CN108840345A - A kind of chirality super-microporous silicon dioxide and preparation method thereof - Google Patents
A kind of chirality super-microporous silicon dioxide and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000011549 crystallization solution Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000013333 ultra-microporous material Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005557 chiral recognition Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 13
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- FYZFRYWTMMVDLR-UHFFFAOYSA-M trimethyl(3-trimethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CO[Si](OC)(OC)CCC[N+](C)(C)C FYZFRYWTMMVDLR-UHFFFAOYSA-M 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention is suitable for chemical technology field, provides a kind of chiral super-microporous silicon dioxide and preparation method thereof, wherein the described method comprises the following steps：Under the conditions of temperature is 25 ~ 38 DEG C, chiral template agent and inorganic silicon source are dissolved in deionized water；Hydrolytic reagent is slowly added dropwise while stirring in the chiral template agent and inorganic silicon source mixed liquor；The mixed liquor that hydrolytic reagent has been added dropwise is moved into hydrothermal reaction kettle；By after the crystallization solution carry out filter wash, drying, calcining to get.The method of the present invention has filled up the blank of the synthesis technical field of chiral ultra-microporous material, and used raw material sources are abundant, and cheap, preparation method is easy to operate, is suitble to large-scale industrial production；And preparation-obtained chiral super-microporous silicon dioxide has high-specific surface area and narrow pore-size distribution, is greater than 1200 m than table product2/ g, aperture about in 1.9 nm or so, can be widely applied to the fields such as chiral catalysis, chiral Recognition and chiral resolution.
Description
Technical field
The invention belongs to chemical technology fields more particularly to a kind of chiral super-microporous silicon dioxide and preparation method thereof.
Background technique
Chirality is one of essential characteristic of nature, if a compound cannot be overlapped with its mirror image, which is
For chipal compounds, and the isomers that both are mutually mirrored into is referred to as enantiomer.Since chiral zeolite material is with regular
Foraminous spiral tract, have in the asymmetric syntheses of chemistry and drug chiral material and selective fractionation field wide before
Scape.
Currently, the research about chiral micropore and meso-porous molecular sieve material has been achieved for certain achievement, but current main
Flow the molecular dimension many places of drug and fine chemicals in（1~2 nm）Between, for micro porous molecular sieve, aperture is too small
（<1.2 nm）, macromolecular is difficult to enter duct；In contrast, the aperture of mesopore molecular sieve is then excessive（2.7~12 nm）, it is difficult to
Show shape-selective fractionation performance.Chiral super micro porous molecular sieve material of the aperture between micropore and mesoporous critical section（1.2~2.7 nm）
At ideal material in order to overcome the problems referred above.
2004, Che etc. was for the first time using anionic surfactant myristoyl-l-Alanine as template, 3- aminopropyl
Trimethoxy silane（APS）Or N- trimethoxy-silylpropyl-N, N, N- trimethyl ammonium chloride（TMAPS）To help structure to lead
To agent, ethyl orthosilicate is silicon source, successfully synthesizes the mesoporous silica molecular sieve material based on left；Yang etc. with
Chiral cation surfactant L-ValPyBr and L-ValPyPF6 derived from isoleucine is respectively synthesized out left spiral
Nanometer ribbon shape and fibrous mesopore molecular sieve, the content of alcohol has larger impact, body for the pattern of sample in reaction system
The increase of alcohol content can cause the further distortion of nanometer ribbon and fiber in system, ultimately form cavity ring or tubular structure.
Although above-mentioned synthetic method successfully synthesizes chirality mesoporous earth silicon material, and is visited in terms of synthesis mechanism
Rope, but report is had not yet to see for the synthesis of chiral super-microporous silicon dioxide material.
Summary of the invention
The embodiment of the present invention provides a kind of preparation method of chiral super-microporous silicon dioxide, it is intended to solve the above technology and ask
Topic.
The embodiments of the present invention are implemented as follows, a kind of preparation method of chirality super-microporous silicon dioxide, which is characterized in that
The method includes：
Under the conditions of temperature is 25 ~ 38 DEG C, chiral template agent and inorganic silicon source are dissolved in deionized water；
Hydrolytic reagent is slowly added dropwise while stirring in the chiral template agent and inorganic silicon source mixed liquor；
The mixed liquor that hydrolytic reagent has been added dropwise is moved into hydrothermal reaction kettle, wherein crystallization temperature is 80 ~ 120 DEG C, specific
Crystallization time is 12 ~ 72 h；
By after the crystallization solution carry out filter wash, drying, calcining to get.
The embodiment of the present invention also provides a kind of resulting chirality of preparation method according to the chiral super-microporous silicon dioxide
Super-microporous silicon dioxide.
In embodiments of the present invention, by temperature be 25 ~ 38 DEG C under the conditions of, chiral template agent and inorganic silicon source is molten
In deionized water；Hydrolytic reagent is slowly added dropwise while stirring in the chiral template agent and inorganic silicon source mixed liquor；By described in
Be added dropwise hydrolytic reagent mixed liquor move into hydrothermal reaction kettle in, wherein crystallization temperature be 80 ~ 120 DEG C, specific crystallization time be 12 ~
72 h；Solution after the crystallization is subjected to filter wash, drying, calcining, preparation-obtained chirality super-microporous silicon dioxide；One side
Face uses natural reproducible resource rosin abundant for Material synthesis template, compared with traditional Longer-chain surfactants, dredges
Water base is chiral tricyclic phenanthrene skeleton structure, and with specific rotatory power, high, self-assembly ability is by force, Nantural non-toxic, resource is renewable, operates
The features such as safe；On the other hand, the method for the present invention has filled up the blank of the synthesis technical field of chiral ultra-microporous material, is used
Raw material sources it is abundant, cheap, preparation method is easy to operate, is suitble to large-scale industrial production；And it is preparation-obtained
Chiral super-microporous silicon dioxide has high-specific surface area and narrow pore-size distribution, is greater than 1200 m than table product2/ g, aperture about exist
1.9 nm or so can be widely applied to the fields such as chiral catalysis, chiral Recognition and chiral resolution.
Detailed description of the invention
Fig. 1 is the sample small angle X-ray diffraction spectrogram that the embodiment of the present invention 1 and embodiment 4 provide；
Fig. 2 is the sample small angle X-ray diffraction spectrogram that the embodiment of the present invention 7 and embodiment 8 provide；
Fig. 3 is the sample transmission Electronic Speculum phenogram that the embodiment of the present invention 7 provides；
Fig. 4 is the sample transmission Electronic Speculum phenogram that the embodiment of the present invention 8 provides.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
A kind of preparation method of chiral super-microporous silicon dioxide provided in an embodiment of the present invention, by by chiral template agent and
Inorganic silicon source is dissolved in deionized water, and after hydrolytic reagent is slowly added dropwise while stirring, moves it into crystallization in hydrothermal reaction kettle,
And filter wash, drying are carried out to the solution after crystallization, it calcines to get chiral super-microporous silicon dioxide；The preparation method has filled up hand
Property ultra-microporous material synthesis technical field blank, used raw material sources are abundant, cheap, preparation method operation letter
It is single, it is suitble to large-scale industrial production；And preparation-obtained chiral super-microporous silicon dioxide has high-specific surface area and narrow
Pore-size distribution, be greater than 1200 m2/g than table product, aperture can be widely applied to chiral catalysis, chiral know about in 1.9 nm or so
The fields such as other and chiral resolution.
In the embodiment of the present invention, chiral template agent uses natural reproducible resource rosin abundant for Material synthesis, preferably
For (+)-dehydrogenation fir base trimethylammonium bromide.
In the embodiment of the present invention, inorganic silicon source is preferably sodium metasilicate.
In the embodiment of the present invention, hydrolytic reagent is preferably ethyl acetate.
In the embodiment of the present invention, the molar ratio of inorganic silicon source and chiral template agent is preferably 1 ︰ 0.08 ~ 0.25.
In the embodiment of the present invention, the molar ratio of inorganic silicon source and hydrolytic reagent is preferably 1 ︰ 1 ~ 3.
In embodiments of the present invention, in calcination process, calcination temperature is preferably risen to the heating rate of 1 ~ 5 DEG C/min
450 ~ 850 DEG C of 2 ~ 8 h of calcining.
Embodiment 1
At 35 DEG C, by sodium metasilicate (Na2SiO3) be dissolved in proportion with (+)-dehydrogenation fir base trimethylammonium bromide (+DTAB)
In ionized water, ethyl acetate (C is slowly added dropwise under stirring conditions4H8O2) solution adjusts pH value, wherein molar ratio of material is
Na2SiO3׃+DTAB׃C4H8O2:H2O=1.00 0.13 1.78 774.02 continues stirring 30 seconds, moves into hydro-thermal after standing 24 h
In reaction kettle, 24 h of crystallization at 100 DEG C, through filter wash, dry chiral super-microporous silicon dioxide precursor powder.
In embodiments of the present invention, small angle X-ray diffraction spectrogram as shown in Figure 1, above-mentioned chirality super-microporous silicon dioxide
Precursor powder sample is in 2 θ=2.90 °, 5.00 ° and 5.76 °（d100=3.04 nm, d110=1.77nm, d200=1.53 nm）Respectively
There are 100,110 and 200 crystallographic plane diffraction peaks of hexagonal phase, illustrates that the chirality super-microporous silicon dioxide precursor powder sample has
The hexagonal phase ultra-microporous of high-sequential.
Embodiment 2
At 38 DEG C, by sodium metasilicate (Na2SiO3) be dissolved in proportion with (+)-dehydrogenation fir base trimethylammonium bromide (+DTAB)
In ionized water, ethyl acetate (C is slowly added dropwise under stirring conditions4H8O2) solution adjusts pH value, wherein molar ratio of material is
Na2SiO3׃+DTAB׃C4H8O2:H2O=1.00 0.08 1.78 774.02 continues stirring 30 seconds, moves into hydro-thermal after standing 24 h
In reaction kettle, 12 h of crystallization at 100 DEG C, through filter wash, dry chiral super-microporous silicon dioxide precursor powder.
In embodiments of the present invention, sample shows 100,110 and 200 crystallographic plane diffraction peaks of hexagonal phase, illustrates sample still
Declined with orderly hexagonal phase ultra-microporous, but relative to each peak sharpness of embodiment 1 with intensity, illustrates sample well
The road degree of order is declined.
Embodiment 3
At 30 DEG C, by sodium metasilicate (Na2SiO3) be dissolved in proportion with (+)-dehydrogenation fir base trimethylammonium bromide (+DTAB)
In ionized water, ethyl acetate (C is slowly added dropwise under stirring conditions4H8O2) solution adjusts pH value, wherein molar ratio of material is
Na2SiO3׃+DTAB׃C4H8O2:H2O=1.00 0.25 1.78 774.02 continues stirring 30 seconds, moves into hydro-thermal after standing 24 h
In reaction kettle, 72 h of crystallization at 90 DEG C, through filter wash, dry chiral super-microporous silicon dioxide precursor powder.
In embodiments of the present invention, sample shows 100,110 and 200 crystallographic plane diffraction peaks of hexagonal phase, illustrates sample still
Declined with orderly hexagonal phase ultra-microporous, but relative to each peak sharpness of embodiment 1 with intensity, illustrates sample well
The road degree of order is declined.
Embodiment 4
At 25 DEG C, by sodium metasilicate (Na2SiO3) be dissolved in proportion with (+)-dehydrogenation fir base trimethylammonium bromide (+DTAB)
In ionized water, ethyl acetate (C is slowly added dropwise under stirring conditions4H8O2) solution adjusts pH value, wherein molar ratio of material is
Na2SiO3׃+DTAB׃C4H8O2:H2O=1.00 0.20 2.61 696.61 continues stirring 30 seconds, moves into hydro-thermal after standing 24 h
In reaction kettle, 12 h of crystallization at 100 DEG C, through filter wash, dry chiral super-microporous silicon dioxide precursor powder.
In embodiments of the present invention, small angle X-ray diffraction spectrogram as shown in Figure 1, above-mentioned chirality super-microporous silicon dioxide
Precursor powder sample is in 2 θ=2.98 °, 5.20 ° and 6.01 °（d100=2.96 nm, d110=1.70nm, d200=1.47 nm）Respectively
There are 100,110 and 200 crystallographic plane diffraction peaks of hexagonal phase, illustrates the chirality super-microporous silicon dioxide precursor powder sample at this time
For the hexagonal phase ultra-microporous of high-sequential.
Embodiment 5
At 30 DEG C, by sodium metasilicate (Na2SiO3) be dissolved in proportion with (+)-dehydrogenation fir base trimethylammonium bromide (+DTAB)
In ionized water, ethyl acetate (C is slowly added dropwise under stirring conditions4H8O2) solution adjusts pH value, wherein molar ratio of material is
Na2SiO3׃+DTAB׃C4H8O2:H2O=1.00 0.13 1.0 774.02 continues stirring 30 seconds, moves into hydro-thermal after standing 24 h
In reaction kettle, 72 h of crystallization at 80 DEG C, through filter wash, dry chiral super-microporous silicon dioxide precursor powder.
In embodiments of the present invention, sample shows 100,110 and 200 crystallographic plane diffraction peaks of hexagonal phase, illustrates the sample
Still there are six orderly side's ultra-microporous.But it is obvious relative to each peak sharpness of embodiment 4 and intensity decline, illustrate sample
The duct degree of order is poor.
Embodiment 6
At 35 DEG C, by sodium metasilicate (Na2SiO3) be dissolved in proportion with (+)-dehydrogenation fir base trimethylammonium bromide (+DTAB)
In ionized water, ethyl acetate (C is slowly added dropwise under stirring conditions4H8O2) solution adjusts pH value, wherein molar ratio of material is
Na2SiO3׃+DTAB׃C4H8O2:H2O=1.00 0.20 3.0 696.61 continues stirring 30 seconds, moves into hydro-thermal after standing 24 h
In reaction kettle, 46 h of crystallization at 120 DEG C, through filter wash, dry chiral super-microporous silicon dioxide precursor powder
In embodiments of the present invention, sample shows 100,110 and 200 crystallographic plane diffraction peaks of hexagonal phase, illustrates the sample still
With six orderly side's ultra-microporous.But it is obvious relative to each peak sharpness of embodiment 4 and intensity decline, illustrate sample duct
The degree of order is poor.
Embodiment 7
Gained presoma is warming up to 823K with the rate of 1 K/min and calcines 4 h, obtained by precursor preparation condition with embodiment 1
Chiral super-microporous silicon dioxide.
In embodiments of the present invention, there are 100,110 and 200 crystallographic plane diffraction peaks of hexagonal phase in sample（Fig. 2）, illustrate sample
Six side's ultra-microporous of high-sequential are still maintained after calcining.Transmission electron microscope phenogram as shown in Figure 3, the chirality are super
Nanoporous silica silicon sample shows fibrous chiral helical pattern, and there are the consistent lines distribution of spacing, aperture is big on surface
Small is about 1.9 nm or so, and pore wall thickness is 1 nm or so；Illustrate the orderly super-microporous silicon dioxide sample for fibrous hand
Property ultra-microporous material.
Embodiment 8
Gained presoma is warming up to 823K with the rate of 1 K/min and calcines 4 h, obtained by precursor preparation condition with embodiment 2
Chiral super-microporous silicon dioxide.
In embodiments of the present invention, there are 100,110 and 200 crystallographic plane diffraction peaks of hexagonal phase in sample（Fig. 2）, illustrate sample
Six side's ultra-microporous of high-sequential are still maintained after calcining.Transmission electron microscope phenogram as shown in Figure 4, the chirality are super
Nanoporous silica silicon sample shows gyroscope-like pattern, is gyroscope-like chirality ultra-microporous material.
To sum up, the test result of 1-8 according to embodiments of the present invention is it is found that preparation-obtained sample according to the method for the present invention
For chiral super-microporous silicon dioxide, which has filled up the blank of the synthesis technical field of chiral ultra-microporous material, has been adopted
Raw material sources are abundant, and cheap, preparation method is easy to operate, are suitble to large-scale industrial production.
The embodiment of the invention also provides a kind of resulting hands of preparation method according to above-mentioned chiral super-microporous silicon dioxide
Property super-microporous silicon dioxide, have high-specific surface area and narrow pore-size distribution, than table product be greater than 1200 m2/ g, aperture about exist
1.9 nm or so can be applied to the fields such as chiral catalysis, chiral Recognition and chiral resolution.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of preparation method of chirality super-microporous silicon dioxide, which is characterized in that the method includes：
Under the conditions of temperature is 25 ~ 38 DEG C, chiral template agent and inorganic silicon source are dissolved in deionized water；
Hydrolytic reagent is slowly added dropwise while stirring in the chiral template agent and inorganic silicon source mixed liquor；
The mixed liquor that hydrolytic reagent has been added dropwise is moved into hydrothermal reaction kettle, wherein crystallization temperature is 80 ~ 120 DEG C, specific
Crystallization time is 12 ~ 72 h；
By after the crystallization solution carry out filter wash, drying, calcining to get.
2. preparation method as described in claim 1, which is characterized in that the chiral template agent is (+)-dehydrogenation fir base trimethyl
Ammonium bromide.
3. preparation method as described in claim 1, which is characterized in that the inorganic silicon source is sodium metasilicate.
4. preparation method as described in claim 1, which is characterized in that the hydrolytic reagent is ethyl acetate.
5. preparation method as described in claim 1, which is characterized in that the inorganic silicon source and the molar ratio of chiral template agent are
1 ︰ 0.08 ~ 0.25.
6. preparation method as described in claim 1, which is characterized in that the inorganic silicon source and the molar ratio of hydrolytic reagent be 1 ︰ 1 ~
3。
7. preparation method as described in claim 1, which is characterized in that the calcination temperature is the heating speed with 1 ~ 5 DEG C/min
Rate rises to 450 ~ 850 DEG C of 2 ~ 8 h of calcining.
8. a kind of such as the resulting chiral super-microporous silicon dioxide of preparation method as claimed in any one of claims 1 to 7.
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