CN107140606A - A kind of preparation method of oxide hollow microsphere - Google Patents
A kind of preparation method of oxide hollow microsphere Download PDFInfo
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- CN107140606A CN107140606A CN201710379916.6A CN201710379916A CN107140606A CN 107140606 A CN107140606 A CN 107140606A CN 201710379916 A CN201710379916 A CN 201710379916A CN 107140606 A CN107140606 A CN 107140606A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
- C01B13/366—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions by hydrothermal processing
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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
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- C01B33/00—Silicon; Compounds thereof
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- C01G23/00—Compounds of titanium
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- C01G23/047—Titanium dioxide
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
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- 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
Abstract
The invention discloses a kind of preparation method of oxide hollow microsphere, it comprises the following steps：(1) using carbon ball as template, make carbon ball surface adsorption water, be then dispersed in having in the solvent of coordination with metal alkoxide, obtain carbon ball template suspension；(2) metal alkoxide is added in carbon ball template suspension, addition has the solvent of coordination with metal alkoxide, the concentration for making metal alkoxide is 0.05~0.5mol/L, stirring reaction；(3) step (2) resulting solution is carried out after high-temperature high-voltage reaction, scrubbed, separation obtains the C/ oxidate microspheres with core shell structure；(4) step (3) the C/ oxidate microspheres obtain oxide hollow microsphere after drying, heat treatment.Water is limited in carbon ball surface by the present invention using the solvent with coordination, can substantially reduce the quantity of homogeneous nucleation, the shell thickness of effective control oxide hollow microsphere has a good application prospect.
Description
Technical field
The invention belongs to the preparing technical field of oxide hollow microsphere, it is more particularly related to a kind of homogeneous
The preparation method for the oxide hollow microsphere that nucleation quantity is few, shell thickness is controllable.
Background technology
Hollow thing microballoon has that density is small, specific surface area is big, light scattering index is high, the low feature of thermal conductivity factor,
The fields such as DSSC, photocatalysis, lithium ion battery, insulating mold coating for construction have potential application value.For
This researcher proposes many methods for preparing hollow microsphere, such as template, the hot method of hydrothermal/solvent, sol-gel process.
Template is the effective ways for preparing inorganic compound hollow microsphere.Under normal circumstances, prepared by template of carbon ball
Hollow oxide microsphere is more in polar solvent (such as absolute ethyl alcohol, water), and metal alkoxide or metal salt are easily hydrolyzed, easily
Generation homogeneous nucleation, and the problems such as be difficult to control to shell thickness.
The content of the invention
It is an object of the invention to：Overcome and existing prepare the easy homogeneous nucleation existed during oxide hollow microsphere and shell
Water is limited in carbon ball surface by the problem of thickness is difficult to control to there is provided one kind, can substantially reduce the quantity of homogeneous nucleation, effectively control
The preparation method of the oxide hollow microsphere of shell thickness processed.
In order to realize foregoing invention purpose, the invention provides a kind of preparation method of oxide hollow microsphere, it includes
Following steps：
(1) using carbon ball as template, make carbon ball surface adsorption water, be then dispersed in that there is the molten of coordination with metal alkoxide
In agent, carbon ball template suspension is obtained；
(2) metal alkoxide is added in carbon ball template suspension, addition has the solvent of coordination with metal alkoxide, makes
The concentration of metal alkoxide is 0.05~0.5mol/L, stirring reaction；
(3) step (2) resulting solution is carried out after high-temperature high-voltage reaction, scrubbed, separation is obtained with core shell structure
C/ oxidate microspheres；
(4) step (3) the C/ oxidate microspheres obtain oxide hollow microsphere after drying, heat treatment；
Wherein, the metal alkoxide can be replaced metal salt, and when replacing with metal salt, addition is molten in step (2)
Agent is the solvent with metal salt with coordination.
Improved as a kind of the of preparation method of oxide hollow microsphere of the present invention, in step (1), the diameter of the carbon ball
For 50~800nm, and carbon ball and the ratio of water are 0.5~2:1.
Improved as a kind of the of preparation method of oxide hollow microsphere of the present invention, in step (2), the metal alkoxide with
The mol ratio of carbon ball is 0.5~5:1；When metal alkoxide replaces with metal salt, the mol ratio of the metal salt and carbon ball is 0.5
~5:1.
Improved as a kind of the of preparation method of oxide hollow microsphere of the present invention, the oxide is titanium dioxide, oxygen
Change tin, zinc oxide, silica, zirconium oxide, alundum (Al2O3), antimony oxide.
Improved as a kind of the of preparation method of oxide hollow microsphere of the present invention, the metal alkoxide is Titanium alkoxides, tin
Alkoxide, zinc alkoxide, silicon alkoxide, zirconium alkoxide, aluminium-alcohol salt, antimony alkoxide.
Improved as a kind of the of preparation method of oxide hollow microsphere of the present invention, the metal salt is titanium salt, pink salt, zinc
Salt, silicon salt, zirconates, aluminium salt, antimonic salt.
Improved as a kind of the of preparation method of oxide hollow microsphere of the present invention, it is described with metal alkoxide to there is coordination to make
There is the solvent of coordination to be acetylacetone,2,4-pentanedione, ethylene glycol, MEA or diethanol amine for solvent, described and metal salt.
Improved as a kind of the of preparation method of oxide hollow microsphere of the present invention, in step (2), during the stirring reaction
Between be 1~3h.
Improved as a kind of the of preparation method of oxide hollow microsphere of the present invention, in step (3), the high temperature high pressure reverse
It should be carried out in autoclave, reaction temperature is 180~240 DEG C, the reaction time is 6~24h, gained oxide hollow microsphere
Shell thickness be directly proportional to the reaction time.
Improved as a kind of the of preparation method of oxide hollow microsphere of the present invention, in step (4), the drying is in sky
Dried in gas, the heat treatment temperature is 450~500 DEG C, and heat treatment time is 2h.
Relative to prior art, the present invention is limited water using the solvent with metal alkoxide/metal salt with coordination
System can substantially reduce the quantity of homogeneous nucleation, and can effectively be controlled by the regulation of reaction time and hydrothermal temperature on carbon ball surface
The shell thickness of oxygenerating thing hollow microsphere, has a good application prospect.
Embodiment
In order that the purpose of the present invention, technical scheme and advantageous effects become apparent from, with reference to embodiments, to this
Invention is further elaborated.It should be appreciated that the embodiment described in this specification is just for the sake of this hair of explanation
It is bright, it is not intended to limit the present invention, parameter, the ratio of embodiment etc. can suit measures to local conditions to make a choice and have no substance to result
Influence.
Titanium dioxide hollow microballoon --- the metal alkoxide of embodiment 1
(1) 0.1g sizes are taken in 200nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 1.5g butyl titanates are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, butyl titanate
Mol ratio with carbon ball is 0.5:1, acetylacetone,2,4-pentanedione is added, the concentration for making butyl titanate is 0.05mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 6h under the conditions of 180 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 300nm, shell thickness 50nm.
Titanium dioxide hollow microballoon --- the metal alkoxide of embodiment 2
(1) 0.05g sizes are taken in 500nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml ethylene glycol；
(2) 3g isopropyl titanates are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, isopropyl titanate with
The mol ratio of carbon ball is 2.5:1, ethylene glycol is added, the concentration for making isopropyl titanate is 0.25mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 12h under the conditions of 200 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 700nm, shell thickness 100nm.
Tin ash hollow microsphere --- the metal alkoxide of embodiment 3
(1) 0.1g sizes are taken in 400nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 1.5g stannic acid butyl esters are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, stannic acid butyl ester and carbon
The mol ratio of ball is 0.5:1, acetylacetone,2,4-pentanedione is added, the concentration for making stannic acid butyl ester is 0.05mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 6h under the conditions of 200 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 520nm, shell thickness 60nm.
Tin ash hollow microsphere --- the metal alkoxide of embodiment 4
(1) 0.05g sizes are taken in 100nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 7.5g stannic acid isopropyl esters are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, stannic acid isopropyl ester
Mol ratio with carbon ball is 5：1, acetylacetone,2,4-pentanedione is added, the concentration for making stannic acid isopropyl ester is 0.5mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 12h under the conditions of 220 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 400nm, shell thickness 150nm.
The hollow zinc oxide microspheres of embodiment 5 --- metal alkoxide
(1) 0.05g sizes are taken in 800nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 4g dimethoxy-ethanol zinc is taken, is added under high velocity agitation in above-mentioned carbon ball template suspension, dimethoxy
The mol ratio of ethanol zinc and carbon ball is 5：1, acetylacetone,2,4-pentanedione is added, it is 0.5mol/l, stirring to make dimethoxy-ethanol zinc concentration
React 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 24h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 1.2um, shell thickness 200nm.
The silicon dioxide hollow microsphere of embodiment 6 --- metal alkoxide
(1) 0.1g sizes are taken in 200nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml MEAs；
(2) 3g tetraethyl orthosilicates are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, tetraethyl orthosilicate with
The mol ratio of carbon ball is 2.5：1, MEA is added, the concentration for making tetraethyl orthosilicate is 0.5mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 12h under the conditions of 200 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 400nm, shell thickness 100nm.
Zirconium dioxide hollow microsphere --- the metal alkoxide of embodiment 7
(1) 0.05g sizes are taken in 400nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml diethanol amine；
(2) 3.5g zirconium iso-propoxides are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, zirconium iso-propoxide and carbon
The mol ratio of ball is 2.5：1, diethanol amine is added, the concentration for making zirconium iso-propoxide is 0.25mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 12h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 700nm, shell thickness 150nm.
Aluminum oxide hollow microsphere --- the metal alkoxide of embodiment 8
(1) 0.2g sizes are taken in 50nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water, and
The carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 1g aluminic acid isopropyl esters are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, aluminic acid isopropyl ester with
The mol ratio of carbon ball is 0.5：1, acetylacetone,2,4-pentanedione is added, the concentration for making aluminic acid isopropyl ester is 0.05mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 6h under the conditions of 200 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 150nm, shell thickness 50nm.
Antimony oxide hollow microsphere --- the metal alkoxide of embodiment 9
(1) 0.1g sizes are taken in 100nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 5g antimony glycols are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, antimony glycol and carbon ball
Mol ratio be 2：1, acetylacetone,2,4-pentanedione is added, the concentration for making antimony glycol is 0.25mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 6h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 500 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 250nm, shell thickness 75nm.
Antimony oxide hollow microsphere --- the metal salt of embodiment 10
(1) 0.05g sizes are taken in 400nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml ethylene glycol；
(2) 4.5g titanium tetrachlorides are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, titanium tetrachloride and carbon
The mol ratio of ball is 5：1, ethylene glycol is added, the concentration for making titanium tetrachloride is 0.5mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 24h under the conditions of 200 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 800nm, shell thickness 200nm.
Tin oxide hollow microsphere --- the metal salt of embodiment 11
(1) 0.1g sizes are taken in 200nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml diethanol amine；
(2) 7.5g butters of tin are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, butter of tin and carbon
The mol ratio of ball is 2.5：1, diethanol amine is added, the concentration for making butter of tin is 0.25mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 6h under the conditions of 180 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 300nm, shell thickness 50nm.
Tin oxide hollow microsphere --- the metal salt of embodiment 12
(1) 0.1g sizes are taken in 800nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 2g stannous chloride is taken, is added under high velocity agitation in above-mentioned carbon ball template suspension, stannous chloride and carbon ball
Mol ratio be 0.5：1, acetylacetone,2,4-pentanedione is added, the concentration for making stannous chloride is 0.05mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 12h under the conditions of 220 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 1000nm, shell thickness 100nm.
Tin oxide hollow microsphere --- the metal salt of embodiment 13
(1) 0.05g sizes are taken in 50nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 4.5g tin oxalates are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, tin oxalate and carbon ball
Mol ratio is 5：1, acetylacetone,2,4-pentanedione is added, the concentration for making tin oxalate is 0.5mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 24h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 450nm, shell thickness 200nm.
The hollow zinc oxide microspheres of embodiment 14 --- metal salt
(1) 0.1g sizes are taken in 400nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml diethanol amine；
(2) 1.5g zinc acetates are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, zinc acetate and carbon ball
Mol ratio is 1：1, diethanol amine is added, it is 0.3mol/l, stirring reaction 2h to make acetic acid zinc concentration；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 24h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 600nm, shell thickness 100nm.
The hollow zinc oxide microspheres of embodiment 15 --- metal salt
(1) 0.1g sizes are taken in 200nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 1.5g zinc oxalates are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, zinc oxalate and carbon ball
Mol ratio is 2：1, acetylacetone,2,4-pentanedione is added, it is 0.2mol/l, stirring reaction 2h to make oxalic acid zinc concentration；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 12h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 400nm, shell thickness 100nm.
Silica hollow microsphere --- the metal salt of embodiment 16
(1) 0.1g sizes are taken in 100nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 5g silicon chlorides are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, silicon chloride and carbon ball are rubbed
You are than being 5：1, acetylacetone,2,4-pentanedione is added, the concentration for making stannic chloride is 0.5mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 20h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 400nm, shell thickness 150nm.
Zirconium oxide hollow microsphere --- the metal salt of embodiment 17
(1) 0.1g sizes are taken in 100nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml MEAs；
(2) 4.5g zirconium chlorides are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, zirconium chloride and carbon
The mol ratio of ball is 2.5：1, MEA is added, the concentration for making zirconium chloride is 0.25mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 12h under the conditions of 220 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 300nm, shell thickness 100nm.
Aluminum oxide hollow microsphere --- the metal salt of embodiment 18
(1) 0.1g sizes are taken in 200nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 2g alchlors are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, alchlor and carbon ball
Mol ratio be 2：1, acetylacetone,2,4-pentanedione is added, the concentration for making alchlor is 0.25mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 24h under the conditions of 220 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 450 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 400nm, shell thickness 100nm.
Antimony oxide hollow microsphere --- the metal salt of embodiment 19
(1) 0.1g sizes are taken in 400nm carbon ball, in mass ratio 1：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 1g trichloride antimonies are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, trichloride antimony and carbon ball
Mol ratio be 0.5：1, acetylacetone,2,4-pentanedione is added, the concentration for making trichloride antimony is 0.05mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 24h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 500 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 600nm, shell thickness 100nm.
Antimony oxide hollow microsphere --- the metal salt of embodiment 20
(1) 0.1g sizes are taken in 400nm carbon ball, in mass ratio 0.5：1 adds deionized water, makes carbon ball adsorption
Water, and the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 1g trichloride antimonies are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, trichloride antimony and carbon ball
Mol ratio be 0.5：1, acetylacetone,2,4-pentanedione is added, the concentration for making trichloride antimony is 0.05mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 24h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 500 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 600nm, shell thickness 100nm.
Antimony oxide hollow microsphere --- the metal salt of embodiment 21
(1) 0.1g sizes are taken in 400nm carbon ball, in mass ratio 2：1 adds deionized water, makes carbon ball surface adsorption water,
And the carbon ball for having adsorbed water is dispersed in 20ml acetylacetone,2,4-pentanediones；
(2) 1g trichloride antimonies are taken, are added under high velocity agitation in above-mentioned carbon ball template suspension, trichloride antimony and carbon ball
Mol ratio be 0.5：1, acetylacetone,2,4-pentanedione is added, the concentration for making trichloride antimony is 0.05mol/l, stirring reaction 2h；
(3) solution for obtaining step (2) is transferred in autoclave, the hydro-thermal reaction 24h under the conditions of 240 DEG C；
(4) wash：Absolute ethyl alcohol washing/centrifugation, repeats 2~4 times, obtains the C/ oxides with core shell structure micro-
Ball；
(5) C/ oxidate microspheres are dried in atmosphere, is then heat-treated 2h at 500 DEG C, obtain hollow thing micro-
Ball.
Gained hollow microsphere size is 600nm, shell thickness 90nm.
Note：Upper table is the important experiment condition and the parameter of gained oxide hollow microsphere in various embodiments of the present invention.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out appropriate change and modification.Therefore, the invention is not limited in embodiment disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.Although in addition, this specification
In used some specific terms, but these terms are merely for convenience of description, do not constitute any limitation to the present invention.
Claims (10)
1. a kind of preparation method of oxide hollow microsphere, it is characterised in that comprise the following steps：
(1) using carbon ball as template, make carbon ball surface adsorption water, be then dispersed in the solvent that there is coordination with metal alkoxide
In, obtain carbon ball template suspension；
(2) metal alkoxide is added in carbon ball template suspension, addition has the solvent of coordination with metal alkoxide, makes metal
The concentration of alkoxide is 0.05~0.5mol/L, stirring reaction；
(3) step (2) resulting solution is carried out after high-temperature high-voltage reaction, scrubbed, separation obtains the C/ oxygen with core shell structure
Compound microballoon；
(4) step (3) the C/ oxidate microspheres obtain oxide hollow microsphere after drying, heat treatment；
Wherein, the metal alkoxide can be replaced metal salt, and when replacing with metal salt, the solvent of addition is in step (2)
There is the solvent of coordination with metal salt.
2. the preparation method of oxide hollow microsphere according to claim 1, it is characterised in that in step (1), the carbon ball
A diameter of 50~800nm, and carbon ball and the ratio of water are 0.5~2:1.
3. the preparation method of oxide hollow microsphere according to claim 1, it is characterised in that in step (2), the metal
The mol ratio of alkoxide and carbon ball is 0.5~5:1；When metal alkoxide replaces with metal salt, mole of the metal salt and carbon ball
Than for 0.5~5:1.
4. the preparation method of oxide hollow microsphere according to claim 1, it is characterised in that the oxide is titanium dioxide
Titanium, tin oxide, zinc oxide, silica, zirconium oxide, alundum (Al2O3) or antimony oxide.
5. the preparation method of oxide hollow microsphere according to claim 1, it is characterised in that the metal alkoxide is titanium alcohol
Salt, tin alkoxide, zinc alkoxide, silicon alkoxide, zirconium alkoxide, aluminium-alcohol salt or antimony alkoxide.
6. the preparation method of oxide hollow microsphere according to claim 1, it is characterised in that the metal salt be titanium salt,
Pink salt, zinc salt, silicon salt, zirconates, aluminium salt or antimonic salt.
7. the preparation method of oxide hollow microsphere according to claim 1, it is characterised in that described to have with metal alkoxide
There is the solvent of coordination to be acetylacetone,2,4-pentanedione, ethylene glycol, MEA or diethyl for the solvent of coordination, described and metal salt
Hydramine.
8. the preparation method of oxide hollow microsphere according to claim 1, it is characterised in that in step (2), the stirring
Reaction time is 1~3h.
9. the preparation method of oxide hollow microsphere according to claim 1, it is characterised in that in step (3), the high temperature
Reaction under high pressure is carried out in autoclave, and reaction temperature is 180~240 DEG C, and the reaction time is 6~24h.
10. the preparation method of oxide hollow microsphere according to claim 1, it is characterised in that in step (4), described dry
It is dry be it is dry in atmosphere, the heat treatment temperature be 450~500 DEG C, heat treatment time is 2h.
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| CN107946087A (en) * | 2017-11-24 | 2018-04-20 | 云南大学 | The preparation and application for the nano-hollow ball being made of trimanganese tetroxide nano particle |
| CN107958995A (en) * | 2017-12-22 | 2018-04-24 | 湖南工业大学 | A kind of dried persimmon shape core shell structure C/ZnO lithium-ion negative pole electrode piece preparation methods and its fastening lithium ionic cell |
| CN108054372A (en) * | 2017-12-22 | 2018-05-18 | 湖南工业大学 | A kind of dried persimmon shape nucleocapsid C/ZnO lithium ion battery negative materials and preparation method thereof |
| CN110180522A (en) * | 2019-05-08 | 2019-08-30 | 陕西科技大学 | A kind of mesoporous carbon@TiO2Nuclear shell ball and preparation method thereof |
| CN110180519A (en) * | 2019-05-08 | 2019-08-30 | 陕西科技大学 | A kind of TiO2Hollow ball and preparation method thereof |
| WO2020132539A1 (en) * | 2018-12-21 | 2020-06-25 | Bio Industrial Technology, Incorporated | In situ production and functionalization of carbon materials via gas-liquid mass transfer and uses thereof |
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| CN107946087A (en) * | 2017-11-24 | 2018-04-20 | 云南大学 | The preparation and application for the nano-hollow ball being made of trimanganese tetroxide nano particle |
| CN107958995A (en) * | 2017-12-22 | 2018-04-24 | 湖南工业大学 | A kind of dried persimmon shape core shell structure C/ZnO lithium-ion negative pole electrode piece preparation methods and its fastening lithium ionic cell |
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| US11332373B2 (en) | 2018-12-21 | 2022-05-17 | Performance Nanocarbon, Inc. | In situ production and functionalization of carbon materials via gas-liquid mass transfer and uses thereof |
| WO2020132539A1 (en) * | 2018-12-21 | 2020-06-25 | Bio Industrial Technology, Incorporated | In situ production and functionalization of carbon materials via gas-liquid mass transfer and uses thereof |
| KR102341186B1 (en) | 2018-12-21 | 2021-12-21 | 퍼포먼스 나노카본, 아이엔씨. | In situ production and functionalization of carbon materials via gas-liquid mass transfer and their use |
| CN110180522A (en) * | 2019-05-08 | 2019-08-30 | 陕西科技大学 | A kind of mesoporous carbon@TiO2Nuclear shell ball and preparation method thereof |
| CN110180519A (en) * | 2019-05-08 | 2019-08-30 | 陕西科技大学 | A kind of TiO2Hollow ball and preparation method thereof |
| CN114057213A (en) * | 2020-07-27 | 2022-02-18 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina material |
| CN114057213B (en) * | 2020-07-27 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina material |
| CN112499680B (en) * | 2020-12-17 | 2021-06-29 | 南昌大学 | Preparation method of spherical nano antimony trioxide |
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| CN113830749A (en) * | 2021-09-24 | 2021-12-24 | 吉林大学 | Method for preparing core-shell structure metal oxide and core-shell structure metal oxide |
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