CN107265437A - The self-assembling method that a kind of surface can drive prepares many cavity charcoal balls and its application - Google Patents
The self-assembling method that a kind of surface can drive prepares many cavity charcoal balls and its application Download PDFInfo
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- CN107265437A CN107265437A CN201710411047.0A CN201710411047A CN107265437A CN 107265437 A CN107265437 A CN 107265437A CN 201710411047 A CN201710411047 A CN 201710411047A CN 107265437 A CN107265437 A CN 107265437A
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The self-assembling method that can be driven the invention discloses a kind of surface prepares many cavity charcoal balls and its application.The key of synthesis is to prepare nanometer emulsion droplet first or is elementary cell from Ludox；With post-consumer polymer in nanometer emulsion droplet or the prepolymerization of Ludox surfaces, the small size secondary structure unit with high surface energy is obtained；With proceeding for hydro-thermal reaction, system free energy reduces, and causes aggregation and assembling that secondary units are spontaneous, forms the aggregation with many cavity structures, and cavity size and cavity numbers can be adjusted by nanometer emulsion droplet size and polymer concentration.Many cavity polymer are pyrolyzed many cavity charcoal balls that can obtain cavity size expansion in the space of inertia silica confinement.When many cavity charcoal balls prepared are used as carrier, due to strong absorption potential in cavity, internal cavities volume all can occupy utilization by guest species.
Description
Technical field
The present invention relates to many cavity polymer drops, the controllable preparation and application of many cavity charcoal balls, more particularly to
The self-assembling method that a kind of surface can drive prepares many cavity Nano carbon balls and its work that cavity diameter is adjustable, cavity numbers are controllable
The application of guest species is encapsulated for main body.
Background technology
Charcoal micro-capsule has the unique structural feature that internal cavities volume is big, external shell wall pore is abundant, is acknowledged as one
Plant ideal carrier.Big cavity volume can realize high guest species encapsulation amount, and outside charcoal wall can effectively prevent from encapsulating species
Leakage, while preventing extraneous chemical substance from entering, it is ensured that form unique chemical micro-environment in cavity.
The size of cavity is the 2-3 order of magnitude of molecular dimension for molecule.Because cavity inner wall energy of adsorption is folded
Extremely weak, guest species are difficult to pass through outside porous charcoal wall by capillary condensation power, into cavity inside, are also had led in cavity
Volume is difficult to be approached and utilize.Numerous studies show, are distributed in guest species in porous charcoal wall more, rather than cavity inside
[Adv.Energy Mater.2015,1401752]。
Then research is gradually found：Cavity inside contains the material of many microporous mediums, and its cavity utilization rate is greatly improved,
This comes from the strong absorption potential of micropore.Therefore, in the recent period a series of nucleocapsid structure materials be designed synthesis be used as carrier, by by
The strong absorption potential of internal nuclear material, realizes a large amount of encapsulation [ACS Nano 2015,9,8504] of guest species.
In order to strengthen the utilization of cavity, the concept that we are managed based on spatial gridding, it is contemplated that if internal cavities are divided
The absorption potential being cut into many grids being connected by porous charcoal wall, cavity will be greatly enhanced, and guest species are also easier to enter
Cavity inside.But, due to lacking effective synthetic method, many cavity structures of this gridding are not reported so far.
At present, ripe embedding method：Template and crystal growth are all suitable only for preparing the sky with homogeneous structural
Core material, and be not used to produce many cavity structures.Template be with monodispersed silica spheres, polymer drops, metal or
Metal oxide nano ball, emulsion droplet etc. be template, make carbon precursor template surface or surrounding polymerization.By selecting suitable dimension
Template, can accurately control the size of cavity.But, the product that template is obtained generally all is with single large-size cavity
Hollow carbon.Because, acted synergistically by surface charge and volume, (diameter is generally big for these large-sized elementary cells
In 100nm) thermodynamics stable state is can be normally reached, it is final that the distribution of single dispersing shape is presented in the solution.Therefore, it is difficult to will be certain
Quantity, thermodynamics stable state elementary particle is grouped in advance, is used as the template for forming many cavity balls.Crystal growth route is also mostly to be
Based on Ostwald ripening mechanism or Kinkendal Effect, material of the synthesis with many shell walls or radial structure
[Adv.Mater.2017,1602914]。
Only have the only a few document report method that many cavity balls are prepared by the micro fluidic device of particular design at present, but
That hundreds of nanometers to several microns are distributed as Product size more, and microflow control technique is difficult to realize a large amount of preparations of product
[J.Am.Chem.Soc.2008,130,7800].It is well known that nano material is shown in the related field of many diffusion absorption
Good performance, this, which is attributed to nano material, can effectively shorten diffusion path and reduce viscosity resistance.Therefore, exploitation is needed badly
A kind of method is controllable, technique is simple, the method for easy scale prepares many cavity charcoal balls of morphology controllable.
The content of the invention
Prepare that cavity size is adjustable present invention aims at the self assembly that provides a kind of surface and can drive, cavity numbers can
Control, size uniformity, monodispersed many cavity polymer drops and charcoal ball.
Technical scheme：
The self-assembling method that a kind of surface can drive prepares many cavity charcoal balls, prepares the nanometer that hydrated diameter is 35-164nm
Emulsion droplet is elementary cell from Ludox；By polymer in nanometer emulsion droplet or the prepolymerization of Ludox surfaces, obtain with high table
The small size secondary structure unit of face energy；With proceeding for hydro-thermal reaction, system free energy reduces, and causes secondary units certainly
The aggregation and assembling of hair, form the aggregation with many cavity structures, cavity size and cavity numbers can pass through nanometer emulsion droplet chi
The regulation of very little and polymer concentration.Many cavity polymer are pyrolyzed in the space of inertia silica confinement can obtain cavity size expansion
Big many cavity charcoal balls.Specific method step is as follows：
(1) grease of n-hexane is dissolved in, is added in the aqueous solution containing surfactant, ultrasonic disperse, obtains semi-transparent
Bright white emulsion, wherein, the mass ratio of grease and surfactant is 1:10-3:1；The mass ratio of surfactant and water is 1:
200-1:10；
(2) obtained translucent white emulsion is subjected to vacuum distillation, removes n-hexane.
(3) phenol and hexamethylenetetramine is soluble in water, stirring mixing adds the translucent white breast that step (2) is obtained
Liquid or Ludox Ludox, continue to be uniformly mixed, obtain mixed liquor；Wherein, the mol ratio of phenol and hexamethylenetetramine is 1:
5-5:1, the mass ratio of phenol and water is 1:200-1:3000, the mass ratio of phenol and grease is 1:2-20:1, phenol and Ludox Ludox
Mass ratio be 1:5-50:1.
(4) mixed liquor for obtaining step (3) is at 90-180 DEG C, hydro-thermal reaction 2-12h；Product is through centrifuging, washing, do
It is dry to obtain many cavity polymer drops；
(5) many cavity polymer drops prepare the modes of many cavity charcoal balls and selected from the following two kinds method：
First method：Under the conditions of inert gas shielding, many cavity polymer drops charings obtain many cavity charcoal balls；
Charing method used：Under the conditions of inert gas shielding, 150 DEG C, perseverance are risen to 1-3 DEG C/min heating rate
Warm 120min, then 500-1200 DEG C of carbonization temperature is risen to 1-5 DEG C/min heating rate, constant temperature 1-12h, charing obtains form
The many cavity charcoal balls kept.
Second method：Silicon dioxide layer is embedded outside many cavity polymer drops, silicon dioxide layer thickness is 10-90nm,
1-12h is carbonized under 500-1200 DEG C of temperature conditionss, finally silicon dioxide layer is removed with sodium hydroxide or hydrofluoric acid, obtains cavity
The many cavity charcoal balls become large-sized.
Described Ludox is AS-30, AS-40, HS-30, HS-40, SM-30, TM-40 or TM-50；It is preferred that AS-40 and
HS-40。
Described grease is that myristin, tripalmitin, glyceryl tristearate, three palmitic acids are sweet
Grease, olein, Trilinoleyl glyceride or three glyceryl linolenates；It is preferred that tripalmitin and three oleic acid are sweet
Grease.
Described surfactant is PVP, polyoxyethylene-poly-oxypropylene polyoxyethylene three block is total to
Polymers P123 or F127, enuatrol or cetyl trimethylammonium bromide；It is preferred that polyoxyethylene-poly-oxypropylene polyoxyethylene three
Block copolymer P123 or F127.
Described phenol is phenol, resorcinol, phloroglucin or bisphenol-A；Especially preferably phenol and resorcinol.
Possess big cavity volume inside many cavity charcoal balls prepared by the present invention, the place that can be stored as guest species；
Cavity diameter is adjustable, and cavity numbers are controllable；Separated between each cavity by porous charcoal wall, separate, each cavity can be used for distinguishing
Encapsulate functional material not of the same race or of the same race；Outside is porous shell wall, it is ensured that intracavitary guest species separate with external substance, forms only
Special chemical micro-environment.Therefore, many cavity charcoal balls that prepared by the present invention are good main bodys, optional for encapsulating guest species
Guest species have electrode active material such as S, MnO2、Fe3O4、TiO2、Co3O4、CoS、LiFePO4、Li2TiO3Deng catalytic activity
Metal or metal oxide such as Pt, Au, Pd, Co, Fe3O4、CuO、Al2O3、In2O3、CeO2Deng, medicine such as anticarcinogen, antitumor
Medicine, antiviral agent, depressor, antibiotic, anodyne, antiphlogistic, antiviral agent etc..
Beneficial effects of the present invention：The invention provides many cavity Nano carbons of self-assembling method system that a kind of surface can drive
Ball；Regulation nanometer emulsion droplet diameter and polymer concentration, which can adjust cavity diameter, can reconcile cavity numbers；Polymer is in silica
Pyrolysis can obtain many cavity charcoal balls of cavity size expansion in the space of confinement；Many cavity knots are synthesized by simple hydrothermal method
Structure charcoal ball.
Brief description of the drawings
Fig. 1 is many cavity charcoal ball transmission electron microscope pictures prepared by present example 2.
Fig. 2 is many cavity charcoal ball transmission electron microscope pictures prepared by present example 3.
Fig. 3 is many cavity charcoal ball transmission electron microscope pictures that the cavity size prepared by present example 4 expands.
Fig. 4 is to obtain compound transmission electron microscope after many cavity charcoal ball sealings dress guest species S prepared by present example 5
Figure.
Embodiment
Below in conjunction with accompanying drawing and technical scheme, the embodiment of the present invention is further illustrated.
Embodiment 1
100mg surfactant F127 are weighed, are added in 10ml deionized waters, 40 DEG C of stirring and dissolving 2h.50mg is stearic
Acid is dissolved in 0.5mL n-hexanes, is poured into the aqueous solution of surfactant, ultrasonic 30min, obtains translucent white breast
Liquid.50 DEG C of vacuum distillation 0.5h, remove the n-hexane in emulsion, obtain solution A.Weigh 275mg resorcinols, 210mg six times
Tetramine, 90ml deionized waters, 40 DEG C stir, and add solution A, are slowly stirred well mixed, obtain solution B.Will be anti-
Liquid B is answered to be transferred in water heating kettle, 110 DEG C of hydro-thermal reaction 4h obtain monodispersed many cavity polymer colloidal solution C, by centrifuging,
Water and ethanol are washed, dried, and obtain many cavity polymer of drying.
Embodiment 2
Many cavity polymer prepared by embodiment 1 are placed in retort and carbonized, and are risen to argon gas protection with 3 DEG C/min
150 DEG C, constant temperature 120min, then 600 DEG C of carbonization temperature is risen to 5 DEG C/min heating rate, constant temperature 120min, charing obtains type
Many cavity charcoal balls that state is kept.
Much cavity charcoal ball cavity size is 12 ± 2nm for the present embodiment institute, and cavity numbers are 40 ± 5, charcoal bulb diameter 105
± 10nm, its transmission electron microscope is as shown in Figure 1.
Embodiment 3
The solution B in 50ml embodiments 1 is taken, deionized water 50ml is added, is mixed evenly, obtained solution is transferred to water
In hot kettle, 110 DEG C of hydro-thermal reaction 4h obtain monodispersed many cavity polymer colloidal solutions, are washed by centrifugation, water and ethanol
Wash, dry, obtain many cavity polymer of drying.Many cavity polymer manufactured in the present embodiment are placed in retort and carbonized,
Method is same as Example 2, obtains many cavity charcoal balls.
Much cavity charcoal ball cavity size is 12 ± 2nm for the present embodiment institute, and cavity numbers are 10 ± 2, charcoal bulb diameter 70
± 5nm, its transmission electron microscope is as shown in Figure 2.
Embodiment 4
Solution C prepared by Example 1 is centrifuged, and obtains many cavity polymer, then by obtained many cavity polymer
Layer of silicon dioxide is embedded, it is 40nm, 600 DEG C of charing 4h, removing silicon dioxide layers that it, which embeds thickness, obtains cavity size expansion
Many cavity charcoal balls.
Much cavity charcoal ball cavity size is 20 ± 2nm, charcoal 100 ± 5nm of bulb diameter for the present embodiment institute, and its transmission electron microscope is such as
Shown in Fig. 3.
Embodiment 5
Many cavity charcoal balls that embodiment 4 is obtained are obtained by melt impregnation guest species S, unnecessary S components of volatilizing, washing
To the compound of many cavity package sulphur.
Charcoal-sulfur compound obtained by the present embodiment still keeps spherical morphology, and its transmission electron microscope is as shown in Figure 4.
Claims (10)
1. the self-assembling method that a kind of surface can drive prepares many cavity charcoal balls, it is characterised in that step is as follows：
(1) grease of n-hexane is dissolved in, is added in the aqueous solution containing surfactant, ultrasonic disperse obtains translucent white
Color emulsion, wherein, the mass ratio of grease and surfactant is 1:10-3:1；The mass ratio of surfactant and water is 1:200-
1:10；
(2) obtained translucent white emulsion is subjected to vacuum distillation, removes n-hexane；
(3) it is phenol and hexamethylenetetramine is soluble in water, stirring mixing, add step (2) obtained translucent white emulsion or
Ludox Ludox, continues to be uniformly mixed, obtains mixed liquor；Wherein, the mol ratio of phenol and hexamethylenetetramine is 1:5-5:
1, the mass ratio of phenol and water is 1:200-1:3000, the mass ratio of phenol and grease is 1:2-20:1, the matter of phenol and Ludox Ludox
Amount is than being 1:5-50:1；
(4) mixed liquor for obtaining step (3) is at 90-180 DEG C, hydro-thermal reaction 2-12h；Product is through centrifugation, washing, dry
To many cavity polymer drops；
(5) many cavity polymer drops prepare the modes of many cavity charcoal balls and selected from the following two kinds method：
First method：Under the conditions of inert gas shielding, many cavity polymer drops charings obtain many cavity charcoal balls；
Charing method used：Under the conditions of inert gas shielding, 150 DEG C, constant temperature are risen to 1-3 DEG C/min heating rate
120min, then 500-1200 DEG C of carbonization temperature, constant temperature 1-12h are risen to 1-5 DEG C/min heating rate, charing obtains form guarantor
The many cavity charcoal balls held；
Second method：Silicon dioxide layer is embedded outside many cavity polymer drops, silicon dioxide layer thickness is 10-90nm,
1-12h is carbonized under 500-1200 DEG C of temperature conditionss, finally silicon dioxide layer is removed with sodium hydroxide or hydrofluoric acid, obtains cavity chi
It is very little to expand greatly many cavity charcoal balls.
2. the self-assembling method that surface according to claim 1 can drive prepares many cavity charcoal balls, it is characterised in that described
Ludox Ludox be AS-30, AS-40, HS-30, HS-40, SM-30, TM-40 or TM-50.
3. the self-assembling method that surface according to claim 1 or 2 can drive prepares many cavity charcoal balls, it is characterised in that
Described grease is myristin, tripalmitin, glyceryl tristearate, tripalmitin, three
Olein, Trilinoleyl glyceride or three glyceryl linolenates.
4. the self-assembling method that surface according to claim 1 or 2 can drive prepares many cavity charcoal balls, it is characterised in that
Described surfactant is PVP, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123
Or F127, enuatrol or cetyl trimethylammonium bromide.
5. the self-assembling method that surface according to claim 3 can drive prepares many cavity charcoal balls, it is characterised in that described
Surfactant for PVP, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 or
F127, enuatrol or cetyl trimethylammonium bromide.
6. the self-assembling method that the surface according to claim 1,2 or 5 can drive prepares many cavity charcoal balls, its feature exists
In described phenol is phenol, resorcinol, phloroglucin or bisphenol-A.
7. the self-assembling method that surface according to claim 3 can drive prepares many cavity charcoal balls, it is characterised in that described
Phenol be phenol, resorcinol, phloroglucin or bisphenol-A.
8. the self-assembling method that surface according to claim 4 can drive prepares many cavity charcoal balls, it is characterised in that described
Phenol be phenol, resorcinol, phloroglucin or bisphenol-A.
9. the application of many cavity charcoal balls prepared by claim 1,2,5,7 or 8, it is characterised in that described many cavity charcoal balls are made
For main body, for encapsulating guest species, guest species include electrode active material, catalytically-active metals, catalytically-active metals oxygen
Compound and medicine.
10. the application of many cavity charcoal balls prepared by claim 6, it is characterised in that described many cavity charcoal balls are used as main body
In encapsulation guest species, guest species include electrode active material, catalytically-active metals, catalytically active metal oxides and medicine
Thing.
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2017
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