CN109503486A - A kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method - Google Patents
A kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method Download PDFInfo
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Abstract
The present invention discloses a kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method, monomer molecule formula C12N5O4H13Heterocycle azo benzene be covalently grafted to graphene surface, every 40~80 carbon atoms are grafted a heterocycle azo benzene；The preparation of heterocycle azo benzene first；Then redox graphene pre-processes；Finally carry out the preparation of heterocycle azo benzene/graphene composite material.The exothermic peak of material is scanned using DSC, and the energy that exothermic peak integral is released then is obtained into fabulous storage density, up to 130Wh/kg then divided by quality using software, is compared favourably with lithium battery energy density.Isomerization rate is up to 96%, improves 20% than monomer molecule；Storage density is up to 130Wh/kg, improves nearly 60% than monomer molecule.More traditional azobenzene molecule is greatly improved in energy value and half-life period, is conducive to that the sun is made full use of to can be carried out energy stores.
Description
Technical field
The invention belongs to composite functional material field, more particularly to a kind of organic carbon composite of function and its
Preparation method has the good prospect of effective use solar energy.
Background technique
It is well known that solar energy has cleaning, environmentally friendly, never advantages such as exhaustion, with the development of the times, industrially for
The demand of the energy is increasing, and traditional fossil fuel has not adapted to energy shortage, climate change and energy-saving and emission-reduction problem
Solve, the utilization of solar energy has become the object that each power, the world will study and use, and using the research of solar energy as
Their key project.The rapid development of China's economy simultaneously is so that increase in demand to the energy, environment caused by traditional energy
Problem can also be solved by the utilization of solar energy.The advantages of solar energy resources are compared with conventional energy resource mainly has:
1, solar energy is known as the title of " clear energy sources " and " safety energy ".Solar energy is nearly free from any pollution；2, too
Sun can continuously feed the earth thus have permanence；3, for other energy, solar radiant energy is distributed in ground
Most area on ball can take on the spot, have great superiority to the energy supply for solving the problems, such as remote districts；4, annual to reach in ground
The rich reserves of the solar radiant energy solar energy of ball surface；5, solar energy source is at low cost, is most to clean 21 century, is most cheap
The energy.There are two types of the light responsive materials of configuration to have heat accumulation characteristic for general tool.Azobenzene is a kind of light-sensitive coloring agent that research is wider
And light responsive material, there are two kinds of isomers of cis and trans for it.Under normal circumstances, under ultraviolet light, anti-configuration
Azobenzene can be changed into cis-configuration；Later under conditions of light and heat, cis-configuration can be restored to anti-configuration.Two kinds of configurations
Between there are the differences of energy, luminous energy is stored using this portion of energy difference, finally in the form of thermal energy discharge.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of heterocycle azo benzene/graphene solar energy storages
Hot material and preparation method are template using graphene, increase the order and intermolecular force of molecule, by cis-trans isomerism
And the energy generated, heterocycle azo benzene/graphene composite material obtained can produce good heat accumulation effect.
Technical purpose of the invention is achieved by following technical proposals:
Heterocycle azo benzene/graphene solar energy heat-storage material, by graphene and monomer molecule formula C12N5O4H13Heterocycle it is even
Pyridine composition, heterocycle azo benzene are covalently grafted to graphene surface, and every 40~80 carbon atoms are grafted a heterocycle
Azobenzene, structural formula are as follows:
In heterocycle azo benzene of the invention/graphene solar energy heat-storage material, restore to obtain stone using graphene oxide
Black alkene, so that damaged structure occurs in the benzene ring structure of composition graphene, there is some carbon original in fine and close hexatomic ring (phenyl ring) structure
The missing of son forms vacancy, provides reaction site for the grafting of heterocycle azo benzene, and preferably every 50~70 carbon atoms are grafted one
Heterocycle azo benzene.
Heterocycle azo benzene/graphene solar energy heat-storage material preparation method carries out: as steps described below in N, N diformazan
Graphene, heterocycle azo benzene and NaOH and evenly dispersed are added in the aqueous solution of base formamide, under inert protective gas atmosphere
It is reacted, reaction temperature is 100-150 degrees Celsius, so that heterocycle azo benzene is covalently grafted to graphene surface
Reaction site, obtain heterocycle azo benzene/graphene solar energy heat-storage material；Wherein graphene uses sodium borohydride and sodium carbonate
Redox graphene is graphene, so that damaged structure, fine and close hexatomic ring (benzene occurs in the benzene ring structure of composition graphene
Ring) there is the missing of carbon atom in structure, and vacancy is formed, provides reaction site for the grafting of heterocycle azo benzene, heterocycle azo benzene
Amino reacts so that it is covalently keyed in graphene-structured；The chemical formula of heterocycle azo benzene is as follows:
In the above-mentioned technical solutions, 20-30 mass parts graphene is added, each mass parts are 1mg, heterocycle azo benzene and hydrogen
The molar ratio of sodium oxide molybdena is 1:(1-1.2).
In the above-mentioned technical solutions, in the aqueous solution of n,N dimethylformamide, n,N dimethylformamide concentration is
0.3-0.9mg/mL。
In the above-mentioned technical solutions, inert protective gas atmosphere is nitrogen, helium or argon gas.
In the above-mentioned technical solutions, reaction temperature is 100-120 degrees Celsius, and the reaction time is 10-20 hours, preferably
10-16 hours.
In the above-mentioned technical solutions, after the completion of reaction, decompression filters, and acetone washing 3-5 times obtains purpose product heterocycle
Azobenzene/graphene solar energy heat-storage material.
In the above-mentioned technical solutions, graphene uses sodium borohydride and sodium carbonate redox graphene for graphene, tool
For body, graphene oxide is placed in water to and is added sodium carbonate adjusting pH to 7-9, sodium borohydride aqueous solution is added to oxidation stone
Black alkene carries out reduction treatment, and the concentration of sodium borohydride is 10-20mg/ml (sodium borohydride quality, mg/ water volume, ml), in 75-
It is placed 6-8 hours under 90 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain required redox graphene (i.e. stone
Black alkene)；Then it is dispersed in water again ultrasound is passed through.
In the above-mentioned technical solutions, heterocycle azo benzene is prepared as follows: by 3- amino 4- carboxypyrazole, hydrogen
Sodium oxide molybdena and sodium nitrite are evenly dispersed in deionized water, and hydrochloric acid is added dropwise, and ice bath reaction adds after carrying out azo
3,5 dimethoxyanilines, reaction obtain heterocycle azo benzene, as follows:
Specifically, 3- amino 4- carboxypyrazole and sodium hydroxide are equimolar ratio, 3- amino 4- carboxypyrazole and nitrous
The molar ratio of sour sodium is 1:(1-1.2), 3- amino 4- carboxypyrazole and 3, the molar ratio of 5 dimethoxyanilines is 1:(1-2),
The molar ratio of 3- amino 4- carboxypyrazole and hydrogen chloride is 1:(3-6), 3- amino 4- carboxypyrazole is 10-30 molar parts, often
One molar part is 1mmol；Ice bath reaction temperature is 0-2 degrees Celsius, and the ice bath reaction time is 1-3 hours；Hydrogen chloride in hydrochloric acid
Concentration is 1mol/L.Dark red or orange-red azo reaction is just formed by faint yellow in the reaction, adds 3,5-dimethoxies
Base aniline is reacted, while adjusting pH to 6-7, generates yellow mercury oxide, i.e. heterocycle azo benzene.
Heterocycle azo benzene/graphene composite material of the invention can efficient storage solar energy, have high-energy density, can
The characteristics of control heat release, carries out energy stores and release using cis-trans isomerism, as follows:
Azo heterocycle/graphene composite material is subjected to ultraviolet spectra characterization, as shown in Fig. 2, showing that the material has very
Good Cis-trans structures have the effect of heat accumulation simultaneously.By azo heterocyclic monomer-azo carboxypyrazole DSC (differential scanning calorimetry
Method), it is discharged using the heat that differential scan calorimeter carries out temperature programmed control measurement material, is then released exothermic peak integral
Energy, then make comparisons with quality, obtain the storage density of material, and repeatedly circulation can be achieved stable energy storage and release
It puts, as shown in Fig. 1.The graphene for connecing azobenzene is placed on respectively in thermal station with infrared heat with the graphene for not connecing azobenzene
As instrument is observed, the variation of directly accurate shooting recording materials exothermic process temperature connects the graphene of azobenzene than the temperature that does not connect
16 DEG C high, exothermal effect is obvious.Through calculating, azo heterocycle/graphene composite material energy storage density of the invention is up to 100-
130Wh/kg improves nearly 60% than monomer molecule, can compare favourably with lithium ion battery.With the ultraviolet light irradiation of 260W
Energy storage material 10min of the invention carries out filling heat, in DSC scanning process, discharges the heat of storage by thermostimulation, heat accumulation
Material has heat release in 70 DEG C and 90 DEG C.
The quality that redox graphene is first weighed before azo molecules and redox graphene are compound, is denoted as m0, even
After nitrogen molecular is reacted with redox graphene, the azo molecules of absorption are washed off, weigh quality after drying again, are denoted as m1,
The relative molecular mass of azo molecules is M, and the relative atomic mass 12 of C atom, grafting rate calculation formula is γ=12 (m1-m0)/
M*m0；Further according to the ratio of energy energy storage and release in cis-trans isomerism, how much isomerization rate is changed into whole transconfigurations
Cis-structure, isomerization rate reach as high as 94-96%, improve 20% than monomer molecule.
The present invention discloses a kind of novel heterocycle azo benzene/graphene composite material and preparation method, by 3- amino 4- carboxyl
Pyrazoles and 3,5 dimethoxyanilines react synthesizing heterocyclic azobenzene, then compound with pretreated redox graphene, obtain
Heterocycle azo benzene/the graphene composite material arrived.In heterocycle azo benzene/graphene composite material of the invention, using oxidation
Graphene also original structure carries out grafting azobenzene, restores to obtain graphene using graphene oxide, so that the benzene of composition graphene
There is damaged structure in ring structure, and the missing of some carbon atom occurs in fine and close hexatomic ring (phenyl ring) structure, forms vacancy, is heterocycle
The grafting of azobenzene provides reaction site；For double benzene ring structures, phenyl ring-hybrid structure of heterocycle azo benzene is (opposite
Less than double benzene ring structures) for Cis-trans structures transformation energy storage is provided, the advantage with long half time is interior per se with miscellaneous original plus ring
Son, and carboxyl is had, therefore be easy to form hydrogen bond with surrounding molecular, more traditional azobenzene molecule is in energy value and half-life period
It is greatly improved, is the excellent material of solar energy heat-storage.
Detailed description of the invention
Fig. 1 is heterocycle azo benzene-azo carboxypyrazole DSC (differential scanning calorimetry) figure.
Fig. 2 is heterocycle azo benzene/graphene composite material ultra-violet absorption spectrum.
Specific embodiment
Here is not intended to limit the scope of the invention to further explanation of the invention, wherein in heterocycle azo benzene system
During standby, by 3- amino 4- carboxypyrazole mole on the basis of, equivalent, 1.1 equivalents are 3- amino 4- carboxypyrazole mole
One times and 1.1 times.
Embodiment 1
1) preparation of heterocycle azo benzene: by the sodium hydroxide and 1.1 of the 3- amino 4- carboxypyrazole equivalent of 10mmol
The sodium nitrite of equivalent is dissolved in the deionized water of 20ml, and the hydrochloric acid of 3 equivalent 1mol/L is added dropwise, and ice bath reacts 3 hours,
3,5 dimethoxyanilines that 2 equivalents are added obtain heterocycle azo benzene；
2) redox graphene pre-processes: using the aqueous sodium carbonate of mass percent 30% by graphene oxide
Aqueous solution adjusts pH to 9, and the graphene oxide that the pH of addition 40ml is mixed up in the aqueous solution of 20mg/ml sodium borohydride is water-soluble
Liquid, and placed 8 hours under 90 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain required RGO (oxygen reduction fossil
Black alkene, i.e., modified RGO)；Then it is dispersed in water again ultrasound is passed through；
3) heterocycle azo benzene/graphene composite material preparation: in the N of 0.9mg/mL, the aqueous solution of N-dimethylformamide
The middle above-mentioned modified RGO of addition 30mg is evenly dispersed to be placed in reactor；The heterocycle azo benzene that 0.5mmol step (1) is obtained
Reactor is added to the NaOH of 1.1 equivalents；N2It is reacted 16 hours under protection at 100 DEG C；Decompression filters, acetone washing 3-5 times,
Obtain purpose product heterocycle azo benzene/graphene composite material.Storage density reaches 100Wh/kg.
Embodiment 2
1) preparation of heterocycle azo benzene: by the sodium hydroxide and 1.2 of the 3- amino 4- carboxypyrazole equivalent of 30mmol
The sodium nitrite of equivalent is dissolved in the deionized water of 10ml, and the hydrochloric acid of 4 equivalent 1mol/L is added dropwise, and ice bath reacts 1 hour,
3,5 dimethoxyanilines that 1 equivalent is added obtain heterocycle azo benzene；
2) redox graphene pre-processes: using the aqueous sodium carbonate of mass percent 20% by graphene oxide
Aqueous solution adjusts pH to 7, and the graphene oxide that the pH of addition 30ml is mixed up in the aqueous solution of 10mg/ml sodium borohydride is water-soluble
Liquid, and placed 6 hours under 75 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain required RGO (oxygen reduction fossil
Black alkene, i.e., modified RGO)；Then it is dispersed in water again ultrasound is passed through；
3) heterocycle azo benzene/graphene composite material preparation: in the N of 0.3mg/mL, the aqueous solution of N-dimethylformamide
The middle above-mentioned modified RGO of addition 20mg is evenly dispersed to be placed in reactor；The heterocycle azo benzene that 0.2mmol step (1) is obtained
Reactor is added to the NaOH of 1.1 equivalents；N2It is reacted 12 hours under protection at 120 DEG C；Decompression filters, acetone washing 3-5 times,
Obtain purpose product heterocycle azo benzene/graphene composite material.Storage density reaches 130Wh/kg.
Embodiment 3
1) preparation of heterocycle azo benzene: by the sodium hydroxide of the 3- amino 4- carboxypyrazole equivalent of 20mmol and etc. work as
The sodium nitrite of amount is dissolved in the deionized water of 15ml, and the hydrochloric acid of 6 equivalent 1mol/L is added dropwise, and ice bath reacts 1 hour, adds
3,5 dimethoxyanilines for entering 1.5 equivalents obtain heterocycle azo benzene；
2) redox graphene pre-processes: using the aqueous sodium carbonate of mass percent 15% by graphene oxide
Aqueous solution adjusts pH to 8, and the graphene oxide that the pH of addition 35ml is mixed up in the aqueous solution of 15mg/ml sodium borohydride is water-soluble
Liquid, and placed 6 hours under 85 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain required RGO (oxygen reduction fossil
Black alkene, i.e., modified RGO)；Then it is dispersed in water again ultrasound is passed through；
3) heterocycle azo benzene/graphene composite material preparation: in the N of 0.6mg/mL, the aqueous solution of N-dimethylformamide
The middle above-mentioned modified RGO of addition 25mg is evenly dispersed to be placed in reactor；The heterocycle azo benzene that 0.4mmol step (1) is obtained
Reactor is added to the NaOH of 1.1 equivalents；N2It is reacted 20 hours under protection at 120 DEG C；Decompression filters, acetone washing 3-5 times,
Obtain purpose product heterocycle azo benzene/graphene composite material.Storage density reaches 110Wh/kg.
The technological parameter that content is recorded according to the present invention is adjusted, and heterocycle azo benzene/graphene composite wood can be achieved
The preparation of material, and show almost the same energy storage and release performance.Illustrative description is done to the present invention above, it should say
It is bright, in the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art
The equivalent replacement of creative work can not be spent to each fall within protection scope of the present invention.
Claims (10)
1. heterocycle azo benzene/graphene solar energy heat-storage material, which is characterized in that by graphene and monomer molecule formula C12N5O4H13
Heterocycle azo benzene composition, restore to obtain graphene using graphene oxide so that composition graphene benzene ring structure break
There is the missing of some carbon atom in damage structure, fine and close six-membered ring structure, form vacancy, provide instead for the grafting of heterocycle azo benzene
Site is answered, heterocycle azo benzene is covalently grafted to graphene surface, and every 40~80 carbon atoms are grafted a heterocycle idol
Pyridine, structural formula are as follows:
2. heterocycle azo benzene according to claim 1/graphene solar energy heat-storage material, which is characterized in that preferably every 50
~70 carbon atoms are grafted a heterocycle azo benzene.
3. heterocycle azo benzene/graphene solar energy heat-storage material preparation method, which is characterized in that carry out as steps described below:
Graphene, heterocycle azo benzene and NaOH and evenly dispersed are added in the aqueous solution of n,N dimethylformamide, protects gas in inertia
It is reacted under body atmosphere, reaction temperature is 100-150 degrees Celsius, so that heterocycle azo benzene is covalently grafted to stone
The reaction site on black alkene surface obtains heterocycle azo benzene/graphene solar energy heat-storage material；Wherein graphene uses sodium borohydride
It is graphene with sodium carbonate redox graphene, so that the damaged structure of benzene ring structure appearance of composition graphene, fine and close six
There is the missing of carbon atom in ring structure, forms vacancy, and the grafting for heterocycle azo benzene provides reaction site；Heterocycle azo benzene
Chemical formula is as follows:
4. heterocycle azo benzene according to claim 3/graphene solar energy heat-storage material preparation method, feature exist
In graphene uses sodium borohydride and sodium carbonate redox graphene for graphene, and specifically, graphene oxide is placed in
In water and sodium carbonate adjusting pH to 7-9 is added, sodium borohydride aqueous solution is added, reduction treatment, hydroboration is carried out to graphene oxide
The concentration of sodium is 10-20mg/ml, is placed 6-8 hours under 75-90 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain
Required redox graphene (i.e. graphene)；Then it is dispersed in water again ultrasound is passed through.
5. heterocycle azo benzene according to claim 3/graphene solar energy heat-storage material preparation method, feature exist
In 20-30 mass parts graphene being added, the molar ratio of heterocycle azo benzene and sodium hydroxide is 1:(1-1.2).
6. heterocycle azo benzene according to claim 3/graphene solar energy heat-storage material preparation method, feature exist
In in the aqueous solution of n,N dimethylformamide, n,N dimethylformamide concentration is 0.3-0.9mg/mL.
7. heterocycle azo benzene according to claim 3/graphene solar energy heat-storage material preparation method, feature exist
In inert protective gas atmosphere is nitrogen, helium or argon gas.
8. heterocycle azo benzene according to claim 3/graphene solar energy heat-storage material preparation method, feature exist
In reaction temperature is 100-120 degrees Celsius, and the reaction time is 10-20 hours, preferably 10-16 hours.
9. heterocycle azo benzene according to claim 3/graphene solar energy heat-storage material preparation method, feature exist
In heterocycle azo benzene is prepared as follows: 3- amino 4- carboxypyrazole, sodium hydroxide and sodium nitrite are uniformly divided
It dissipates in deionized water, hydrochloric acid is added dropwise, ice bath reaction adds 3,5 dimethoxyanilines after carrying out azo, reacts
To heterocycle azo benzene, 3- amino 4- carboxypyrazole and sodium hydroxide are equimolar ratio, 3- amino 4- carboxypyrazole and sodium nitrite
Molar ratio be 1:(1-1.2), 3- amino 4- carboxypyrazole and 3, the molar ratio of 5 dimethoxyanilines is 1:(1-2), 3- ammonia
The molar ratio of base 4- carboxypyrazole and hydrogen chloride is 1:(3-6), 3- amino 4- carboxypyrazole is 10-30 molar parts；Ice bath is anti-
Answering temperature is 0-2 degrees Celsius, and the ice bath reaction time is 1-3 hours；Hydrogen cloride concentration is 1mol/L in hydrochloric acid.
10. heterocycle azo benzene/graphene solar energy heat-storage material as described in claim 1 is in preparing solar energy heat-storage material
Application, which is characterized in that energy storage density reaches as high as 94-96% up to 100-130Wh/kg, isomerization rate.
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