CN104261416B - A kind of preparation method of special-shaped looks mesoporous silicon oxide - Google Patents
A kind of preparation method of special-shaped looks mesoporous silicon oxide Download PDFInfo
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- CN104261416B CN104261416B CN201410496179.4A CN201410496179A CN104261416B CN 104261416 B CN104261416 B CN 104261416B CN 201410496179 A CN201410496179 A CN 201410496179A CN 104261416 B CN104261416 B CN 104261416B
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Abstract
A kind of preparation method of special-shaped looks mesoporous silicon oxide, belong to inorganic porous material technical field, be specifically related to the agent of a kind of employing cationic quaternary ammonium salt surfactants as template, in the gentle acid system that acetic acid and non-hydrolytic inorganic sodium are formed, by changing the kind of sodium salt, comprise SODIUMNITRATE, sodium-chlor and sodium sulfate, room temperature leave standstill synthesis have volution, spherical and rope shape specific surface area be 1659.2-1756.1m
2/ g, does is pore volume 0.97-0.98? cm
3/ g, does is aperture 22.5-24.2? the method of six side's ordered mesoporous silica dioxides.Present invention reduces preparation cost and the synthesis difficulty of acid system mesoporous silicon oxide, decrease building-up process to environment and the degree to the infringement that equipment causes, also contribute to variously there is bioactive guest molecule if protein, enzyme etc. are by the encapsulation of mode in mesopore orbit of directly synthesis, and then extend the range of application of mesoporous silicon oxide.
Description
Technical field
The preparation method of a kind of special-shaped looks mesoporous silicon oxide of the present invention
,belong to inorganic porous material technical field, be specifically related to the agent of a kind of employing cationic quaternary ammonium salt surfactants as template, in the gentle acid system that acetic acid and non-hydrolytic inorganic sodium are formed, by changing the kind of sodium salt, comprise SODIUMNITRATE, sodium-chlor and sodium sulfate, room temperature leaves standstill the method that synthesis has volution, spherical and rope shape six side ordered mesoporous silica dioxide.
Background technology
Mesoporous silicon oxide is (J.Am.Chem.Soc. since last century, the early 1990s successfully synthesized; 1992; 114; 10834); wide application prospect (Chem.Rev., 1997,97 are demonstrated in many research fields such as catalysis, absorption, separation, biological medicine, environment protection, host-guest chemistry and new function materials due to features such as its large specific surface area, high pore volume and apertures adjustable flexibly; 2373 etc.) focus of inorganic porous material research field, has now been become.Current mesoporous silicon oxide normally adopts dissimilar surfactants as template agent to be carried out (Chem.Rev., 2007,107 (7), 2281 etc.) of synthesizing under acid or alkaline conditions by different self-assembly modes.
Compared with the synthesis of alkaline system mesoporous silicon oxide, acid synthetic medium is more conducive to the control (Nature. to material macro morphology usually, 1997,386,, and mesoporous silicon oxide has its specific pattern (Chem.Rev., 2007 in the application general requirement of every field 692 etc.), 107 (7), 2281 etc.).Simultaneously, the synthesis of acid system mesoporous silicon oxide does not often need heating or hydrothermal conditions, usually can carry out under room temperature or lower temperature, and synthetic product does not also need washing procedure, template can adopt solvent-extracted mode to remove easily, and therefore this synthetic method receives and pays close attention to (Chem.Rev., 2007 widely, 107 (7), 2281 etc.).But, when adopting the acid system of cationic quaternary ammonium salt surfactants as template agent to carry out synthesis and the morphology control thereof of mesoporous silicon oxide, usually need at HCl, H
2sO
4, HNO
3or carry out (Chem.Rev. in the acidic medium that provides of the strong acid such as HBr, 2007,, and in a kind of synthetic system of specific components, often only can form a kind of Metaporous silicon dioxide material (as CN1556033A and CN1994879A etc.) of specific morphology 107 (7), 2281 etc.).And when adopting acid relatively gentle organic acid to make silicon source hydrolyst as acetic acid, even if under high acetate concentration, the earth silicon material (J.Phys.Chem.B. no matter adopting stirring reaction or standing operation all cannot be formed there is mesoporous thing phase, 2000,104,7885, Chem.Mater., 2005,17,4103 and Chem.Rev., 2007,107 (7), 2281 etc.) control, let alone to material morphology.Obviously, strong acid synthetic medium, there is operational hazards in not only etching apparatus, and easily causes environmental pollution, is unfavorable for large-scale production.The more important thing is, this synthetic medium is also unfavorable for having bioactive guest molecule such as protein, enzyme etc. and has the encapsulation of the original position in different-shape mesoporous silicon oxide duct and coated by the mode of directly synthesis, and then greatly limit the applicable scope of material.Therefore, how to realize ordered mesoporous silica dioxide in the synthesis of relatively gentle acid system and morphology control thereof, be the target that those skilled in the art pursue always.
Summary of the invention
The preparation method of a kind of special-shaped looks mesoporous silicon oxide of the present invention, object is for above-mentioned the deficiencies in the prior art, thus the agent of open a kind of employing cationic quaternary ammonium salt surfactants as template, in the gentle acid system that acetic acid and non-hydrolytic inorganic sodium are formed, by changing the kind of sodium salt, comprise SODIUMNITRATE, sodium-chlor and sodium sulfate, room temperature leaves standstill the method that synthesis has volution, spherical and rope shape six side ordered mesoporous silica dioxide.
The preparation method of a kind of special-shaped looks mesoporous silicon oxide of the present invention, it is characterized in that the agent of a kind of employing cationic quaternary ammonium salt surfactants as template, in the gentle acid system that acetic acid and non-hydrolytic inorganic sodium are formed, by changing the kind of sodium salt, comprise SODIUMNITRATE, sodium-chlor and sodium sulfate, room temperature leaves standstill synthesis and has volution, the method of spherical and rope shape six side ordered mesoporous silica dioxide, the method adopts the agent of cationic quaternary ammonium salt surfactants as template, silicon source is done with methyl silicate (TMOS) or tetraethoxy (TEOS), the Glacial acetic acid (HAc) relatively gentle by acidity substitutes traditional strong acid HCl, H
2sO
4, HNO
3or HBr makes silicon source hydrolyst, do not affect non-hydrolytic inorganic sodium NaCl, NaNO of solution ph by introducing the ionic strength that only can change synthetic system
3or Na
2sO
4make reaction promotor, with water as solvent, room temperature leaves standstill and prepares the specific surface area with spherical, volution and rope shape is 1659.2-1756.1m
2/ g, pore volume is 0.97-0.98cm
3/ g, aperture is six side's ordered mesoporous silica dioxides of 22.5-24.2, and its concrete technology step is as follows:
1) template, sodium salt, Glacial acetic acid, silicon source and water are at room temperature uniformly mixed successively, the mol ratio of its initial reactant is silicon source: template: Glacial acetic acid: sodium salt: water=1:0.184:(0.56-1.12): (0.5-2): (100-110);
2) stop stirring after the complete homogeneous phase of system, room temperature leaves standstill process 24 hours, by the precipitation and centrifugal separation separated out, in 60-100 DEG C of oven dry;
3) again with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550-600 DEG C of roasting 6 hours with removed template method, obtain six side's ordered mesoporous silica dioxides of special-shaped looks.
The preparation method of above-mentioned a kind of special-shaped looks mesoporous silicon oxide, is characterized in that described cationic quaternary ammonium salt tensio-active agent is: Tetradecyl Trimethyl Ammonium Bromide (MTAB), cetyl trimethylammonium bromide (CTAB) or Cetyltrimethylammonium bromide (STAB).
The preparation method of above-mentioned a kind of special-shaped looks mesoporous silicon oxide, is characterized in that described ambient temperature scope is 0-28 DEG C.
The preparation method of the above-mentioned a kind of special-shaped looks mesoporous silicon oxide of the present invention, its advantage is:
1, be difficult to be formed in the acetate system of mesoporous thing phase at one, by introducing the non-hydrolytic inorganic sodium not affecting solution ph, namely basic in neutral strong acid and strong base salt sodium-chlor, sodium sulfate or SODIUMNITRATE after dissolving, room temperature leaves standstill the six side's ordered mesoporous silica dioxides having synthesized different shape characteristic.Because present method has dangerous and corrosive strong acid make silicon source hydrolyst without the need to using, therefore compared with prior art, present method not only reduces preparation cost and the synthesis difficulty of acid system mesoporous silicon oxide, decreases to work the mischief to environment and to the hurtful degree of equipment.Simultaneously, relatively gentle synthetic medium is also more conducive to variously having the original position encapsulation of bioactive guest molecule in mesopore orbit, and the ordered mesoporous silicon-dioxide material obtaining different-shape based on different non-hydrolytic sodium salt will further expand its applicable scope.
2, in the synthetic system used in present method, according to stirring reaction, six side's ordered mesoporous silica dioxides are also formed.
3, in the silicon source-template-aqueous systems used in present method, acetic acid or non-hydrolytic inorganic sodium is individually added, no matter stirring reaction or leaving standstill operation all cannot obtain the silica product that has order mesoporous phase structure.
4, in the reaction system used in present method, only by the kind changing non-hydrolytic inorganic sodium, namely the negatively charged ion in sodium salt, just achieve the synthesis of volution, spherical and rope shape six side ordered mesoporous silica dioxide, not yet find that there is the research report of this adjustment pattern method at present, it contributes to the selection of different application field to granule-morphology demand, can further expand the range of application of Metaporous silicon dioxide material.
5, the silicon source hydrolyst used in present method can also be other non-strong acid, as phosphoric acid, boric acid, formic acid or citric acid etc.
accompanying drawing illustrates:
Fig. 1 is the x-ray diffractogram of powder (XRD) of roasting sample in embodiment 1.
Fig. 2 is nitrogen adsorption isotherm and the pore size distribution thereof of roasting sample in embodiment 1.
Fig. 3 is the stereoscan photograph (SEM) of roasting sample in embodiment 1.
Fig. 4 is the stereoscan photograph (SEM) of roasting sample in embodiment 2.
Fig. 5 is the stereoscan photograph (SEM) of roasting sample in embodiment 3.
Embodiment
Embodiment 1:
By 0.75 gram of CTAB, 0.95 gram of NaNO
3, 1 milliliter of Glacial acetic acid, 2.5 milliliters of TEOS and 20 milliliter H
2o is uniformly mixed successively at 15 DEG C, stop stirring after the complete homogeneous phase of system, process 24 hours are left standstill at 15 DEG C, by the precipitation and centrifugal separation separated out, in 60 DEG C of oven dry, then with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550 DEG C of roastings 6 hours with removed template method, obtain six side's ordered mesoporous silica dioxides with volution pattern, its XRD figure is shown in Fig. 1, its N
2adsorption isothermal line and corresponding pore size distribution curve are shown in Fig. 2, and Fig. 3 is shown in by its SEM photo, and its specific surface area is 1659.2m
2/ g, pore volume is 0.97cm
3/ g, aperture is 23.5.
Embodiment 2:
By 0.75 gram of CTAB, 0.65 gram of NaCl, 1 milliliter of Glacial acetic acid, 2.5 milliliters of TEOS and 20 milliliter H
2o is uniformly mixed successively at 15 DEG C, stop stirring after the complete homogeneous phase of system, process 24 hours are left standstill at 15 DEG C, by the precipitation and centrifugal separation separated out, in 60 DEG C of oven dry, then with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550 DEG C of roastings 6 hours with removed template method, obtain the ordered mesoporous silica dioxide molecular sieve with spherical morphology, Fig. 4 is shown in by its SEM photo, and its specific surface area is 1683.7m
2/ g, pore volume is 0.98cm
3/ g, aperture is 24.2.
Embodiment 3:
By 0.75 gram of CTAB, 1.59 grams of Na
2sO
4, 1 milliliter of Glacial acetic acid, 2.5 milliliters of TEOS and 20 milliliter H
2o is uniformly mixed successively at 15 DEG C, stop stirring after the complete homogeneous phase of system, process 24 hours are left standstill at 15 DEG C, by the precipitation and centrifugal separation separated out, in 60 DEG C of oven dry, then with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550 DEG C of roastings 6 hours with removed template method, obtain the ordered mesoporous silica dioxide molecular sieve with rope shape pattern, Fig. 5 is shown in by its SEM photo, and its specific surface area is 1756.1m
2/ g, pore volume is 0.98cm
3/ g, aperture is 22.5.
Claims (2)
1. the preparation method of a special-shaped looks mesoporous silicon oxide, it is characterized in that the agent of a kind of employing cationic quaternary ammonium salt surfactants as template, in the gentle acid system that acetic acid and non-hydrolytic inorganic sodium are formed, by changing the kind of sodium salt, comprise SODIUMNITRATE, sodium-chlor and sodium sulfate, room temperature leaves standstill synthesis and has volution, the method of spherical or rope shape six side ordered mesoporous silica dioxide, the method adopts the agent of cationic quaternary ammonium salt surfactants as template, silicon source is done with methyl silicate (TMOS) or tetraethoxy (TEOS), the Glacial acetic acid (HAc) relatively gentle by acidity substitutes traditional strong acid HCl, H
2sO
4, HNO
3or HBr makes silicon source hydrolyst, do not affect non-hydrolytic inorganic sodium NaCl, NaNO of solution ph by introducing the ionic strength that only can change synthetic system
3or Na
2sO
4make reaction promotor, with water as solvent, room temperature leaves standstill and prepares the specific surface area with spherical, volution or rope shape is 1659.2-1756.1m
2/ g, pore volume is 0.97-0.98cm
3/ g, aperture is six side's ordered mesoporous silica dioxides of 22.5-24.2, and its concrete technology step is as follows:
1) template, sodium salt, Glacial acetic acid, silicon source and water are at room temperature uniformly mixed successively, the mol ratio of its initial reactant is silicon source: template: Glacial acetic acid: sodium salt: water=1:0.184:(0.56-1.12): (0.5-2): (100-110);
2) stop stirring after the complete homogeneous phase of system, room temperature leaves standstill process 24 hours, by the precipitation and centrifugal separation separated out, in 60-100 DEG C of oven dry;
3) again with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550-600 DEG C of roasting 6 hours with removed template method, obtain six side's ordered mesoporous silica dioxides of special-shaped looks;
Described ambient temperature scope is 0-28 DEG C.
2., according to a kind of described in claim 1 preparation method of special-shaped looks mesoporous silicon oxide, it is characterized in that described cationic quaternary ammonium salt tensio-active agent is: Tetradecyl Trimethyl Ammonium Bromide (MTAB), cetyl trimethylammonium bromide (CTAB) or Cetyltrimethylammonium bromide (STAB).
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| CN109817929B (en) * | 2019-01-25 | 2020-11-03 | 安徽师范大学 | Spiral silicon dioxide/cobaltosic oxide composite nano material, preparation method thereof and application thereof in lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168440A (en) * | 2007-09-27 | 2008-04-30 | 上海交通大学 | Silicon oxide mesoporous material and preparing method thereof |
| CN101786639A (en) * | 2010-03-08 | 2010-07-28 | 天津大学 | Mesoporous silicon dioxide molecular sieve and preparation method thereof |
| CN101857234A (en) * | 2010-06-10 | 2010-10-13 | 天津大学 | Monodisperse mesoporous silicon dioxide hollow nano-microsphere and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168440A (en) * | 2007-09-27 | 2008-04-30 | 上海交通大学 | Silicon oxide mesoporous material and preparing method thereof |
| CN101786639A (en) * | 2010-03-08 | 2010-07-28 | 天津大学 | Mesoporous silicon dioxide molecular sieve and preparation method thereof |
| CN101857234A (en) * | 2010-06-10 | 2010-10-13 | 天津大学 | Monodisperse mesoporous silicon dioxide hollow nano-microsphere and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| Inorganic salt aided synthesis of monolithic silica with meso/macro hierarchical structure;Hua Zhong et al.;《Microporous and Mesoporous Materials》;20090324;第123卷;第63-70页 * |
| Low temperature effect on the morphological control of mesoporous silica nanofibers at near-neutral pH:A biomimetic strategy;Qiang Xiao et al.;《Microporous and Mesoporous Materials》;20070503;第109卷;第233-238页 * |
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Inventor after: Wang Xiaozhong Inventor after: Bai Yadong Inventor after: Fu Simei Inventor after: Wang Jinping Inventor after: Xie Kechang Inventor before: Wang Xiaozhong Inventor before: Wang Jinping Inventor before: Fu Simei Inventor before: Xie Kechang |
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