oxide by partial reduction, is reacted one day in ice bath,
Indoles azobenzene/graphene composite material can be prepared.
Detailed description of the invention
Fig. 1 is the ultraviolet spectra of condensed azo benzene graphene composite material；
Fig. 2 is the scanning electron microscope (SEM) photograph of azobenzene graphene composite material.
Specific implementation method
Here is not intended to limit the scope of the invention to further explanation of the invention.
Embodiment 1
1) preparation of azo molecules: -5 chloro-indole of 3- amino of 0.02mol is added in the beaker with distilled water, is used
The hydrochloric acid of 0.06mol is dissolved, and 0.015mol sodium nitrite solution is added after dissolution under condition of ice bath, and ice bath reaction 3 is small
When, diazonium salt is made.The 3 of 1.5 equivalents are added, 5 dimethoxyanilines simultaneously react in argon atmosphere, and indoles type can be obtained
Azo benzene monomer；
2) graphene oxide is carried out partial reduction: the sodium carbonate for being 20% with mass fraction is by the water-soluble of graphene oxide
Liquid adjusts pH to 8, the solution that the pH of 30ml is mixed up is added in 15 mg/ml sodium borohydride solutions, and place under 85 degrees Celsius
4 hours.By centrifugation, filter operation finally obtains the graphene oxide Jing Guo partial reduction, then divides again ultrasound is passed through
It dissipates in water；
3) azobenzene graft grapheme: the addition of the sodium nitrite of 0.005mol indoles type azobenzene and 0.005mol is filled
In the beaker of 10ml deionized water, diazonium salt is made in the hydrochloric acid that the 1mol/L of 15ml is slowly added dropwise under condition of ice bath.It will obtain
Diazonium salt be slowly added dropwise into it is previously obtained by reduction graphene oxide, reacted one day in ice bath, Yin can be prepared
Diindyl azobenzene/graphene composite material.Product energy storage density is made and reaches 140Wh/kg.
Embodiment 2
1) preparation of azo molecules: -5 chloro-indole of 3- amino of 0.01mol is added in the beaker with distilled water, is used
The hydrochloric acid of 0.03mol is dissolved, and 0.015mol sodium nitrite solution is added after dissolution under condition of ice bath, and ice bath reaction 2 is small
When, diazonium salt is made.The 3 of 1 equivalent are added, 5 dimethoxyanilines simultaneously react in argon atmosphere, and indoles type azo can be obtained
Benzene monomer；
2) graphene oxide is carried out partial reduction: the sodium carbonate for being 20%-30% with mass fraction is by graphene oxide
Aqueous solution adjust pH to 8, the solution that mixes up of pH of 40ml is added in 15mg/ml sodium borohydride solution, and at 75 degrees Celsius
It is lower to place 6 hours.By centrifugation, filter operation finally obtains the graphene oxide Jing Guo partial reduction, then passing through ultrasound
Again it is dispersed in water；
3) azobenzene graft grapheme: the addition of the sodium nitrite of 0.005mol indoles type azobenzene and 0.005mol is filled
In the beaker of 10ml deionized water, diazonium salt is made in the hydrochloric acid that the 1mol/L of 15ml is slowly added dropwise under condition of ice bath.It will obtain
Diazonium salt be slowly added dropwise into it is previously obtained by reduction graphene oxide, reacted one day in ice bath, Yin can be prepared
Diindyl azobenzene/graphene composite material.Product energy storage density is made and reaches 130Wh/kg.
The preparation method of indoles type azobenzene of the invention, as follows:
Cis-trans isomerism effect is as follows:
According to azo/graphene composite material ultraviolet spectrogram of patent synthesis as shown in Figure 1, showing that the material has really
There is response characteristics to light.
Embodiment 3
1) preparation of azo molecules: -5 chloro-indole of 3- amino of 0.02mol is added in the beaker with distilled water, is used
The hydrochloric acid of 0.07mol is dissolved, and 0.02mol sodium nitrite solution is added after dissolution under condition of ice bath, and ice bath reaction 2 is small
When, diazonium salt is made.The 3 of 1 equivalent are added, 5 dimethoxyanilines simultaneously react in argon atmosphere, and indoles type azo can be obtained
Benzene monomer；
2) graphene oxide is carried out partial reduction: the sodium carbonate for being 30% with mass fraction is by the water-soluble of graphene oxide
Liquid adjusts pH to 7, the solution that the pH of 40ml is mixed up is added in 20 mg/ml sodium borohydride solutions, and place under 75 degrees Celsius
8 hours.By centrifugation, filter operation finally obtains the graphene oxide Jing Guo partial reduction, then divides again ultrasound is passed through
It dissipates in water；
3) azobenzene graft grapheme: the addition of the sodium nitrite of 0.005mol indoles type azobenzene and 0.005mol is filled
In the beaker of 10ml deionized water, diazonium salt is made in the hydrochloric acid that the 1mol/L of 15ml is slowly added dropwise under condition of ice bath.It will obtain
Diazonium salt be slowly added dropwise into it is previously obtained by reduction graphene oxide, reacted one day in ice bath, Yin can be prepared
Diindyl azobenzene/graphene composite material.Product energy storage density is made and reaches 120Wh/kg.
A kind of indoles type azobenzene/graphene solar energy heat-storage material preparation method that the present invention is disclosed and proposed, this
Field technical staff can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although method of the invention and
Technology of preparing is described by preferred embodiment, and related technical personnel can obviously not depart from the content of present invention, essence
Methods and techniques described herein route is modified or is reconfigured in mind and range, to realize final technology of preparing.
In particular, it should be pointed out that all similar replacements and change are apparent to those skilled in the art, they
It is considered as being included in spirit of that invention, range and content.
Claims (2)
1. a kind of indoles azobenzene/graphene composite solar heat accumulating, the indoles azo molecules of monomer are with covalent bond side
Formula is grafted to graphene surface, and every 30~50 carbon atoms are grafted an azo molecules, and structural formula is as follows:
2. indoles azobenzene described in claim 1/graphene composite solar heat accumulating preparation method, steps are as follows:
1) preparation of azo molecules: by -5 chloro-indole of 3- amino be added the beaker with distilled water in, hydrochloric acid is dissolved,
Sodium nitrite solution is added after dissolution under condition of ice bath, ice bath reacts 1-3 hours, and diazonium salt is made, the 3 of 1-2 equivalent are added,
5 dimethoxyanilines simultaneously react in argon atmosphere, obtain indoles type azo benzene monomer, wherein -5 chloro-indole of 3- amino, hydrochloric acid
Molar ratio with sodium nitrite is 1:(3-4): (1.05-1.2).
2) graphene oxide is carried out partial reduction: the sodium carbonate for being 20%-30% with mass fraction is by the water of graphene oxide
Solution adjusts pH to 7-9, the aqueous solution for the graphene oxide that pH is mixed up is added in sodium borohydride solution, and Celsius in 75-90
Degree is lower to be placed 6-8 hours, and by centrifugation, filter operation finally obtains the graphene oxide Jing Guo partial reduction, then by super
It is low voice speaking to be newly dispersed in water；
3) azobenzene graft grapheme: the sodium nitrite of indoles type azobenzene and equimolar amounts is added in deionized water, in ice
Diazonium salt is made in the hydrochloric acid that 1mol/L is slowly added dropwise under the conditions of bath, and wherein the molar ratio of azobenzene and hydrochloric acid is 1:(3-4), it will obtain
The diazonium salt obtained is slowly added dropwise into the previously obtained graphene oxide by partial reduction, reacts one day, can make in ice bath
Standby indoles azobenzene/graphene composite material out.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174241A (en) * | 2020-10-29 | 2021-07-27 | 山西大同大学 | Graphene synergistic heat storage composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870467A (en) * | 2010-06-02 | 2010-10-27 | 天津大学 | Optical responsive azobenzene graft grapheme material and preparation method thereof |
| CN106047307A (en) * | 2016-05-24 | 2016-10-26 | 天津大学 | Tri-branched azobenzene/graphene composite energy storage material and preparation method thereof |
| CN107201214A (en) * | 2017-04-29 | 2017-09-26 | 天津大学 | A kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method |
-
2018
- 2018-09-14 CN CN201811071506.6A patent/CN109293552A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870467A (en) * | 2010-06-02 | 2010-10-27 | 天津大学 | Optical responsive azobenzene graft grapheme material and preparation method thereof |
| CN106047307A (en) * | 2016-05-24 | 2016-10-26 | 天津大学 | Tri-branched azobenzene/graphene composite energy storage material and preparation method thereof |
| CN107201214A (en) * | 2017-04-29 | 2017-09-26 | 天津大学 | A kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174241A (en) * | 2020-10-29 | 2021-07-27 | 山西大同大学 | Graphene synergistic heat storage composite material and preparation method and application thereof |
| CN113174241B (en) * | 2020-10-29 | 2022-04-08 | 山西大同大学 | Graphene synergistic heat storage composite material and preparation method and application thereof |
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