CN101857233A - Method for synthesizing mesoporous silicon dioxide microsphere through regulating and controlling of anionic surface active agent - Google Patents
Method for synthesizing mesoporous silicon dioxide microsphere through regulating and controlling of anionic surface active agent Download PDFInfo
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- CN101857233A CN101857233A CN 201010190652 CN201010190652A CN101857233A CN 101857233 A CN101857233 A CN 101857233A CN 201010190652 CN201010190652 CN 201010190652 CN 201010190652 A CN201010190652 A CN 201010190652A CN 101857233 A CN101857233 A CN 101857233A
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Abstract
The invention relates to the field of preparation of inorganic mesoporous materials, in particular to a method for synthesizing a mesoporous silicon dioxide microsphere through regulating and controlling of an anionic surface active agent. The method is characterized by comprising the following steps of: adding cosolvent and acid regulating liquid into aqueous solution of sodium dedecyl sulfate and a non-ionic surface active agent; regulating the pH value of the solution to be 0.5 to 2.0; adding butyl silicate dropwise into the solution to perform reaction; and removing a template agent after calcining the product to obtain the mesoporous silicon dioxide microsphere. The mesoporous silicon dioxide microsphere prepared by the method has the advantages of high monodispersity, uniform grain diameter of 3 to 5 mu m, specific surface area of 700 m<2>/g and high mechanical property.
Description
Technical field
The present invention relates to inorganic mesoporous field of material preparation, be specifically related to a kind of method of synthesizing mesoporous silicon dioxide microsphere, comprise method by anion surfactant sodium laurylsulfonate synthesizing mesoporous silicon dioxide microsphere through regulating and controlling.
Background technology
After Nature in 1992 had reported M41S series ordered meso-porous silicon oxide material, ordered mesoporous material obtained scientist's extensive concern because of its particular performances in fields such as catalysis, separation science, biologies.The particularly appearance of micron order mesoporous silica particles makes it be expected to become the chromatograph packing material of a class excellent performance.Big specific surface area (＞1000m
2/ g), regularly arranged duct, narrower pore size distribution and favorable mechanical performance etc., these characteristics make its shown with silica filler in the past different specific performance, better separation selectivity for example, lower resistance to mass transfer.
The synthetic method of mesoporous silicon dioxide micro-sphere has bibliographical information.As (T.Martin, A.Galarneau, F.DiRenzo such as Martin, F.Fajula, D.Plee, Angew.Chem.Int.Ed, 2002,41,2590) being the silicon source with commercialization spherical silica gel particle, preparing MCM-41 and MCM-48 by " false form synthesis method (Pseudomorphic synthesis) ", is raw material with commercialization spherical silica gel particle still, cost an arm and a leg, can not be used for suitability for industrialized production.A plurality of problem group is that template has been synthesized silicon dioxide microsphere with nonionogenic tenside P123, but must add co-template-cetyl trimethylammonium bromide, water-soluble polymers or ionogen Repone K in order to obtain spherical morphology, sticking connection between the microballoon of preparing, size distribution broad (document 1 J.W Zhao, F Gao, Y.L Fu, W Jin, P.Y Yang, D.Y Zhao, Chem.Commun.2002,752; Document 2 Z.T.Zhang, L.M.Yang, Y.J Wang, G.S.Luo, Y.Y Dai, Microporous and Mesoporous Materials, 2008,115,447; Document 3 L.N Wang, T Qi, Y Zhang, J.L Chu, Microporous and Mesoporous Materials, 2006,91,156).Up to the present, the preparation mesoporous silicon dioxide micro-sphere utilizes mainly that cats product or positively charged ion and nonionogenic tenside are composite to prepare, with respect to cats product, negatively charged ion and nonionogenic tenside are used more extensive at industrial circle, they synthetic, purification technique is more ripe, therefore use negatively charged ion and nonionic surfactant to come synthesizing mesoporous silicon dioxide microsphere as template, be expected to reduce the material produce cost, realize the scale operation and the practical application of such material.
Summary of the invention
The object of the present invention is to provide a kind of method, adopt present method technology simple, and can reduce production costs by anion surfactant sodium laurylsulfonate synthesizing mesoporous silicon dioxide microsphere through regulating and controlling.
For achieving the above object, the technical solution used in the present invention is: with anion surfactant sodium laurylsulfonate and nonionogenic tenside as hybrid template, positive silicon ester is the silicon source, passes through to add the solubility promoter synthesizing mesoporous silicon dioxide microsphere under solutions of weak acidity.More specifically method is: add solubility promoter and sour regulator solution in sodium laurylsulfonate and nonionic surfactant water-soluble liquid, the pH of regulator solution is 0.5～2.0, drip positive silicon ester reaction, remove template after the product calcining, promptly get mesoporous silicon dioxide micro-sphere.
Solubility promoter preferred alcohol among the above-mentioned preparation method.
Nonionogenic tenside among the above-mentioned preparation method: sodium laurylsulfonate: solubility promoter: the mol ratio of water is 1: 0.01～0.016: 0.02～0.08: 5.00～20.00: 100～250.
The amount of acid is fixed according to the pH of solution.
Acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid preferably.
Nonionogenic tenside is the block polymer nonionogenic tenside, preferred EO
20PO
70EO
20(P123) or EO
27PO
61EO
27(P104).
Positive silicon ester is generally all with methyl silicate or tetraethoxy.
More preferred manufacturing procedure comprises:
A. sodium laurylsulfonate and nonionogenic tenside are dissolved in the deionized water, under 20～35 ℃ of temperature, stir to clarify;
B. add ethanol and sour regulator solution, the pH of regulator solution is between 0.5～2.0;
C. positive silicon ester is added drop-wise in the above-mentioned reaction solution, stirs 6～12h under the room temperature;
D. above-mentioned reaction solution is transferred in the reactor standing and reacting 10-24h under 60～120 ℃ of temperature, the white precipitate of filtration, washing gained, drying;
E. the product of gained is calcined 5～12h at 500～600 ℃, remove template, obtain mesoporous silicon dioxide micro-sphere.
Creativeness of the present invention is:
1. the price of the cats product of now selling on the market is about more than 5 times of anion surfactant, therefore adopt the anion surfactant sodium laurylsulfonate as the template synthesizing mesoporous silicon dioxide microsphere, production cost is low, is easy to realize the practical application of this type of material.
2. good, the uniform particle diameter of mesoporous silicon dioxide micro-sphere monodispersity for preparing of the present invention concentrates on 3～5 μ m (see figure 1)s, and specific surface area is 700m
2/ g, good mechanical property are for next step derivatize modification is provided convenience.
3. by changing the amount of sodium laurylsulfonate, can synthesize the particle diameter different mesoporous silicon dioxide micro-sphere of particle size range between 3～10 μ m, can be used as the compartment analysis research of various objectives.
4. the mesoporous silicon dioxide micro-sphere for preparing of the present invention has mesoporous passage of running through of sequential 2 D, can accelerate mass transfer, with this material dress post (250mm * 4.6mmI.D.), flow velocity is 3mL/min, under three kinds of moving phase conditions (100% methyl alcohol, methyl alcohol: water=50%: 50%, normal hexane), post is pressed and to be respectively 9,23,5MPa, far below commercially available similar chromatographic column.Therefore be applicable to the liquid phase sharp separation analysis under the high flow rate.(seeing Fig. 6 and Fig. 7)
Description of drawings
Fig. 1 is the stereoscan photograph of embodiment 1 synthetic mesoporous silicon dioxide micro-sphere, and sample is the monodisperse spherical particle, and particle diameter concentrates on 5 μ m.
Fig. 2 is the powder x-ray diffraction collection of illustrative plates of embodiment 1 synthetic mesoporous silicon dioxide micro-sphere.
Fig. 3 is the N of embodiment 1 synthetic mesoporous silicon dioxide micro-sphere
2The attached curve of absorption-desorption.
Fig. 4 is the pore size distribution curve of embodiment 1 synthetic mesoporous silicon dioxide micro-sphere.
The infared spectrum (wherein curve a, b are respectively the sample curve that does not remove template and remove template) of mesoporous silicon dioxide micro-sphere after Fig. 5 does not remove template and removes template for embodiment 1 synthetic.
Fig. 6 is the flow velocity of embodiment 4 preparation mesoporous silicon dioxide micro-sphere chromatographic columns and the relation curve that post is pressed.
Fig. 7 is the chromatographic fractionation figures of embodiment 4 preparation mesoporous silicon dioxide micro-sphere chromatographic columns to toluene, biphenyl, naphthalene and anthracene.
Embodiment
Synthesizing of mesoporous silicon dioxide micro-sphere
Under 35 ℃ of conditions, take by weighing P123 0.93g and SDS 0.2g places the 50mL round-bottomed flask, add deionized water 28mL, continue stirring until dissolving.(4M 1.25mL), is stirred to room temperature, dropwise adds tetraethoxy 3mL, and it is transparent to solution to continue to stir 6h to add ethanol 7.5mL and hydrochloric acid soln successively.Then reaction solution is transferred in the reactor 90 ℃ of standing and reacting 12h.Filter white precipitate deionized water wash, 60 ℃ of constant pressure and dries 24 hours.At last the product of gained is calcined 6h, the mesoporous silicon dioxide micro-sphere of the template that is removed at 500 ℃.
Fig. 1 is the stereoscan photograph of the mesoporous silicon dioxide micro-sphere of present embodiment preparation, and sample is the monodisperse spherical particle as seen from the figure, and particle diameter concentrates on 5 μ m.
The powder x-ray diffraction collection of illustrative plates of mesoporous silicon dioxide micro-sphere is seen Fig. 2.
The N of mesoporous silicon dioxide micro-sphere
2The attached curve of absorption-desorption is seen Fig. 3, and curve belongs to typical VI type thermoisopleth as seen from Figure 3, is typical mesoporous adsorpting characteristic curve.
The pore size distribution curve of mesoporous silicon dioxide micro-sphere is seen Fig. 4, and the sample pore size distribution is comparatively concentrated as seen from Figure 4, is about 3.5nm, and total pore volume is 0.44cm3/g, and pore wall thickness is 7.28nm.
Remove template and remove after the template infared spectrum of mesoporous silicon dioxide micro-sphere and do not see Fig. 5 (wherein curve a, b are respectively the sample curve that does not remove template and remove template), as seen from Figure 5 3741,1128,1021,985 and 825cm
-1There is absorption peak at the place, belongs to the charateristic avsorption band of mesoporous silicon oxide.After high-temperature calcination, the charateristic avsorption band of P123 and SDS (1461,1380,2974 and 2879cm
-1) disappear or weaken, illustrate by the template in the calcined materials to be removed substantially.
Synthesizing of mesoporous silicon dioxide micro-sphere
Under 25 ℃ of conditions, take by weighing P123 0.93g and SDS 0.24g places the 50mL round-bottomed flask, add deionized water 28mL, continue stirring until dissolving.(4M 3.125mL), is stirred to room temperature, dropwise adds tetraethoxy 3mL, and it is transparent to solution to continue to stir 12h to add ethanol 7.5mL and hydrochloric acid soln successively.Then reaction solution is transferred in the reactor 90 ℃ of standing and reacting 24h.Filter white precipitate deionized water thorough washing, 60 ℃ of constant pressure and dries 24 hours.At last the product of gained is calcined 6h, the mesoporous silicon dioxide micro-sphere of the template that is removed at 550 ℃.
Synthesizing of mesoporous silicon dioxide micro-sphere
Under 25 ℃ of conditions, take by weighing P104 0.950g and SDS 0.2g places the 50mL round-bottomed flask, add deionized water 28mL, continue stirring until dissolving.(4M 3.125mL), is stirred to room temperature, dropwise adds methyl silicate 3mL, and it is transparent to solution to continue to stir 10h to add ethanol 7.5mL and hydrochloric acid soln successively.Then reaction solution is transferred in the poly-tetrafluoro reactor 90 ℃ of standing and reacting 24h.Filter the white precipitate that obtains deionized water thorough washing, 60 ℃ of constant pressure and dries 24 hours.At last the product of gained is calcined 6h, the mesoporous silicon dioxide micro-sphere of the template that is removed at 600 ℃.
Get the mesoporous silicon dioxide micro-sphere of embodiment 2 preparations, after it is carried out activation treatment, adopt the homogenate method to load in stainless steel column jecket (250mm * 4.6mm, I.D.), measure the post of chromatographic column under the different in flow rate and press, the results are shown in Figure 6, as can be seen from the figure, under three kinds of moving phase conditions (normal hexane, 100% methyl alcohol, 50% methyl alcohol), the chromatographic column post is pressed and to be respectively 1.2,2.2,5.7MPa, presses far below general merchandise silica gel chromatographic column post; And adopt this self-control post that toluene, naphthalene, biphenyl and anthracene are separated, and moving phase is selected normal hexane, and flow velocity is 1mL/min, and peak sequence is toluene, naphthalene, biphenyl and anthracene, and separating resulting is seen Fig. 7.As can be seen from Figure 7, toluene, naphthalene, biphenyl three can realize baseline separation, and biphenyl and anthracene are for to separate substantially.
Claims (7)
1. the preparation method of a mesoporous silicon dioxide micro-sphere, comprise: in nonionic surfactant water-soluble liquid, add solubility promoter and sour regulator solution, the pH of regulator solution is 0.5～2.0, drip positive silicon ester reaction, remove template after the product calcining, promptly get mesoporous silicon dioxide micro-sphere, it is characterized in that: in nonionogenic tenside, add sodium laurylsulfonate again.
2. the preparation method of claim 1, wherein solubility promoter is an ethanol.
3. the preparation method of claim 1, wherein nonionogenic tenside: sodium laurylsulfonate: solubility promoter: the mol ratio of water is 1: 0.01～0.016: 0.02～0.08: 5.00～20.00: 100～250.
4. the preparation method of claim 1, wherein acid is selected from one or more in hydrochloric acid, sulfuric acid, phosphoric acid, the nitric acid.
5. the preparation method of claim 1, wherein nonionogenic tenside is block polymer nonionogenic tenside P123 or P104.
6. the preparation method of claim 1, wherein positive silicon ester is methyl silicate or tetraethoxy.
7. the preparation method of claim 1, comprising:
A. sodium laurylsulfonate and nonionogenic tenside are dissolved in the deionized water, under 20～35 ℃ of temperature, stir to clarify;
B. add ethanol and sour regulator solution, the pH of regulator solution is between 0.5～2.0;
C. positive silicon ester is added drop-wise in the above-mentioned reaction solution, stirs 6～12h under the room temperature;
D. above-mentioned reaction solution is transferred in the reactor standing and reacting 10-24h under 60～120 ℃ of temperature, the white precipitate of filtration, washing gained, drying;
E. the product of gained is calcined 5～12h at 500～600 ℃, remove template, obtain mesoporous silicon dioxide micro-sphere.
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| CN102276840A (en) * | 2011-05-06 | 2011-12-14 | 中国药科大学 | Camphor sulfonamide doped ethane bridge bond spherical mesoporous silica gel |
| CN102676493A (en) * | 2011-03-31 | 2012-09-19 | 南京工业大学 | Mesoporous biomaterial containing porcine pancreatic lipase and preparation method thereof |
| CN102701226A (en) * | 2012-05-14 | 2012-10-03 | 无锡润鹏复合新材料有限公司 | Preparation method of mono-dispersed silicon dioxide nanometer microspheres |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143724A (en) * | 2006-09-11 | 2008-03-19 | 中国科学院过程工程研究所 | Method for synthesizing silicon dioxide hollow sphere with mesoporous channel controlled by dodecyl sulfonic acid sodium salt |
-
2010
- 2010-06-03 CN CN2010101906528A patent/CN101857233B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143724A (en) * | 2006-09-11 | 2008-03-19 | 中国科学院过程工程研究所 | Method for synthesizing silicon dioxide hollow sphere with mesoporous channel controlled by dodecyl sulfonic acid sodium salt |
Non-Patent Citations (2)
| Title |
|---|
| 《Chem. Mater.》 20050514 Dehong Chen et al. Nonionic Block Copolymer and Anionic Mixed Surfactants Directed Synthesis of Highly Ordered Mesoporous Silica with Bicontinuous Cubic Structure 3228-3234 1-7 第17卷, 第12期 2 * |
| 《化学通报》 20051231 庞雪蕾 等 利用廉价硅酸盐为硅源合成介孔SiO2 球 140-144，149 1-7 , 第2期 2 * |
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