CN107216267A - A kind of azobenzene grafting fullerene nano hybridization compound and preparation method - Google Patents
A kind of azobenzene grafting fullerene nano hybridization compound and preparation method Download PDFInfo
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- CN107216267A CN107216267A CN201710532659.5A CN201710532659A CN107216267A CN 107216267 A CN107216267 A CN 107216267A CN 201710532659 A CN201710532659 A CN 201710532659A CN 107216267 A CN107216267 A CN 107216267A
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- 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
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- 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
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Abstract
Fullerene nano hybridization compound is grafted the invention provides azobenzene of the one kind as shown in formula (I)：Wherein, FC is fullerene Cm, and m is the carbon number of fullerene, m=50~120；N=1~8；X1、X2、X3、X4The independent alkyl selected from H, C1~C3, the one or more in C1~C3 alkoxy and halogen atom；Y1、Y2、Y3One or more in the independent alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8.The polysubstituted azobenzene molecule that the present invention contains amino by one end grafts on fullerene surface and forms azobenzene grafting fullerene nano hybridization compound.This compound has heat endurance good, the characteristics of grafting rate is high；Simultaneously by strengthening intermolecular interaction, improve energy density and reply half-life period.
Description
Technical field
The present invention relates to technical field of energy material, fullerene nano hybridization chemical combination is grafted more particularly, to a kind of azobenzene
Thing and preparation method.
Background technology
With the development of global economy, energy crisis is on the rise.Research, development and utilization cleaning, the reproducible sun
The important channel that today's society solves energy crisis can be had become.
Azobenzene (Azobenzenes) is a class phenodiazine ene derivative, and an azo group (- N=N-), two are contained in centre
The hydrogen atom on side is replaced by two phenyl ring respectively, with trans (trans) and cis (cis) two kinds of configurations.Azobenzene system
Photo-isomerisable characteristic be by intramolecular-N=N- groups the external conditions such as light, heat effect under carry out cis-trans isomerization drawn
Rise.Illumination is carried out to azo group using the light beam of different wave length, its can be made reversible in two kinds of isomers of cis and trans
Between changed.Potentiality of the reversible photoisomerization reaction with storage solar energy of azobenzene molecule, but traditional azo
Benzene molecular has that unimolecule energy density is low and replys, and limits its application in light heat accumulation field.
1985, Curl et al. had found fullerene C first60, Huffman in 1991 et al. have found one kind can be with magnanimity system
Standby C60Method, thus expand the research boom of fullerene, including fullerene C28、C32、C60、C70、C80Deng.Fullerene has
Unique cage structure, electrophilic C=C keys can carry out addition reaction with free radical wherein in six-membered ring structure.Fullerene knot
Structure is stable, and with preferable catalytic, optical, superconductivity and heat endurance.
In the prior art, azobenzene has that grafting rate is low, energy density is low, stability is poor with fullerene nano composite material
Technological deficiency, limit its practical application in light energy storage field.Therefore, develop that a kind of grafting rate is high, energy density is high,
Replying the azobenzene grafting fullerene nano-hybrid material of long half time turns into those skilled in the art's urgent problem to be solved.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of azobenzene grafting fullerene nano hybridization material
Material, the azobenzene grafting fullerene nano-hybrid material grafting rate that the present invention is prepared is high, and energy density is high, reply half-life period
It is long.
Fullerene nano hybridization compound is grafted the invention provides azobenzene of the one kind as shown in formula (I)：
Wherein, FC is fullerene Cm, and m is the carbon number of fullerene, m=50~120；N=1~8；
X1、X2、X3、X4The independent alkyl selected from H, C1~C3, one kind in C1~C3 alkoxy and halogen atom or several
Kind；
Y1、Y2、Y3One kind in the independent alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8
Or it is several.
It is preferred that, the m is 60~90；N=1~6.
It is preferred that, the one or more in H, methyl, ethyl, methoxyl group, ethyoxyl, halogen atom of the X independences；
One kind or several in the alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C5 of Y independences
Kind.
The invention provides the preparation side that azobenzene of the one kind as shown in formula (I) is grafted fullerene nano hybridization compound
Method, including：
A) fullerene is pre-processed, the fullerene after being modified；
By the azobenzene diazotising of formula (II) structure, diazol is obtained；
B) by the fowler alkene reaction after diazol and modification, the azobenzene grafting fullerene nanometer as shown in formula (I) is obtained
Hybrid compounds；
Wherein, X1、X2、X3、X4The independent alkyl selected from H, C1~C3, one in C1~C3 alkoxy and halogen atom
Plant or several；
Y1、Y2、Y3One kind in the independent alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8
Or it is several.
It is preferred that, step A) the fullerene progress pretreatment is acidifying or uses surfactant modified.
It is preferred that, the acid of the acidifying is V (dense H2SO4)：V (dense HNO3)=(5~1):1；The surfactant is selected from
One kind in DTAB, neopelex, lauryl sodium sulfate and dodecyl sodium sulfate
Or it is several.
It is preferred that, step B) diazol and modification after fullerene mol ratio be (10~60):1.
It is preferred that, step B) reaction is specially：0~5 DEG C reaction 2~4h, be warming up to 25~35 DEG C reaction 12~
48h。
It is preferred that, step B) diazotising is specially：The azobenzene of formula (II) structure is reacted 1 in 0~5 DEG C of ice bath
~2h obtains diazol.
The invention provides a kind of photo-thermal fuel, as the compound or above-mentioned technical proposal described in including above-mentioned technical proposal
The compound that described preparation method is prepared is prepared.
Compared with prior art, the azobenzene the invention provides one kind as shown in formula (I) is grafted fullerene nano hybridization
Compound：Wherein, FC is fullerene Cm, and m is the carbon number of fullerene, m=50~120；N=1~8；X1、X2、X3、X4Solely
The vertical alkyl selected from H, C1~C3, the one or more in C1~C3 alkoxy and halogen atom；Y1、Y2、Y3Independent is selected from
One or more in H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8 alkyl.The present invention contains ammonia by one end
The polysubstituted azobenzene molecule of base grafts on fullerene surface formation azobenzene grafting fullerene nano hybridization compound, this chemical combination
Thing has heat endurance good, the characteristics of grafting rate is high；Simultaneously by strengthening intermolecular interaction, improve energy density and return
Multiple half-life period.
Brief description of the drawings
Fig. 1 is grafted the composition principle figure of fullerene nano-hybrid material for the azobenzene that the present invention is provided；
Fig. 2 is fullerene C in the embodiment of the present invention60FT-IR spectrograms；
Fig. 3 is the FT-IR spectrograms of 4- amino -2,6- dimethyl -4 '-carboxyl azobenzenes；
Fig. 4 is that 4- amino -2,6- dimethyl -4 '-carboxyl azobenzenes are grafted on fullerene C60On hybrid material FT-IR
Spectrogram.
Embodiment
Fullerene nano hybridization compound is grafted the invention provides azobenzene of the one kind as shown in formula (I)：
Wherein, FC is fullerene Cm, and m is the carbon number of fullerene, m=50~120；N=1~8；
X1、X2、X3、X4The independent alkyl selected from H, C1~C3, one kind in C1~C3 alkoxy and halogen atom or several
Kind；
Y1、Y2、Y3One kind in the independent alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8
Or it is several.
In the present invention, FC is fullerene, and the present invention is for the fullerene without limiting, and those skilled in the art are ripe
The fullerene known.The structure of fullerene is Cm, and wherein m is the carbon number of fullerene, m=50~120；It is preferred that, m=60~
90。
Wherein n is the number of the molecule of the azobenzene in grafting, n=1~8；It is preferred that, n=1~6.
Wherein, X1、X2、X3、X4The independent alkyl selected from H, C1~C3, one in C1~C3 alkoxy and halogen atom
Plant or several；X1、X2、X3、X4It is preferred that independent one kind or several in H, methyl, ethyl, methoxyl group, ethyoxyl, halogen atom
Kind；The halogen atom is preferably fluorine, chlorine, bromine or iodine.As X1、X2、X3、X4, can be with identical or not for the substituent on phenyl ring
Together.
Y1、Y2、Y3One kind in the independent alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8
Or it is several；It is preferred that, one kind in the alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C5 of Y independences
Or it is several；Most preferably, the one or more in H, hydroxyl, carboxyl, sulfonic group, nitro and amide groups of Y independences.As
Y1、Y2、Y3, can be with identical or different for the substituent on phenyl ring.
Fullerene nano hybridization compound is grafted the invention provides azobenzene of the one kind as shown in formula (I)：Wherein, FC is
Fullerene Cm, m are the carbon number of fullerene, m=50~120；N=1~8；X1、X2、X3、X4Independent is selected from H, C1~C3
Alkyl, the one or more in C1~C3 alkoxy and halogen atom；Y1、Y2、Y3Independent is selected from H, hydroxyl, carboxyl, sulfonic acid
One or more in base, nitro, amide groups and C1~C8 alkyl.The present invention is contained the polysubstituted azobenzene of amino by one end
Molecule grafts on fullerene surface formation azobenzene grafting fullerene nano hybridization compound, and this compound has heat endurance
It is good, the characteristics of grafting rate is high；Simultaneously by strengthening intermolecular interaction, improve energy density and reply half-life period.
The invention provides the preparation side that azobenzene of the one kind as shown in formula (I) is grafted fullerene nano hybridization compound
Method, including：
A) fullerene is pre-processed, the fullerene after being modified；
By the azobenzene diazotising of formula (II) structure, diazol is obtained；
B) by the fowler alkene reaction after diazol and modification, the azobenzene grafting fullerene nanometer as shown in formula (I) is obtained
Hybrid compounds；
Wherein, X1、X2、X3、X4The independent alkyl selected from H, C1~C3, one in C1~C3 alkoxy and halogen atom
Plant or several；
Y1、Y2、Y3One kind in the independent alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8
Or it is several.
The present invention first will be pre-processed fullerene, the fullerene after being modified.
Fullerene of the present invention carries out pretreatment for acidifying or using surfactant modified.
The concrete mode that the present invention is acidified to fullerene is without limiting, and those skilled in the art know；It is excellent
Choosing is specially：Weigh appropriate fullerene and be added to nitration mixture V (dense H2SO4)：V (dense HNO3)=(5~1):In 1 solution, room temperature surpasses
Sound disperses 2~4h, washing centrifugation.
Wherein, the acid of the acidifying is preferably V (dense H2SO4)：V (dense HNO3)=(5~1):1；More preferably V is (dense
H2SO4)：V (dense HNO3)=(4~1):1；Most preferably V (dense H2SO4)：V (dense HNO3)=(4~2):1.
It is preferably to wash to neutrality after acidifying；Concrete mode of the invention for the washing is without limiting, this area
Known to technical staff.
The present invention uses surfactant modified concrete mode without limiting fullerene, and those skilled in the art are ripe
Know；It is preferred that being specially：Weigh appropriate fullerene and be added to the surfactant water that mass fraction is 0.1%~2%
In solution, 2~4h of room temperature ultrasonic disperse formation solution.
Surfactant of the present invention is preferably selected from DTAB, neopelex, ten
One or more in sodium dialkyl sulfate and dodecyl sodium sulfate；More preferably neopelex, dodecyl
One or more in sodium sulphate and dodecyl sodium sulfate；Most preferably lauryl sodium sulfate or dodecyl sodium sulfate.
The mass concentration of surfactant of the present invention is preferably 0.1%~2%；More preferably 0.5%~1.5%.
By the azobenzene diazotising of formula (II) structure, diazol is obtained.
Wherein, X1、X2、X3、X4The independent alkyl selected from H, C1~C3, one in C1~C3 alkoxy and halogen atom
Plant or several；X1、X2、X3、X4It is preferred that independent one kind or several in H, methyl, ethyl, methoxyl group, ethyoxyl, halogen atom
Kind；The halogen atom is preferably fluorine, chlorine, bromine or iodine.As X1、X2、X3、X4, can be with identical or not for the substituent on phenyl ring
Together.
Y1、Y2、Y3One kind in the independent alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8
Or it is several；It is preferred that, one kind in the alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C5 of Y independences
Or it is several；Most preferably, the one or more in H, hydroxyl, carboxyl, sulfonic group, nitro and amide groups of Y independences.As
Y1、Y2、Y3, can be with identical or different for the substituent on phenyl ring.
Diazotising of the present invention is preferably specially the azo for using natrium nitrosum and hydrochloric acid or sulfuric acid to formula (II) structure
Benzene diazotising.
The concentration of wherein described hydrochloric acid or sulfuric acid is preferably 0.3~0.7mol/L；More preferably 0.5~0.6mol/L.
The diazotizing condition is preferably specially：The azobenzene of formula (II) structure is reacted 1 in 0~5 DEG C of ice bath~
2h obtains diazol.The azobenzene of formula (II) structure is more preferably reacted into 1~1.5h in 0~4 DEG C of ice bath and obtains diazol.
After fullerene and diazol after being modified, the fowler alkene reaction after diazol and modification is obtained such as formula (I)
Shown azobenzene grafting fullerene nano hybridization compound.
Wherein, the mol ratio of the diazol and the fullerene after modification is preferably (10~60):1；More preferably (15~
55):1；Most preferably (20~50):1.
The reaction is preferably specially：0~5 DEG C of 2~4h of reaction, is warming up to 25~35 DEG C of 12~48h of reaction；More preferably have
Body is：2~3h is reacted in 0~4 DEG C of ice bath, 25~35 DEG C of 12~36h of reaction are warming up to.
After reaction, preferably product is filtered, cleaned with solvent, until filtrate through UV-Vis spectral detections does not have azobenzene point
The characteristic absorption peak of son；Then vacuum drying obtains product.
Wherein described solvent is preferably the one or more in deionized water, acetone and DMF；The vacuum drying temperature
Preferably 30~50 DEG C；More preferably 35~40 DEG C.The vacuum drying time is preferably 20~30h；Preferably 20~
24h。
The composition principle figure for the azobenzene grafting fullerene nano hybridization compound that the present invention is provided is as shown in figure 1, this hair
Fullerene C in bright embodiment60FT-IR spectrograms it is as shown in Figure 2.
The invention provides a kind of photo-thermal fuel, as the compound or above-mentioned technical proposal described in including above-mentioned technical proposal
The compound that described preparation method is prepared is prepared.
Compound of the present invention is used as luminous energy conversion and storage material in photo-thermal fuel.
Present invention also offers the compound described in above-mentioned technical proposal or the synthetic method system described in above-mentioned technical proposal
Application of the standby obtained compound in photo-thermal fuel is prepared.
Fullerene nano hybridization chemical combination is grafted the invention provides the azobenzene the invention provides one kind as shown in formula (I)
The preparation method of thing, including：A) fullerene is pre-processed, the fullerene after being modified；By the azo of formula (II) structure
Benzene diazotising, obtains diazol；B) by the fowler alkene reaction after diazol and modification, obtain the azobenzene as shown in formula (I) and connect
Branch fullerene nano hybridization compound；Wherein, X1、X2、X3、X4The independent alkyl selected from H, C1~C3, C1~C3 alkoxy
With the one or more in halogen atom；Y1、Y2、Y3It is independent selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~
One or more in C8 alkyl.The present invention first passes through pretreatment, and fullerene is changed into water-soluble easily dispersed substance, then will
The polysubstituted azobenzene molecule that amino is contained in one end grafts on fullerene surface formation azobenzene grafting fullerene nano hybridization
Compound.The present invention can need not react in organic solvent and grafting rate is high.The thermally-stabilised good, energy of compound obtained simultaneously is close
Degree is high, reply long half time.
In order to further illustrate the present invention, fullerene nanometer is grafted to the azobenzene that the present invention is provided with reference to embodiments
Hybrid compounds are described in detail.
Embodiment 1
Weigh 1.3450g 4- amino -2,6- dimethyl -4 '-carboxyl azobenzenes, 0.2000g NaOH, 0.3450g's
NaNO2In the deionized water for dissolving in 60mL.The burning for filling 50mL HCI (0.5mol/L) solution is slowly added into after stirring again
In cup, it is placed in reaction 1h in ice bath and obtains diazonium salt solution.Then the acidified C of 120mL are slowly dropped into60(1mg/mL) solution
In, 2h is reacted in continuation in ice bath, is then warmed to room temperature reaction 12h.Product is filtered, and with deionized water, acetone and
DMF is cleaned repeatedly, until filtrate through UV-vis spectral detections does not have a characteristic absorption peak of azobenzene molecule, 35 DEG C of vacuum drying
24h obtains product AZO-1-C60.This product energies density improves about 70%~170% compared to AZO molecules, replys half-life period and improves
3~5 orders of magnitude, while keeping excellent cyclical stability during 30~50 repetition light energy storage/heat releases..
Embodiment 2
Weigh 1.2050g 4- amino -2,6- -4 '-hydroxyazobenzenes of dimethyl, 0.2000g NaOH, 0.3450g's
NaNO2In the deionized water for dissolving in 60mL.The burning for filling 50mL HCI (0.5mol/L) solution is slowly added into after stirring again
In cup, it is placed in reaction 1h in ice bath and obtains diazonium salt solution.Then it is slowly dropped into what 120mL was modified by lauryl sodium sulfate
C60In (1mg/mL) solution, 2h is reacted in continuation in ice bath, is then warmed to room temperature reaction 24h.Product is filtered, and spent
Ionized water, acetone and DMF are cleaned repeatedly, until filtrate through UV-vis spectral detections does not have the characteristic absorption peak of azobenzene molecule,
35 DEG C of vacuum drying 24h obtain product AZO-2-C60.This product energies density improves about 60%~140% compared to AZO molecules, returns
Multiple half-life period improves 3~4 orders of magnitude, while keeping excellent circulation steady during 30~50 repetition light energy storage/heat releases
It is qualitative.
Embodiment 3
Weigh 1.5250g 4- amino -2,6- dimethyl -4 '-sulfonic group azobenzenes, 0.2000g NaOH, 0.3450g
NaNO2In the deionized water for dissolving in 60mL.It is slowly added into again after stirring and fills 50mL HCI (0.5mol/L) solution
In beaker, it is placed in reaction 1h in ice bath and obtains diazonium salt solution.Then the acidified C of 120mL are slowly dropped into70(1mg/mL) is molten
In liquid, 3h is reacted in continuation in ice bath, is then warmed to room temperature reaction 36h.Product is filtered, and with deionized water, acetone
Cleaned repeatedly with DMF, until filtrate through UV-vis spectral detections does not have a characteristic absorption peak of azobenzene molecule, 35 DEG C of vacuum drying
24h obtains product AZO-3-C70.This product energies density improves about 60%~130% compared to AZO molecules, replys half-life period and improves
3~4 orders of magnitude, while keeping excellent cyclical stability during 30~50 repetition light energy storage/heat releases.
Embodiment 4
Weigh 1.5050g 4- amino -2,6- dimethoxy-4 ' '-carboxyl azobenzene, 0.2000g NaOH, 0.3450g
NaNO2In the deionized water for dissolving in 60mL.It is slowly added into again after stirring and fills 50mL HCI (0.5mol/L) solution
In beaker, it is placed in reaction 1h in ice bath and obtains diazonium salt solution.Then 120mL is slowly dropped into modify by lauryl sodium sulfate
C70In (1mg/mL) solution, 2h is reacted in continuation in ice bath, is then warmed to room temperature reaction 12h.Product is filtered, is used in combination
Deionized water, acetone and DMF are cleaned repeatedly, until filtrate through UV-vis spectral detections does not have the characteristic absorption of azobenzene molecule
Peak, 35 DEG C of vacuum drying 24h obtain product AZO-4-C70.This product energies density compared to AZO molecules improve about 70%~
150%, reply half-life period and improve 3~5 orders of magnitude, while keeping excellent during 30~50 repetition light energy storage/heat releases
Cyclical stability.
Embodiment 5
Weigh 1.5650g 4- amino -2,6- dimethyl -3 ', 5 '-dicarboxyl azobenzene, 0.2000g NaOH,
0.3450g NaNO2In the deionized water for dissolving in 60mL.It is slowly added into again after stirring and fills 50mL HCI (0.5mol/L)
In the beaker of solution, it is placed in reaction 1h in ice bath and obtains diazonium salt solution.Then the acidified C of 120mL are slowly dropped into90
In (1mg/mL) solution, 2h is reacted in continuation in ice bath, is then warmed to room temperature reaction 24h.Product is filtered, and spend from
Sub- water, acetone and DMF are cleaned repeatedly, until filtrate through UV-vis spectral detections does not have the characteristic absorption peak of azobenzene molecule, 35
DEG C vacuum drying 24h obtain product AZO-5-C90.This product energies density improves about 90%~220% compared to AZO molecules, replys
Half-life period improves 3~5 orders of magnitude, while keeping excellent stable circulation during 30~50 repetition light energy storage/heat releases
Property.
Embodiment 6
Weigh 1.6450g 4- amino -2,6- dimethoxy -2 ', 6 '-dimethyl azobenzene, 0.2000g NaOH,
0.3450g NaNO2In the deionized water for dissolving in 60mL.It is slowly added into again after stirring and fills 50mLHCI (0.5mol/L)
In the beaker of solution, it is placed in reaction 1h in ice bath and obtains diazonium salt solution.Then it is slowly dropped into 120mL and passes through dodecyl sodium sulfonate
The C of sodium modification90In (1mg/mL) solution, 3h is reacted in continuation in ice bath, is then warmed to room temperature reaction 36h.Product was carried out
Filter, and is cleaned repeatedly with deionized water, acetone and DMF, until filtrate through UV-vis spectral detections does not have the spy of azobenzene molecule
Absworption peak is levied, 35 DEG C of vacuum drying 24h obtain product AZO-6-C90.This product energies density improves about 50% compared to AZO molecules
~130%, reply half-life period and improve 2~4 orders of magnitude, while keeping excellent during 30~50 repetition light energy storage/heat releases
Different cyclical stability.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of azobenzene grafting fullerene nano hybridization compound as shown in formula (I)：
Wherein, FC is fullerene Cm, and m is the carbon number of fullerene, m=50~120；N=1~8；
X1、X2、X3、X4The independent alkyl selected from H, C1~C3, the one or more in C1~C3 alkoxy and halogen atom；
Y1、Y2、Y3One kind or several in the independent alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8
Kind.
2. compound according to claim 1, it is characterised in that the m is 60~90；N=1~6.
3. compound according to claim 1, it is characterised in that the X independences selected from H, methyl, ethyl, methoxyl group,
One or more in ethyoxyl, halogen atom；
One or more in the alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C5 of Y independences.
4. a kind of azobenzene as shown in formula (I) is grafted the preparation method of fullerene nano hybridization compound, it is characterised in that bag
Include：
A) fullerene is pre-processed, the fullerene after being modified；
By the azobenzene diazotising of formula (II) structure, diazol is obtained；
B) by the fowler alkene reaction after diazol and modification, the azobenzene grafting fullerene nano hybridization as shown in formula (I) is obtained
Compound；
Wherein, X1、X2、X3、X4The independent alkyl selected from H, C1~C3, one kind in C1~C3 alkoxy and halogen atom or several
Kind；
Y1、Y2、Y3One kind or several in the independent alkyl selected from H, hydroxyl, carboxyl, sulfonic group, nitro, amide groups and C1~C8
Kind.
5. preparation method according to claim 4, it is characterised in that step A) to carry out pretreatment be acidifying to the fullerene
Or using surfactant modified.
6. preparation method according to claim 5, it is characterised in that the acid of the acidifying is V (dense H2SO4)：V is (dense
HNO3)=(5~1):1；The surfactant is selected from DTAB, neopelex, 12
One or more in sodium alkyl sulfate and dodecyl sodium sulfate.
7. preparation method according to claim 4, it is characterised in that step B) fullerene after the diazol and modification
Mol ratio be (10~60):1.
8. preparation method according to claim 4, it is characterised in that step B) reaction is specially：0~5 DEG C of reaction 2
~4h, is warming up to 25~35 DEG C of 12~48h of reaction.
9. preparation method according to claim 4, it is characterised in that step B) diazotising is specially：By formula (II)
The azobenzene of structure reacts 1~2h in 0~5 DEG C of ice bath and obtains diazol.
10. a kind of photo-thermal cell, it is characterised in that will as the compound or right described in including claims 1 to 3 any one
The compound synthesized by the method described in 4~9 any one is asked to prepare.
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| 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 |
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