CN107879348A - A kind of preparation method of the monodisperse silica nanosphere of novel green - Google Patents
A kind of preparation method of the monodisperse silica nanosphere of novel green Download PDFInfo
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- CN107879348A CN107879348A CN201710953405.0A CN201710953405A CN107879348A CN 107879348 A CN107879348 A CN 107879348A CN 201710953405 A CN201710953405 A CN 201710953405A CN 107879348 A CN107879348 A CN 107879348A
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- nanosphere
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- microemulsion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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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
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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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The invention provides a kind of preparation method of the monodisperse silica nanosphere of novel green, including：Prepare O/W types water/ethanol/dichloromethane surfactant-free microemulsion；By tetraethyl orthosilicate (TEOS) in ultrasound with being completely dissolved under stirring action in the ball-type " oily core " of prepared O/W type surfactant-free microemulsions, then under ammonia-catalyzed, tetraethyl orthosilicate realizes hydrolytie polycondensation, is centrifuged after completion of the reaction.Solid constituent is washed with polar solvent and repeatedly produces single dispersing SiO2Nanosphere, remaining liq component carry out distillation and collect ethanol and dichloromethane.This method is simple to operate, cost is low, environment-friendly, system repeats utilization, efficiency high.The SiO of preparation2Nanosphere yardstick is uniform, and there is universality and large-scale production to be worth.Step is simple and convenient to operate, is practical.
Description
Technical field
The invention belongs to field of nanometer material technology, the system of the monodisperse silica nanosphere of more particularly to a kind of novel green
Preparation Method.
Background technology
Monodispersed SiO2Nanosphere, because its specific surface area is big, good dispersion, while there is good optics and power again
Characteristic is learned, there is important application value in fields such as biomedicine, catalysis, functional material, high-performance ceramic, coating.Method is current preparation SiO2One of conventional method of nanosphere, this method has titanium dioxide simple to operate, prepared
The advantages that silicon nanosphere clean surface.But the method prepares silica merely with the interaction between solvent, no preparation template
The controllability and repeatability of nanosphere are poor, it is difficult to obtain the SiO of high quality2Nanosphere.Another preparation SiO2Nanosphere is commonly used
Method is microemulsion method, the SiO prepared by this method2Nanosphere, monodispersity is good, size adjustable, but is constructing microemulsion
, it is necessary to consume substantial amounts of surfactant and cosurfactant during template, two kinds of components remove the interfacial film into microemulsion
Outside, part is also soluble in the aqueous phase and oil phase, is not easily recycled utilizations, and environment is polluted, and the surface loaded by material surface
Activating agent is difficult to washing and removes and influence purity of material etc., and these problems seriously constrain microemulsion method and preparing silica
Popularization and application in terms of nano material.
The content of the invention
In view of the above-mentioned problems, prepare SiO using O/W type surfactant-frees microemulsion for template we have proposed one kind2
The method of nanosphere.Surfactant-free microemulsion component is simple, only by water, oil and " two solvophilics " composition.It is this new
Surfactant-free microemulsion system does not contain surfactant, but has the microstructure and property similar to microemulsion,
Due to using shortcoming caused by exhibiting high surface activating agent, not only can significantly save when can overcome Preparing Nano-Materials in Microemulsions
About cost, and the nano material purity prepared is higher.
Pattern is homogeneous in order to obtain, the single dispersing SiO of uniform particle sizes2Nanosphere, the application is in a variety of surfactant-frees
SiO has been carried out in microemulsion system2The preparation of nanosphere.System research SiO2Nanosphere is in surfactant-free Emulsions
Shaping rule in system, found after many experiments screen：Using O/W types ethanol/dichloromethane/water surfactant-free micro emulsion
Liquid system has the advantages of pattern is homogeneous, uniform particle sizes as template, the silica nanosphere of preparation.And in this system,
Ethanol is used as " solvent pairs ", and dichloromethane is as oil phase, and not only cost is cheap for both solvents, and because its boiling point is relatively low,
Can be in SiO2After the completion of prepared by nanosphere, it is recyclable by the simple way of distillation, reaches the purpose recycled.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of preparation method of the monodisperse silica nanosphere of novel green, including：
Prepare O/W types water/ethanol/dichloromethane surfactant-free microemulsion；
By tetraethyl orthosilicate (TEOS) under ultrasound or stirring condition, prepared O/W types are dissolved completely in without surface
In the ball-type " oily core " of activating agent microemulsion, then under ammonia-catalyzed, tetraethyl orthosilicate realizes hydrolytie polycondensation, after completion of the reaction
Solid constituent is collected by centrifuging, polar solvent washing obtains SiO for several times2Nanosphere, liquid component are distilled, and collect second
Alcohol and dichloromethane component.
Preferably, in the surfactant-free microemulsion, mass fraction of the fixed dichloromethane in system is 20%,
Water is respectively 4-9.5: 6-0.5 with ethanol mass ratio.
Preferably, the volume ratio of the tetraethyl orthosilicate and ammoniacal liquor (25 ﹪ wt) is 1.3: 3.
Preferably, it is described that tetraethyl orthosilicate is dissolved in concretely comprising the following steps in above-mentioned surfactant-free microemulsion：
Quantitative tetraethyl orthosilicate (TEOS) is added slowly with stirring in the surfactant-free microemulsion, ultrasound or machine
Tool stirs certain time.
Preferably, the ammoniacal liquor is slowly added into the O/W dissolved with tetraethyl orthosilicate without surface under ice-water bath, stirring condition
In activating agent microemulsion system.
Preferably, the condition of the hydrolytie polycondensation is：Reaction more than 18h is stood under 25-30 DEG C of water-bath.
Preferably, the separation concretely comprises the following steps：Each component after completion of the reaction is centrifuged, collects solid
Component, washed for several times with polar solvent, liquid component is distilled, collect ethanol, dichloromethane component.
Preferably, the polar solvent is ethanol, methanol, Huo Zheshui.
Present invention also offers monodisperse silica nanosphere prepared by any above-mentioned method.
Preferably, the particle diameter of the silica nanosphere is 170~785mm.
Present invention also offers any above-mentioned monodisperse silica nanosphere to prepare biomedical material, catalysis material
Application in material, functional material, high-performance ceramic or coating.
" green " in the present invention refers to：A kind of green synthesis method.
Beneficial effects of the present invention
(1) SiO is prepared compared to traditional w/o type microemulsion method2Nanosphere, the present invention is using O/W types without surface-active
Agent microemulsion is that template prepares SiO2Nanosphere, the dosage of oil phase is significantly reduced, has saved cost.Utilize O/W types water/second
Alcohol/dichloromethane surfactant-free microemulsion is that template prepares SiO2Nanosphere, this method is simple to operate, cost is low, environment
Friendly, system is repeatable to be utilized, efficiency high, and the silica nanosphere pattern of preparation is homogeneous, uniform particle sizes, have universality and
Large-scale production is worth.
(2) silica nanosphere prepared by the present invention, pattern is good, and yardstick is homogeneous, and particle diameter adjustable extent is big, and surface is clean
Only, subsequent treatment is simple.Surfactant-free microemulsion system component is simple, recoverable, without using surfactant, energy
It is enough a large amount of cost-effective.
(3) preparation method of the present invention is simple, preparation efficiency is high, practical, easy to spread.
Brief description of the drawings
The Figure of description for forming the part of the present invention is used for providing the further explanation to the application.The application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
Fig. 1 is to change the silica nanosphere that the mass ratio of water and ethanol obtains in the timing of dichloromethane content one
TEM schemes；
Fig. 2 is the EDS figures of the silica nanosphere of preparation when water alcohol ratio is 0.5: 9.5；
Fig. 3 is the TEM figures of silica nanosphere prepared by comparative example 1.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
A kind of method for preparing silica nanosphere using surfactant-free microemulsion for template, including following step
Suddenly：
(1) preparation of O/W types surfactant-free microemulsion template：Under agitation, by appropriate water, ethanol and
Dichloromethane is well mixed, and certain time is persistently stirred after mixing.
(2) by quantitative tetraethyl orthosilicate (TEOS), be added slowly with stirring O/W types prepared by step (1) without
In surfactant microemulsion system, certain time is persistently stirred, tetraethyl orthosilicate is completely dissolved in O/W surfactant-frees micro-
Among emulsion " oily core ".
(3) under ice-water bath stirring condition, quantitative ammoniacal liquor (25 ﹪ wt) is slowly added into the system obtained by step (2)
In, continue ice-water bath after addition and stir several minutes, then move into 25 DEG C of water-baths and stand reaction more than 18 hours.
(4) it is centrifuged, gained white solid, is washed with water 3 times after completion of the reaction, remaining liq is distilled,
Reclaim ethanol and dichloromethane.
The present invention principle be：First with water, ethanol and dichloromethane prepare O/W surfactant-free microemulsion moulds
Plate, then reactant tetraethyl orthosilicate is added in system, is completely dissolved in tetraethyl orthosilicate by ultrasound or mechanical agitation
Among " the oily core " of O/W surfactant-free microemulsion systems.Ammonia spirit is slowly added under the conditions of ice-water bath, ensures ammoniacal liquor
It is soluble in the aqueous phase, reaction unit is moved into 25 DEG C of water-baths, proceeds by reaction.
The reaction mechanism mechanism of reaction of silica nanosphere prepared by the method is as follows：
Hydrolysis：
Polycondensation：
After tetraethyl orthosilicate (TEOS) is added to O/W without in the microemulsion of surface, it is completely into O/W types without surface-active
Among " the oily core " of agent microemulsion, because the interfacial film of O/W drops is made up of a large amount of ethanol molecules and hydrone, hydrone can
It is hydrolyzed into " oily core " with TEOS and condensation reaction, by monohydroxy silicate monomer to polyhydroxy esters of silicon acis until being formed
Nucleus.Finally in " the oily core " of O/W surfactant-free microemulsion systems, spherical silicon dioxide nano particle is formed.
Embodiment 1：
(1) bis- ultra-pure waters of 4g are mixed with 76g ethanol, 20g dichloromethane is added under agitation, after addition
Persistently stir 10min.
(2) 1.3ml tetraethyl orthosilicates are slowly added into the O/W types obtained by step (1) under stirring to live without surface
Property agent microemulsion system in, ultrasonic 10min successively after addition, stir 20min.
(3) the O/W type surfactant-frees microemulsion system containing tetraethyl orthosilicate obtained by step (2) is moved into frozen water
Bath, under agitation, 3ml ammoniacal liquor (25wt ﹪) is slowly added thereto, and reaction unit persistently is moved into 25 after stirring 10min
DEG C water-bath stands reaction 24h.
(4) after reaction terminates, by being centrifugally separating to obtain white solid, white solid is washed 3 times and obtains SiO2Nanometer
Ball.Remaining liq component is distilled, and collects ethanol and dichloromethane component.By SiO2Nanosphere is scattered in ethanol again,
Its TEM is shown in that figure (1) d, EDS figure is shown in figure (2).
Embodiment 2：
(1) bis- ultra-pure waters of 4g are mixed with 36g ethanol, 10g dichloromethane is added under agitation, after addition
Persistently stir 10min.
(2) 1.3ml tetraethyl orthosilicates are slowly added into the O/W types obtained by step (1) under stirring to live without surface
Property agent microemulsion system in, ultrasonic 10min successively after addition, stir 20min.
(3) the O/W type surfactant-frees microemulsion system containing tetraethyl orthosilicate obtained by step (2) is moved into frozen water
Bath, under agitation, 3ml ammoniacal liquor (25wt ﹪) is slowly added thereto, and reaction unit persistently is moved into 25 after stirring 10min
DEG C water-bath stands reaction 24h.
(4) after reaction terminates, by being centrifugally separating to obtain white solid, white solid is washed 3 times and obtains SiO2Nanometer
Ball.Remaining liq component is distilled, collects ethanol and dichloromethane component.By SiO2Nanosphere is scattered in ethanol again
In, its TEM is as shown in figure (1) c.
Embodiment 3：
(1) bis- ultra-pure waters of 4g are mixed with 16g ethanol, 5g dichloromethane is added under agitation, after addition
Persistently stir 10min.
(2) 1.3ml tetraethyl orthosilicates are slowly added into the O/W types obtained by step (1) under stirring to live without surface
Property agent microemulsion system in, ultrasonic 10min successively after addition, stir 20min.
(3) the O/W type surfactant-frees microemulsion system containing tetraethyl orthosilicate obtained by step (2) is moved into frozen water
Bath, under agitation, 3ml ammoniacal liquor (25wt ﹪) is slowly added thereto, and reaction unit persistently is moved into 25 after stirring 10min
DEG C water-bath stands reaction 24h.
(4) after reaction terminates, by being centrifugally separating to obtain white solid, white solid is washed 3 times and obtains SiO2Nanometer
Ball.Remaining liq component is distilled, and collects ethanol and dichloromethane component.By SiO2Nanosphere is scattered in ethanol again,
TEM is as shown in figure (1) b.
Embodiment 4：
(1) bis- ultra-pure waters of 4g are mixed with 9.3g ethanol, adds 3.3g dichloromethane under agitation, addition finishes
10min is persistently stirred afterwards.
(2) 1.3ml tetraethyl orthosilicates are slowly added into the O/W types obtained by step (1) under stirring to live without surface
Property agent microemulsion system in, ultrasonic 10min successively after addition, stir 20min.
(3) the O/W type surfactant-frees microemulsion system containing tetraethyl orthosilicate obtained by step (2) is moved into frozen water
Bath, under agitation, 3ml ammoniacal liquor (25wt ﹪) is slowly added thereto, and reaction unit persistently is moved into 25 after stirring 10min
DEG C water-bath stands reaction 24h.
(4) after reaction terminates, by being centrifugally separating to obtain white solid, white solid is washed 3 times and obtains SiO2Nanometer
Ball.Remaining liq component is distilled, and collects ethanol and dichloromethane component.By SiO2Nanosphere is scattered in ethanol again,
TEM is as shown in figure (1) a.
The different water alcohol ratio (R of table 1.w/e) under the conditions of the obtained particle diameter of silica nanosphere
Comparative example 1：
(1) bis- ultra-pure waters of 4g are mixed with 36g ethanol.
(2) 1.3ml tetraethyl orthosilicates are slowly added under stirring in the mixed system of ethanol and water, lasting stirring
20min。
(3) under agitation, 3.0ml ammoniacal liquor (25wt ﹪) is slowly added to contain positive silicic acid second obtained by step (2)
In the ethanol of ester and the mixed system of water, reaction unit is persistently moved into 25 DEG C of water-baths after stirring 30min and stands reaction 24h.
(4) after reaction terminates, it is centrifuged collection white solid, ethanol washs 3 times, and water washing obtains dioxy 1 time
SiClx nano particle.Nano SiO 2 particle is scattered in ethanol again, TEM is as schemed shown in (3).
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
- A kind of 1. preparation method of the monodisperse silica nanosphere of novel green, it is characterised in that including：Prepare O/W types water/ethanol/dichloromethane surfactant-free microemulsion；Tetraethyl orthosilicate TEOS is dissolved in the ball-type " oily core " of above-mentioned O/W types surfactant-free microemulsion, existed in ammoniacal liquor Under the conditions of, teos hydrolysis polycondensation, separation, washing, produce single dispersing SiO2Nanosphere.
- 2. the method as described in claim 1, it is characterised in that in the surfactant-free microemulsion, fixed dichloromethane Mass fraction is 20%, and the mass ratio of water and ethanol is 6-9.5:4-0.5.
- 3. the method as described in claim 1, it is characterised in that the volume ratio of the tetraethyl orthosilicate and the ﹪ wt of ammoniacal liquor 25 is 1.3：3.
- 4. the method as described in claim 1, it is characterised in that described that tetraethyl orthosilicate is dissolved in above-mentioned surfactant-free Concretely comprising the following steps in microemulsion：By quantitative tetraethyl orthosilicate TEOS, it is added slowly with stirring the O/W and is lived without surface Property agent microemulsion system in, 8~10min of ultrasound successively after addition, stir 8~10min.
- 5. the method as described in claim 1, it is characterised in that the ammoniacal liquor is slowly added under ice-water bath, stirring condition Dissolved with the O/W type surfactant-free microemulsion systems of silester.
- 6. the method as described in claim 1, it is characterised in that the condition of the hydrolytie polycondensation is：It is quiet under 25-35 DEG C of water-bath Put reaction more than 18h.
- 7. the method as described in claim 1, it is characterised in that the separation concretely comprises the following steps：By body after completion of the reaction System is centrifuged, and solid constituent washs 3 times with polar solvent and distills to obtain silica nanosphere, and remaining liq component is carried out Ethanol is collected in distillation, and dichloromethane recycles.
- 8. monodisperse silica nanosphere prepared by the method described in claim any one of 1-7.
- 9. monodisperse silica nanosphere as claimed in claim 8, it is characterised in that the grain of the silica nanosphere Footpath is 165~785mm.
- 10. the monodisperse silica nanosphere described in any one of claim 8 or 9 is preparing biomedical material, catalysis material Application in material, functional material, high-performance ceramic or coating.
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| CN2017106662729 | 2017-08-07 | ||
| CN201710666272.9A CN107285325A (en) | 2017-08-07 | 2017-08-07 | A kind of preparation method of the monodisperse silica nanosphere of novel green |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110371991A (en) * | 2019-07-05 | 2019-10-25 | 山东师范大学 | The preparation method of core-shell structure silica spherical shape nano particle |
| CN110760298A (en) * | 2019-10-23 | 2020-02-07 | 中国海洋石油集团有限公司 | Surfactant-free microemulsion and preparation method thereof |
| CN112969526A (en) * | 2018-11-13 | 2021-06-15 | 硅循环股份有限公司 | Hydrophobic/hydrophilic adjustable organic siloxane nanosphere/microsphere and preparation method thereof |
| CN115725081A (en) * | 2022-11-18 | 2023-03-03 | 齐鲁师范学院 | Preparation method of monodisperse organic silicon microspheres |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108751208B (en) * | 2018-06-05 | 2020-06-30 | 山东师范大学 | Monodisperse silicon dioxide nanospheres prepared from surfactant-free microemulsion and preparation method thereof |
| RU2758782C1 (en) * | 2020-12-11 | 2021-11-01 | Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" (Сколковский институт науки и технологий) | Environmentally sustainable method for processing bulk silicon into silicon dioxide nanoparticles in an aqueous solution |
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| CN101492164A (en) * | 2009-03-09 | 2009-07-29 | 东南大学 | Method of manufacturing monodisperse silicon dioxide microsphere |
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| CN101492164A (en) * | 2009-03-09 | 2009-07-29 | 东南大学 | Method of manufacturing monodisperse silicon dioxide microsphere |
| CN104003410A (en) * | 2014-06-16 | 2014-08-27 | 深圳迈思瑞尔科技有限公司 | Preparing method of monodisperse silicon dioxide pellets |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112969526A (en) * | 2018-11-13 | 2021-06-15 | 硅循环股份有限公司 | Hydrophobic/hydrophilic adjustable organic siloxane nanosphere/microsphere and preparation method thereof |
| CN110371991A (en) * | 2019-07-05 | 2019-10-25 | 山东师范大学 | The preparation method of core-shell structure silica spherical shape nano particle |
| CN110371991B (en) * | 2019-07-05 | 2021-06-25 | 山东师范大学 | Preparation method of core-shell structure silicon dioxide spherical nano-particles |
| CN110760298A (en) * | 2019-10-23 | 2020-02-07 | 中国海洋石油集团有限公司 | Surfactant-free microemulsion and preparation method thereof |
| CN110760298B (en) * | 2019-10-23 | 2022-02-11 | 中国海洋石油集团有限公司 | Surfactant-free microemulsion and preparation method thereof |
| CN115725081A (en) * | 2022-11-18 | 2023-03-03 | 齐鲁师范学院 | Preparation method of monodisperse organic silicon microspheres |
| CN115725081B (en) * | 2022-11-18 | 2023-11-14 | 齐鲁师范学院 | Preparation method of monodisperse organic silicon microsphere |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107879348B (en) | 2019-07-23 |
| CN107285325A (en) | 2017-10-24 |
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