CN109879291A - A kind of eggshell-egg yolk structure Metaporous silicon dioxide material and preparation method thereof - Google Patents
A kind of eggshell-egg yolk structure Metaporous silicon dioxide material and preparation method thereof Download PDFInfo
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- CN109879291A CN109879291A CN201711276596.8A CN201711276596A CN109879291A CN 109879291 A CN109879291 A CN 109879291A CN 201711276596 A CN201711276596 A CN 201711276596A CN 109879291 A CN109879291 A CN 109879291A
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Abstract
The present invention provides a kind of with eggshell-egg yolk structure Metaporous silicon dioxide material and preparation method thereof.The material generally spherical morphology, specific surface area 500-800m2/g.Wherein, " yolk " is the silica medicine ball of diameter 200-500nm, and " eggshell " is thickness 20-100nm hollow silica ball, and cavity diameter 240-800nm, " eggshell " and " yolk " all has order mesoporous, the aperture 2.5-3.5nm of rule.The material is prepared using simple one kettle way, silicon source and carbon source are added in ethyl alcohol/deionized water/ammonium hydroxide/cetyl trimethylammonium bromide mixed solution, appropriate silicon source is added after reaction a period of time, obtained solid product obtains the mesoporous silicon oxide of " eggshell-yolk " structure by dry, roasting.The invention has the advantages that provided material, compound with regular structure, large specific surface area have good application prospect in fields such as catalysis, adsorbing separation, medicament slow releases.
Description
Technical field
The invention belongs to field of material preparation, and in particular to a kind of eggshell-egg yolk structure Metaporous silicon dioxide material and its
Preparation method.
Background technique
In recent years, the Metaporous silicon dioxide material with particular configuration (such as core-shell structure, hollow ball structure) receives
The extensive concern of researchers.Compared with conventional Metaporous silicon dioxide material, these multilevel structure materials often have bigger
Specific surface area and structural functionality, the fields such as catalysis, adsorbing separation have wide application space (Science, 1998,
282,1302；Chem.Mater.,2009,21,4122；Chem.Commun.,2008,2629.).
In contrast, core-shell structure is often more more advantageous in functional material design than hollow ball structure.As one kind
Typical Core-shell structure material, " eggshell-yolk " structure (yolk-shell) material are applied in catalyst building, medicament slow release etc.
In show brilliant performance (Adv.Mater., 2010,22,4885；Angew.Chem.Int.Ed.,2011,50,10208；
Chem.Commun.,2013,49,2332；Chem.Mater.2009,21,2547.).However, because of the particularity of structure, system
The standby material with " eggshell-yolk " structure usually requires cumbersome step and complicated technique.For example, Tan etc. passes through synthesis
Then hybrid inorganic-organic silicon oxide ball with " sandwich " structure removes organic component by etching, is had " egg
The earth silicon material (Adv.Mater., 2009,21,3804.) of shell-yolk " structure, although its shell is meso-hole structure,
Be its kernel be non-porous medicine ball, cause the specific surface area of material smaller, and its synthesis used in N- (2- aminoethyl) -3-
Aminopropyl trimethoxysilane is expensive, is not suitable for large-scale production.Zhang etc. (Angew.Chem.Int.Ed., 2008,
47,5806.) selective etch is carried out to colloidal silicon dioxide bead using sodium borohydride solution, it is available " eggshell-yolk "
The silica of structure, but the material porosity is lower, specific surface area is small, is restricted its application.Therefore, exploitation letter
The silica of single stronger " eggshell-yolk " structure of preparation process synthesis application is still a challenge.
Summary of the invention
The object of the present invention is to provide a kind of eggshell-egg yolk structure Metaporous silicon dioxide materials and preparation method thereof.
A kind of Metaporous silicon dioxide material of eggshell-egg yolk structure has spherical morphology, specific surface area 500-800m2/
G, kernel are the silica medicine ball of diameter 200-500nm, and shell is the hollow silica ball of thickness 20-100nm, cavity
Diameter 240-800nm, kernel and shell have uniform order mesoporous, aperture 2.5-3.5nm.
According to Yi Chun ﹕ Qu Li Shui ﹕ NH4Six alkyl trimethyl bromination An ﹕ Zheng Gui Suan Yi Zhi ﹕ Jian Ben bis- Fen ﹕ formaldehyde of OH ﹕ Shi
0.0019~0.038 ﹕ of=1 ﹕ 4.5~6.5 ﹕, 0.03~0.09 ﹕, 0.005~0.02 ﹕, 0.0015~0.0105 ﹕ 0.0035~
0.012 successively adds, and 4~48h mixed material derived above is stirred at 30~50 DEG C, continues to add in gained mixed material
Ethyl orthosilicate stirs 6~48h at 30~50 DEG C, and products therefrom is by filtering, after dry, roast 4 at 550~700 DEG C~
6h obtains eggshell-egg yolk structure mesoporous silicon oxide.
The molar ratio for continuing the ethyl alcohol in the ethyl orthosilicate and mixed material of addition in gained mixed material is 0.0019
~0.0095:1.
The reaction condition of mixed material preferably at 30~40 DEG C stirring 6~obtain mixed material for 24 hours.
The NH4OH is the ammonia spirit that mass concentration is 25~28%.
The formaldehyde is the aqueous solution that mass concentration is 40%.
" eggshell-yolk " structure mesoporous silica regular appearance provided by the invention, structure is adjustable, and preparation process letter
It is single easy.
Detailed description of the invention
Fig. 1 is eggshell-egg yolk structure mesoporous silicon oxide transmission electron microscope photo of the embodiment of the present invention 1.
Specific embodiment
Embodiment 1
It takes 2g cetyl trimethylammonium bromide to be dissolved in 60ml dehydrated alcohol and 100ml deionized water, sequentially adds
28% ammonium hydroxide of 3ml mass concentration, 0.5ml ethyl orthosilicate, 0.2g resorcinol, 0.3ml formalin, 40 DEG C of stirring 6h, then
0.3ml ethyl orthosilicate is added, continues to stir 6h, filters out solid product in 550 DEG C of roasting 4h after drying and obtains eggshell-egg
Yellow structure mesoporous silica.
Embodiment 2
It takes 2g cetyl trimethylammonium bromide to be dissolved in 60ml dehydrated alcohol and 100ml deionized water, sequentially adds
25% ammonium hydroxide of 3ml mass concentration, 4ml ethyl orthosilicate, 0.2g resorcinol, 0.3ml formalin, 40 DEG C of stirring 6h, then plus
Enter 0.5ml ethyl orthosilicate, continue to stir 6h, filters out solid product in 550 DEG C of roasting 4h after drying and obtain eggshell-yolk
Structure mesoporous silica.
Embodiment 3
It takes 3g cetyl trimethylammonium bromide to be dissolved in 60ml dehydrated alcohol and 100ml deionized water, sequentially adds
28% ammonium hydroxide of 3ml mass concentration, 0.5ml ethyl orthosilicate, 0.6g resorcinol, 0.9ml formalin, 40 DEG C of stirring 6h, then
0.5ml ethyl orthosilicate is added, continues to stir 6h, filters out solid product in 550 DEG C of roasting 4h after drying and obtains eggshell-egg
Yellow structure mesoporous silica.
Embodiment 4
It takes 2g cetyl trimethylammonium bromide to be dissolved in 30ml dehydrated alcohol and 50ml deionized water, sequentially adds
25% ammonium hydroxide of 2ml mass concentration, 0.5ml ethyl orthosilicate, 0.2g resorcinol, 0.3ml formalin, 40 DEG C of stirring 6h, then
0.3ml ethyl orthosilicate is added, continues to stir 6h, filters out solid product in 550 DEG C of roasting 4h after drying and obtains eggshell-egg
Yellow structure mesoporous silica.
Application examples 1
" eggshell-yolk " of methylene blue solution and 0.05g that 40ml 10ppm is added in 100ml beaker is structure mesoporous
30min is mixed in silica at room temperature, takes supernatant, dense using ultraviolet-visible spectrophotometer measurement methylene blue
Degree.Reaction result: methylene blue is adsorbed removing 90%.
Application examples 2
The HAuCl of 10ml 5mM is added in 50ml beaker4, add 0.2g " eggshell-yolk " structure mesoporous titanium dioxide
Silicon is evaporated in 60 DEG C of stirrings after mixing, and obtained solid is stayed overnight in 80 DEG C of drying, then in 400 DEG C of roasting 4h, is obtained
" eggshell-yolk " structure mesoporous silicon dioxide carried Au catalyst.Take the 0.1g catalyst for being catalyzed CO oxidation reaction,
30 reaction 30min, CO conversion ratio are 80%.
Claims (6)
1. a kind of Metaporous silicon dioxide material of eggshell-egg yolk structure, feature in: there is spherical morphology, specific surface area is
500-800m2/ g, kernel are the silica medicine ball of diameter 200-500nm, and shell is the silica of thickness 20-100nm
Hollow sphere, cavity diameter 240-800nm, kernel and shell have uniform order mesoporous, aperture 2.5-3.5nm.
2. a kind of preparation method of the Metaporous silicon dioxide material of eggshell-egg yolk structure according to claim 1, feature
In: according to molar ratio Yi Chun ﹕ Qu Li Shui ﹕ NH4Six alkyl trimethyl bromination An ﹕ Zheng Gui Suan Yi Zhi ﹕ Jian Ben bis- Fen ﹕ first of OH ﹕ Shi
0.0015~0.0105 ﹕ 0.0035 of aldehyde=1 ﹕, 4.5~6.5 ﹕, 0.03~0.09 ﹕, 0.005~0.02 ﹕, 0.0019~0.038 ﹕~
0.012 successively adds, and 4~48h is stirred at 30~50 DEG C and obtains mixed material, continues to add positive silicon in gained mixed material
Acetoacetic ester stirs 6~48h at 30~50 DEG C, and products therefrom is by filtering, after dry, in 550~700 DEG C of 4~6h of roasting,
Obtain eggshell-egg yolk structure mesoporous silicon oxide.
3. the preparation method of the Metaporous silicon dioxide material of eggshell-egg yolk structure according to claim 2, feature in:
The molar ratio for continuing the ethyl alcohol in the ethyl orthosilicate and mixed material of addition in gained mixed material is 0.0019~0.0095:
1。
4. the preparation method of the Metaporous silicon dioxide material of eggshell-egg yolk structure according to claim 2, feature in:
The reaction condition of mixed material preferably at 30~40 DEG C stirring 6~obtain mixed material for 24 hours.
5. the preparation method of the Metaporous silicon dioxide material of eggshell-egg yolk structure according to claim 2, feature in:
The NH4OH is the ammonia spirit that mass concentration is 25~28%.
6. the preparation method of the Metaporous silicon dioxide material of eggshell-egg yolk structure according to claim 2, feature in:
The formaldehyde is the aqueous solution that mass concentration is 40%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921644A (en) * | 2019-11-13 | 2020-03-27 | 首都师范大学 | Method for preparing hierarchical porous material based on rapid solvent evaporation in reverse microemulsion system |
| CN111446440A (en) * | 2020-05-22 | 2020-07-24 | 扬州大学 | Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof |
| CN112652758A (en) * | 2020-12-14 | 2021-04-13 | 云帆(镇江)新能源材料有限公司 | Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof |
| CN112844258A (en) * | 2019-11-27 | 2021-05-28 | 中国科学院大连化学物理研究所 | Cysteine-modified nano core-shell silica gel material and preparation and application thereof |
| CN113318480A (en) * | 2020-02-28 | 2021-08-31 | 北方民族大学 | Hydrophilic nano core-shell material and preparation method and application thereof |
| CN113385170A (en) * | 2021-04-28 | 2021-09-14 | 西安交通大学 | Spherical yolk-eggshell structure mesoporous manganese oxide nanoenzyme, and preparation method and application thereof |
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| CN103193237A (en) * | 2013-03-08 | 2013-07-10 | 中国人民解放军***南京总医院 | Mesoporous silica with yolk-shell structure and preparation method thereof |
| CN103714929A (en) * | 2013-12-25 | 2014-04-09 | 复旦大学 | Magnetic mesoporous silica composite microsphere with Yolk-Shell structure and manufacturing method thereof |
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| CN103193237A (en) * | 2013-03-08 | 2013-07-10 | 中国人民解放军***南京总医院 | Mesoporous silica with yolk-shell structure and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921644A (en) * | 2019-11-13 | 2020-03-27 | 首都师范大学 | Method for preparing hierarchical porous material based on rapid solvent evaporation in reverse microemulsion system |
| CN112844258A (en) * | 2019-11-27 | 2021-05-28 | 中国科学院大连化学物理研究所 | Cysteine-modified nano core-shell silica gel material and preparation and application thereof |
| CN112844258B (en) * | 2019-11-27 | 2022-09-20 | 中国科学院大连化学物理研究所 | Cysteine-modified nano core-shell silica gel material and preparation and application thereof |
| CN113318480A (en) * | 2020-02-28 | 2021-08-31 | 北方民族大学 | Hydrophilic nano core-shell material and preparation method and application thereof |
| CN111446440A (en) * | 2020-05-22 | 2020-07-24 | 扬州大学 | Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof |
| CN111446440B (en) * | 2020-05-22 | 2022-07-05 | 扬州大学 | Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof |
| CN112652758A (en) * | 2020-12-14 | 2021-04-13 | 云帆(镇江)新能源材料有限公司 | Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof |
| CN113385170A (en) * | 2021-04-28 | 2021-09-14 | 西安交通大学 | Spherical yolk-eggshell structure mesoporous manganese oxide nanoenzyme, and preparation method and application thereof |
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Application publication date: 20190614 |