CN108975312A - A kind of preparation method of the three-dimensional manometer array forming process of morphology controllable - Google Patents
A kind of preparation method of the three-dimensional manometer array forming process of morphology controllable Download PDFInfo
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- CN108975312A CN108975312A CN201811002172.7A CN201811002172A CN108975312A CN 108975312 A CN108975312 A CN 108975312A CN 201811002172 A CN201811002172 A CN 201811002172A CN 108975312 A CN108975312 A CN 108975312A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a kind of preparation methods of the three-dimensional manometer array forming process of morphology controllable, this preparation method is with block copolymer polystyrene-bPoly- 4 vinylpyridine (PS-b- P4VP) it is template, chloroform is solvent, three-dimensional manometer array structure is synthesized by the method for solvent anneal, the structure that the method for the present invention is extremely simple, is easy to regulate and control, prepares intermediate forming process, have found the evolution process of three-dimensional manometer array, in the preparation of porous carbon materials, photonic crystal, energy storage/conversion equipment etc. has broad application prospects.
Description
Technical field
The present invention relates to a kind of preparation methods of the process of the formation three-dimensional manometer array of morphology controllable, belong to nano material
Technical field.
Background technique
In recent years, people are more and more interested in porous carbon materials, in order to meet high efficiency and high activity requirement, mentioned
The new method of many control pore structures is gone out, wherein being closed extensively by the shape that the method for solvent anneal controls material
Note.To block polymer membrane structure carry out solvent anneal, i.e., it is carried out it is solvent-induced, when membrane structure is exposed to the steaming of the solvent
When in gas, that preferable section of dissolubility can be swollen, and being equivalent to reduces its glass transition temperature, enhance its movable energy
Power can make membrane structure more tend to ordering, have wide hair in terms of the pattern of control porous carbon materials using this point
Exhibition prospect.
It is living to high efficiency and height that there is three-dimensional manometer array structure high porosity and big specific surface area can satisfy people
Property requirement, be widely used in the photovoltaic cell of dye sensitization, the anode (DSA) of dimensionally stable, metal ion battery, electrification
Supercapacitor, hydrogen storage device and biology and gas sensor etc. are learned, to develop new functional porous material, reality
Now more preferable and optimization performance is had laid a good foundation.And traditional method for preparing three-dimensional manometer array is complicated for operation and item
Part is not easy to control, so to obtain three-dimensional manometer array, there is also certain difficulties.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of mistakes of the formation three-dimensional manometer array of morphology controllable
The preparation method of journey, with block copolymer PS-b- P4VP is template, adjusted and controlled by solvent anneal, ultimately forms three wieners
The structure of rice array, the preparation method reaction condition is relatively mild, and preparation method is simple.
The present invention selects block copolymer PS-b- P4VP is template, and chloroform is solvent, is synthesized using solvent anneal method
Three-dimensional manometer array structure.
Specific technical solution of the present invention is as follows:
A kind of preparation method of the process of the formation three-dimensional manometer array of morphology controllable, it is characterized in that the following steps are included:
(1) by block copolymer PS-b- P4VP is dissolved in good solvent, forms stable weak solution after stirring a period of time；
(2) weak solution is placed in solvent anneal in the chloroform atmosphere of saturation for a period of time, makes its self assembly, places it in vacuum baking
Solvent flashing is stayed overnight in case, is thermally formed final product using a period of time.
Further, three-dimensional manometer array structure described in the method for the present invention, wherein intermediate pattern is respectively mesh nanometer knot
Structure and nano wire and nano net mixing array structure, nanometer porous array structure.
Further, in step (1), the block copolymer PS-b- P4VP, whereinf PS=0.64-0.75, f P4VP=
0.25-0.36(is whereinfFor the volume fraction of a certain segment), preferablyf PS=0.72-0.74,f P4VP=0.26-0.28。
Further, in step (1), concentration of the block copolymer in good solvent is 0.5 wt%-2 wt%, preferably
For 1 wt%-1.5 wt%.
Further, in step (1), stirring carries out at room temperature；The good solvent is chloroform.
Further, in step (1), the mixing time is 4 h.
Further, in step (2), the chloroform atmosphere that solution is placed in saturation, annealing conditions are room temperature and closed
Environment.
Further, in step (2), several days of annealing time are 1 d-18 d, preferably 9 d-15 d.
Further, in step (2), the temperature of the vacuum drying oven solvent flashing is 40 DEG C, and the time is 12 h-15 h.
Further, in step (2), the heating temperature is 100 DEG C -200 DEG C, and preferable temperature is 130 DEG C -140 DEG C, is added
The hot time is 10 min-60 min, and the preferably time is 20 min-30 min.
The method of the present invention is with block copolymer PS-b- P4VP is template, regulates and controls its structure by solvent anneal, ultimately forms
Three-dimensional manometer array structure, the preparation method is simple, and reaction condition is relatively mild.The method that the present invention is annealed by adjusting solvent
It has found the evolution process of three-dimensional manometer array, forms the structure of three-dimensional manometer array, in the preparation of porous carbon materials, photon is brilliant
Body, energy storage/conversion equipment etc. have broad application prospects.
Detailed description of the invention
The cold field emission electron scanning micrograph of three-dimensional manometer array structure prepared by Fig. 1 embodiment 1.
The cold field emission electron scanning micrograph of nanometer porous array structure prepared by Fig. 2 embodiment 2.
The cold field emission scanning electron microscope of nano wire and nano net mixing array structure prepared by Fig. 3 embodiment 3
Photo.
The cold field emission electron scanning micrograph of nanometer web frame prepared by Fig. 4 embodiment 4.
The cold field emission electron scanning micrograph of nanometer web frame prepared by Fig. 5 embodiment 5.
Specific embodiment
The present invention is further described in detail combined with specific embodiments below.In following embodiments, block used
Copolymer, chloroform etc. are the commodity from market purchasing.
Embodiment 1
(1) block copolymer PS-b- P4VP, which is dissolved in, forms stable weak solution in good solvent:
By block copolymer PS-b- P4VP is dissolved in chloroform, forms the weak solution of 1.5 wt%, 4 h are stirred at room temperature
Under the conditions of, obtain stable weak solution.
(2) preparation of three-dimensional manometer array:
The PS- for being 1 wt% by the mass fraction of obtained clearbThe stable weak solution of-P4VP/ chloroform is placed in saturation
Chloroform atmosphere in (room temperature confined space), by the method for solvent anneal, control its anneal number of days, make its annealing 15 days carry out
Sample after assembling is placed in 30 DEG C of vacuum drying oven solvent flashing overnight, then in 130 DEG C of vacuum drying ovens by self assembly
Middle 20 min of heating and thermal insulation makes the configuration state of its further stable formation, and finally obtained is three-dimensional manometer array structure.
Fig. 1 is product cold field emission electron scanning micrograph, can be seen that in figure and obtains the three-dimensional manometer battle array of rule
Array structure, and structure is single, the top of array is the uniform porous structure of co-continuous, and hole average-size is about 26.92 nm.
Embodiment 2
According to the method for embodiment 1, unlike: in step (2), the time of solvent anneal being changed and is contracted to 12 days, through SEM
Detection, the SEM photograph of products therefrom are illustrated in figure 2 uniform nanometer porous array structure.
Embodiment 3
According to the method for embodiment 1, unlike: in step (2), the time of solvent anneal being changed and is contracted to 9 days, through SEM
Detection, the SEM photograph of products therefrom are illustrated in figure 3 uniform nano wire and nano net mixing array structure.
Embodiment 4
According to the method for embodiment 1, unlike: in step (2), the time of solvent anneal being changed and is contracted to 3 days, gained produces
The photo of object as shown in figure 4, it can be seen from the figure that products therefrom be not be well-proportioned Nanostructure Network, wherein netted
Aperture size be about 16.81 nm.
Embodiment 5
According to the method for embodiment 1, unlike: in step (2), the time of solvent anneal being changed and is contracted to 1 day, gained produces
The photo of object is as shown in figure 5, it can be seen from the figure that products therefrom is uniform Nanostructure Network, and than in embodiment 4
The reticular structure that structure is formed is more uniform, and single structure is all reticular structure, wherein netted aperture size is 16.03 nm.
Embodiment 6
Three-dimensional manometer array is prepared according to the method for embodiment 1, unlike: in step (1), by block copolymer PS-b-
The mass concentration of P4VP/ chloroform liquid is diluted to 1 wt%, detects through SEM, and products therefrom is nanowire structure.
Embodiment 7
Three-dimensional manometer array is prepared according to the method for embodiment 1, unlike: in step (1), by block copolymer PS-b-
The mass concentration of P4VP/ chloroform liquid increases by 5 wt%, detects through SEM, products therefrom is nanowire structure.
Embodiment 8
Three-dimensional manometer array is prepared according to the method for embodiment 1, unlike: in step (2), heating temperature is increased to 150
DEG C, the time increases to 40 min, detects through SEM, and products therefrom is random structure.
Embodiment 9
Three-dimensional manometer array is prepared according to the method for embodiment 1, unlike: in step (2), heating temperature is reduced to 100
DEG C, the time is reduced to 10 min, is detected through SEM, and products therefrom is random structure.
Comparative example 1
Three-dimensional manometer array is prepared according to the method for embodiment 1, unlike: in step (1), by block copolymer in good solvent
In concentration narrow down to 0.05 wt%, products therefrom is random structure, the too low influence film forming thickness of concentration.
Comparative example 2
Three-dimensional manometer array is prepared according to the method for embodiment 1, unlike: in step (2), the time of solvent anneal is increased
To 20 days, annealing time was too long, and products therefrom is random structure.
Comparative example 3
Three-dimensional manometer array is prepared according to the method for embodiment 1, unlike: in step (2), heating temperature increases by 200 DEG C, adds
The hot time increases to 60 min, and the excessively high overlong time of heating temperature, products therefrom is random structure.
Claims (10)
1. a kind of preparation method of the forming process of the three-dimensional manometer array of morphology controllable, it is characterized in that the following steps are included:
(1) by block copolymer PS-b- P4VP is dissolved in good solvent, forms stable weak solution after stirring a period of time；
(2) weak solution is placed in solvent anneal certain time in the chloroform atmosphere of saturation, makes its self assembly, place it in vacuum baking
Solvent flashing is stayed overnight in case, is thermally formed final product using a period of time.
2. preparation method according to claim 1, it is characterized in that: in step (1), the block copolymer PS-b- P4VP,
Whereinf PS=0.64-0.75,f P4VP=0.25-0.36(fFor the volume fraction of a certain segment), preferablyf PS=0.72-0.74,f P4VP=0.26-0.28。
3. preparation method according to claim 1, it is characterized in that: the final pattern that the morphology controllable is formed is three-dimensional
Nano array structure, wherein intermediate pattern is respectively Nanostructure Network and nano wire and nano net mixing array structure,
Nanometer porous array structure.
4. preparation method according to claim 1, it is characterized in that: the block copolymer is in good solvent in step (1)
Concentration be 0.5 wt%-2 wt%, preferably 1 wt%-1.5 wt%.
5. preparation method according to claim 1, it is characterized in that: stirring carries out at room temperature in step (1)；It is described good
Solvent is chloroform.
6. preparation method according to claim 1, it is characterized in that: in step (1), the mixing time is 2 h-6 h, excellent
It is selected as 4 h.
7. preparation method according to claim 1, it is characterized in that: in step (2), the chloroform that solution is placed in saturation
Atmosphere, annealing conditions are room temperature and closed environment.
8. preparation method according to claim 1, it is characterized in that: the annealing time is 1 d-18 d in step (2),
Preferably 9 d-15 d.
9. preparation method according to claim 1, it is characterized in that: in step (2), the temperature of the vacuum drying oven solvent flashing
Degree is 40 DEG C, and the volatilization time is 12 h-15 h.
10. preparation method according to claim 1, it is characterized in that: the heating temperature is 100 DEG C -200 in step (2)
DEG C, preferable temperature is 130 DEG C -140 DEG C, and heating time is 10 min-60 min, and the preferably time is 20 min-30 min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111029443A (en) * | 2019-12-06 | 2020-04-17 | 松山湖材料实验室 | Method for enhancing luminous efficiency of nitride-based LED by using metal nanoparticles |
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Application publication date: 20181211 |