CN104530110A - Method for preparing extra-large pore diameter hollow mesoporous organic silicon nanoparticles - Google Patents
Method for preparing extra-large pore diameter hollow mesoporous organic silicon nanoparticles Download PDFInfo
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- CN104530110A CN104530110A CN201410802340.6A CN201410802340A CN104530110A CN 104530110 A CN104530110 A CN 104530110A CN 201410802340 A CN201410802340 A CN 201410802340A CN 104530110 A CN104530110 A CN 104530110A
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Abstract
The invention provides a method for preparing extra-large pore diameter hollow mesoporous organic silicon nanoparticles. The method comprises the following steps: (1) mixing solid SiO2 microspheres, a surfactant solution, water and ammonia water, adding an organic silicon source under stirring conditions, reacting, thereby obtaining solid core SiO2 microspheres or organic silicon microspheres of mesoporous shell structures; (2) dispersing the solid core SiO2 microspheres or organic silicon microspheres of mesoporous shell structures in an alkaline solution, etching to remove the solid cores, and separating the solid products; and (3) dispersing the solid products in water, performing hydrothermal treatment for the specified time, thereby obtaining the organic silicon microspheres of the extra-large pore diameter hollow mesoporous shell structures.
Description
Technical field
The invention belongs to technical field of nano material, relate to the novel processing step of the hollow mesoporous organosilicon nano particle of ultra-large aperture bivalve layer.
Background technology
Mesoporous material is due to its high specific surface area, and large pore volume, regulatable mesoscopic structure and aperture size, be subject to the extensive research of scientists.But, the hollow mesoporous material with ultra-large aperture can be synthesized and be still huge challenge.
Order mesoporous organosilicon (Periodic mesoporous organosilia, PMOs) material is by silicoorganic compound (RO)
3-R '-Si (OR)
3for the mesoporous silicon material with organic group R ' in the skeleton that silicon source obtains.The high introduction volume of its orderly meso-hole structure, organic group and homogeneous distribution, spacious pore passage structure and regulatable physics and chemistry character etc., the kind of extreme enrichment mesoporous material and function, become the focus of research gradually.In the PMO material of report, due to aperture size problem, namely reactant can only be wrapped in the outside surface of mesoporous material, is difficult to enter into duct, therefore greatly limit it and shows characteristic in some applications, especially has the reaction that macromole participates in.The meso-hole structure of ultra-large aperture can provide mass transfer that is more efficient, that optimize, avoids the accumulation of material in reaction process, the transport being conducive to macromolecular reaction product be separated, thus extend the Application Areas of mesoporous material.Therefore, how to prepare the order mesoporous organosilicon with ultra-large aperture, for those skilled in the art wish one of technological difficulties solved.
Summary of the invention
The present invention is intended to overcome the technical barrier that prior art cannot prepare ultra-large aperture organic silicon nano particle, the invention provides a kind of preparation method of hollow mesoporous organosilicon nano particle.
The invention provides a kind of preparation method of ultra-large aperture hollow mesoporous organosilicon nano particle, comprising:
1) by solid SiO
2after the mixing of ball, surfactant soln, water, ammoniacal liquor, add organosilicon source under agitation, be obtained by reacting solid core SiO
2the organic silicon sphere of ball/mesoporous shell structure;
2) by solid core SiO
2the organic silicon sphere of ball/mesoporous shell structure is first dispersed in etching removing solid core in basic solution, is then separated wherein solid product, and wash, dry;
3) by step 2) solid product that obtains is dispersed in water, and the hydrothermal treatment consists specified time, obtains the organic silicon sphere of hollow mesoporous shell structure.
Preferably, step 1) in, solid SiO
2the particle diameter of ball is 100-200nm.
Preferably, step 1) in, described solid SiO
2the preparation method of ball comprises:
Ethanol, water and ammoniacal liquor are mixed, adds tetraethoxy under agitation condition, be obtained by reacting solid SiO
2ball.
Preferably, the volume ratio of ethanol, water, ammoniacal liquor, tetraethoxy is (50-80): (5-15): (2.5-4): (5-8); Temperature of reaction is 25-45 DEG C, and the reaction times is 0.5-2.5 hour.
Preferably, step 1) in, tensio-active agent comprises at least one in cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride and octadecyl trimethoxysilane, in surfactant soln, solvent is water and ethanol, and the volume ratio of water and ethanol is (1-5): (1-3).
Preferably, step 1) in, organosilicon source comprises at least one in two (triethoxyl silane) ethene, Isosorbide-5-Nitrae-bis-(triethoxy is silica-based) benzene, two (triethoxyl silane) ethane.
Preferably, step 1) in, the amount ratio in surfactant soln, water, ammoniacal liquor, organosilicon source is (20-40mL): (80-150mL): (2-5mL): (2-6mL), and the reaction times is 4-10 hour.
Preferably, step 2) in, basic solution comprises NaOH solution, Na
2cO
3solution, KOH, concentration is 0.4-1M; Etching temperature is 60-90 DEG C, and the time is 0.5-2.5 hour.
Preferably, step 3) in, in hydrothermal treatment process, the amount ratio of solid product and water is (20-50mg): (25-45mL), and hydrothermal temperature is 140-180 DEG C, and the time is 2-4 days.
Preferably, the specific surface area of hollow mesoporous organosilicon ball is 400 ~ 700m
2g
-1, pore volume is 1 ~ 4cm
3g
-1, aperture is 15 ~ 30nm.
Beneficial effect of the present invention:
The present invention explores the ultra-large aperture bivalve layer of preparation, and (layer outside and inside in this bivalve is all silicone layer, can see that from element mapping figure outside and interior shell has C element) hollow mesoporous organosilicon nano particle, utilize the difference of Si-R ' key and Si-O key thermostability in mesoporous lamella, under hydrothermal condition, prepare the nano particle with unique ultra-large aperture, bivalve layer and hollow structure.The structure of this excellence can accelerate the transmission speed of material, and can substantially increase the loading capacity of guest molecule, has wide application prospect.
Accompanying drawing explanation
Fig. 1 shows transmission electron microscope (TEM) photo of the hollow mesoporous organosilicon nano particle of embodiment 1 gained; The element mapping that Fig. 2 shows the hollow mesoporous organosilicon nano particle of embodiment 1 gained schemes (Si, O and C element);
Fig. 3 shows N2 adsorption/desorption isothermal curve (a) of the hollow mesoporous organosilicon nano particle of embodiment 1 gained and the corresponding graph of pore diameter distribution of hollow mesoporous organosilicon nano particle of embodiment 1 gained.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The present invention relates to the preparation method of the hollow mesoporous organosilicon nano particle of a kind of ultra-large aperture bivalve layer.First add by sol-gel method the organic silicon sphere of solid core/mesoporous shell that tensio-active agent guiding method synthesizes high dispersing, uniform particle diameter; Then etching removes solid core in the basic conditions; Process under last hydrothermal condition, obtain the hollow mesoporous organosilicon nano particle of ultra-large aperture bivalve layer.Described mesoporous organosilicon nano particle has unique bivalve layer and hollow structure, and aperture is very large, is beneficial to very much the reaction that macromole participates in, biological example macromole and oil catalysate etc.Synthetic method of the present invention is simple, and method is novel, and cost is low; The nano particle of synthesis has application prospect extremely widely in fields such as the loading of biomacromolecule and catalysis.
The invention provides a kind of method preparing the hollow mesoporous organosilicon nano particle of ultra-large aperture bivalve layer, comprise the following steps:
A () a certain amount of dehydrated alcohol, deionized water and ammoniacal liquor mix, add tetraethoxy fast under agitation condition, obtain solid SiO after reaction for some time
2ball;
B () is by the solid SiO of step (a) gained
2ball mixes with a certain amount of deionized water, surfactant soln and ammoniacal liquor, adds organosilicon source fast under agitation condition, and sustained reaction obtains solid core SiO after for some time
2the organic silicon sphere of ball/mesoporous shell structure;
C () is by the solid core SiO described in step (b)
2the organic silicon sphere of ball/mesoporous shell structure is dispersed in etching removing solid core in basic solution, and deionized water wash is also dry, obtains the organic silicon sphere of hollow mesoporous shell structure;
D () gets the organic silicon sphere ultrasonic disperse of the hollow mesoporous shell structure described in a certain amount of step (c) in deionized water, process certain hour under hydrothermal condition, centrifugal, and deionized water wash is also dry.
The volume of dehydrated alcohol described in step (a) is 50-80mL, and deionized water volume is 5-15mL, and ammoniacal liquor volume is 2.5-4mL, and tetraethoxy volume is 5-8mL.
In step (a), temperature of reaction is 25-45 DEG C, and the reaction times is 0.5-2.5h.
Tensio-active agent described in step (b) is selected from cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride and octadecyl trimethoxysilane, and the surfactant soln of preparation is the mixing solutions of water and dehydrated alcohol, its volume ratio is (1-5): (1-3), and total liquor capacity is 20-40mL.
Deionized water volume described in step (b) is 80-150mL, and ammoniacal liquor volume is 2-5mL.
Organosilicon source described in step (b) is selected from two (triethoxyl silane) ethene, Isosorbide-5-Nitrae-bis-(triethoxy is silica-based) benzene or two (triethoxyl silane) ethane, and its volume is 2-6mL.
Reaction times described in step (b) is 4-10h.
Alkaline solution described in step (c) is selected from NaOH solution, Na
2cO
3solution or KOH, and its concentration is 0.4-1M, volume is 20-40mL.
In step (c), etching temperature is 60-90 DEG C, and the time is 0.5-2.5h.
The organic silicon sphere quality of the hollow mesoporous shell structure described in step (d) is 20-50mg, and deionized water volume is 25-45mL.
In step (d), hydrothermal temperature is 140-180 DEG C, and the time is 2-4d.
The specific surface area of described hollow mesoporous organosilicon ball is 400 ~ 700m
2g
-1, pore volume is 1 ~ 4cm
3g
-1, aperture is 15 ~ 30nm.
The invention provides and a kind ofly prepare the novel method of hollow mesoporous organosilicon nano particle with ultra-large aperture, bivalve Rotating fields, little to solve the hollow organic silicon nano particle aperture existed in prior art, the problems such as pattern irregularity.Synthetic method of the present invention is simple, and method is novel, and cost is low; The nano particle of synthesis has application prospect extremely widely in fields such as the loading of biomacromolecule and catalysis.
Fig. 1 (a and b) be transmission electron microscope (TEM) photo of the hollow mesoporous organosilicon nano particle of embodiment 1 gained.As can be seen from photo: prepared mesoporous organosilicon nano particle is hollow and bivalve Rotating fields;
Fig. 2 is that the element mapping of the hollow mesoporous organosilicon nano particle of embodiment 1 gained schemes (Si, O and C element);
The N of the hollow mesoporous organosilicon nano particle that (a) is embodiment 1 gained in Fig. 3
2adsorption/desorption isothermal curve; B () is the corresponding graph of pore diameter distribution of hollow mesoporous organosilicon nano particle for embodiment 1 gained.Composition graphs 3a and b can illustrate that prepared mesoporous organosilicon nano particle specific surface area is high, and pore volume is large, and hole dimension is very large.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
74mL dehydrated alcohol, the ammoniacal liquor mixing of 10mL deionized water and 3.14mL, stirs 10min under 30 DEG C of conditions; Add 6mL tetraethoxy fast, magnetic stirring 1h obtains solid SiO
2ball; Preparation surfactant soln, namely 1.2g cetyl trimethylammonium bromide is dissolved in 20mL water and 10mL dehydrated alcohol; By the solid SiO obtained
2ball (quality that the back that the amount of SiO2 ball is exactly obtains) mixes with 100mL deionized water, 30mL surfactant soln and 3mL ammoniacal liquor, 3mL1 is added fast under agitation condition, two (triethoxy is silica-based) the benzene organosilicon source of 4-, obtains the organic silicon sphere of the mesoporous shell structure of solid core after reaction 6h;
The organic silicon sphere of mesoporous for the solid core@obtained shell structure (quality that the organic silicon sphere of the mesoporous shell structure of solid core@obtains before being exactly) is dispersed in 0.6M, the Na of 30mL
2cO
3in solution, 80 DEG C of etching 1h obtain the organic silicon sphere of hollow mesoporous shell structure.Get the organic silicon sphere of the hollow mesoporous shell structure of 40mg, ultrasonic disperse, in 30mL deionized water, processes 3d under 160 DEG C of hydrothermal conditions, and the centrifugal rear deionized water wash of product is also dry.
Claims (10)
1. a preparation method for ultra-large aperture hollow mesoporous organosilicon nano particle, is characterized in that, comprising:
1) by solid SiO
2after the mixing of ball, surfactant soln, water, ammoniacal liquor, add organosilicon source under agitation, be obtained by reacting solid core SiO
2the organic silicon sphere of ball/mesoporous shell structure;
2) by solid core SiO
2the organic silicon sphere of ball/mesoporous shell structure is first dispersed in etching removing solid core in basic solution, is then separated wherein solid product, and wash, dry;
3) by step 2) solid product that obtains is dispersed in water, and the hydrothermal treatment consists specified time, obtains the organic silicon sphere of the hollow mesoporous shell structure of ultra-large aperture.
2. preparation method according to claim 1, is characterized in that, in step 1), and solid SiO
2the particle diameter of ball is 100-200 nm.
3. preparation method according to claim 1 and 2, is characterized in that, in step 1), and described solid SiO
2the preparation method of ball comprises: ethanol, water and ammoniacal liquor are mixed, add tetraethoxy, be obtained by reacting solid SiO under agitation condition
2ball.
4. preparation method according to claim 3, is characterized in that, the volume ratio of ethanol, water, ammoniacal liquor, tetraethoxy is (50-80): (5-15): (2.5-4): (5-8); Temperature of reaction is 25-45 DEG C, and the reaction times is 0.5-2.5 hour.
5. according to described preparation method arbitrary in claim 1-4, it is characterized in that, in step 1), tensio-active agent comprises at least one in cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride and octadecyl trimethoxysilane, in surfactant soln, solvent is water and ethanol, and the volume ratio of water and ethanol is (1-5): (1-3).
6., according to described preparation method arbitrary in claim 1-5, it is characterized in that, in step 1), organosilicon source comprises at least one in two (triethoxyl silane) ethene, Isosorbide-5-Nitrae-bis-(triethoxy is silica-based) benzene, two (triethoxyl silane) ethane.
7. according to described preparation method arbitrary in claim 1-6, it is characterized in that, in step 1), the amount ratio in surfactant soln, water, ammoniacal liquor, organosilicon source is: (20-40 mL): (80-150 mL): (2-5 mL): (2-6 mL), and the reaction times is 4-10 hour.
8., according to described preparation method arbitrary in claim 1-7, it is characterized in that, step 2) in, basic solution comprises NaOH solution, Na
2cO
3solution, KOH, concentration is 0.4-1 M; Etching temperature is 60-90 DEG C, and the time is 0.5-2.5 hour.
9., according to described preparation method arbitrary in claim 1-8, it is characterized in that, in step 3), in hydrothermal treatment process, the amount ratio of solid product and water is (20-50mg): (25-45mL), and hydrothermal temperature is 140-180 DEG C, and the time is 2-4 days.
10., according to described preparation method arbitrary in claim 1-9, it is characterized in that, the specific surface area of hollow mesoporous organosilicon ball is 400 ~ 700 m
2g
-1, pore volume is 1 ~ 4 cm
3g
-1, aperture is 15 ~ 30 nm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000246A (en) * | 2016-05-18 | 2016-10-12 | 中国科学院上海光学精密机械研究所 | Mesoporous organosilica hollow nanoparticles with asymmetric morphology and synthetic method of mesoporous organosilica hollow nanoparticles |
| CN109771666A (en) * | 2019-03-27 | 2019-05-21 | 南京邮电大学 | A kind of flexibility mesoporous organosilicon nanometer rods and its preparation method and application |
| CN109850953A (en) * | 2019-03-20 | 2019-06-07 | 浙江工业大学 | A kind of preparation method of the magnetic composite microsphere based on the efficient package assembly of ferroferric oxide nano granules |
| CN110683860A (en) * | 2019-11-18 | 2020-01-14 | 萍乡学院 | Ceramic hollow ball with double-shell structure and preparation method thereof |
| CN110771623A (en) * | 2019-10-14 | 2020-02-11 | 东华大学 | Preparation method of mesoporous silica long-acting antibacterial nanomaterial with high selenium loading |
| CN111871393A (en) * | 2020-07-28 | 2020-11-03 | 常州大学 | Mesoporous organic silicon hollow sphere synthesized by double-template method and adsorption application thereof |
| CN113150028A (en) * | 2021-04-09 | 2021-07-23 | 浙江理工大学 | Preparation method of mesoporous organic silicon nanowire and mesoporous organic silicon nanowire |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060300A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Method for synthesizing high-dispersibility high-specific surface area large-pore volume SiO2 hollow spheres |
| CN103833040A (en) * | 2014-01-29 | 2014-06-04 | 中国科学院上海硅酸盐研究所 | Preparation methods of hollow mesoporous silicon oxide spheres and hollow mesoporous organosilicone spheres |
| CN104059096A (en) * | 2014-07-03 | 2014-09-24 | 中国科学院上海硅酸盐研究所 | Small-particle-size oversized-aperture mesopore organic silicon nanometer particles and preparation method thereof |
-
2014
- 2014-12-18 CN CN201410802340.6A patent/CN104530110A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060300A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Method for synthesizing high-dispersibility high-specific surface area large-pore volume SiO2 hollow spheres |
| CN103833040A (en) * | 2014-01-29 | 2014-06-04 | 中国科学院上海硅酸盐研究所 | Preparation methods of hollow mesoporous silicon oxide spheres and hollow mesoporous organosilicone spheres |
| CN104059096A (en) * | 2014-07-03 | 2014-09-24 | 中国科学院上海硅酸盐研究所 | Small-particle-size oversized-aperture mesopore organic silicon nanometer particles and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| MANIK MANDAL等,: "Versatile approach to synthesis of 2-D hexagonal ultra-large-pore periodic mesoporous organosilicas", 《J. MATER. CHEM.》 * |
| YU CHEN等,: "Colloidal HPMO Nanoparticles: Silica-Etching Chemistry Tailoring, Topological Transformation, and Nano-Biomedical Applications", 《ADV. MATER.》 * |
| 王连洲等,: "介孔氧化硅材料的研究进展", 《无机材料学报》 * |
| 马桂岑: "有序超大孔介孔二氧化硅的合成及其作为金催化载体的应用", 《浙江大学博士学位论文》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106000246A (en) * | 2016-05-18 | 2016-10-12 | 中国科学院上海光学精密机械研究所 | Mesoporous organosilica hollow nanoparticles with asymmetric morphology and synthetic method of mesoporous organosilica hollow nanoparticles |
| CN109850953A (en) * | 2019-03-20 | 2019-06-07 | 浙江工业大学 | A kind of preparation method of the magnetic composite microsphere based on the efficient package assembly of ferroferric oxide nano granules |
| CN109771666A (en) * | 2019-03-27 | 2019-05-21 | 南京邮电大学 | A kind of flexibility mesoporous organosilicon nanometer rods and its preparation method and application |
| CN109771666B (en) * | 2019-03-27 | 2022-02-15 | 南京邮电大学 | Flexible mesoporous organosilicon nanorod and preparation method and application thereof |
| CN110771623A (en) * | 2019-10-14 | 2020-02-11 | 东华大学 | Preparation method of mesoporous silica long-acting antibacterial nanomaterial with high selenium loading |
| CN110771623B (en) * | 2019-10-14 | 2021-10-26 | 东华大学 | Preparation method of mesoporous silica long-acting antibacterial nanomaterial with high selenium loading |
| CN110683860A (en) * | 2019-11-18 | 2020-01-14 | 萍乡学院 | Ceramic hollow ball with double-shell structure and preparation method thereof |
| CN111871393A (en) * | 2020-07-28 | 2020-11-03 | 常州大学 | Mesoporous organic silicon hollow sphere synthesized by double-template method and adsorption application thereof |
| CN111871393B (en) * | 2020-07-28 | 2023-04-11 | 常州大学 | Mesoporous organic silicon hollow sphere synthesized by double-template method and adsorption application thereof |
| CN113150028A (en) * | 2021-04-09 | 2021-07-23 | 浙江理工大学 | Preparation method of mesoporous organic silicon nanowire and mesoporous organic silicon nanowire |
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Application publication date: 20150422 |