CN100387520C - Process for preparing monox mesoporous material with helical structure - Google Patents
Process for preparing monox mesoporous material with helical structure Download PDFInfo
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- CN100387520C CN100387520C CNB2005100275838A CN200510027583A CN100387520C CN 100387520 C CN100387520 C CN 100387520C CN B2005100275838 A CNB2005100275838 A CN B2005100275838A CN 200510027583 A CN200510027583 A CN 200510027583A CN 100387520 C CN100387520 C CN 100387520C
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- mesoporous material
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- monox mesoporous
- anion surfactant
- monox
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Abstract
The present invention discloses a preparation method of a mesoporous silicon oxide material with a helical structure. The mesoporous silicon oxide material is synthesized from various organosilane as the material sources of silicon oxide by the structure directing function of achiral anionic surfactant, and with the utilization of the silicane of quaternary ammonium salt as a co-structure directing agent. The obtained mesoporous silicon oxide material is provided with ordered helical passages which rotates around the center of a hexagon prism, and the helical passages which is arranged in two-dimensional hexagonal crystal system p6 mm structure have different curvatures; the material has wide application foreground in the technical fields of electron, macromolecular material, etc.
Description
Technical field
The invention belongs to the preparation method of inorganic porous material, particularly with the synthetic preparation method of achiral anion surfactant with monox mesoporous material of spirane structure.
Background technology
Inorganic porous material has big specific surface area and pore volume, adjustable pore structure, adjustable aperture, the surface properties that can modify and the appearance that can control or the like, thereby in separation, catalysis, sensing and as the every field such as template of synthetic other materials very large application potential is arranged all.Inorganic porous material comprises: poromerics, mesoporous material, large pore material and multilevel hole material.At the inorganic hole of preparation material, when especially having the porous material of orderly hole pore passage structure, all need to use the organic structure directed agents under most of conditions.For micro porous molecular sieve, the structure directing agent that is adopted when synthetic mostly is the small molecule amine or the quaternary ammonium salt of short chain; For mesopore molecular sieve, the structure directing agent that people adopt is amphipathic tensio-active agent, mainly comprise cats product and nonionogenic tenside, document Nature 359,710-712 (1992) have reported and have used the cats product synthesize meso-porous material.Document J.Am.Chem.Soc.120,6024-6036 (1998) and two China's patent, publication number is respectively that CN1435373 and CN1425606A report respectively and disclose with nonionic and show the promoting agent synthesize meso-porous material.Recently, document Nature Materials 2,801 (2003) reported first utilize anion surfactant successfully to synthesize mesoporous material.Nature 429, and 281-284 (2004) and Chinese patent, disclose the novel meso pore silicon oxide material of the special construction that utilizes the chirality anion surfactant successfully to synthesize to have chirality at publication number CN 1569632 reported first.
Summary of the invention
The objective of the invention is to propose with the synthetic preparation method of cheap achiral anion surfactant with monox mesoporous material of spirane structure, this material is a kind of two-dimentional hexagonal system p6mm structural arrangement that has, and has the spiral monox mesoporous material of the orderly spirrillum duct of different curvature around the center rotation of hexagonal column.
The concrete preparation method of monox mesoporous material that the present invention has spirane structure is as follows:
Earlier achiral anion surfactant is dissolved in the ion exchanged water, under stirring at room, the achirality anion surfactant is dissolved fully after, regulate pH=8-10, at room temperature stirred again 20-120 minute, make it to form homodisperse solution; Add silane and the organosilane help the structure directing agent quaternary ammonium salt then, 0-100 ℃ of reaction 1-4 day, through centrifugation or filtration, washing, drying, roasting obtains having the monox mesoporous material of spirane structure; Achirality anion surfactant wherein: ion exchanged water: help the silane of structure directing agent quaternary ammonium salt, the mol ratio of organosilane is 1: 500-4000: 0.05-0.95: 3-15.
Achiral anion surfactant used in the present invention is RCOOM, ROSO
3M or RPO
4M
2Wherein R is C
nH
2n+1, n=10-24;
R
1Be C
nH
2n+1,
N=8-22 or H
2nC
n=C
nH
2n-1-, n=5-12; M is Na or K.
The dodecyl carboxylic acid sodium is wherein arranged, the tetradecyl carboxylic acid sodium, the hexadecyl carboxylic acid sodium, sodium oleate, the dodecyl acyl is for glycine sodium salt, the tetradecyl acyl is for glycine sodium salt, the hexadecyl acyl is for glycine sodium salt, sodium lauryl sulphate salt, Trombovar salt, Sodium palmityl sulfate salt, the dodecylphosphoric acid sodium salt, the tetradecyl sodium phosphate salt, the hexadecyl sodium phosphate salt, dodecyl carboxylic acid potassium, tetradecyl carboxylic acid potassium, hexadecyl carboxylic acid potassium, potassium oleate, the dodecyl acyl is for glycine sylvite, the tetradecyl acyl is for glycine sylvite, the hexadecyl acyl is for glycine sylvite, dodecyl sulphate sylvite, tetradecyl sulfuric acid sylvite, hexadecyl hydrosulfate sylvite, Potassium dodecyl phosphate salt, tetradecyl potassium phosphate salt or potassium cetyl phosphate salt.
The structure directing agent that helps used in the present invention is the silane of quaternary ammonium salt, and its structural formula is shown below:
(R
1O)
3Si——B——N
+R
2R
3R
4X
-
Wherein, R
1, R
2, R
3And R
4Be selected from C respectively
1-C
4The straight or branched alkyl; B is selected from C respectively
1-C
4Straight or branched alkane; X
-Be selected from chlorion or bromide anion respectively; N-trimethoxy propyl silane-N is wherein arranged, N, N-trimethyl ammonium chloride or N-trimethoxy propyl silane-N, N, N-tributyl brometo de amonio.
The structural formula of organosilane used in the present invention is shown below:
(R
1O)
m——Si——X
n
Wherein, the integer of the integer of m=2-4, n=0-2, R
1Be selected from C respectively
1-C
4Straight chain, branched-chain alkyl or hydrogen atom; X is selected from C respectively
1-C
4Straight chain or branched chain alkyl; Tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, dimethoxy dimethylsilane, trimethoxymethylsila,e or dimethoxy di-isopropyl silane etc. are wherein arranged.
Principle of the present invention is seen figure one, and promptly the silane of quaternary ammonium salt forms the monox mesoporous material with spirane structure as helping structure directing agent that achiral anion surfactant and organosilane are combined
The present invention as the silicon source, as the main structure directed agents, is the monox mesoporous material that help structure directing agent prepare have spirane structure with the silane of quaternary ammonium salt by the achirality anion surfactant with various organosilanes.The constitutional features of the monox mesoporous material with spirane structure of the present invention's preparation is as follows: have the 2-3nm aperture of two-dimentional hexagonal system p6mm structural arrangement, have the monox mesoporous material of the orderly spirrillum duct of different curvature around the center rotation of hexagonal column.
The present invention has the monox mesoporous material of spirane structure, because its duct is orderly, the evenly about 2-3nm in aperture has higher specific surface area 500-700m
2/ g, so it will be in biological chemistry, pharmaceutical chemistry has wide practical use in the fields such as electronics and polymer chemistry.
Description of drawings
Fig. 1 is the synthesis mechanism synoptic diagram with monox mesoporous material of spirane structure.
Embodiment
Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
Earlier 0.30g (1mmol) sodium lauryl sulphate is dissolved in the 30g ion exchanged water, at room temperature stirred 10 minutes; Add 1.35g tetraethoxysilane (TEOS) and 0.25g then and help structure directing agent N-trimethoxy propyl silane-N, N, the mixture of N-trimethyl ammonium chloride (TMAPS) (50% methanol solution) was 80 ℃ of reactions 1 day.Through centrifugation, washing, drying, roasting obtains the spiral monox mesoporous material.Resulting monox mesoporous material has the center rotation of the orderly spirrillum duct with different curvature of two-dimentional hexagonal system p6mm structure around hexagonal column.By electronic scanning Electronic Speculum, nitrogen adsorption and electron projection Electronic Speculum instrument this material being characterized the aperture that draws this material is the 2.5nm aperture, and pore volume is 490mm
3g
-1, specific surface area is 678m
2g
-1, the diameter of spirrillum hexagonal column and length are respectively and are 100-200nm and 1.6-4.0 μ m, and spiralization cycle length is 1.5 μ m, and right-hand man's directivity reaches left hand: the right hand=1: 1.
Embodiment 2
Earlier 0.305g (1mmol) tetradecyl acyl is dissolved in the 30g ion exchanged water for glycine sodium salt, at room temperature stirred 10 minutes; Add 1.40g (0.14mmol) 0.1M hydrochloric acid soln, at room temperature stirred 60 minutes; Add 1.35g tetraethoxysilane (TEOS) and 0.25g then and help structure directing agent N-trimethoxy propyl silane-N, N, the mixture of N-trimethyl ammonium chloride (TMAPS) (50% methanol solution) was 80 ℃ of reactions 1 day.Through centrifugation, washing, drying, roasting obtains the spiral monox mesoporous material.Resulting monox mesoporous material has the center rotation of the orderly spirrillum duct with different curvature of two-dimentional hexagonal system p6mm structure around hexagonal column.By electronic scanning Electronic Speculum, nitrogen adsorption and electron projection Electronic Speculum instrument this material being characterized the aperture that draws this material is the 2.7nm aperture, and pore volume is 520mm
3g
-1, specific surface area is 680m
2g
-1, the diameter of spirrillum hexagonal column and length are respectively and are 120-170nm and 1.3-4.0 μ m, and spiralization cycle length is 1.5 μ m, and right-hand man's directivity reaches left hand: the right hand=1: 1.
Claims (4)
1. the preparation method who has the monox mesoporous material of spirane structure is characterized in that the preparation method is as follows:
Earlier achiral anion surfactant is dissolved in the ion exchanged water, under stirring at room, the achirality anion surfactant is dissolved fully after, regulate pH=8-10, at room temperature stirred again 20-120 minute, make it to form homodisperse solution; Add silane and the organosilane help the structure directing agent quaternary ammonium salt then, 0-100 ℃ of reaction 1-4 day, through centrifugation or filtration, washing, drying, roasting obtains having the monox mesoporous material of spirane structure; Achirality anion surfactant wherein: ion exchanged water: help the silane of structure directing agent quaternary ammonium salt, the mol ratio of organosilane is 1: 500-4000: 0.05-0.95: 3-15.
2. the preparation method with monox mesoporous material of spirane structure according to claim 1 is characterized in that achiral anion surfactant structural formula is RCOOM, ROSO
3M or RPO
4M
2Wherein R is C
nH
2n+1, n=10-24;
R
1Be C
nH
2n+1, n=8-22 or H
2nC
n=C
nH
2n-1-, n=5-12; M is Na or K.
3. the preparation method with monox mesoporous material of spirane structure according to claim 1 is characterized in that helping the structural formula of the silane of structure directing agent quaternary ammonium salt to be shown below:
(R
1O)
3Si——B——N
+R
2R
3R
4X
-
Wherein, R
1, R
2, R
3And R
4Be selected from C respectively
1-C
4Straight chain, branched-chain alkyl; B is selected from C respectively
1-C
4Straight or branched alkane; X
-Be selected from chlorion or bromide anion respectively.
4. the preparation method with monox mesoporous material of spirane structure according to claim 1 is characterized in that organosilane is shown below:
(R
1O)
m——Si——X
n
Wherein, the integer of the integer of m=2-4, n=0-2, R
1Be selected from C respectively
1-C
4Straight chain, branched-chain alkyl or hydrogen atom; X is selected from C respectively
1-C
4The straight or branched alkyl.
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| CNB2005100275838A CN100387520C (en) | 2005-07-07 | 2005-07-07 | Process for preparing monox mesoporous material with helical structure |
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|---|---|---|---|
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|---|---|
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| CN100387520C true CN100387520C (en) | 2008-05-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431956C (en) * | 2006-07-10 | 2008-11-12 | 南京大学 | Process for preparing mesoporous silicon dioxide spiral coil |
| CN101168440B (en) * | 2007-09-27 | 2011-07-20 | 上海交通大学 | Silicon oxide mesoporous material and preparing method thereof |
| CN101173042B (en) * | 2007-10-25 | 2010-08-11 | 上海交通大学 | Chirality mesoporous organic polymer material with even and adjustable diameter and method for producing the same |
| CN103224239A (en) * | 2013-04-08 | 2013-07-31 | 天津大学 | Chiral mesoporous silica nano-rod and preparation method thereof |
| CN103449450A (en) * | 2013-08-29 | 2013-12-18 | 华南理工大学 | Preparation method of hollow mesoporous silica material |
| CN103449453B (en) * | 2013-09-05 | 2015-08-05 | 南开大学 | A kind of take anion surfactant as the preparation method of the mesoporous silicon oxide of template |
| CN115974055A (en) * | 2022-12-28 | 2023-04-18 | 山东复元新材料科技有限公司 | Mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569632A (en) * | 2004-04-29 | 2005-01-26 | 上海交通大学 | silicon oxide mesoporous material having chiral structure and method for preparing same |
| CN1590301A (en) * | 2004-04-29 | 2005-03-09 | 上海交通大学 | Spiral metal or oxide wire material having different curvature and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569632A (en) * | 2004-04-29 | 2005-01-26 | 上海交通大学 | silicon oxide mesoporous material having chiral structure and method for preparing same |
| CN1590301A (en) * | 2004-04-29 | 2005-03-09 | 上海交通大学 | Spiral metal or oxide wire material having different curvature and its preparation method |
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