CN106744813A - A kind of method that fullerene crystal is cultivated in supermolecular gel medium - Google Patents
A kind of method that fullerene crystal is cultivated in supermolecular gel medium Download PDFInfo
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Abstract
The invention discloses a kind of method that fullerene crystal is cultivated in supermolecular gel medium, the method is with molecular gel as matrix, the influence that the unfavorable factors such as solvent convection effect, crystal subsidence effect, container wall effect that traditional method for crystallising is difficult to avoid that are crystallized to fullerene can be effectively prevented from, the fullerene crystal of high-quality can be turned out by adding suitable precipitating reagent.The features such as gel-type vehicle used by the present invention has the high grade of transparency, stimulating responsive, is capable of achieving the visualization of crystal growth and effectively realizes that crystal is separated with gel media.Using method for crystallising of the present invention, can fast culture goes out to arrange high-sequential, diameter is evenly distributed overlength C60Fiber, its length diameter ratio may be up to 23000, and C60The length of crystal fibre can obtain Effective Regulation by changing the height of fullerene gel.Method for crystallising of the present invention can not only realize the crystallization of fullerene, it is also possible to carry out other organic semi-conductor crystallizations.
Description
Technical field
The invention belongs to the preparing technical field of fullerene crystal, and in particular to one kind is cultivated in supermolecular gel medium
The method of fullerene crystal.
Background technology
Fullerene is a class novel globular molecule, is formed by covalent bonding by simple carbon atom, is after graphite, gold
After hard rock, the elemental crystal form of the third carbon presence of discovery.In miscellaneous fullerene family, people couple
C60Research it is the most deep, it is the simple stable molecule combined to form by carbon atom, with 60 summits and 32 faces, wherein
12 is regular pentagon, and 20 is regular hexagon, and its relative molecular mass is about 720, can be rated as stability in fullerene family
Highest is a kind of.Fullerene makes it have physics, the chemical property of uniqueness due to its own unique molecular structure.Thus, it is rich
The research for strangling alkene and its derivative has become one of important focus of current scientist's research.
Fullerene molecule can act on the crystalline solid for being self-assembly of different-shape, including fibre by intermolecular pi-pi accumulation
Dimension shape (J.Am.Chem.Soc., 2008,130,2527-2534), bar-shaped (J.Mater.Chem., 2008,18,328-332),
Tubulose (Chem.Mater., 2008,20,1667-1669), sheet (J.Am.Chem.Soc., 2007,129,13816-
13817), starlike (Carbon, 2013,64,370-376), bowl-shape (Chem.Eur.J., 2011,17,4921-4926) etc..Its
The middle dilute nanofiber of fowler is in solar cell, crystal diode, field-effect transistor, photoelectric sensor, superconductor, hydrogen storage
The fields such as material, catalysis material have a wide range of applications, and cause the extensive concern of people【Representational bibliography】.So far
Untill the present, preparing the method for fullerene crystal mainly has vapour deposition process (J.Phys.Chem.Solids., 2000,61,1047-
1050), mesoporous lamina membranacea method (Chem.Mater., 2008,20,1667-1669), solvent evaporation method (J.Am.Chem.Soc.,
2008,130,2527-2534), rapid precipitation method (CrystEngComm, 2012,14,7787-7791), liquid-liquid interface precipitation
Method (J.Am.Chem.Soc., 2009,131,6372-6373), gel secondary solvent volatility process (Chem.Eur.J., 2012,18,
14954-14956), gel auxiliary energy matches crystallisation (Sci.Advances, 2016,2 (9), e1600142) etc..Wherein
The liquid-liquid interface precipitation method are current a kind of the most widely used methods, but because the liquid-liquid interface precipitation method cannot eliminate molten
The influence of agent convection effect, crystal subsidence effect, container wall effect etc., cause that experimental repeatability is poor, fiber distribution is at random,
Distribution of fiber diameters is uneven, length is uncontrollable etc..In addition, existing method cannot also realize that fullerene growth length is effectively controllable
And the growth of overlength crystal, so, a kind of new effective fullerene method for crystallising of exploitation is particularly important.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of super with the high grade of transparency and with stimuli responsive characteristic
Molecular gel is the method for matrix culture fullerene crystal.
The technical scheme that solution above-mentioned technical problem is used is made up of following step：
1st, fullerene solution is prepared
Fullerene is dissolved in solvent, fullerene solution is configured to.
2nd, the gel containing fullerene is prepared
By in fullerene solution and gelling agent addition vial, heating is completely dissolved gelling agent, and natural cooling makes its shape
Into the gel containing fullerene.
3rd, the crystallization of fullerene
The crystallization of fullerene is carried out using any one in following method for crystallising I~III：
Method for crystallising I：Precipitating reagent is added on the gel of step (2) containing fullerene, bottleneck is sealed, be subsequently placed in perseverance
Crystallized in warm reaction chamber.
Method for crystallising II：By in gelling agent addition solvent, heating is completely dissolved gelling agent, and step is added it to while hot
(2) on the gel containing fullerene, natural cooling makes it that one layer of Blank gel cushion is formed on the gel containing fullerene,
Precipitating reagent is added on the buffer layer, bottleneck is sealed, be subsequently placed in isothermal reaction case and crystallized.
Method for crystallising III：The vial bottleneck of the gel of step (2) containing fullerene is sealed with aluminium-foil paper, and in aluminium
Upper aperture is pricked on foil paper, is then put it into the carboy for filling precipitating reagent, seal carboy bottleneck, be placed in constant temperature anti-
Answer in case and crystallized.
4th, fullerene crystal is separated
After terminating, by vial, solution is suctioned out at the middle and upper levels, is subsequently adding methyl alcohol destruction gel, takes out fullerene brilliant
Body, dries after being cleaned up repeatedly with methyl alcohol.
Above-mentioned gelling agent is any one in following gel a~j
In wherein gelling agent f, m=2 or 4, and during m=2, gelling agent f is LL or DD configurations, during m=4, gelling agent f is LL
Configuration；In gelling agent g, n=2,3 or 4；A is represented in gelling agent hOrIn gelling agent i R represent H orGelling agent j is DD configurations.
Above-mentioned solvent is appointing in benzene, toluene, ortho-xylene, meta-xylene, paraxylene, mesitylene, styrene
Meaning is a kind of.
Above-mentioned precipitating reagent is any one in tetrahydrofuran, acetone, acetonitrile, dichloromethane, hexamethylene, n-hexane solvent
Kind or two kinds of mixture.
In above-mentioned steps 1, the concentration of the fullerene solution being preferably formulated to is 0.1~10.0mg/mL.
In above-mentioned rapid 2, the concentration of gelling agent is 0.1~50mg/mL, preferably gel in the gel containing fullerene
Concentration be 10~30mg/mL.
In above-mentioned steps 3, the precipitating reagent volume that the method for crystallising I and method for crystallising II is added is solidifying containing fullerene
0.5~5 times of colloid product, preferably precipitating reagent volume is 1~2 times of the gel volume containing fullerene；The method for crystallising III
The precipitating reagent volume of addition is 1~5 times of the gel volume containing fullerene, and preferably precipitating reagent volume is solidifying containing fullerene
2~3 times of colloid product.
In above-mentioned steps 3, the concentration of gelling agent is 10 in the Blank gel cushion that preferably described method for crystallising II is formed
~30mg/mL, the height of cushion is 0.1~2.0cm.
In above-mentioned steps 3, the crystallization temperature of preferably described method for crystallising I~III is 0~30 DEG C, and crystallization time is 2~20
My god.
Compared with prior art, the invention has the advantages that：
1st, the present invention carries out fullerene (such as C in gel media60、C70Deng) crystallization, traditional crystallization can be effectively prevented from
What the unfavorable factors such as solvent convection effect, crystal subsidence effect, container wall effect that method is difficult to avoid that were crystallized to fullerene
Influence, can turn out the fullerene crystal of high-quality.
2nd, the features such as gel used by the present invention has the high grade of transparency, stimulating responsive, the separation to crystal brings pole
Big advantage, and whole crystallization process can realize visualization.
3rd, the gel used by the present invention is to C60The booster action of crystallization, can turn out arrangement high-sequential, fibre diameter
Be evenly distributed, the overlength C that length is controllable60Fiber, its length diameter ratio can reach 23000, the not disclosed report of the method, institute
Obtain overlength C60Crystal fibre is that other method cannot be realized.
4th, method for crystallising of the present invention is simple to operate, and crystal is easily prepared, and can not only realize the crystallization of fullerene, it is also possible to
Carry out other organic semi-conductor crystallizations.
Brief description of the drawings
Fig. 1 is the C that embodiment 1 is obtained60The photo of crystal.
Fig. 2 is the C that embodiment 2 is obtained60The photo of crystal.
Fig. 3 is the C that embodiment 3 is obtained60The photo of crystal.
Fig. 4 is the C that embodiment 4 is obtained60The photo of crystal.
Fig. 5 is the C that embodiment 4 is obtained60The scanning electron microscope (SEM) photograph of crystal.
Fig. 6 is the C that embodiment 5 is obtained60The photo of crystal.
Fig. 7 is the C that embodiment 5 is obtained60The scanning electron microscope (SEM) photograph of crystal.
Fig. 8 is the C that embodiment 6 is obtained60The photo of crystal.
Fig. 9 is the C that embodiment 6 is obtained60The scanning electron microscope (SEM) photograph of crystal.
Figure 10 is the C that embodiment 10 is obtained60The photo of crystal.
Figure 11 is the C that embodiment 10 is obtained60The scanning electron microscope (SEM) photograph of crystal.
Figure 12 is the C that embodiment 11 is obtained60The photo of crystal.
Figure 13 is the C that embodiment 11 is obtained60The scanning electron microscope (SEM) photograph of crystal.
Figure 14 is the C that embodiment 12 is obtained60The photo of crystal.
Figure 15 is the C that embodiment 14 is obtained60The photo of crystal.
Figure 16 is the C that embodiment 14 is obtained60The enlarged photograph of crystal.
Figure 17 is the C that embodiment 14 is obtained60The scanning electron microscope (SEM) photograph of crystal.
Figure 18 is the hexagonal columnar C that embodiment 14 is obtained60The scanning electron microscope (SEM) photograph of crystal.
Figure 19 is the C that embodiment 14 is obtained60The transmission electron microscope and electron diffraction diagram of crystal.
Figure 20 is original C60The C that powder and embodiment 14 are obtained60The XRD of crystal.
Figure 21 is the C that embodiment 14 is obtained60Crystal be vacuum dried at different temperatures after XRD.
Figure 22 is original C60The C that powder, embodiment 14 are obtained60Crystal and the C after drying 4 hours at 120 DEG C60It is brilliant
The INFRARED ABSORPTION figure of body.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1st, C is prepared60Solution
By 0.035g C60Powder is dissolved in 25mL meta-xylenes, is configured to the C that concentration is 1.4mg/mL60Solution.
2nd, prepare and contain C60Gel
By in 0.02g gelling agents e addition vials, the C that 1mL concentration is 1.4mg/mL is subsequently adding60Solution, heating makes glue
Solidifying agent e is completely dissolved, and natural cooling is formed it into and contains C60Gel.
3、C60Crystallization
Containing C60Gel on add 1mL acetone as precipitating reagent, after vial bottleneck is sealed, be placed in isothermal reaction
20 DEG C crystallize 2 days in case.As shown in figure 1, forming dendritic C in gel60Crystal.
4th, C is separated60Crystal
After terminating, the solution in vial is outwelled, be subsequently adding methyl alcohol destruction gel, take out C60Crystal, uses first
Alcohol is cleaned up, and is preserved after drying.
Embodiment 2
In embodiment 1, acetone used is replaced with isometric acetonitrile, and other steps are same as Example 1, obtain rod
The C of shape60Crystal (see Fig. 2).
Embodiment 3
1st, C is prepared60Solution
By 0.035g C60It is dissolved in 25mL meta-xylenes, is configured to the C that concentration is 1.4mg/mL60Solution.
2nd, prepare and contain C60Gel
By in 0.02g gelling agents e addition vials, the C that 1mL concentration is 1.4mg/mL is subsequently adding60Solution, heating makes glue
Solidifying agent e is completely dissolved, and natural cooling is formed it into and contains C60Gel.
3、C60Crystallization
By in 0.02g gel e, 1mL meta-xylene addition vial, heating is completely dissolved gelling agent e, then while hot
Add it to contain C60Gel on, natural cooling makes it contain C60Gel on form one layer of 1.0cm blank high and coagulate
Glue cushion, adds 1mL acetonitriles as precipitating reagent on the buffer layer, after vial bottleneck is sealed, is placed in isothermal reaction case
20 DEG C crystallize 3 days.As shown in figure 3, forming fibrous C in gel60Crystal.
4th, C is separated60Crystal
After terminating, the solution in vial is drawn and is finished, be subsequently adding methyl alcohol destruction gel, take out C60Crystal,
Cleaned up with methyl alcohol, preserved after drying.
Embodiment 4
1st, C is prepared60Solution
By 0.035g C60It is dissolved in 25mL meta-xylenes, is configured to the C that concentration is 1.4mg/mL60Solution.
2nd, prepare and contain C60Gel
By in 0.01g gelling agents e addition vials, the C that 1mL concentration is 1.4mg/mL is subsequently adding60Solution, heating makes glue
Solidifying agent e is completely dissolved, and natural cooling is formed it into and contains C60Gel.
3、C60Crystallization
Vial bottleneck containing fullerene gel is sealed with aluminium-foil paper, and aperture is pricked on aluminium-foil paper, then will
It is put into the carboy equipped with 3mL acetone, seals carboy bottleneck, is placed in isothermal reaction case 25 DEG C and is crystallized 5 days.Such as
Shown in Fig. 4, a large amount of threadiness C are formed in gel60Crystal.
4th, C is separated60Crystal
After terminating, the solution in vial is drawn completely or outwelled, be subsequently adding methyl alcohol destruction gel, take out C60
Crystal, is cleaned up with methyl alcohol, is preserved after drying.ESEM shows, gained C60Crystal is the threadiness (see Fig. 5) of rule.
Embodiment 5
In example 4, acetone used is replaced with isometric acetonitrile, and other steps are same as Example 4, obtain rod
The C of shape60Crystal (see Fig. 6), ESEM shows the C60Crystal is made up of (see Fig. 7) less irregular fiber.
Embodiment 6
In example 4, acetone used is replaced with isometric tetrahydrofuran, and other steps are same as Example 4, obtain
To the C of tufted60Crystal (see Fig. 8), ESEM shows the C60Crystal is corynebacterium structure (see Fig. 9).
Embodiment 7
In example 4, the gelling agent a of gelling agent e equivalent used is replaced, and other steps are same as Example 4, obtain
To C60Crystal.
Embodiment 8
In example 4, the gelling agent d of gelling agent e equivalent used is replaced, and other steps are same as Example 4, obtain
To C60Crystal.
Embodiment 9
In example 4, the gelling agent j of gelling agent e equivalent used is replaced, and other steps are same as Example 4, obtain
To C60Crystal.
Embodiment 10
1st, C is prepared60Solution
By 0.035g C60It is dissolved in 25mL paraxylene, is configured to the C that concentration is 1.4mg/mL60Solution.
2nd, prepare and contain C60Gel
By in 0.01g gelling agents e addition vials, the C that 1mL concentration is 1.4mg/mL is subsequently adding60Solution, heating makes glue
Solidifying agent e is completely dissolved, and natural cooling is formed it into and contains C60Gel.
3、C60Crystallization
Vial bottleneck containing fullerene gel is sealed with aluminium-foil paper, and aperture is pricked on aluminium-foil paper, then will
It is put into the carboy equipped with 3mL acetonitriles, seals carboy bottleneck, is placed in isothermal reaction case 25 DEG C and is crystallized 5 days.Such as
Shown in Figure 10, the C of sheet is formed in gel60Crystal.
4th, C is separated60Crystal
After terminating, the solution in vial is outwelled, be subsequently adding methyl alcohol destruction gel, take out C60Crystal, uses first
Alcohol is cleaned up, and is preserved after drying.ESEM shows the C60Crystal is sheet (see Figure 11).
Embodiment 11
1st, C is prepared60Solution
By 0.035g C60It is dissolved in 25mL benzene, is configured to the C that concentration is 1.4mg/mL60Solution.
2nd, prepare and contain C60Gel
By in 0.01g gelling agents e addition vials, the C that 1mL concentration is 1.4mg/mL is subsequently adding60Solution, heating makes glue
Solidifying agent e is completely dissolved, and natural cooling is formed it into and contains C60Gel.
3、C60Crystallization
Vial bottleneck containing fullerene gel is sealed with aluminium-foil paper, and aperture is pricked on aluminium-foil paper, then will
It is put into the carboy equipped with 3mL tetrahydrofurans, seals carboy bottleneck, is placed in 25 DEG C of crystallizations 5 in isothermal reaction case
My god.As shown in figure 12, irregular C is formed in gel60Crystal.
4th, C is separated60Crystal
After terminating, the solution in vial is outwelled, be subsequently adding methyl alcohol destruction gel, take out C60Crystal, uses first
Alcohol is cleaned up, and is preserved after drying.ESEM shows the C60Crystal is porous irregular shape (see Figure 13).
Embodiment 12
1st, C is prepared60Solution
By 0.0275g C60It is dissolved in 25mL mesitylene, is configured to the C that concentration is 1.1mg/mL60Solution.
2nd, prepare and contain C60Gel
By in 0.02g gelling agents e addition vials, the C that 1mL concentration is 1.1mg/mL is subsequently adding60Solution, heating makes glue
Solidifying agent e is completely dissolved, and natural cooling is formed it into and contains C60Gel.
3、C60Crystallization
Vial bottleneck containing fullerene gel is sealed with aluminium-foil paper, and aperture is pricked on aluminium-foil paper, then will
It is put into the carboy equipped with 3mL acetonitriles, seals carboy bottleneck, is placed in isothermal reaction case 25 DEG C and is crystallized 5 days.Such as
Shown in Figure 14, the C of branch-like is formed in gel60Crystal.
4th, C is separated60Crystal
After terminating, the solution in vial is outwelled, be subsequently adding methyl alcohol destruction gel, take out C60Crystal, uses first
Alcohol is cleaned up, and is preserved after drying.
Embodiment 13
1st, C is prepared70Solution
By 0.035g C70It is dissolved in 25mL meta-xylenes, is configured to the C that concentration is 1.4mg/mL70Solution.
2nd, prepare and contain C70Gel
By in 0.02g gelling agents e addition vials, the C that 1mL concentration is 1.4mg/mL is subsequently adding70Solution, heating makes glue
Solidifying agent e is completely dissolved, and natural cooling is formed it into and contains C70Gel.
3、C70Crystallization
Vial bottleneck containing fullerene gel is sealed with aluminium-foil paper, and aperture is pricked on aluminium-foil paper, then will
It is put into the carboy equipped with 3mL acetonitriles, seals carboy bottleneck, is placed in isothermal reaction case 25 DEG C and is crystallized 5 days.
4th, C is separated70Crystal
After terminating, the solution in vial is outwelled, be subsequently adding methyl alcohol destruction gel, take out C70Crystal, uses first
Alcohol is cleaned up, and is preserved after drying.
Embodiment 14
1st, C is prepared60Solution
By 0.14g C60It is dissolved in 100mL meta-xylenes, is configured to the C that concentration is 1.4mg/mL60Solution.
2nd, prepare and contain C60Gel
By in 0.05g gelling agents e addition vials, the C that 25mL concentration is 1.4mg/mL is subsequently adding60Solution, heating makes
Gelling agent e is completely dissolved, and natural cooling is formed it into and contains C60Gel.
3、C60Crystallization
By in 0.04g gel e, 2mL meta-xylene addition vial, heating is completely dissolved gelling agent e, then while hot
Add it to contain C60Gel on, natural cooling makes it contain C60Gel on formed a layer height be 1.0cm sky
White gel cushion, adds 25mL acetonitriles as precipitating reagent on the buffer layer, after vial bottleneck is sealed, is placed in isothermal reaction
25 DEG C crystallize 5 days in case.As shown in figure 15, fibrous C is formed in gel60Crystal.The photo of amplification shows fibrous
C60Crystal is distributed in order in gel, pattern rule (see Figure 16).
4th, C is separated60Crystal
After terminating, the solution in vial is outwelled, be subsequently adding methyl alcohol destruction gel, take out C60Crystal, uses first
Alcohol is cleaned up, and is preserved after drying.ESEM show its fiber alignment in order, diameter be evenly distributed (see Figure 17), microcosmic shape
Looks are hexagonal columnar (see Figure 18).Transmission electron microscope and electronic diffraction display C60Fiber is hexagonal closs packing structure (see Figure 19).Figure
20 is original C60Powder and C60The XRD of fiber, shows C60Fiber is the hexagonal closs packing knot of meta-xylene solvation
Structure.As shown in figure 21, with the rising of drying temperature, the C of solvation60Crystal is gradually changed into the center of area by hexagonal closs packing structure
Cubic closest packing structure.As shown in figure 22, C60Raw material has 4 infrared absorption peaks, the C of meta-xylene solvation60Crystal is except tool
Have outside four absworption peaks of raw material, the also two solvent absorption peaks of meta-xylene, and meta-xylene can be by 120 DEG C
It is vacuum dried to remove.
In above-described embodiment 14, gel e used can be replaced with any one in gel a~j, meta-xylene
Can be replaced with any one in benzene, toluene, ortho-xylene, paraxylene, mesitylene, styrene, precipitating reagent acetonitrile also may be used
Replaced with tetrahydrofuran, acetone, dichloromethane, hexamethylene, n-hexane and its mixed solvent, in protection scope of the present invention
It is interior.
Claims (10)
1. it is a kind of in supermolecular gel medium cultivate fullerene crystal method, it is characterised in that it is made up of following step：
(1) fullerene solution is prepared
Fullerene is dissolved in solvent, fullerene solution is configured to；
(2) gel containing fullerene is prepared
By in fullerene solution and gelling agent addition vial, heating is completely dissolved gelling agent, and natural cooling is formed it into and contained
There is the gel of fullerene；
(3) crystallization of fullerene
The crystallization of fullerene is carried out using any one in following method for crystallising I~III：
Method for crystallising I：Precipitating reagent is added on the gel of step (2) containing fullerene, bottleneck is sealed, be subsequently placed in constant temperature anti-
Answer in case and crystallized；
Method for crystallising II：By in gelling agent addition solvent, heating is completely dissolved gelling agent, and step (2) is added it to while hot
On gel containing fullerene, natural cooling makes it that one layer of Blank gel cushion is formed on the gel containing fullerene,
Precipitating reagent is added on cushion, bottleneck is sealed, be subsequently placed in isothermal reaction case and crystallized；
Method for crystallising III：The vial bottleneck of the gel of step (2) containing fullerene is sealed with aluminium-foil paper, and in aluminium-foil paper
Aperture on upper bundle, then puts it into the carboy for filling precipitating reagent, seals carboy bottleneck, is placed in isothermal reaction case
Inside crystallized；
(4) fullerene crystal is separated
After terminating, by vial, solution is suctioned out at the middle and upper levels, is subsequently adding methyl alcohol destruction gel, takes out fullerene crystal, is used
Methyl alcohol is dried after cleaning up repeatedly；
Above-mentioned gelling agent is any one in following gel a~j
In wherein gelling agent f, m=2 or 4, and during m=2, gelling agent f is LL or DD configurations, during m=4, gelling agent f is LL structures
Type；In gelling agent g, n=2,3 or 4；A is represented in gelling agent hIn gelling agent i R represent H or
Gelling agent j is DD configurations；
Above-mentioned solvent is any one in benzene, toluene, ortho-xylene, meta-xylene, paraxylene, mesitylene, styrene
Kind；Above-mentioned precipitating reagent is any one or two kinds in tetrahydrofuran, acetone, acetonitrile, dichloromethane, hexamethylene, n-hexane
Mixture.
2. it is according to claim 1 in supermolecular gel medium cultivate fullerene crystal method, it is characterised in that：
In step (1), the concentration of the fullerene solution being configured to is 0.1~10.0mg/mL.
3. it is according to claim 1 in supermolecular gel medium cultivate fullerene crystal method, it is characterised in that：
In step (2), the concentration of gelling agent is 0.1~50mg/mL in the gel containing fullerene.
4. it is according to claim 1 in supermolecular gel medium cultivate fullerene crystal method, it is characterised in that：
In step (2), the concentration of gelling agent is 10~30mg/mL in the gel containing fullerene.
5. it is according to claim 1 in supermolecular gel medium cultivate fullerene crystal method, it is characterised in that：
In step (3), the precipitating reagent volume that the method for crystallising I and method for crystallising II is added is the gel volume containing fullerene
0.5~5 times.
6. it is according to claim 1 in supermolecular gel medium cultivate fullerene crystal method, it is characterised in that：
In step (3), the precipitating reagent volume that the method for crystallising I and method for crystallising II is added is 1 of the gel volume containing fullerene
~2 times.
7. it is according to claim 1 in supermolecular gel medium cultivate fullerene crystal method, it is characterised in that：
In step (3), the precipitating reagent volume that the method for crystallising III is added is 1~5 times of the gel volume containing fullerene.
8. it is according to claim 1 in supermolecular gel medium cultivate fullerene crystal method, it is characterised in that：
In step (3), the precipitating reagent volume that the method for crystallising III is added is 2~3 times of the gel volume containing fullerene.
9. it is according to claim 1 in supermolecular gel medium cultivate fullerene crystal method, it is characterised in that：
In step (3), the concentration of gelling agent is 10~30mg/mL, buffering in the Blank gel cushion that the method for crystallising II is formed
The height of layer is 0.1~2.0cm.
10. according to claim 1~9 any one in supermolecular gel medium cultivate fullerene crystal method,
It is characterized in that：In step (3), the crystallization temperature of the method for crystallising I~III is 0~30 DEG C, and crystallization time is 2~20
My god.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205591A (en) * | 2018-07-05 | 2019-01-15 | 南京理工大学 | A kind of preparation method of novel fullerene derivate microballoon |
| CN114057211A (en) * | 2020-07-27 | 2022-02-18 | 中国石油化工股份有限公司 | Preparation method of aluminum oxide material |
| WO2023040991A1 (en) * | 2021-09-16 | 2023-03-23 | 浙江大学 | Precursor composition and preparation method therefor, and preparation method for inorganic nanocrystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854741A (en) * | 2016-03-21 | 2016-08-17 | 清华大学深圳研究生院 | Rapid preparation method for gel |
| CN105945277A (en) * | 2016-05-17 | 2016-09-21 | 中国工程物理研究院激光聚变研究中心 | Onion-shaped fullerene clad metal palladium core shell structure nano-particle and preparation method thereof |
-
2016
- 2016-11-28 CN CN201611065457.6A patent/CN106744813B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854741A (en) * | 2016-03-21 | 2016-08-17 | 清华大学深圳研究生院 | Rapid preparation method for gel |
| CN105945277A (en) * | 2016-05-17 | 2016-09-21 | 中国工程物理研究院激光聚变研究中心 | Onion-shaped fullerene clad metal palladium core shell structure nano-particle and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| CHUN ZHANG ET AL.: "Supramolecular Gel-Assisted Formation of Fullerene Nanorods", 《CHEMISTRY-A EUROPEAN JOURNAL》 * |
| NAIR V S ET AL.: "A π-gel scaffold for assembling fullerene to photoconducting supramolecular rods", 《SCIENCE ADVANCES》 * |
| 刘超等: "富勒烯的超分子自组装研究进展", 《化学通报》 * |
| 张云峰等: "基于氢键的超分子自组装研究进展", 《信仰师范学院学报：自然科学版》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205591A (en) * | 2018-07-05 | 2019-01-15 | 南京理工大学 | A kind of preparation method of novel fullerene derivate microballoon |
| CN109205591B (en) * | 2018-07-05 | 2022-04-26 | 南京理工大学 | Preparation method of novel fullerene derivative microspheres |
| CN114057211A (en) * | 2020-07-27 | 2022-02-18 | 中国石油化工股份有限公司 | Preparation method of aluminum oxide material |
| CN114057211B (en) * | 2020-07-27 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of alumina material |
| WO2023040991A1 (en) * | 2021-09-16 | 2023-03-23 | 浙江大学 | Precursor composition and preparation method therefor, and preparation method for inorganic nanocrystal |
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