CN101654252A - Preparation method of mono-disperse silica mesoporous sphere material - Google Patents
Preparation method of mono-disperse silica mesoporous sphere material Download PDFInfo
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- CN101654252A CN101654252A CN200910195137A CN200910195137A CN101654252A CN 101654252 A CN101654252 A CN 101654252A CN 200910195137 A CN200910195137 A CN 200910195137A CN 200910195137 A CN200910195137 A CN 200910195137A CN 101654252 A CN101654252 A CN 101654252A
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Abstract
The invention discloses a preparation method of a mono-disperse silica mesoporous sphere material in the technical field of inorganic materials, comprising the following steps: taking quaternary ammonium salt gemini surfactant as a template, organic solvent as an auxiliary solvent and organosiloxane as a silica resource, adjusting solution alkalinity and preparing the silica mesoporous sphere material with a structure in which pore canals are arranged to disperse from the centre of the sphere to the outer surface of the sphere. The silica mesoporous sphere material has single dispersed sphereappearance, with the relative standard deviation of the diameter being lower than 10 percent and the diameter of 70490 nm.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of inorganic material, specifically is a kind of preparation method of mono-disperse silica mesoporous sphere material.
Background technology
Inorganic mesoporous material have big specific surface area and pore volume, adjustable pore structure, adjustable aperture, can adorned surface properties and can controlled appearance; Have single mesoporous silica spheres shape material of particle diameter that disperses and very large application potential is arranged in fields such as chromatographic column, makeup, photonic crystals.
Find through literature search prior art, Yano, K etc. have delivered at " Journal of MaterialsChemistry " (materials chemistry magazine) 2003 the 13rd phase 2577-2581 pages or leaves and have been entitled as " Particlesize control of mono-dispersed super-microporous silica spheres " (single particle diameter control that disperses the ultramicropore silica spheres) literary composition, mention in the literary composition, can control the particle diameter of monodisperse silica sphere particle by the control reaction conditions; Suzuki, T.M. wait to have delivered and be entitled as " Synthesis and catalytic properties of sulfonic acid-functionalizedmonodispersed mesoporous silica spheres " (synthetic and catalysis of the monodisperse mesoporous ball of sulfonic acid functional) literary composition at " Microporous and MesoporousMaterials " (micropore and mesoporous material) 2008 the 111st phase 350-358 pages or leaves, point out in the literary composition, by in reaction system, adding the organosilane that contains the sulfonic acid functional group, can synthesize the mesoporous SiO 2 silicon ball of sulfonic acid functional.The sphere material particle diameter that the synthetic method that these two pieces of documents propose obtains is even inadequately, and implementation method is more special.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of preparation method of mono-disperse silica mesoporous sphere material is provided, prepare SiO 2 mesoporous materials, has the monodisperse spherical profile, diameter 70nm～490nm, the relative standard deviation of its particle diameter is lower than 10%, has the pore passage structure that begins to disperse to the outside surface of ball arrangement from the centre of sphere.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
The mol ratio of described quaternary ammonium salt type gemini surfactant and deionized water, organic cosolvent, alkali and organosilane is 1: 4000～65000: 300～5000: 0.8～13: 0.2～5: 10～40;
The described stirring of heating is meant under 0 ℃～90 ℃ environment stirs.
The structure of described quaternary ammonium salt type gemini surfactant is:
R
1N(R
2)
2X-B-N(R
3)
3X；
Wherein: R
1Be C
12-C
20Straight chained alkyl, R
2Be C
1-C
2Straight chained alkyl, B are C
2-C
3Straight chained alkyl, R
3Be C
1-C
2Straight chained alkyl, X
-Be chlorion or bromide anion.
Described organic cosolvent is a kind of in ethanol, methyl alcohol, Virahol, acetone, acetonitrile or the methyl-sulphoxide.
Described alkali is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor, methylamine or the ethamine.
Described organosilane is a kind of in tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, dimethoxy dimethylsilane, trimethoxymethylsila,e or the dimethoxy di-isopropyl silane.
Described hybrid reaction is meant: the silicon-dioxide mixed solution is fully stirred be placed under 0 ℃～90 ℃ environment standing and reacting in 10 minutes 0.5～120 hour;
Described calcination process is meant: roasting is 6 hours under 550 ℃ of air ambients.
The present invention is a template with ammonium salt type Gemini surface active agent, with the organic solvent is solubility promoter, with the organo-siloxane is silica source, regulator solution basicity, prepare to have and begin to disperse the SiO 2 mesoporous materials of arranging pore passage structure to the outside surface of ball from the centre of sphere, have the monodisperse spherical profile, the relative standard deviation of its diameter is lower than 10%, diameter 70nm～490nm.
Description of drawings
Fig. 1 is the electromicroscopic photograph of the mono-disperse silica mesoporous ball of embodiment 1 preparation.
Fig. 2 is the X ray diffracting spectrum of the mono-disperse silica mesoporous ball of embodiment 1 preparation.
Fig. 3 is the nitrogen adsorption isotherm of the mono-disperse silica mesoporous ball of embodiment 1 preparation.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
As shown in Figure 1, with 0.11g C
18H
37NBr (CH
3)
2CH
2CH
2CH
2N (CH
3)
3Br is dissolved in the 38g deionized water, adds 9.2g ethanol then, under 80 ℃ of stirrings, adds the sodium hydroxide of 6.5g0.1mol/l in the aqueous solution of this tensio-active agent, adds the 0.8g tetraethoxysilane in this system; This system is stirred 10min,, filter 80 ℃ of standing and reacting 48 hours, washing, drying in 550 ℃ of following roastings 6 hours, obtains removing the mono-disperse silica mesoporous sphere material of organic formwork and functional group.
By transmission electron microscope, X-ray diffraction, scanning electron microscope, the nitrogen adsorption instrument characterizes this material.Fig. 2 and Fig. 3 are respectively electromicroscopic photograph, X ray diffracting spectrum and the nitrogen adsorption isotherm of this mesoporous material.Silica mesoporous sphere material has from the centre of sphere and begins to disperse the arrangement pore passage structure to the outside surface of ball as can be seen from Figure 2, median size 420nm, and the particle diameter relative standard deviation is 2.5%, unit cell parameters is 4.3nm.As can be seen from Figure 3, mesoporous material has IV type nitrogen adsorption isotherm, can also draw the aperture that mesoporous material has 2.5nm from the nitrogen adsorption isotherm of Fig. 3, and calculating pore wall thickness is 1.3nm.
As shown in Figure 1, with 0.04g C
18H
37NCl (CH
3)
2CH
2CH
2CH
2N (CH
3)
3Cl is dissolved in the 38g deionized water, adds 13.8g ethanol then, under 50 ℃ of stirrings, adds the sodium hydroxide of 6.5g0.1mol/l in the aqueous solution of this tensio-active agent, adds the 0.15g tetramethoxy-silicane in this system; This system is stirred 10min,, filter 50 ℃ of standing and reacting 48 hours, washing, drying in 550 ℃ of following roastings 6 hours, obtains removing the mono-disperse silica mesoporous sphere material of organic formwork and functional group.
By X-ray diffraction, scanning electron microscope, nitrogen adsorption and transmission electron microscope instrument characterize this material.Draw the median size 280nm of this material, the particle diameter relative standard deviation is 8.9%, and unit cell parameters is 4.4nm, and the aperture is 2.5nm, and calculating pore wall thickness is 1.3nm.
As shown in Figure 1, with 0.11g C
18H
37NBr (CH
3)
2CH
2CH
2CH
2N (CH
3)
3Br is dissolved in the 38g deionized water, adds 13.8g ethanol then, under 80 ℃ of stirrings, adds the sodium hydroxide of 6.5g0.1mol/l in the aqueous solution of this tensio-active agent, adds the 0.8g tetraethoxysilane in this system; This system is stirred 10min,, filter 80 ℃ of standing and reacting 48 hours, washing, drying in 550 ℃ of following roastings 6 hours, obtains removing the mono-disperse silica mesoporous sphere material of organic formwork and functional group.
By X-ray diffraction, scanning electron microscope, nitrogen adsorption and transmission electron microscope instrument characterize this material.Draw the median size 460nm of this material, the particle diameter relative standard deviation is 3.9%, and unit cell parameters is 4.0nm, and the aperture is 2.5nm, and calculating pore wall thickness is 1.0nm.
As shown in Figure 1, with 0.11g C
18H
37NBr (CH
3)
2CH
2CH
2CH
2N (CH
3)
3Br is dissolved in the 38g deionized water, adds 13.8g ethanol then, under 80 ℃ of stirrings, adds the sodium hydroxide of 10g0.1mol/l in the aqueous solution of this tensio-active agent, adds the 1.0g tetrapropoxysilane in this system; This system is stirred 10min,, filter 80 ℃ of standing and reacting 48 hours, washing, drying in 550 ℃ of following roastings 6 hours, obtains removing the mono-disperse silica mesoporous sphere material of organic formwork and functional group.
By X-ray diffraction, scanning electron microscope, nitrogen adsorption and transmission electron microscope instrument characterize this material.Draw the median size 490nm of this material, the particle diameter relative standard deviation is 5.6%, and unit cell parameters is 4.1nm, and the aperture is 2.5nm, and calculating pore wall thickness is 1.1nm.
As shown in Figure 1, with 0.11g C
18H
37NBr (CH
3)
2CH
2CH
2CH
2N (CH
3)
3In the molten 38g deionized water of Br, add the 8g Virahol then, under 80 ℃ of stirrings, in the aqueous solution of this tensio-active agent, add the sodium hydroxide of 6.5g0.1mol/l, in this system, add the 1.0g tetraisopropoxysilan; This system is stirred 10min,, filter 80 ℃ of standing and reacting 48 hours, washing, drying in 550 ℃ of following roastings 6 hours, obtains removing the mono-disperse silica mesoporous sphere material of organic formwork and functional group.
By X-ray diffraction, scanning electron microscope, nitrogen adsorption and transmission electron microscope instrument characterize this material.Draw the median size 180nm of this material, the particle diameter relative standard deviation is 8.0%, and unit cell parameters is 4.4nm, and the aperture is 2.5nm, and calculating pore wall thickness is 1.4nm.
As shown in Figure 1, with 0.11g C
18H
37NBr (CH
3)
2CH
2CH
2CH
2N (CH
3)
3Br is dissolved in the 38g deionized water, adds 8g acetone then, under 80 ℃ of stirrings, adds the sodium hydroxide of 6.5g0.1mol/l in the aqueous solution of this tensio-active agent, adds 1.2g four butoxy silanes in this system; This system is stirred 10min,, filter 80 ℃ of standing and reacting 48 hours, washing, drying in 550 ℃ of following roastings 6 hours, obtains removing the mono-disperse silica mesoporous sphere material of organic formwork and functional group.
By X-ray diffraction, scanning electron microscope, nitrogen adsorption and transmission electron microscope instrument characterize this material.Draw the median size 230nm of this material, the particle diameter relative standard deviation is 7.2%, and unit cell parameters is 4.7nm, and the aperture is 2.7nm, and calculating pore wall thickness is 1.3nm.
Embodiment 7
As shown in Figure 1, with 0.11g C
18H
37NBr (CH
3)
2CH
2CH
2CH
2N (CH
3)
3Br is dissolved in the 38g deionized water, adds the 8g acetonitrile then under 80 ℃ of stirrings, adds the sodium hydroxide of 6.5g0.1mol/l in the aqueous solution of this tensio-active agent, adds 0.5g dimethoxy dimethylsilane in this system; This system is stirred 10min,, filter 80 ℃ of standing and reacting 48 hours, washing, drying in 550 ℃ of following roastings 6 hours, obtains removing the mono-disperse silica mesoporous sphere material of organic formwork and functional group.
By X-ray diffraction, scanning electron microscope, nitrogen adsorption and transmission electron microscope instrument characterize this material.Draw the median size 280nm of this material, the particle diameter relative standard deviation is 2.8%, and unit cell parameters is 4.7nm, and the aperture is 2.7nm, and calculating pore wall thickness is 1.3nm.
Embodiment 8
As shown in Figure 1, with 0.11g C
18H
37NBr (CH
3)
2CH
2CH
2CH
2N (CH
3)
3Br is dissolved in the 38g deionized water, adds the 24g methyl-sulphoxide then under 80 ℃ of stirrings, adds the sodium hydroxide of 6.5g0.1mol/l in the aqueous solution of this tensio-active agent, adds the 0.5g trimethoxymethylsila,e in this system; This system is stirred 10min,, filter 80 ℃ of standing and reacting 48 hours, washing, drying in 550 ℃ of following roastings 6 hours, obtains removing the mono-disperse silica mesoporous sphere material of organic formwork and functional group.
By X-ray diffraction, scanning electron microscope, nitrogen adsorption and transmission electron microscope instrument characterize this material.Draw the median size 290nm of this material, the particle diameter relative standard deviation is 4.4%, and unit cell parameters is 4.4nm, and the aperture is 2.5nm, and calculating pore wall thickness is 1.3nm.
Embodiment 9
As shown in Figure 1, with 0.11g C
18H
37NBr (CH
3)
2CH
2CH
2CH
2N (CH
3)
3Br is dissolved in the 38g deionized water, adds 16g methyl alcohol then under 80 ℃ of stirrings, adds the sodium hydroxide of 6.5g0.1mol/l in the aqueous solution of this tensio-active agent, adds 0.7g dimethoxy di-isopropyl silane in this system; This system is stirred 10min,, filter 80 ℃ of standing and reacting 48 hours, washing, drying in 550 ℃ of following roastings 6 hours, obtains removing the mono-disperse silica mesoporous sphere material of organic formwork and functional group.
By X-ray diffraction, scanning electron microscope, nitrogen adsorption and transmission electron microscope instrument characterize this material.Draw the median size 380nm of this material, the particle diameter relative standard deviation is 2.8%, and unit cell parameters is 4.4nm, and the aperture is 2.5nm, and calculating pore wall thickness is 1.3nm.
Claims (9)
1, a kind of preparation method of mono-disperse silica mesoporous sphere material is characterized in that, may further comprise the steps:
Step 1 is dissolved in quaternary ammonium salt type gemini surfactant in the deionized water, adds the organic cosolvent and the stirring of heating then in deionized water, adds alkali and organosilane at last in deionized water successively, makes the silicon-dioxide mixed solution.
Step 2, the silicon-dioxide mixed solution carried out hybrid reaction after, after the dry and calcination process, obtain SiO 2 mesoporous materials through diafiltration successively.
2, the preparation method of mono-disperse silica mesoporous sphere material according to claim 1, it is characterized in that the mol ratio of described quaternary ammonium salt type gemini surfactant and deionized water, organic cosolvent, alkali and organosilane is 1: 4000～65000: 300～5000: 0.8～13: 0.2～5: 10～40.
3, the preparation method of mono-disperse silica mesoporous sphere material according to claim 1 is characterized in that, the described stirring of heating is meant under 0 ℃～90 ℃ environment stirs.
4, the preparation method of mono-disperse silica mesoporous sphere material according to claim 1 is characterized in that, the structure of described quaternary ammonium salt type gemini surfactant is:
R
1N(R
2)
2X-B-N(R
3)
3X；
Wherein: R
1Be C
12-C
20Straight chained alkyl, R
2Be C
1-C
2Straight chained alkyl, B are C
2-C
3Straight chained alkyl, R
3Be C
1-C
2Straight chained alkyl, X
-Be chlorion or bromide anion.
5, the preparation method of mono-disperse silica mesoporous sphere material according to claim 1 is characterized in that, described organic cosolvent is a kind of in ethanol, methyl alcohol, Virahol, acetone, acetonitrile or the methyl-sulphoxide.
6, the preparation method of mono-disperse silica mesoporous sphere material according to claim 1 is characterized in that, described alkali is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor, methylamine or the ethamine.
7, the preparation method of mono-disperse silica mesoporous sphere material according to claim 1, it is characterized in that described organosilane is a kind of in tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, dimethoxy dimethylsilane, trimethoxymethylsila,e or the dimethoxy di-isopropyl silane.
8, the preparation method of mono-disperse silica mesoporous sphere material according to claim 1, it is characterized in that described hybrid reaction is meant: the silicon-dioxide mixed solution is fully stirred be placed under 0 ℃～90 ℃ environment standing and reacting in 10 minutes 0.5～120 hour.
9, the preparation method of mono-disperse silica mesoporous sphere material according to claim 1 is characterized in that, described calcination process is meant: roasting is 6 hours under 550 ℃ of air ambients.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381715A (en) * | 2010-09-03 | 2012-03-21 | 中国科学院上海硅酸盐研究所 | Large-pore-wall cage-shaped silica hollow sphere and preparation method thereof |
| CN103738969A (en) * | 2013-12-25 | 2014-04-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Mesoporous silica and preparation method thereof |
| CN104788997A (en) * | 2015-03-18 | 2015-07-22 | 四川长虹技佳精工有限公司 | Modified oxide and powder coating, and preparation methods and applications thereof |
| WO2018133586A1 (en) * | 2017-01-22 | 2018-07-26 | 华东师范大学 | Uniform silica microsphere, preparation method therefor, and application thereof |
| CN109553111A (en) * | 2018-12-25 | 2019-04-02 | 国联汽车动力电池研究院有限责任公司 | A kind of silicon dioxide microsphere of core-shell structure and preparation method thereof |
| CN114950340A (en) * | 2022-04-08 | 2022-08-30 | 中国原子能科学研究院 | Silica gel and preparation method thereof |
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2009
- 2009-09-04 CN CN200910195137A patent/CN101654252A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381715A (en) * | 2010-09-03 | 2012-03-21 | 中国科学院上海硅酸盐研究所 | Large-pore-wall cage-shaped silica hollow sphere and preparation method thereof |
| CN102381715B (en) * | 2010-09-03 | 2013-04-17 | 中国科学院上海硅酸盐研究所 | Large-pore-wall cage-shaped silica hollow sphere and preparation method thereof |
| CN103738969A (en) * | 2013-12-25 | 2014-04-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Mesoporous silica and preparation method thereof |
| CN103738969B (en) * | 2013-12-25 | 2015-07-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Mesoporous silica and preparation method thereof |
| CN104788997A (en) * | 2015-03-18 | 2015-07-22 | 四川长虹技佳精工有限公司 | Modified oxide and powder coating, and preparation methods and applications thereof |
| CN104788997B (en) * | 2015-03-18 | 2017-10-24 | 四川长虹技佳精工有限公司 | Modified oxide, powdery paints and its preparation method and application |
| WO2018133586A1 (en) * | 2017-01-22 | 2018-07-26 | 华东师范大学 | Uniform silica microsphere, preparation method therefor, and application thereof |
| CN109553111A (en) * | 2018-12-25 | 2019-04-02 | 国联汽车动力电池研究院有限责任公司 | A kind of silicon dioxide microsphere of core-shell structure and preparation method thereof |
| CN109553111B (en) * | 2018-12-25 | 2022-04-12 | 国联汽车动力电池研究院有限责任公司 | Silicon dioxide microsphere with core-shell structure and preparation method thereof |
| CN114950340A (en) * | 2022-04-08 | 2022-08-30 | 中国原子能科学研究院 | Silica gel and preparation method thereof |
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Application publication date: 20100224 |