CN105969321A - Double-branch azobenzene/graphene energy storage material and preparing method - Google Patents
Double-branch azobenzene/graphene energy storage material and preparing method Download PDFInfo
- Publication number
- CN105969321A CN105969321A CN201610377097.7A CN201610377097A CN105969321A CN 105969321 A CN105969321 A CN 105969321A CN 201610377097 A CN201610377097 A CN 201610377097A CN 105969321 A CN105969321 A CN 105969321A
- Authority
- CN
- China
- Prior art keywords
- double
- graphene
- water
- solution
- azobenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/47—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton having at least one of the sulfo groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a double-branch azobenzene/graphene energy storage material and a preparing method. Double-branch azobenzene is grafted to a reduced-oxidized graphene patch in an array mode. The composite is prepared through synthesis of double-branch azobenzene and hybrid compounding of azobenzene and graphene. The preparing method comprises the steps that firstly, 5-aminoisophthalic acid is subjected to amino protection, and then subjected to amidation with 4'-Aminoazobenzene-4-sulphonic acid, and amino-protected double-branch azobenzene is obtained; then, amino deportection is carried out; finally, prepared double-branch azobenzene and reduced-oxidized graphene are subjected to hybrid compounding through diazotization, and the end product is obtained. Compared with small azobenzene micro-molecules, according to the obtained double-branch azobenzene/graphene hybrid material, the energy value is greatly increased, the half-life period is greatly prolonged, the energy density is stabilized at 150 Wh/Kg, and the half-life period is greatly prolonged to be 1000 h or longer; besides, the double-branch azobenzene/graphene energy storage material has good thermal stability and circulation performance, and is expected to be used for solar energy heat storage.
Description
Technical field
The present invention relates to a kind of double branch diphenyl diimide/Graphene hydridization energy storage material and preparation method, it stores at solar energy
Field is with a wide range of applications, and belongs to composite functional material field.
Background technology
The development of World Economics has benefited from the fossil energies such as coal, oil, natural gas, but these energy are the shortest, people
Class brings serious environmental problem such as acid rain, greenhouse effect etc. while consuming these energy, and these problems have threatened
Existence and the sustainable development of World Economics to the mankind.
Solar energy is hydrogen nuclei huge energy of fusion release when superhigh temperature, and the overwhelming majority of necessary for human energy is all
Directly or indirectly from the sun.Solar flux is huge, but solar radiation is a kind of intermittent energy source, therefore solar energy
Storage be the important step of Solar use
Research and development may utilize cleaning, the new material of reproducible solar energy and new opplication has become society solution
The important channel of energy crisis.The center of gravity of many researchers researchs in photovoltaic, photocatalysis and light transconversion into heat etc., but up till now
Till do not have surprising achievement in solar heat field of storage.
Photoresponse compound azobenzene molecule has good absorption, capable of circulation due to it between 350nm and 450nm
Isomerization characteristic and the advantage such as design of specific groups structure, there is certain hot storage capacity when metastable state, but commonly
Azobenzene molecule because its relatively low energy density and the application in terms of energy storage of the shorter half-life are extremely limited.
In the last few years, there is scientist to be combined with material with carbon element by azobenzene molecule, but up to the present, do not utilize containing substituted
Base and the double dendritic diphenyl diimide and Graphene that can form hydrogen bond group carry out the report being combined.Therefore, we devise one
Novel double branch diphenyl diimide/Graphene hybrid composite materials reach the purpose improving energy with extending the half-life.
Summary of the invention
It is an object of the invention to study a kind of composite that can store solar energy, prepare and a kind of new there is energy storage
Density, long half-lift double branch diphenyl diimide/graphene hybrid material.
The present invention is by the following technical solutions:
A kind of double branch diphenyl diimide/Graphene hydridization energy storage material, is that double branch diphenyl diimide is grafted on oxygen reduction with array way
On functionalized graphene lamella, its structure is as follows:
Double branch diphenyl diimides of the present invention/Graphene hydridization energy storage material preparation method, its step is as follows:
1) amido protecting: N,N-dimethylformamide/water mixing that 5-amino isophthalic acid is dissolved in sodium hydroxide is molten
In liquid；Ice-water bath is added drop-wise in Bis(tert-butoxycarbonyl)oxide solution to above-mentioned solution；Then room temperature reaction 24～30 hours；
Product is first acidified with hydrochloric acid, then is diluted with water to the half of acidity to 1/3rd；Afterwards precipitation is filtered and use water and
Saline cyclic washing；The 5-amino isophthalic acid being dried to obtain solid amido protecting is steamed in finally rotation；
2) prepared by the double branch diphenyl diimide of amido protecting: thionyl chloride is added to the 5-amino isophthalic acid containing amido protecting
Dichloromethane solution in, in solution drip DMF, under room temperature react 4～8 hours；Then reaction is produced
Thing decompression distillation and concentration, is re-dissolved in concentrate in dichloromethane, then is added drop-wise in above-mentioned solution dissolved with even to amino
In the dichloromethane solution of pyridyl-4-sulfonic acid and DIPEA, it is stirred overnight；Product dichloromethane and ammonium chloride solution
Liquid extracts, and is recrystallized to give double branch diphenyl diimides of orange solids amido protecting after being spin-dried for DMF；
3) amino deprotection: double branch diphenyl diimide solids of amido protecting are dissolved in the mixed solution of methanol and trifluoroacetic acid
In, stir 8～10 hours under room temperature；Then remove solvent, add water ammonia regulation pH value to 8～9；By organic layer second
Acetoacetic ester extracts, and with anhydrous sodium sulfate except water；Then it is spin-dried for solvent obtaining double branch azobenzene molecule；
4) preparation of double diphenyl diimide/graphene hybrid material: double azobenzene molecules and sodium nitrite are dissolved in
In ionized water, then it is added drop-wise in hydrochloric acid solution under condition of ice bath, reaction 1～2 hours, obtains diazonium salt solution (product
IV)；During the redox graphene that is added drop-wise to by diazonium salt solution under condition of ice bath is water-soluble, ice bath reacts 8～10 little
Time, the most at room temperature reaction 24～48 hours；With deionized water and DMF cyclic washing until filtrate does not has in ultraviolet spectra
There is absworption peak；Finally it is dried to obtain double branch diphenyl diimide/graphene hybrid material.
Described step 1) in the mol ratio of 5-amino isophthalic acid and sodium hydroxide be 1:1～1:1.5；Two dimethyl dicarbonates
Butyl ester is 1:1 with the mol ratio of 5-amino isophthalic acid.
Described step 1) in the mol ratio of acidifying hydrochloric acid and 5-amino isophthalic acid be about 3:1～4:1.
Described step 2) in the molar ratio of thionyl chloride and 5-amino isophthalic acid be 1.5:1～1:1.
Described step 2) in dropping N,N-dimethylformamide be the 1～2% of 5-amino isophthalic acid mol ratio.
Described step 2) in the molar ratio of P-aminoazobenzene base-4-sulfonic acid and DIPEA be 1:1～1:1.5.
Described step 2) in dichloromethane and aqueous ammonium chloride solution volume ratio be 1:1～1:1.5.
Described step 3) in the mol ratio of methanol and trifluoroacetic acid be 1:3～1:3.5.
Described step 4) in redox graphene water-soluble be 1:1～2:1 with diazonium salt solution volume ratio.
The present invention also designs the preparation method of above-mentioned pair of branch azobenzene derivatives and the grafting method of composite, the method
Can improve grafting density largely, described method reaction equation is described as follows:
Recording according to up-to-date patent and document, existing simple diphenyl diimide energy storage density only has 30Wh/Kg, and the half-life is also
The most several seconds to a few minutes, and double branch diphenyl diimides/little point of the more existing diphenyl diimide of graphene hybrid material obtained by the present invention
Son is greatly improved at energy storage density and half-life, and energy density is stable at 150Wh/Kg, and the half-life is greatly prolonged
More than 1000 hours, say, that can use after once exciting at least 2.5 months (having concrete corresponding data to illustrate) below with
List is analyzed, and possesses good heat stability and cycle performance, is expected to be used for solar energy heat-storage.
Accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectroscopy of 3 pairs of branch diphenyl diimide/graphene hybrid material of embodiment, therefrom our energy
Enough find out that material has response to ultraviolet light.
Fig. 2 is the electron scanning micrograph of 3 pairs of branch diphenyl diimide/graphene hybrid material of embodiment, therefrom our energy
Enough find out that material maintains the ordered distribution of graphene sheet layer.
Detailed description of the invention
It is presented herein below and the present invention is further illustrated rather than limits the scope of the present invention.
The present invention relates to double branch diphenyl diimide/graphene hybrid material preparation method, its course of reaction and explanation step as follows:
1) amido protecting: N,N-dimethylformamide/water mixing that 5-amino isophthalic acid is dissolved in sodium hydroxide is molten
In liquid, wherein 5-amino isophthalic acid is 1:1～1:1.5 with the mol ratio of sodium hydroxide.To above-mentioned solution in ice-water bath
Being added drop-wise in Bis(tert-butoxycarbonyl)oxide solution, wherein Bis(tert-butoxycarbonyl)oxide is 1:1 with the mol ratio of 5-amino isophthalic acid；
Then clear-cutting forestland was to room temperature reaction 24～30 hours.Product is first acidified (with 5-amino isophthalic acid with hydrochloric acid
Mol ratio is about 3:1～4:1, is diluted with water to the half of acidity the most again to 1/3rd.Afterwards precipitation filtered and use water
With saline cyclic washing 2～3 times.Finally rotation steaming is dried to obtain solid (product I, the 5-amino isophthalic acid of amido protecting).
2) 1. prepared by the double branch diphenyl diimide of amido protecting: be added drop-wise to by thionyl chloride in the dichloromethane solution containing product I,
Wherein thionyl chloride is 1.5:1～1:1 with the molar ratio of product I.N, N-dimethyl formyl is dripped afterwards in above-mentioned solution
Amine (one of percentage for product I mol ratio to two), reacts 4～8 hours under room temperature.Then by dense for product decompression distillation
Contracting.Concentrate is re-dissolved in dichloromethane, then is added drop-wise in above-mentioned solution dissolved with P-aminoazobenzene base-4-sulfonic acid
With in the dichloromethane solution of DIPEA, wherein the molar ratio of P-aminoazobenzene base-4-sulfonic acid and DIPEA is 1:1～1:
1.5, it is stirred overnight.Product dichloromethane and aqueous ammonium chloride solution (volume ratio is 1:1～1:1.5) extract three times, rotation
It is recrystallized to give orange solids (product II, double branch diphenyl diimides of amido protecting) with DMF after Gan.
2. amino deprotection: product II solid is dissolved in the mixed solution of methanol and trifluoroacetic acid (wherein methanol and
The mol ratio of trifluoroacetic acid is about 1:3～1:3.5), stir 8～10 hours under room temperature.Remove solvent afterwards and add water ammonia
Water regulation pH value is to 8～9.Organic layer is extracted with ethyl acetate, and with anhydrous sodium sulfate except water.Then solvent is spin-dried for
To double branch azobenzene molecules (product III).
3) preparation of double diphenyl diimide/graphene hybrid material: product III and sodium nitrite are dissolved in about 40mL go from
In sub-water, wherein the molar ratio of product III and sodium nitrite is 1:1, is then slowly dropped to the salt of 1M under condition of ice bath
In acid solution (being 4～6 with sodium nitrite mol ratio), reaction 1～2 hours, obtain diazonium salt solution (product IV)；At ice bath
Under the conditions of the redox graphene of 1 mg/ml that above-mentioned diazonium salt solution is slowly dropped to water-soluble in (molten with diazol
Liquid volume ratio is 1:1～2:1.Ice bath reacts 8～10 hours, the most at room temperature reaction 24～48 hours.Finally, use
Deionized water and DMF cyclic washing said mixture be not until filtrate has absworption peak in ultraviolet spectra.Finally it is dried to obtain double
Branch diphenyl diimide/graphene hybrid material (product V).
Embodiment 1
1) 1.087 grams of (12 mmoles) 5-amino isophthalic acid are dissolved in 30 containing 0.720g sodium hydroxide (18 mmoles)
Milliliter 1:1N, in dinethylformamide/water mixed solution.To the dropping of above-mentioned solution containing 2.619g (12 millis in ice-water bath
Rub) in Bis(tert-butoxycarbonyl)oxide solution.Then clear-cutting forestland was to room temperature reaction 24 hours.Product is first with 3M hydrochloric acid (5 millis
Rise) acidifying, the most again with 30 milliliters of water dilutions.Precipitation filters and uses water and saline cyclic washing 2 times afterwards.Finally rotation is evaporated
Dry obtain product I.
2) 1. 1.096 milliliters of (12.432 mmoles) thionyl chlorides are added drop-wise to 40 milliliters of dichloros containing 1.405g product I
In dichloromethane.Drip the DMF of 250 microlitres afterwards to above-mentioned solution, react 4 hours under room temperature.Then will
Product decompression distillation and concentration.Concentrate is re-dissolved in the dichloromethane of 20 milliliters, then drips in above-mentioned solution
40 milliliters dissolved with 2.496g gram of (9 mmoles) P-aminoazobenzene base-4-sulfonic acid and the dichloro of 2.096 milliliters of (12 mmoles) DIPEA
Dichloromethane is also stirred overnight.Product 100 milliliters of dichloromethane and 100 milliliters of aqueous ammonium chloride solutions extract three times, rotation
It is recrystallized to give orange solids (product II) with N,N-dimethylformamide after Gan.
2. 3.963 grams of product II are dissolved in the mixed solution of 12 ml methanol and 48 milliliters of trifluoroacetic acids, under room temperature
Stir 8 hours.Remove solvent afterwards and add water ammonia regulation pH value to 8.Organic layer is extracted with ethyl acetate, and uses nothing
Aqueous sodium persulfate removes water.Then it is spin-dried for solvent obtaining product III.
3) 2.787 grams of (4mmol) product III and 0.276g (4mmol) sodium nitrite are dissolved in 40mL deionized water,
Then it is slowly dropped under condition of ice bath in the hydrochloric acid solution of 20mL 1M, reacts 1 hour, obtain diazonium salt solution (product
IV)；The redox graphene that above-mentioned diazonium salt solution is slowly dropped under condition of ice bath 50mL 1 mg/ml is water-soluble
In.Ice bath reacts 8 hours, the most at room temperature reaction 24 hours.Then, with on deionized water and DMF cyclic washing
State mixture until filtrate does not has absworption peak in ultraviolet spectra.Finally it is dried to obtain double branch diphenyl diimide/graphene hybrid material
203 milligrams.
Embodiment 2
1) 1.087 grams of (12 mmoles) 5-amino isophthalic acid are dissolved in 30 containing 0.520g sodium hydroxide (13 mmoles)
Milliliter 1:1N, in dinethylformamide/water mixed solution.To the dropping of above-mentioned solution containing 2.728g (12.5 in ice-water bath
Mmoles) in Bis(tert-butoxycarbonyl)oxide solution.Then clear-cutting forestland was to room temperature reaction 25 hours.Product is first with 3M hydrochloric acid (5
Milliliter) acidifying, the most again with 30 milliliters of water dilutions.Precipitation filters and uses water and saline cyclic washing 3 times afterwards.Finally revolve steaming
It is dried to obtain product I.
2) 1. 1.096 milliliters of (12.432 mmoles) thionyl chlorides are added drop-wise to 40 milliliters of dichloromethanes containing 1.42g product I
In alkane solution.Drip the DMF of 250 microlitres afterwards to above-mentioned solution, react 4 hours under room temperature.Then will be anti-
Answer product at reduced pressure distillation and concentration.Concentrate is re-dissolved in the dichloromethane of 20 milliliters, then in above-mentioned solution, drips 40
Milliliter is dissolved with 2.496g gram of (9 mmoles) P-aminoazobenzene base-4-sulfonic acid and the dichloromethane of 2.096 milliliters of (12 mmoles) DIPEA
Alkane solution & stir is overnight.Product 100 milliliters of dichloromethane and 100 milliliters of aqueous ammonium chloride solutions extract three times, are spin-dried for
It is recrystallized to give orange solids (product II) afterwards with N,N-dimethylformamide.
2. 3.963 grams of product II are dissolved in the mixed solution of 12 ml methanol and 50 milliliters of trifluoroacetic acids, under room temperature
Stir 8 hours.Remove solvent afterwards and add water ammonia regulation pH value to 8.Organic layer is extracted with ethyl acetate, and uses nothing
Aqueous sodium persulfate removes water.Then it is spin-dried for solvent obtaining product III.
3) 2.787 grams of (4mmol) product III and 0.276g (4mmol) sodium nitrite are dissolved in 40mL deionized water,
Then it is slowly dropped under condition of ice bath in the hydrochloric acid solution of 20mL 1M, reacts and within 2 hours, obtain diazonium salt solution (product
IV)；Under condition of ice bath, above-mentioned diazonium salt solution is slowly dropped to the redox graphene water of 100mL 1 mg/ml
In molten.Ice bath reacts 8 hours, the most at room temperature reaction 48 hours.Then, with deionized water and DMF cyclic washing
Said mixture is not until filtrate has absworption peak in ultraviolet spectra.Finally it is dried to obtain double branch diphenyl diimide/Graphene hydridization material
Expect 307 milligrams.
Embodiment 3
1) 1.087 grams of (12 mmoles) 5-amino isophthalic acid are dissolved in 30 containing 0.520g sodium hydroxide (13 mmoles)
Milliliter 1:1N, in dinethylformamide/water mixed solution.To the dropping of above-mentioned solution containing 2.728g (12.5 in ice-water bath
Mmoles) in Bis(tert-butoxycarbonyl)oxide solution.Then clear-cutting forestland was to room temperature reaction 26 hours.Product first uses 3M hydrochloric acid
(10 milliliters) are acidified, the most again with 30 milliliters of water dilutions.Precipitation filters and uses water and saline cyclic washing 2 times afterwards.Finally
Rotation steaming is dried to obtain product I.
2) 1. 1.644 milliliters of (18.648 mmoles) thionyl chlorides are added drop-wise to 40 milliliters of dichloros containing 1.407g product I
In dichloromethane.Drip the DMF of 250 microlitres afterwards to above-mentioned solution, react 4 hours under room temperature.Then will
Product decompression distillation and concentration.Concentrate is re-dissolved in the dichloromethane of 20 milliliters, then drips in above-mentioned solution
40 milliliters dissolved with 2.496g gram of (9 mmoles) P-aminoazobenzene base-4-sulfonic acid and the dichloro of 2.096 milliliters of (12 mmoles) DIPEA
Dichloromethane is also stirred overnight.Product 100 milliliters of dichloromethane and 100 milliliters of aqueous ammonium chloride solutions extract three times, rotation
It is recrystallized to give orange solids (product II) with N,N-dimethylformamide after Gan.
2. 3.963 grams of product II are dissolved in the mixed solution of 12 ml methanol and 55 milliliters of trifluoroacetic acids, under room temperature
Stir 8 hours.Remove solvent afterwards and add water ammonia regulation pH value to 9.Organic layer is extracted with ethyl acetate, and uses nothing
Aqueous sodium persulfate removes water.Then it is spin-dried for solvent obtaining product III.
3) 2.787 grams of (4mmol) product III and 0.276g (4mmol) sodium nitrite are dissolved in 40mL deionized water,
Then it is slowly dropped under condition of ice bath in the hydrochloric acid solution of 20mL 1M, reacts 1 hour, obtain diazonium salt solution (product
IV)；The redox graphene that above-mentioned diazonium salt solution is slowly dropped under condition of ice bath 50mL 1 mg/ml is water-soluble
In.Ice bath reacts 9 hours, the most at room temperature reaction 24 hours.Then, with on deionized water and DMF cyclic washing
State mixture until filtrate does not has absworption peak in ultraviolet spectra, be finally dried to obtain double branch diphenyl diimide/graphene hybrid material
203 milligrams.Fig. 1 is the uv-visible absorption spectroscopy of the double branch diphenyl diimide/graphene hybrid material of the present embodiment, therefrom we
It can be seen that material has response to ultraviolet light.Fig. 2 is the scanning electricity of 3 pairs of branch diphenyl diimide/graphene hybrid material of embodiment
Sub-microphotograph, therefrom we can see that material maintains the ordered distribution of graphene sheet layer.
Embodiment 4
1) 1.087 grams of (12 mmoles) 5-amino isophthalic acid are dissolved in 30 containing 0.520g sodium hydroxide (13 mmoles)
Milliliter 1:1N, in dinethylformamide/water mixed solution.To the dropping of above-mentioned solution containing 2.728g (12.5 in ice-water bath
Mmoles) in Bis(tert-butoxycarbonyl)oxide solution.Then clear-cutting forestland was to room temperature reaction 28 hours.Product is first with 3M hydrochloric acid (5
Milliliter) acidifying, the most again with 30 milliliters of water dilutions.Precipitation filters and uses water and saline cyclic washing 3 times afterwards.Finally revolve steaming
It is dried to obtain product I.
2) 1. 1.096 milliliters of (12.432 mmoles) thionyl chlorides are added drop-wise to 40 milliliters of dichloros containing 1.405g product I
In dichloromethane.Drip the DMF of 250 microlitres afterwards to above-mentioned solution, react 8 hours under room temperature.Then will
Product decompression distillation and concentration.Concentrate is re-dissolved in the dichloromethane of 20 milliliters, then drips in above-mentioned solution
40 milliliters dissolved with 2.496g gram of (9 mmoles) P-aminoazobenzene base-4-sulfonic acid and the dichloro of 2.096 milliliters of (12 mmoles) DIPEA
Dichloromethane is also stirred overnight.Product 100 milliliters of dichloromethane and 100 milliliters of aqueous ammonium chloride solutions extract three times, rotation
It is recrystallized to give orange solids (product II) with N,N-dimethylformamide after Gan.
2. 3.963 grams of product II are dissolved in the mixed solution of 12 ml methanol and 60 milliliters of trifluoroacetic acids, under room temperature
Stir 8 hours.Remove solvent afterwards and add water ammonia regulation pH value to 8.Organic layer is extracted with ethyl acetate, and uses nothing
Aqueous sodium persulfate removes water.Then it is spin-dried for solvent obtaining product III.
3) 2.787 grams of (4mmol) product III and 0.276g (4mmol) sodium nitrite are dissolved in 40mL deionized water,
Then it is slowly dropped under condition of ice bath in the hydrochloric acid solution of 20mL 1M, reacts 2 hours, obtain diazonium salt solution (product
IV)；The redox graphene that above-mentioned diazonium salt solution is slowly dropped under condition of ice bath 50mL 1 mg/ml is water-soluble
In.Ice bath reacts 10 hours, the most at room temperature reaction 48 hours.Then, with on deionized water and DMF cyclic washing
State mixture until filtrate does not has absworption peak in ultraviolet spectra.Finally it is dried to obtain double branch diphenyl diimide/graphene hybrid material
215 milligrams.
Embodiment 5
1) 1.087 grams of (12 mmoles) 5-amino isophthalic acid are dissolved in 30 containing 0.520g sodium hydroxide (13 mmoles)
Milliliter 1:1N, in dinethylformamide/water mixed solution.To the dropping of above-mentioned solution containing 2.728g (12.5 in ice-water bath
Mmoles) in Bis(tert-butoxycarbonyl)oxide solution.Then clear-cutting forestland was to room temperature reaction 30 hours.Product first uses 3M hydrochloric acid
(10 milliliters) are acidified, the most again with 30 milliliters of water dilutions.Precipitation filters and uses water and saline cyclic washing 2 times afterwards.Finally
Rotation steaming is dried to obtain product I.
2) 1. 1.096 milliliters of (12.432 mmoles) thionyl chlorides are added drop-wise to 40 milliliters of dichloros containing 1.405g product I
In dichloromethane.Drip the DMF of 250 microlitres afterwards to above-mentioned solution, react 8 hours under room temperature.Then will
Product decompression distillation and concentration.Concentrate is re-dissolved in the dichloromethane of 20 milliliters, then drips in above-mentioned solution
40 milliliters dissolved with 3.744g gram of (12 mmoles) P-aminoazobenzene base-4-sulfonic acid and the dichloro of 2.096 milliliters of (12 mmoles) DIPEA
Dichloromethane is also stirred overnight.Product 100 milliliters of dichloromethane and 100 milliliters of aqueous ammonium chloride solutions extract three times, rotation
It is recrystallized to give orange solids (product II) with N,N-dimethylformamide after Gan.
2. 4.016 grams of product II are dissolved in the mixed solution of 12 ml methanol and 50 milliliters of trifluoroacetic acids, under room temperature
Stir 8 hours.Remove solvent afterwards and add water ammonia regulation pH value to 8.Organic layer is extracted with ethyl acetate, and uses nothing
Aqueous sodium persulfate removes water.Then it is spin-dried for solvent obtaining product III.
3) 2.787 grams of (4mmol) product III and 0.276g (4mmol) sodium nitrite are dissolved in 40mL deionized water,
Then it is slowly dropped under condition of ice bath in the hydrochloric acid solution of 20mL 1M, reacts 1 hour, obtain diazonium salt solution (product
IV)；Under condition of ice bath, above-mentioned diazonium salt solution is slowly dropped to the redox graphene water of 100mL 1 mg/ml
In molten.Ice bath reacts 8 hours, the most at room temperature reaction 48 hours.Then, with deionized water and DMF cyclic washing
Said mixture is not until filtrate has absworption peak in ultraviolet spectra.Finally it is dried to obtain double branch diphenyl diimide/Graphene hydridization material
Expect 303 milligrams.
The test result of two important performance characteristic of the present invention is as follows:
1. energy density is to record according to DSC
2. the half-life is to record according to ultraviolet-visible light time spectra
3. grafting density is calculated jointly by TGA and XPS, corresponding to the double branch azobenzene molecule of its numeric representation one
Graphene on carbon number. this value is the least shows that percent grafting is the highest.
Claims (10)
1. double branch diphenyl diimide/Graphene hydridization energy storage materials, is characterized in that double branch diphenyl diimide is grafted on also with array way
On former graphene oxide lamella, its structure is as follows:
2. double branch diphenyl diimides of claim 1/Graphene hydridization energy storage material preparation method, is characterized in that step is as follows:
1) amido protecting: 5-amino isophthalic acid is dissolved in the N,N-dimethylformamide/water mixed solution of sodium hydroxide；
Ice-water bath is added drop-wise in Bis(tert-butoxycarbonyl)oxide solution to above-mentioned solution；Then room temperature reaction 24～30 hours；Reaction
Product is first acidified with hydrochloric acid, then is diluted with water to the half of acidity to 1/3rd；Precipitation filters and uses water and saline afterwards
Cyclic washing；The 5-amino isophthalic acid being dried to obtain solid amido protecting is steamed in finally rotation；
2) prepared by the double branch diphenyl diimide of amido protecting: thionyl chloride is added to two of 5-amino isophthalic acid containing amido protecting
In chloromethanes solution, in solution, drip DMF, react 4～8 hours under room temperature；Then product is subtracted
Pressure distillation and concentration, is re-dissolved in concentrate in dichloromethane, then is added drop-wise to dissolved with P-aminoazobenzene in above-mentioned solution
In the dichloromethane solution of base-4-sulfonic acid and DIPEA, it is stirred overnight；Product dichloromethane and aqueous ammonium chloride solution extraction
Take, after being spin-dried for, be recrystallized to give double branch diphenyl diimides of orange solids amido protecting with DMF；
3) amino deprotection: double branch diphenyl diimide solids of amido protecting are dissolved in the mixed solution of methanol and trifluoroacetic acid,
8～10 hours are stirred under room temperature；Then remove solvent, add water ammonia regulation pH value to 8～9；By organic layer acetic acid
Ethyl ester extracts, and with anhydrous sodium sulfate except water；Then it is spin-dried for solvent obtaining double branch azobenzene molecule；
4) preparation of double diphenyl diimide/graphene hybrid material: double azobenzene molecules and sodium nitrite are dissolved in deionization
In water, then it is added drop-wise in hydrochloric acid solution under condition of ice bath, reaction 1～2 hours, obtains diazonium salt solution；At ice bath bar
During the redox graphene that is added drop-wise to by diazonium salt solution under part is water-soluble, ice bath reacts 8～10 hours, then in room temperature
Lower reaction 24～48 hours；With deionized water and DMF cyclic washing until filtrate does not has absworption peak in ultraviolet spectra；Finally
It is dried to obtain double branch diphenyl diimide/graphene hybrid material.
3. method as claimed in claim 2, is characterized in that described step 1) in 5-amino isophthalic acid and sodium hydroxide
Mol ratio is 1:1～1:1.5；Bis(tert-butoxycarbonyl)oxide is 1:1 with the mol ratio of 5-amino isophthalic acid.
4. method as claimed in claim 2, is characterized in that described step 1) in acidifying hydrochloric acid and 5-amino isophthalic acid
Mol ratio be about 3:1～4:1.
5. method as claimed in claim 2, is characterized in that described step 2) in thionyl chloride and 5-amino isophthalic acid
Molar ratio is 1.5:1～1:1.
6. method as claimed in claim 2, is characterized in that described step 2) in dropping DMF be 5-amino
The 1～2% of M-phthalic acid mol ratio.
7. method as claimed in claim 2, is characterized in that described step 2) in P-aminoazobenzene base-4-sulfonic acid and DIPEA
Molar ratio be 1:1～1:1.5.
8. method as claimed in claim 2, is characterized in that described step 2) in dichloromethane and aqueous ammonium chloride solution volume ratio
For 1:1～1:1.5.
9. method as claimed in claim 2, is characterized in that described step 3) in the mol ratio of methanol and trifluoroacetic acid be 1:3～
1:3.5。
10. method as claimed in claim 2, is characterized in that described step 4) in redox graphene water-soluble molten with diazol
Liquid volume ratio is 1:1～2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610377097.7A CN105969321B (en) | 2016-05-30 | 2016-05-30 | A kind of double branch azobenzene/graphene energy storage materials and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610377097.7A CN105969321B (en) | 2016-05-30 | 2016-05-30 | A kind of double branch azobenzene/graphene energy storage materials and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105969321A true CN105969321A (en) | 2016-09-28 |
| CN105969321B CN105969321B (en) | 2019-05-24 |
Family
ID=57010554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610377097.7A Active CN105969321B (en) | 2016-05-30 | 2016-05-30 | A kind of double branch azobenzene/graphene energy storage materials and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105969321B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966929A (en) * | 2017-03-14 | 2017-07-21 | 天津大学 | A kind of Linear Double branch azobenzene/graphene composite material and preparation method and application |
| 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 |
| CN107488135A (en) * | 2017-07-20 | 2017-12-19 | 莆田学院 | Graphene quantum dot is grafted azo derivative composite and preparation method and application |
| CN107963626A (en) * | 2017-12-21 | 2018-04-27 | 东南大学 | A kind of preparation method of photothermal conversion composite setting phase-change material |
| CN108728042A (en) * | 2017-04-22 | 2018-11-02 | 天津大学 | Application of the azobenzene-graphene composite material in preparing anti-icing material |
| CN108728049A (en) * | 2017-04-22 | 2018-11-02 | 天津大学 | Anti-icing material of heat accumulation based on alumina formwork and preparation method thereof |
| CN109294527A (en) * | 2018-09-29 | 2019-02-01 | 天津大学 | A kind of preparation method of double branch heterocycle azo benzene/graphene composite energy-storage materials |
| CN109503420A (en) * | 2017-09-15 | 2019-03-22 | 天津大学 | A kind of dual graft azobenzene/graphene composite energy-storage material and preparation method |
| CN109503486A (en) * | 2017-09-15 | 2019-03-22 | 天津大学 | A kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method |
| CN109503419A (en) * | 2017-09-15 | 2019-03-22 | 天津大学 | A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method |
| CN109762174A (en) * | 2019-01-09 | 2019-05-17 | 北京科技大学 | A kind of preparation method of the azobenzene containing dissaving structure-graphene energy storage material |
| CN110734410A (en) * | 2018-07-20 | 2020-01-31 | 天津大学 | double-grafted heterocyclic azobenzene graphene energy storage material and preparation method thereof |
| CN110872287A (en) * | 2018-09-03 | 2020-03-10 | 天津大学 | Double-branch heterocyclic azobenzene molecule, preparation method and application in solar heat storage |
| CN111086986A (en) * | 2018-10-23 | 2020-05-01 | 天津大学 | P-aminoazobenzene functionalized graphene material and preparation method thereof |
| CN111704895A (en) * | 2020-07-07 | 2020-09-25 | 天津大学 | Mercapto/nanogold modified azo/graphene composite heat storage material based on coordination bond and preparation method thereof |
| CN111777531A (en) * | 2020-07-07 | 2020-10-16 | 天津大学 | Azo/graphene composite heat storage material based on metal coordination bond and preparation thereof |
| CN112239561A (en) * | 2020-09-24 | 2021-01-19 | 东华大学 | Organic-inorganic hybrid anti-dripping functional material and preparation method and application thereof |
| 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 (5)
| 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 |
| CN104045754A (en) * | 2014-06-18 | 2014-09-17 | 北京科技大学 | Method for synthesizing visible-light response type azobenzene polymer |
| CN105218411A (en) * | 2015-09-10 | 2016-01-06 | 天津大学 | A kind of azobenzene molecule that can be used for solar energy heat-storage and preparation method thereof |
| CN105295045A (en) * | 2015-10-28 | 2016-02-03 | 江苏大学 | Preparation method and application of oxidized graphene/azobenzene polyimide composite thermo-optical material |
| CN105542584A (en) * | 2016-01-29 | 2016-05-04 | 天津大学 | Thermal-inductive fluorocarbon function coating containing azobenzene/carbon-hybrid material and preparation method of thermal-inductive fluorocarbon function coating |
-
2016
- 2016-05-30 CN CN201610377097.7A patent/CN105969321B/en active Active
Patent Citations (5)
| 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 |
| CN104045754A (en) * | 2014-06-18 | 2014-09-17 | 北京科技大学 | Method for synthesizing visible-light response type azobenzene polymer |
| CN105218411A (en) * | 2015-09-10 | 2016-01-06 | 天津大学 | A kind of azobenzene molecule that can be used for solar energy heat-storage and preparation method thereof |
| CN105295045A (en) * | 2015-10-28 | 2016-02-03 | 江苏大学 | Preparation method and application of oxidized graphene/azobenzene polyimide composite thermo-optical material |
| CN105542584A (en) * | 2016-01-29 | 2016-05-04 | 天津大学 | Thermal-inductive fluorocarbon function coating containing azobenzene/carbon-hybrid material and preparation method of thermal-inductive fluorocarbon function coating |
Non-Patent Citations (3)
| Title |
|---|
| WEI FENG 等: ""An energy-dense and thermal-stable bis-azobenzene/hybrid templated assembly for solar thermal fuel"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| WEN LUO 等: ""A high energy density azobenzene/graphene hybrid: a nano-templated platform for solar thermal storage"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| WEN LUO 等: ""High-energy,stable and recycled molecular solar thermal storage materials using AZO/graphene hybrids by optimizing hydrogen bonds"", 《NANOSCALE》 * |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966929B (en) * | 2017-03-14 | 2018-10-09 | 天津大学 | A kind of Linear Double branch azobenzene/graphene composite material and preparation method and application |
| CN106966929A (en) * | 2017-03-14 | 2017-07-21 | 天津大学 | A kind of Linear Double branch azobenzene/graphene composite material and preparation method and application |
| CN108728042B (en) * | 2017-04-22 | 2020-09-15 | 天津大学 | Application of azobenzene-graphene composite material in preparation of anti-icing material |
| CN108728042A (en) * | 2017-04-22 | 2018-11-02 | 天津大学 | Application of the azobenzene-graphene composite material in preparing anti-icing material |
| CN108728049A (en) * | 2017-04-22 | 2018-11-02 | 天津大学 | Anti-icing material of heat accumulation based on alumina formwork 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 |
| CN107488135A (en) * | 2017-07-20 | 2017-12-19 | 莆田学院 | Graphene quantum dot is grafted azo derivative composite and preparation method and application |
| CN107488135B (en) * | 2017-07-20 | 2019-11-12 | 莆田学院 | Graphene quantum dot is grafted azo derivative composite material and preparation method and application |
| CN109503486A (en) * | 2017-09-15 | 2019-03-22 | 天津大学 | A kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method |
| CN109503420A (en) * | 2017-09-15 | 2019-03-22 | 天津大学 | A kind of dual graft azobenzene/graphene composite energy-storage material and preparation method |
| CN109503419A (en) * | 2017-09-15 | 2019-03-22 | 天津大学 | A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method |
| CN107963626A (en) * | 2017-12-21 | 2018-04-27 | 东南大学 | A kind of preparation method of photothermal conversion composite setting phase-change material |
| CN110734410A (en) * | 2018-07-20 | 2020-01-31 | 天津大学 | double-grafted heterocyclic azobenzene graphene energy storage material and preparation method thereof |
| CN110872287B (en) * | 2018-09-03 | 2021-11-23 | 天津大学 | Double-branch heterocyclic azobenzene molecule, preparation method and application in solar heat storage |
| CN110872287A (en) * | 2018-09-03 | 2020-03-10 | 天津大学 | Double-branch heterocyclic azobenzene molecule, preparation method and application in solar heat storage |
| CN109294527A (en) * | 2018-09-29 | 2019-02-01 | 天津大学 | A kind of preparation method of double branch heterocycle azo benzene/graphene composite energy-storage materials |
| CN109294527B (en) * | 2018-09-29 | 2020-10-30 | 天津大学 | Preparation method of double-branch heterocyclic azobenzene/graphene composite energy storage material |
| CN111086986A (en) * | 2018-10-23 | 2020-05-01 | 天津大学 | P-aminoazobenzene functionalized graphene material and preparation method thereof |
| CN109762174B (en) * | 2019-01-09 | 2020-09-11 | 北京科技大学 | Preparation method of azobenzene-graphene energy storage material containing hyperbranched structure |
| CN109762174A (en) * | 2019-01-09 | 2019-05-17 | 北京科技大学 | A kind of preparation method of the azobenzene containing dissaving structure-graphene energy storage material |
| CN111704895A (en) * | 2020-07-07 | 2020-09-25 | 天津大学 | Mercapto/nanogold modified azo/graphene composite heat storage material based on coordination bond and preparation method thereof |
| CN111777531A (en) * | 2020-07-07 | 2020-10-16 | 天津大学 | Azo/graphene composite heat storage material based on metal coordination bond and preparation thereof |
| US20220010188A1 (en) * | 2020-07-07 | 2022-01-13 | Tianjin University | Azobenzene-graphene metal coordination solar photothermal energy storage material and preparation thereof |
| US11898083B2 (en) * | 2020-07-07 | 2024-02-13 | Tianjin University | Azobenzene-graphene metal coordination solar photothermal energy storage material and preparation thereof |
| CN112239561A (en) * | 2020-09-24 | 2021-01-19 | 东华大学 | Organic-inorganic hybrid anti-dripping functional material and preparation method and application thereof |
| CN112239561B (en) * | 2020-09-24 | 2021-07-20 | 东华大学 | Organic-inorganic hybrid anti-dripping functional material and preparation method and application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105969321B (en) | 2019-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105969321A (en) | Double-branch azobenzene/graphene energy storage material and preparing method | |
| CN106966929B (en) | A kind of Linear Double branch azobenzene/graphene composite material and preparation method and application | |
| CN105906624B (en) | One kind has the fluorescent chemicals of sensing function to aniline and ortho-aminotoluene gas and its fluorescence sense film prepares and application | |
| CN104844464B (en) | A kind of 9,9 '-Spirobifluorene dendrimer and preparation method and application | |
| CN101270094B (en) | Phenyl s-triazine ligand for metallic organic frame complex and synthesizing process therefor | |
| CN103779597B (en) | A kind of preparation method of high temperature proton exchange film | |
| CN106866497B (en) | A kind of norborneol vinyl compound and its preparation method and application | |
| Yuan et al. | Cooperation of carbon doping and carbon loading boosts photocatalytic activity by the optimum photo-induced electron trapping and interfacial charge transfer | |
| CN105218411A (en) | A kind of azobenzene molecule that can be used for solar energy heat-storage and preparation method thereof | |
| Long et al. | Novel carboxyethyl amine sodium salts as draw solutes with superior forward osmosis performance | |
| CN107141243A (en) | The nitrogenous cyclosubstituted bowl alkene molecule of one five yuan of class and derivative and its preparation and application | |
| CN103043650A (en) | Modified CNT (carbon nano tube) | |
| Wang et al. | Ionothermal synthesis of carbon dots from cellulose in deep eutectic solvent: A sensitive probe for detecting Cu2+ and glutathione with “off-on” pattern | |
| Wang et al. | Self-assembly of mixed valence polyoxovanadate-based metal-organic frameworks for enhanced CO2 photoreduction | |
| CN110734410A (en) | double-grafted heterocyclic azobenzene graphene energy storage material and preparation method thereof | |
| CN100503692C (en) | Method for preparing poly 1,5-naphthalene diamine nano pipe | |
| CN106540750B (en) | With visible light-responded small numerator modified catalysis material and preparation method | |
| CN105732676A (en) | Eu complex based on asymmetric dicarboxylate ligand and preparation method thereof | |
| CN106397239B (en) | Amino-acid ester cationic chiral ionic liquid and preparation method thereof | |
| CN102569657B (en) | Preparation for photo-response Pyr-AZO non-covalent decorating carbon nano tube material | |
| CN102443165B (en) | Semiaromatic polyarylene sulfide amine and preparation method thereof | |
| CN109294527A (en) | A kind of preparation method of double branch heterocycle azo benzene/graphene composite energy-storage materials | |
| KR100847554B1 (en) | Improved process for preparing cis-dithiocyanato-N,N'-bis2,2'-bipyridyl-4,4'-dicarboxylic acidruthenium(II) | |
| CN105669764A (en) | Ruthenium complex containing bisphenol hydroxyl azo naphthol structure and synthesis method and application thereof | |
| CN107628966B (en) | Preparation method of three-arm chain transfer agent with photoresponse |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |