CN1302991C - Preparation method of short hole SBA-15 mesopore silicon base material - Google Patents
Preparation method of short hole SBA-15 mesopore silicon base material Download PDFInfo
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- CN1302991C CN1302991C CNB2004100627936A CN200410062793A CN1302991C CN 1302991 C CN1302991 C CN 1302991C CN B2004100627936 A CNB2004100627936 A CN B2004100627936A CN 200410062793 A CN200410062793 A CN 200410062793A CN 1302991 C CN1302991 C CN 1302991C
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Abstract
The present invention relates to a preparation method of an SBA-15 mesopore silicon base material with short pores. The present invention is characterized in that a large amount of organic cosolvent is introduced in a traditional system for synthesizing SBA-15 to create a large amount of gaps in the system; in addition, under the catalytic action of F<->, the SBA-15 mesopore material with short pores is obtained by hydrolyzing TEOS fast.
Description
Technical field
The present invention relates to the preparation of short hole SBA-15 mesopore material, specifically a kind of method that adds a large amount of organic cosolvents that adopts is utilized this cosolvent and micellar reactive force to suppress growth on the direction of duct, and then is obtained lacking hole SBA-15 mesoporous silicon sill.
Background technology
Mesoporous silicon sill MCM-41 and SBA-15 have obtained broad research owing to have the pore passage structure and the high-specific surface area of high-sequential at aspects such as catalysis, separation, absorption and assembled semiconductors.Regulation and control to pattern, aperture and the granular size of mesopore material have become focus in recent years.Organic cosolvent, as TMB (1), alkane and amine etc. has been used in the research of adjustment aperture.For example, decane has reaming performance preferably in MCM-41 synthetic, but the material that obtains has often lost high-sequential.
Short hole and high-sequential SBA-15 mesoporous silicon sill more help the diffusion of reaction molecular, therefore receive very big concern.And the realization in short hole can be adopted two kinds of methods usually: a kind of is to reduce size of particles.Another kind is the direction that changes the duct.The SBA-15 that traditional method makes is vermiform, and the duct direction is main consistent with long axis direction, and orifice throat length is about 1 μ m.Therefore short hole SBA-15 can make its duct direction realize with the particulate short-axis direction is consistent.Nano level mesopore material MCM-41 preparation is in the news.And short being prepared into of hole SBA-15 do not seen bibliographical information so far as yet.
Summary of the invention
The object of the present invention is to provide a kind of preparation more to help the method for the short hole SBA-15 mesoporous silicon sill of reaction molecular diffusion.
The object of the present invention is achieved like this, a large amount of organic cosolvents is incorporated in the synthetic system of SBA-15, and under the prerequisite that does not influence the micella order, a large amount of spaces that utilize organic cosolvent to set up in system suppress the growth of SBA-15 duct direction.
Purpose of the present invention mainly is achieved in that
At first prepare the aqueous hydrochloric acid of 1.0-2.0M concentration, add an amount of template then and make the concentration of template in OK range, a large amount of organic cosolvents is joined in the system, stir for some time under the certain temperature.Add NH
4F and tetraethoxy (TEOS) heat up to stir 20-24h, during this period, a large amount of spaces that organic cosolvent is set up in system and with the micellar phase mutual effect, thereby suppress the growth of micella duct direction.
The concentration of template is extremely important in the hydrochloric acid soln among the present invention, otherwise template can not form micella, thereby can not get mesopore material.In addition, hydrochloric acid mainly contains two effects: the first, and one side H
+Carry out protonated to template and tetraethoxy; On the other hand, effect in the middle of the chlorion between plays fits together the formation micella with protonated template and protonated tetraethoxy by the Coulomb's force effect; The second, the acidity that hydrochloric acid produces helps the hydrolysis of tetraethoxy, and suitable concentration helps the hydrolysis and the condensation of tetraethoxy, thereby forms the mesoporous silicon material.
Its key step is as follows:
(a) under the normal temperature, with template EO
20PO
70EO
20Adding concentration is in the aqueous hydrochloric acid of 1.2-2.0M, obtains transparent liquid with magnetic stirrer, adds organic cosolvent then, and the mass ratio of organic cosolvent and template is 1-60, and continues to stir 10-100 minute, obtains a mixing solutions;
(b) with NH
4F joins in the mixing solutions of step a preparation after the dissolving, adds tetraethyl orthosilicate, continues to stir 20-24 hour in the 303-373K temperature range, obtains milky white solution;
(c) milky white solution that step b is obtained changes in the reactor, and the sealing back is at 313-423K crystallization 48h; Behind cooling, filtration, the natural airing, removed template in 3-7 hour, can obtain the SBA-15 mesoporous silicon sill in short hole in the 750-780K roasting;
Count tetraethoxy: template: HCl: NH in molar ratio
4F=1: 0.0068-0.034: 0.082-0.142: 0.003-3.
The present invention has following advantage:
The SBA-15 orifice throat length homogeneous that 1. obtains (～200nm), short duct helps the diffusion of reaction molecular.
2. duct high-sequential, the aperture can reach 12nm.
Description of drawings
Fig. 1 is the scanning picture of the short hole SBA-15 mesoporous silicon sill for preparing of cosolvent with the decane for the present invention.
Fig. 2 is the high resolution scanning picture of the short hole SBA-15 mesoporous silicon sill sample for preparing of cosolvent with the decane for the present invention.
Fig. 3 is the scanning picture of the short hole SBA-15 mesoporous silicon sill for preparing of cosolvent with the dodecane for the present invention.
Fig. 4 the present invention is the high resolution scanning picture of the short hole SBA-15 mesoporous silicon sill sample for preparing of cosolvent with the dodecane.
Embodiment
The present invention is further described below by example, but application of the present invention is not subjected to the restriction of these examples.
Embodiment 1
Under the normal temperature, the template P123 of 2.4g is dissolved in the aqueous hydrochloric acid of 84ml (1.20M), obtain transparent liquid, add the decane of 14.0g then and under this temperature, continue and stir 1h, obtain a white mixing solutions with magnetic stirrer.NH with 0.0276g
4After F joins and dissolves in the mixing solutions, be warming up to 313K after adding the TEOS of 5.5ml and stirring 5-10min.Under this temperature, continue to stir 20-24h, obtain milky white solution.
(b) milky white solution that (a) obtained changes in the stainless steel still, and the sealing back is at 473K crystallization 48h.Behind cooling, filtration, the natural airing, 5h removes template in the 773K roasting, can obtain the SBA-15 mesoporous silicon sill in short hole.
The scanner uni high resolution scanning picture of gained sample is seen Fig. 1,2.
Embodiment 2
Under the normal temperature, the template P123 of 2.4g is dissolved in the aqueous hydrochloric acid of 75ml (2.0M), obtain transparent liquid, add the undecane of 15.6g then and under this temperature, continue and stir 2h, obtain a white mixing solutions with magnetic stirrer.NH with 0.0276g
4After F joins and dissolves in the mixing solutions, be warming up to 308K after adding the TEOS of 5.5ml and stirring 10min, under this temperature, continue to stir 20-24h, obtain milky white solution.
(b) milky white solution that (a) obtained changes in the stainless steel still, and the sealing back is at 353K crystallization 48h.Behind cooling, filtration, the natural airing, 5h removes template in the 773K roasting, can obtain the SBA-15 mesoporous silicon sill in short hole.
Embodiment 3
Under the normal temperature, the template P123 of 2.4g is dissolved in the aqueous hydrochloric acid of 84ml (1.70M), obtain transparent liquid, add the dodecane of 17.0g then and under this temperature, continue and stir 1h, obtain a white mixing solutions with magnetic stirrer.NH with 0.0276g
4After F joins and dissolves in the mixing solutions, be warming up to 313K after adding the TEOS of 5.5ml and stirring 5-10min.Under this temperature, continue to stir 20-24h, obtain milky white solution.
(b) milky white solution that (a) obtained changes in the stainless steel still, and the sealing back is at 373K crystallization 48h.Behind cooling, filtration, the natural airing, 5h removes template in the 773K roasting, can obtain the SBA-15 mesoporous silicon sill in short hole.
The scanner uni high resolution scanning Electronic Speculum picture of gained sample is seen Fig. 3,4.
Claims (2)
1. preparation method who lacks hole SBA-15 mesoporous silicon sill, key step is as follows:
(a) under the normal temperature, with template EO
20PO
70EO
20Adding concentration is in the aqueous hydrochloric acid of 1.2-2.0M, obtains transparent liquid with magnetic stirrer, adds organic cosolvent then, and the mass ratio of organic cosolvent and template is 1-60, and continues to stir 10-100 minute, obtains mixing solutions;
(b) with NH
4F joins in the mixing solutions of step a preparation after the dissolving, adds tetraethoxy, continues to stir 20-24 hour in the 303-373K temperature range, obtains milky white solution;
(c) milky white solution that step b is obtained changes in the reactor, and the sealing back is at 313-423K crystallization 48h; Behind cooling, filtration, the natural airing, removed template in 3-7 hour, can obtain SBA-15 mesoporous silicon sill in the 750-780K roasting;
Count tetraethoxy: template: HCl: NH in molar ratio
4F=1: 0.0068-0.034: 0.082-0.142: 0.003-3;
The orifice throat length of described short hole SBA-15 mesoporous silicon sill is 200nm;
Described organic cosolvent is decane, undecane or dodecane.
2. the method for claim 1 is characterized in that, reactor is a stainless steel cauldron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100627936A CN1302991C (en) | 2004-07-09 | 2004-07-09 | Preparation method of short hole SBA-15 mesopore silicon base material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100627936A CN1302991C (en) | 2004-07-09 | 2004-07-09 | Preparation method of short hole SBA-15 mesopore silicon base material |
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| CN1718541A CN1718541A (en) | 2006-01-11 |
| CN1302991C true CN1302991C (en) | 2007-03-07 |
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| CNB2004100627936A Expired - Fee Related CN1302991C (en) | 2004-07-09 | 2004-07-09 | Preparation method of short hole SBA-15 mesopore silicon base material |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396146A (en) * | 2002-08-21 | 2003-02-12 | 复旦大学 | Process for preparing nano catalyst used to prepare propene by oxidizing and dehydrogenating propane |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396146A (en) * | 2002-08-21 | 2003-02-12 | 复旦大学 | Process for preparing nano catalyst used to prepare propene by oxidizing and dehydrogenating propane |
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Owner name: JINKAI INSTRUMENT (DALIAN) CO., LTD. Free format text: FORMER OWNER: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Effective date: 20141010 |
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Effective date of registration: 20141010 Address after: 506, room 911, Chinese Academy of science and Technology Innovation Park, 116023 Huangpu Road, hi tech Zone, Liaoning, Dalian Patentee after: Golden Armor instrument (Dalian) Co. Ltd. Address before: 116023 Zhongshan Road, Liaoning, No. 457, Patentee before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences |
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Granted publication date: 20070307 Termination date: 20160709 |
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