CN104418333A - Method for preparing mesoporous silica hollow spheres - Google Patents
Method for preparing mesoporous silica hollow spheres Download PDFInfo
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- CN104418333A CN104418333A CN201310409492.5A CN201310409492A CN104418333A CN 104418333 A CN104418333 A CN 104418333A CN 201310409492 A CN201310409492 A CN 201310409492A CN 104418333 A CN104418333 A CN 104418333A
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Abstract
The invention discloses a method for preparing mesoporous silica hollow spheres. The preparation method specifically includes the following steps: dispersing a phenolic resin polymer bead as a hard template into deionized water and ethyl alcohol; adding a quaternary ammonium cationic surfactant or linear chain fatty amine neutral surfactant, uniformly mixing, adding a silicon source, reacting at a proper pH value, and drying and roasting the prepared product to prepare the mesoporous silica hollow spheres. The preparation method is mild in condition, simple in process, and strong in controllability; the prepared product is regular in appearance, and adjustable in shell thickness, pore size and structure, thus the preparation method is wide in industrial application prospect.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to a kind of method that hard template technology prepares mesoporous silica hollow ball.
Background technology
In recent years, the hollow silica ball with mesoporous lamella receives the extensive concern of investigators.Compared with the Metaporous silicon dioxide material of routine, meso-porous hollow ball material has larger specific surface area and pore volume, has wide application space in fields such as catalysis, fractionation by adsorption, drug loadings.
At present, template prepares the most effective means of mesoporous silica hollow ball, comprising soft template method and hard template method.The former is that the micella or other state of aggregation that are formed in the solution with tensio-active agent, vesica or micro emulsion are for template is to synthesize hollow ball material (Science, 1998,282,1302; Chem.Mater., 2009,21,4122; Chem.Commun., 2008,2629.).This method is higher to synthesis process control requirements, the slight change of synthesis condition can cause the pattern of product and structure uneven.By contrast, preparation process based on hard template method is easy to control, this method is at the coated one deck mesoporous silicon oxide of organic polymer, metal or nonmetal oxide bead surface, remove inner core materials again and obtain silicon dioxide hollow sphere material, the product obtained by this method not only structure is homogeneous, and structural parameter to a certain extent can modulation.Typical work has: Qi etc. adopt polystyrene (PS) bead to be the mesoporous silica hollow ball (Chem.Mater., 2010,22,2693) that hard template has synthesized different scale; Zhao etc. take ferric oxide nanometer particle as hard template, and octadecyl trimethoxysilane is pore-forming material, synthesize mesoporous silica hollow ball (J.Mater.Chem., 2009,19,2778).But the preparation process of hard template material used in these synthesis is loaded down with trivial details, and relate to the use of tensio-active agent of some costlinesses, be unfavorable for carrying out on a large scale.
Summary of the invention
The object of this invention is to provide a kind of preparation method of mesoporous silica hollow ball.
The preparation method of a kind of mesoporous silica hollow ball provided by the invention, for hard template with novalac polymer bead, detailed process: novalac polymer bead, deionized water, ethanol and tensio-active agent are mixed successively, the pH value of regulation system, add silicon source, reaction 4 ~ 24h at room temperature ~ 40 DEG C, products therefrom after super-dry, at 550 DEG C of roastings removing organism.
Proportioning between described material is: 1g novalac polymer little Qiu ﹕ (8.3 ~ 33.3) mol Qu Li Shui ﹕ (1.5 ~ 3.4) mol Yi Chun ﹕ (0.0015 ~ 0.003) mol Biao Mian Huo Ji ﹕ (0.0086 ~ 0.029) mol silicon source.Described novalac polymer bead be with Resorcinol and formaldehyde for raw material, pass through in deionized water and ethanol system
legal system is standby.
Described tensio-active agent is general formula is C
nh
2n+1(CH
3)
3the quaternary ammonium salt cationic surfactant of NBr, wherein n=12 ~ 16, or be straight-chain fatty amine neutral surface active agent amino dodecane.
Described silicon source is tetraethyl silicane acid esters;
Described adjust ph refers in quaternary ammonium salt cationic surfactant system, adopts ammoniacal liquor adjust ph to 9 ~ 11 of mass concentration 25-28%, in straight-chain fatty amine neutral surface active agent amino dodecane system, without the need to adjust ph.
The present invention with the simple novalac polymer bead of preparation technology for hard template, quaternary ammonium salt cationic surfactant or straight-chain fatty amine neutral surface active agent amino dodecane are structure directing agent, efficiently prepare mesoporous silica hollow ball material, preparation condition gentleness is controlled, and the structural parameter of product are adjustable.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of mesoporous silica hollow ball of the present invention, corresponding embodiment 1.
Fig. 2 is the X-ray diffractogram of mesoporous silica hollow ball of the present invention, corresponding embodiment 1.
Embodiment
Prepare novalac polymer bead
Get 50ml deionized water to mix with 10ml dehydrated alcohol, add 0.3g ammoniacal liquor, stir 10min, add 0.4g Resorcinol, 30min is stirred at 30 DEG C, then add 0.6g formalin (37%), at 30 DEG C of Keep agitation 24h, reaction solution is loaded with in teflon-lined stainless steel autoclave, at 100 DEG C of process 24h, centrifugation goes out solid product, 80 DEG C of oven dry, and grind into powder.
Embodiment 1
Getting 0.05g novalac polymer bead is scattered in 25ml deionized water, add 15ml dehydrated alcohol, add 0.053g cetyl trimethylammonium bromide, stir 30min, add 0.3g ammoniacal liquor, add 0.15g tetraethyl silicane acid esters again, at 40 DEG C, Keep agitation 24h, filters out solid product, 80 DEG C of oven dry, 550 DEG C of roasting 5h, obtain the mesoporous silica hollow ball that shell thickness is 50nm.
Embodiment 2
Getting 0.05g novalac polymer bead is scattered in 25ml deionized water, add 15ml dehydrated alcohol, add 0.053g cetyl trimethylammonium bromide, stir 30min, add 0.3g ammoniacal liquor, add 0.30g tetraethyl silicane acid esters again, at 40 DEG C, Keep agitation 24h, filters out solid product, 80 DEG C of oven dry, 550 DEG C of roasting 5h, obtain the mesoporous silica hollow ball that shell thickness is 67nm.
Embodiment 3
Getting 0.05g novalac polymer bead is scattered in 30ml deionized water, add 10ml dehydrated alcohol, add 0.053g cetyl trimethylammonium bromide, stir 30min, add 0.3g ammoniacal liquor, add 0.15g tetraethyl silicane acid esters again, at 40 DEG C, Keep agitation 24h, filters out solid product, 80 DEG C of oven dry, 550 DEG C of roasting 5h, obtain mesoporous silica hollow ball.
Embodiment 4
Getting 0.05g novalac polymer bead is scattered in 25ml deionized water, add 15ml dehydrated alcohol, add 0.053g cetyl trimethylammonium bromide, stir 30min, add 0.3g ammoniacal liquor, add 0.15g tetraethyl silicane acid esters again, at 40 DEG C, Keep agitation 2h, filters out solid product, 80 DEG C of oven dry, 550 DEG C of roasting 5h, obtain mesoporous silica hollow ball.
Embodiment 5
Getting 0.05g novalac polymer bead is scattered in 25ml deionized water, add 15ml dehydrated alcohol, add 0.053g cetyl trimethylammonium bromide, stir 30min, add 0.3g ammoniacal liquor, add 0.15g tetraethyl silicane acid esters again, room temperature with constant stirs 24h, filters out solid product, 80 DEG C of oven dry, 550 DEG C of roasting 5h, obtain mesoporous silica hollow ball.
Embodiment 6
Getting 0.05g novalac polymer bead is scattered in 25ml deionized water, add 15ml dehydrated alcohol, add 0.053g Trimethyllaurylammonium bromide, stir 30min, add 0.3g ammoniacal liquor, add 0.15g tetraethyl silicane acid esters again, at 40 DEG C, Keep agitation 24h, filters out solid product, 80 DEG C of oven dry, 550 DEG C of roasting 5h, obtain mesoporous silica hollow ball.
Embodiment 7
Getting 0.1g novalac polymer bead is scattered in 18ml deionized water, add 20ml dehydrated alcohol, add 0.050g amino dodecane, stir 30min, then add 0.26g tetraethyl silicane acid esters, Keep agitation 18h at 40 DEG C, filter out solid product, 80 DEG C of oven dry, 550 DEG C of roasting 5h, obtain mesoporous silica hollow ball.
Embodiment 8
Getting 0.33g novalac polymer bead is scattered in 50ml deionized water, add 30ml dehydrated alcohol, add 0.2g cetyl trimethylammonium bromide, stir 30min, add 0.6g ammoniacal liquor, add 0.6g tetraethyl silicane acid esters again, at 40 DEG C, Keep agitation 24h, filters out solid product, 80 DEG C of oven dry, 550 DEG C of roasting 5h, mesoporous silica hollow ball.
Claims (6)
1. the preparation method of a mesoporous silica hollow ball, concrete preparation process is: be first scattered in by novalac polymer bead in the mixed solvent of deionized water and ethanol, then tensio-active agent is added, after it dissolves completely, the pH value of adjustment or not regulation system, finally add silicon source, stir 2 ~ 24h at 20 ~ 40 DEG C, product removes organism 500-550 DEG C of roasting after super-dry.
2. the preparation method of a kind of mesoporous silica hollow ball according to claim 1, is characterized in that: the proportioning between material is: 1g novalac polymer little Qiu ﹕ (8.3 ~ 33.3) mol Qu Li Shui ﹕ (1.5 ~ 5.1) mol Yi Chun ﹕ (0.0015 ~ 0.003) mol Biao Mian Huo Ji ﹕ (0.0086 ~ 0.029) mol silicon source.
3. preparation method according to claim 1 and 2, is characterized in that: described novalac polymer bead be with Resorcinol and formaldehyde for raw material, pass through in deionized water and ethanol system
legal system is standby; The diameter of bead is 250-400nm.
4. preparation method according to claim 1 and 2, is characterized in that: described tensio-active agent is general formula is C
nh
2n+1(CH
3)
3the quaternary cationics of NBr, one or two or more kinds wherein in n=12 ~ 16, or be straight-chain fatty amine neutral surface active agent amino dodecane.
5. preparation method according to claim 1 and 2, is characterized in that: described silicon source is tetraethyl silicane acid esters.
6. preparation method according to claim 1, it is characterized in that: described adjust ph refers in quaternary ammonium salt cationic surfactant system, adopt ammoniacal liquor adjust ph to 9 ~ 11 of mass concentration 25-28%, in straight-chain fatty amine neutral surface active agent amino dodecane system, without the need to adjust ph.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694356A (en) * | 2016-03-14 | 2016-06-22 | 北京科技大学 | Porous hollow phenolic resin nanospheres and carbon nanospheres and preparation method |
| CN109395592A (en) * | 2018-10-30 | 2019-03-01 | 同济大学 | Modified seperation film of a kind of pollen silicon loading nano silvery and preparation method thereof |
| CN110589794A (en) * | 2019-09-06 | 2019-12-20 | 鞍钢化学科技有限公司 | Preparation method of large-size porous carbon material |
| CN111232993A (en) * | 2020-03-06 | 2020-06-05 | 山东国瓷功能材料股份有限公司 | 5G high-frequency ultralow dielectric constant hollow silicon dioxide and preparation method thereof |
| CN114497892A (en) * | 2021-12-30 | 2022-05-13 | 苏州大学 | Mesoporous silicon oxide/polymer composite lithium ion battery diaphragm and preparation thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101683983A (en) * | 2008-09-27 | 2010-03-31 | 中国科学院大连化学物理研究所 | Method for preparing hollow mesoporous lamella spherical silica material |
| CN102992329A (en) * | 2011-09-15 | 2013-03-27 | 同济大学 | Method for preparing mesoporous silicon oxide microspheres |
-
2013
- 2013-09-10 CN CN201310409492.5A patent/CN104418333A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101683983A (en) * | 2008-09-27 | 2010-03-31 | 中国科学院大连化学物理研究所 | Method for preparing hollow mesoporous lamella spherical silica material |
| CN102992329A (en) * | 2011-09-15 | 2013-03-27 | 同济大学 | Method for preparing mesoporous silicon oxide microspheres |
Non-Patent Citations (3)
| Title |
|---|
| JIAN LIU ET AL.: "Extension of The St ber Method to the Preparation of Monodisperse Resorcinol–Formaldehyde Resin Polymer and Carbon Spheres", 《ANGEW. CHEM. INT. ED》 * |
| WERNER STOBER ET AL.: "Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range", 《JOUNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 郝志显等: "表面活性剂存在条件下脲醛树脂杂化氧化硅微球的合成和表征", 《化学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694356A (en) * | 2016-03-14 | 2016-06-22 | 北京科技大学 | Porous hollow phenolic resin nanospheres and carbon nanospheres and preparation method |
| CN109395592A (en) * | 2018-10-30 | 2019-03-01 | 同济大学 | Modified seperation film of a kind of pollen silicon loading nano silvery and preparation method thereof |
| CN110589794A (en) * | 2019-09-06 | 2019-12-20 | 鞍钢化学科技有限公司 | Preparation method of large-size porous carbon material |
| CN111232993A (en) * | 2020-03-06 | 2020-06-05 | 山东国瓷功能材料股份有限公司 | 5G high-frequency ultralow dielectric constant hollow silicon dioxide and preparation method thereof |
| CN111232993B (en) * | 2020-03-06 | 2021-09-14 | 山东国瓷功能材料股份有限公司 | 5G high-frequency ultralow dielectric constant hollow silicon dioxide and preparation method thereof |
| CN114497892A (en) * | 2021-12-30 | 2022-05-13 | 苏州大学 | Mesoporous silicon oxide/polymer composite lithium ion battery diaphragm and preparation thereof |
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Application publication date: 20150318 |