CN109503419A - A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method - Google Patents
A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method Download PDFInfo
- Publication number
- CN109503419A CN109503419A CN201710833143.4A CN201710833143A CN109503419A CN 109503419 A CN109503419 A CN 109503419A CN 201710833143 A CN201710833143 A CN 201710833143A CN 109503419 A CN109503419 A CN 109503419A
- Authority
- CN
- China
- Prior art keywords
- azobenzene
- graphene
- azo
- graphene composite
- energy
- 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.)
- Pending
Links
Classifications
-
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
-
- 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
- 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 discloses a kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method, and monomer molecule azo molecules are covalently grafted to graphene surface, and every 30~50 carbon atoms are grafted an azo molecules；The preparation of two kinds first azo molecules；Then redox graphene pre-processes；Finally carry out the preparation of azo molecules/graphene composite material be blended.Energy storage material of the invention has good storage density, and up to 155Wh/kg has surmounted the energy density of common lithium battery.Isomerization rate is up to 98%, improves 30% than monomer molecule；Storage density is up to 160Wh/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 fields, more particularly, are related to a kind of alternately double-deck azobenzene/graphene
Composite energy-storage material and preparation method, before future has important application in Solar use and in terms of making long-range photo-thermal switch
Scape.
Background technique
Solar energy is a kind of inexhaustible, clean renewable energy, is developing new energy and guarantor using solar power generation
Retaining ring border, energy-saving and emission-reduction effective way.American-European some developed countries, which have begun concern, has more high energy source utilization rate too
Positive energy photo-thermal power generation technology, and the demonstration plant of different types is established in succession.The rapid development of China's economy is so as to the energy
Increase in demand, caused by environmental problem it is also urgently to be resolved.While enjoyment scientific and technological progress lives to us and offers convenience, I
Also should clearly recognize: China's energy resources natural endowment is not high, average resource per capita be far below world average level；Resource
Environmental constraints contradiction becomes increasingly conspicuous, and energy resources external dependence degree is constantly soaring；National diplomacy stake is responsible for, energy strategy
Status is higher and higher.Therefore, Optimization of Energy Structure, realize using energy source diversification be to maintain energy sustainable development, it is ensured that
The important guarantee of the economic steady and rapid growth in China.Renewable energy is developed and utilized, improves renewable energy in China's energy
Structure.In this case, development new and renewable energy is very urgent, and increasing to the utilization of solar energy is it in weight
Weight.
Solar energy advantage mainly has:
1, the solar energy total energy value for reaching ground daily is quite big；
2, solar energy has inexhaustible advantage；
3, energy convenient sources, for other energy, solar radiant energy is distributed most area on earth, can
It takes on the spot, has great superiority to the energy supply for solving the problems, such as remote districts；
4, solar energy is completely pollution-free, and any pollution is nearly free from use process；
Azo molecules with cis-trans isomerism various configuration are the important objects of photo-thermal research, in the ultraviolet light of specific wavelength
Under irradiation, the azobenzene of anti-configuration can be changed into cis-configuration；Later under conditions of light and heat, cis-configuration can be restored to
Anti-configuration.There are the difference of energy between two kinds of configurations, by it is trans- be transitioned into it is cis- can store energy, otherwise can discharge
Heat.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of alternately double-deck azobenzene/graphene is compound
Energy storage material and preparation method are template, the energy generated by cis-trans isomerism, the double-deck azo/stone of alternating using graphene
For black alkene material by Supramolecular self assembly, molecularly oriented isomerization rate is bigger, final alternately double-deck azobenzene/graphene composite wood
Material reveals fairly good heat accumulation effect, can store solar energy, has high-energy density, long half-lift.
Technical purpose of the invention is achieved by following technical proposals:
Alternately double-deck azobenzene/graphene composite energy-storage material, by graphene and two kinds of azobenzene monomer compositions, wherein the
One azo benzene monomer, which is covalently grafted in graphene-structured, forms the first azobenzene-graphene composite material, and every 30
~50 carbon atoms are grafted first azobenzene molecule, and structure is as follows:
Second azo benzene monomer is covalently grafted in graphene-structured that form the second azobenzene-graphene multiple
Condensation material, every 30~50 carbon atoms are grafted second azobenzene molecule, and structure is as follows:
Pass through the molecule between the first azobenzene-graphene composite material and the second azobenzene-graphene composite material
Between interaction force carry out Supramolecular self assembly, to form alternately double-deck azobenzene/graphene composite energy-storage material, i.e., first is even
Second azobenzene of the first azobenzene molecule of pyridine-graphene composite material and the second azobenzene-graphene composite material
Intermolecular hydrogen bonding is formed between molecule, such as the nitrogen-atoms of the hydrogen atom of the carboxyl of the first azobenzene molecule and the second azobenzene molecule
Between form hydrogen bond, at this point, between two layers of graphene-structured formed hydrogen bond action the first azobenzene molecule and the second azo
Benzene molecular double-layer structure.
In alternating bilayer azobenzene/graphene composite energy-storage material of the invention, restore to obtain using graphene oxide
Graphene, so that damaged structure occurs in the benzene ring structure of composition graphene, there is some carbon in fine and close hexatomic ring (phenyl ring) structure
The missing of atom forms vacancy, provides reaction site for the grafting of two kinds of azobenzene molecules, preferably every 40~50 carbon atoms connect
One the first azobenzene molecule of branch, every 40~50 carbon atoms are grafted second azobenzene molecule.
The alternately preparation method of double-deck azobenzene/graphene composite energy-storage material, carries out as steps described below:
Graphene, the first azo benzene monomer and NaOH and evenly dispersed are added in the aqueous solution of methyl pyrrolidone,
It is reacted under inert protective gas atmosphere, reaction temperature is 100-150 degrees Celsius, so that the first azo benzene monomer is with covalent
Key mode is grafted to the reaction site of graphene-structured, obtains the first azobenzene-graphene composite material；In crassitude
Graphene, the second azo benzene monomer and NaOH and evenly dispersed are added in the aqueous solution of ketone, under inert protective gas atmosphere into
Row reaction, reaction temperature is 100-150 degrees Celsius, so that the second azo benzene monomer is covalently grafted to graphene knot
The reaction site of structure obtains the second azobenzene-graphene composite material；Finally by the first azobenzene-graphene composite material,
Second azobenzene-graphene composite material, which is dispersed in water phase, to be blended, and carries out supermolecule using interaction of hydrogen bond
Self assembly finally obtains target product alternately double-deck azo/graphene composite material；Wherein graphene uses sodium borohydride and carbon
Sour sodium reduction graphene oxide is graphene, so that damaged structure, fine and close hexatomic ring occurs in the benzene ring structure of composition graphene
There is the missing of carbon atom in (phenyl ring) structure, forms vacancy, and the grafting for two kinds of azo benzene monomers provides reaction site；First is even
Pyridine monomer is double carboxyl azobenzenes, and the second azo benzene monomer is pyrimidine azobenzene, the amino difference on two kinds of azo benzene monomers
It is reacted with graphene reaction site, so that it is covalently keyed in graphene-structured.
In the above-mentioned technical solutions, 20-30 mass parts graphene is added, each mass parts are 1mg, the first azo benzene monomer
Molar ratio with sodium hydroxide is 1:(1-1.2), the molar ratio of the second azo benzene monomer and sodium hydroxide is 1:(1-1.2).
In the above-mentioned technical solutions, in the aqueous solution of methyl pyrrolidone, methyl pyrrolidone 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 be 120-140 degrees Celsius, the reaction time be 5-10 hours, preferably 7-
8 hours.
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.
First azo benzene monomer is double carboxyl azobenzenes, is prepared as steps described below: by 3,5 dicarboxyanylines, Asia
Sodium nitrate and sodium hydroxide are evenly dispersed in deionized water, and hydrochloric acid is added dropwise, and ice bath reaction adds 3,5 two after carrying out azo
Reaction obtains double carboxyl azobenzenes under inert protective gas atmosphere in aminoanisole, as follows:
Specifically, 3,5 dicarboxyanylines, sodium nitrite and sodium hydroxide are equimolar ratio, 3,5 dicarboxyanylines and chlorine
The molar ratio for changing hydrogen is 1:(3-6), 3,5 dicarboxyanylines and 3, the molar ratio of 5 dimethoxyanilines is 1:(1-2), 3,5 two
Carboxyanilino is 10-30 molar parts, and each molar part is 1mmol；Ice bath reaction temperature is 0-2 degrees Celsius, when ice bath reacts
Between be 1-3 hours；Hydrogen cloride concentration is 1mol/L in hydrochloric acid.In the reaction by it is faint yellow just formed it is dark red or orange-red
Azo reaction, adds 3,5-dimethoxyanilines and is reacted, while adjusting pH to 6-7, generates yellow mercury oxide, i.e., double carboxylics
Base azobenzene.
Second azo benzene monomer is pyrimidine azobenzene, is prepared as steps described below: by 5- aminopyrimidine, sodium nitrite
It is evenly dispersed in deionized water with sodium hydroxide, hydrochloric acid is added dropwise, ice bath reaction adds 3,5 dimethoxys after carrying out azo
Reaction obtains pyrimidine azo under inert protective gas atmosphere in aniline, as follows:
Specifically, 5- aminopyrimidine, sodium nitrite and sodium hydroxide are equimolar ratio, 5- aminopyrimidine and hydrogen chloride
Molar ratio is 1:(3-6), 5- aminopyrimidine and 3, the molar ratio of 5 dimethoxyanilines is 1:(1-2), 5- aminopyrimidine is
10-30 molar parts, each molar part are 1mmol；Ice bath reaction temperature is 0-2 degrees Celsius, and the ice bath reaction time is 1-3 small
When；Hydrogen cloride concentration is 1mol/L in hydrochloric acid.It is just formed dark red or orange-red azo by faint yellow in the reaction and is reacted, then
3,5-dimethoxyanilines are added to be reacted, while adjusting pH to 6-7, generate yellow mercury oxide, i.e. pyrimidine azobenzene.
Alternating bilayer azobenzene/graphene composite energy-storage material of the invention can efficient storage solar energy, have high energy
The characteristics of metric density, controlled thermal release, carries out energy stores and release using cis-trans isomerism, as follows:
Alternately ultraviolet spectra characterization, as shown in Fig. 1, peak institute will be carried out by double-deck azobenzene/graphene composite energy-storage material
Locate the ultraviolet absorption peak that position is material.Fig. 2 is the transmission spectrum of the composite material after grafting.It will the double-deck azobenzene/stone of alternating
Black alkene composite energy-storage material DSC (differential scanning calorimetry) carries out temperature programmed control measurement material using differential scan calorimeter
Exothermic peak, is then integrated the energy being released, then makes comparisons with quality, obtain the storage density of material by heat release,
As shown in Fig. 3, showing the material really has the effect of Cis-trans structures while having heat accumulation.The alternating two-layer compound of heat will be filled
Material is observed in thermal station with thermal infrared imager with the single composite material for filling heat there are also hot composite material is not filled respectively, directly
The variation of accurate shooting recording materials exothermic process temperature, alternately double-deck ratio single is 5 DEG C high, than not filling the 17 DEG C high of heat,
Exothermal effect is quite obvious.Through calculating, dual graft azobenzene/graphene composite energy-storage material energy storage density of the invention is reachable
140-160Wh/kg improve nearly 60% than monomer molecule, have surmounted the energy density of common lithium battery.It is ultraviolet with 260W
Energy storage material light irradiation 10min of the invention carries out filling heat, in DSC scanning process, releases the heat of storage by thermostimulation
It puts, heat accumulating is in 90 DEG C of beginning heat releases.
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；Isomerization rate is calculated further according to the ratio of energy energy storage and release in cis-trans isomerism, i.e., how many turns in whole transconfigurations
Become cis-structure, isomerization rate reaches as high as 96-98%, improves 30% than monomer molecule.
The present invention discloses a kind of novel alternately bilayer azobenzene/graphene composite material and preparation method, by double carboxyl benzene
Amine and the close pyridine of amino are respectively with 3,5 dimethoxyanilines reaction synthesis azo molecules, then with pretreated oxygen reduction fossil
Black alkene is compound, the alternating bilayer azobenzene/graphene composite material obtained eventually by the method for solution blending.Of the invention
In heterocycle azo benzene/graphene composite material, grafting azobenzene is carried out using graphene oxide also original structure, using graphite oxide
Alkene restores to obtain graphene, so that damaged structure, fine and close hexatomic ring (phenyl ring) structure occurs in the benzene ring structure of composition graphene
There is the missing of some carbon atom, forms vacancy, provide reaction site for the grafting of azobenzene；Two azobenzene lists are utilized simultaneously
The composite material of hydrogen bond between body, more traditional single grafting azobenzene is greatly improved in energy value and half-life period, is conducive to
It makes full use of the sun to can be carried out energy stores, and the graft ratio and two kinds of azobenzene-stones of two kinds of azo benzene monomers can be passed through
The blending ratio of black alkene composite material carries out the adjustment of composite property.
Detailed description of the invention:
Fig. 1 is alternating bilayer azobenzene/graphene composite material ultraviolet spectrogram of the invention.
Fig. 2 is alternating bilayer azobenzene/graphene composite material TEM photo of the invention.
Fig. 3 is alternating bilayer azobenzene/graphene composite material DSC test curve figure of the invention.
Specific embodiment
Here is not intended to limit the scope of the invention to further explanation of the invention.Preparing double carboxyl azobenzenes
In the process, with 3,5 dicarboxyanylines mole on the basis of, equivalent, 1-2 equivalent be one times of 3,5 dicarboxyanylines mole and
1-2 times.During preparing pyrimidine azobenzene, by 5- aminopyrimidine mole on the basis of, equivalent, 1-2 equivalent be 5- amino
One times of pyrimidine mole and 1-2 times.During preparing azobenzene, in the reaction by it is faint yellow just formed it is dark red or orange red
The azo of color reacts, and adds 3,5-dimethoxyanilines and is reacted, while adjusting pH to 6-7, generates inclined yellow mercury oxide.
Embodiment 1
1) 3,5 dicarboxyanylines of 30mmol and the sodium hydroxide of equivalent and the sodium nitrite of equivalent are dissolved in
In ionized water, be added drop-wise to the hydrochloric acid of 6 equivalent 1mol/L, ice bath reacts 1 hour, be added 3,5 dimethoxyanilines of 1 equivalent and
Reaction obtains double carboxyl azos in argon gas；
2) by the 5- aminopyrimidine of 30mmol and the sodium hydroxide of equivalent and the sodium nitrite of equivalent be dissolved in from
In sub- water, it is added drop-wise to the hydrochloric acid of 6 equivalent 1mol/L, ice bath reacts 1 hour, 3,5 dimethoxyanilines of 2 equivalents is added and in argon
Reaction obtains pyrimidine azo in gas；
3) redox graphene pre-processes: will disperse graphite oxide with the aqueous sodium carbonate that mass percent is 20%
The aqueous solution of alkene adjusts pH to 7, and the graphene oxide that the pH of addition 40ml is mixed up in 20mg/ml sodium borohydride aqueous solution is water-soluble
Liquid, and placed 6 hours under 90 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain required RGO；Then passing through
Ultrasound is dispersed in water again；
4) it the alternately preparation of double-deck azobenzene/graphene composite material: is added in 0.9mg/mL methyl pyrrolidone
The above-mentioned RGO of 20mg is evenly dispersed to be placed in two reactors；In a reactor, be added the bis- carboxyl azos of 0.2mmol with
0.2mmol pyrimidine azo and equimolar NaOH, N is added in another reactor in equimolar NaOH2At 120 DEG C under protection
Reaction 8 hours；Decompression filters, and acetone washing 3-5 times obtains two kinds of azo/graphene composite materials；Again by two kinds of composite materials
It is dispersed in water and is blended, carry out Supramolecular self assembly using interaction of hydrogen bond, it is alternately double-deck to finally obtain target product
Azo/graphene composite material.Storage density reaches 160Wh/kg.
Embodiment 2
1) 3,5 dicarboxyanylines of 10mmol and the sodium hydroxide of equivalent and the sodium nitrite of equivalent are dissolved in
In ionized water, be added drop-wise to the hydrochloric acid of 3 equivalent 1mol/L, ice bath reacts 3 hours, be added 3,5 dimethoxyanilines of 2 equivalents and
Reaction obtains double carboxyl azos in argon gas；
2) by the 5- aminopyrimidine of 10mmol and the sodium hydroxide of equivalent and the sodium nitrite of equivalent be dissolved in from
In sub- water, it is added drop-wise to the hydrochloric acid of 3 equivalent 1mol/L, ice bath reacts 3 hours, 3,5 dimethoxyanilines of 1 equivalent is added and in argon
Reaction obtains pyrimidine azo in gas；
3) redox graphene pre-processes: will disperse graphite oxide with the aqueous sodium carbonate that mass percent is 30%
The aqueous solution of alkene adjusts pH to 8, and the graphene oxide that the pH of addition 30ml is mixed up in 10mg/ml sodium borohydride aqueous solution is water-soluble
Liquid, and placed 8 hours under 75 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain required RGO；Then passing through
Ultrasound is dispersed in water again；
4) it the alternately preparation of double-deck azobenzene/graphene composite material: is added in 0.3mg/mL methyl pyrrolidone
The above-mentioned RGO of 30mg is evenly dispersed to be placed in two reactors；In a reactor, be added the bis- carboxyl azos of 0.6mmol with
0.6mmol pyrimidine azo and equimolar NaOH, N is added in another reactor in equimolar NaOH2At 140 DEG C under protection
Reaction 7 hours；Decompression filters, and acetone washing 3-5 times obtains two kinds of azo/graphene composite materials；Again by two kinds of composite materials
It is dispersed in water and is blended, carry out Supramolecular self assembly using interaction of hydrogen bond, it is alternately double-deck to finally obtain target product
Azo/graphene composite material.Storage density reaches 150Wh/kg.
Embodiment 3
1) 3,5 dicarboxyanylines of 20mmol and the sodium hydroxide of equivalent and the sodium nitrite of equivalent are dissolved in
In ionized water, be added drop-wise to the hydrochloric acid of 4 equivalent 1mol/L, ice bath reacts 2 hours, be added 3,5 dimethoxyanilines of 2 equivalents and
Reaction obtains double carboxyl azos in argon gas；
2) by the 5- aminopyrimidine of 20mmol and the sodium hydroxide of equivalent and the sodium nitrite of equivalent be dissolved in from
In sub- water, it is added drop-wise to the hydrochloric acid of 5 equivalent 1mol/L, ice bath reacts 2 hours, 3,5 dimethoxyanilines of 2 equivalents is added and in argon
Reaction obtains pyrimidine azo in gas；
3) redox graphene pre-processes: will disperse graphite oxide with the aqueous sodium carbonate that mass percent is 25%
The aqueous solution of alkene adjusts pH to 9, and the graphene oxide that the pH of addition 35ml is mixed up in 15mg/ml sodium borohydride solution is water-soluble
Liquid, and placed 7 hours under 85 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain required RGO；Then passing through
Ultrasound is dispersed in water again；
4) it the alternately preparation of double-deck azobenzene/graphene composite material: is added in 0.6mg/mL methyl pyrrolidone
The above-mentioned RGO of 15mg is evenly dispersed to be placed in two reactors；In a reactor, be added the bis- carboxyl azos of 0.4mmol with
0.4mmol pyrimidine azo and equimolar NaOH, N is added in another reactor in equimolar NaOH2At 120 DEG C under protection
Reaction 10 hours；Decompression filters, and acetone washing 3-5 times obtains two kinds of azo/graphene composite materials；Again by two kinds of composite woods
Material, which is dispersed in water, to be blended, and carries out Supramolecular self assembly using interaction of hydrogen bond, it is alternately double to finally obtain target product
Layer azo/graphene composite material.Storage density reaches 140Wh/kg.
Content carries out the adjustment of technological parameter according to the present invention, can prepare alternately double-deck azo/graphene composite material,
And show almost the same energy storage-release performance.Illustrative description has been done to the present invention above, it should explanation,
In the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art can not be spent
The equivalent replacement of expense creative work each falls within protection scope of the present invention.
Claims (10)
1. alternately double-deck azobenzene/graphene composite energy-storage material, which is characterized in that by graphene and two kinds of azo benzene monomer groups
At wherein the first azo benzene monomer is covalently grafted in graphene-structured, to form the first azobenzene-graphene compound
Material, every 30~50 carbon atoms are grafted first azobenzene molecule, and structure is as follows:
Second azo benzene monomer, which is covalently grafted in graphene-structured, forms the second azobenzene-graphene composite wood
Material, every 30~50 carbon atoms are grafted second azobenzene molecule, and structure is as follows:
Pass through the intermolecular phase between the first azobenzene-graphene composite material and the second azobenzene-graphene composite material
Interreaction force carries out Supramolecular self assembly, to form alternately double-deck azobenzene/graphene composite energy-storage material, i.e. the first azo
Second azobenzene of the first azobenzene molecule of benzene-graphene composite material and the second azobenzene-graphene composite material point
Intermolecular hydrogen bonding is formed between son, and the first azobenzene molecule and second of hydrogen bond action is formed between two layers of graphene-structured occasionally
Pyridine molecule double-layer structure.
2. alternately double-deck azobenzene/graphene composite energy-storage material according to claim 1, which is characterized in that use oxygen
Graphite alkene restores to obtain graphene, so that damaged structure, fine and close six-membered ring structure occurs in the benzene ring structure of composition graphene
There is the missing of some carbon atom, forms vacancy, provide reaction site, two kinds of azobenzene lists for the grafting of two kinds of azobenzene molecules
Amino on body is reacted with graphene reaction site respectively, so that it is covalently keyed in graphene-structured；It is preferred that every 40~50
A carbon atom is grafted first azobenzene molecule, and every 40~50 carbon atoms are grafted second azobenzene molecule.
3. the alternately preparation method of double-deck azobenzene/graphene composite energy-storage material, which is characterized in that as steps described below into
Row: graphene, the first azo benzene monomer and NaOH and evenly dispersed are added in the aqueous solution of methyl pyrrolidone, is protected in inertia
It is reacted under shield gas atmosphere, reaction temperature is 100-150 degrees Celsius, so that the first azo benzene monomer is covalently
It is grafted to the reaction site of graphene-structured, obtains the first azobenzene-graphene composite material；In the water of methyl pyrrolidone
Graphene, the second azo benzene monomer and NaOH and evenly dispersed are added in solution, is reacted under inert protective gas atmosphere,
Reaction temperature is 100-150 degrees Celsius, so that the second azo benzene monomer is covalently grafted to the reaction of graphene-structured
Site obtains the second azobenzene-graphene composite material；Finally by the first azobenzene-graphene composite material, the second azo
Benzene-graphene composite material is dispersed in water phase and is blended, and carries out Supramolecular self assembly using interaction of hydrogen bond,
Finally obtain target product alternately double-deck azo/graphene composite material；Wherein graphene uses sodium borohydride and sodium carbonate also
Former graphene oxide is graphene, so that damaged structure, fine and close hexatomic ring (phenyl ring) occurs in the benzene ring structure of composition graphene
There is the missing of carbon atom in structure, forms vacancy, and the grafting for two kinds of azo benzene monomers provides reaction site；First azobenzene list
Body is double carboxyl azobenzenes, and the second azo benzene monomer is pyrimidine azobenzene, the amino on two kinds of azo benzene monomers respectively with graphite
Alkene reaction site reaction, so that it is covalently keyed in graphene-structured.
4. the preparation method of alternately double-deck azobenzene/graphene composite energy-storage material according to claim 1, 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；Then it is dispersed in water again ultrasound is passed through.
5. the preparation method of alternately double-deck azobenzene/graphene composite energy-storage material according to claim 1, feature exist
In 20-30 mass parts graphene being added, each mass parts are 1mg, and the molar ratio of the first azo benzene monomer and sodium hydroxide is 1:
The molar ratio of (1-1.2), the second azo benzene monomer and sodium hydroxide is 1:(1-1.2).
6. the preparation method of alternately double-deck azobenzene/graphene composite energy-storage material according to claim 1, feature exist
In in the aqueous solution of methyl pyrrolidone, methyl pyrrolidone concentration is 0.3-0.9mg/mL.
7. the preparation method of alternately double-deck azobenzene/graphene composite energy-storage material according to claim 1, feature exist
In inert protective gas atmosphere is nitrogen, helium or argon gas.
8. the preparation method of alternately double-deck azobenzene/graphene composite energy-storage material according to claim 1, feature exist
In the first azo benzene monomer is double carboxyl azobenzenes, is prepared as steps described below: by 3,5 dicarboxyanylines, sodium nitrite
It is evenly dispersed in deionized water with sodium hydroxide, hydrochloric acid is added dropwise, ice bath reaction adds 3,5 dimethoxys after carrying out azo
Reaction obtains double carboxyl azobenzenes under inert protective gas atmosphere in aniline；Second azo benzene monomer is pyrimidine azobenzene, is pressed
It is prepared according to following step: 5- aminopyrimidine, sodium nitrite and sodium hydroxide is evenly dispersed in deionized water, salt is added dropwise
Acid, ice bath reaction add in 3,5 dimethoxyanilines after azo the reaction under inert protective gas atmosphere obtain it is phonetic
Pyridine azo.
9. the preparation method of alternately double-deck azobenzene/graphene composite energy-storage material according to claim 1, feature exist
In being carried out by the graft ratio and two kinds of azobenzene-graphene composite material blending ratio of two kinds of azo benzene monomers
The adjustment of composite property.
10. alternately double-deck azobenzene/graphene composite energy-storage material as described in claim 1 is preparing solar energy storage material
In application, which is characterized in that energy storage density reaches as high as 96-98% up to 140-160Wh/kg, isomerization rate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710833143.4A CN109503419A (en) | 2017-09-15 | 2017-09-15 | A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710833143.4A CN109503419A (en) | 2017-09-15 | 2017-09-15 | A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109503419A true CN109503419A (en) | 2019-03-22 |
Family
ID=65745036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710833143.4A Pending CN109503419A (en) | 2017-09-15 | 2017-09-15 | A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109503419A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111122431A (en) * | 2019-12-30 | 2020-05-08 | 清华大学 | Self-assembly model, preparation method thereof and self-assembly method of light-adjustable friction coefficient film |
| 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 |
| CN113173865A (en) * | 2021-03-12 | 2021-07-27 | 山西大同大学 | Graphene synergistic heat storage composite material driven by visible light 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 |
| CN105969321A (en) * | 2016-05-30 | 2016-09-28 | 天津大学 | Double-branch azobenzene/graphene energy storage material and preparing method |
| 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
- 2017-09-15 CN CN201710833143.4A patent/CN109503419A/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 |
| CN105969321A (en) * | 2016-05-30 | 2016-09-28 | 天津大学 | Double-branch azobenzene/graphene energy storage material and preparing method |
Non-Patent Citations (3)
| Title |
|---|
| JUNKAI HAN等: "Using multiple hydrogen bonding cross-linkers to access reversibly responsive three dimensional graphene oxide architecture", 《NANOSCALE》 * |
| 王东瑞: "石墨烯/偶氮杂化材料研究进展", 《中国科学：化学》 * |
| 罗文: "偶氮苯-石墨烯杂化材料的合成及其氢键调控分子储能研究", 《天津大学博士学位论文》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111122431A (en) * | 2019-12-30 | 2020-05-08 | 清华大学 | Self-assembly model, preparation method thereof and self-assembly method of light-adjustable friction coefficient film |
| CN111122431B (en) * | 2019-12-30 | 2021-06-22 | 清华大学 | Self-assembly model, preparation method thereof and self-assembly method of light-adjustable friction coefficient film |
| 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 |
| CN113173865A (en) * | 2021-03-12 | 2021-07-27 | 山西大同大学 | Graphene synergistic heat storage composite material driven by visible light and preparation method and application thereof |
| CN113173865B (en) * | 2021-03-12 | 2023-03-28 | 山西大同大学 | Graphene synergistic heat storage composite material driven by visible light and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Covalent organic frameworks: Design, synthesis, and performance for photocatalytic applications | |
| Sun et al. | Synthesis of particulate hierarchical tandem heterojunctions toward optimized photocatalytic hydrogen production | |
| Yadav et al. | Graphene–BODIPY as a photocatalyst in the photocatalytic–biocatalytic coupled system for solar fuel production from CO 2 | |
| Hu et al. | HKUST‐1 Derived Hollow C‐Cu2− xS Nanotube/g‐C3N4 Composites for Visible‐Light CO2 Photoreduction with H2O Vapor | |
| Han et al. | 0D CoP cocatalyst/2D g‐C3N4 nanosheets: an efficient photocatalyst for promoting photocatalytic hydrogen evolution | |
| Xu et al. | Montmorillonite-hybridized g-C3N4 composite modified by NiCoP cocatalyst for efficient visible-light-driven photocatalytic hydrogen evolution by dye-sensitization | |
| CN109503419A (en) | A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method | |
| CN102838085B (en) | High-capacity high-molecular polymer hydrogen storing material and preparation method thereof | |
| CN106966929A (en) | A kind of Linear Double branch azobenzene/graphene composite material and preparation method and application | |
| CN110586183B (en) | Method for preparing TiO by using supercritical carbon dioxide2Method for preparing/COF catalytic material | |
| CN112427045A (en) | CdS/g-C synthesized by hydrothermal method and having Z-shaped heterojunction3N4Preparation method of composite photocatalyst material | |
| CN107201214A (en) | A kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method | |
| Hayat et al. | A Targeted Review of Current Progress, Challenges and Future Perspective of g‐C3N4 based Hybrid Photocatalyst Toward Multidimensional Applications | |
| Prakash et al. | Strategic design of covalent organic frameworks (COFs) for photocatalytic hydrogen generation | |
| Shi et al. | Boosting photothermal-assisted photocatalytic water/seawater splitting into hydrogen based on greenhouse-induced photothermal effect | |
| Urbani et al. | Photoinduced Energy and Electron Transfer in Phenylethynyl‐Bridged Zinc Porphyrin–Oligothienylenevinylene–C60 Ensembles | |
| Xu et al. | The photocatalytic H2O2 production by metal-free photocatalysts under visible-light irradiation | |
| Cai et al. | Review on CeO2-based photocatalysts for photocatalytic reduction of CO2: progresses and perspectives | |
| Zhou et al. | Novelty All‐Inorganic Titanium‐Based Halide Perovskite for Highly Efficient Photocatalytic CO2 Conversion | |
| Baby et al. | Photoresponsive Carbon‐Azobenzene Hybrids: A Promising Material for Energy Devices | |
| CN112547125B (en) | CdS/NiPc photocatalyst for water photolysis and preparation method thereof | |
| CN109503420A (en) | A kind of dual graft azobenzene/graphene composite energy-storage material and preparation method | |
| CN108759119A (en) | Solar energy cascade energy storage device | |
| Chen et al. | Sustainable Energy Resources for Driving Methane Conversion | |
| CN105312090B (en) | One kind (C5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190322 |