CN102070148B - Synthesis method and application of mono-disperse micron-scale spherical mesoporous silicon oxide MCM-41 - Google Patents

Synthesis method and application of mono-disperse micron-scale spherical mesoporous silicon oxide MCM-41 Download PDF

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CN102070148B
CN102070148B CN200910073248XA CN200910073248A CN102070148B CN 102070148 B CN102070148 B CN 102070148B CN 200910073248X A CN200910073248X A CN 200910073248XA CN 200910073248 A CN200910073248 A CN 200910073248A CN 102070148 B CN102070148 B CN 102070148B
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CN102070148A (en
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刘献斌
孙艳
孙晓君
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Harbin University of Science and Technology
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Abstract

The invention discloses a preparation method and application of a mono-disperse micron-scale spherical mesoporous silicon oxide MCM-41 material, and relates to the fields of preparation of porous materials and separation of biomacromolecules. The material is prepared by the following steps of: adding hexadecyl trimethyl ammonium bromide serving as a template agent and an alkali source into a water phase to obtain settled solution; adding amorphous silicon oxide spheres at room temperature; introducing amino alkoxy silane (3-amio propyl trimethoxy silane or 3-(2-amino ethyl)propyl trimethoxy silane) serving as an appearance adjusting and controlling agent; crystallizing to form raw powder; filtering and drying; and forging at the temperature of 550 DEG C for 4 hours or extracting with acidic ethanol solution and washing to obtain a product, wherein the specific surface area of the product is 500 to 900m<2>/g, and the pore volume is 0.7 to 1.0cm<3>/g. The MCM-41 microspheres prepared by the method have perfect spherical appearances and wider particle diameter distribution. The invention also relates to competitive separation of hen egg white lysozyme and bovine serum albumin by the material.

Description

Monodisperse micron level spherical mesopore silicon oxide MCM-41 compound method and application
Technical field:
The present invention relates to a kind of inorganic materials preparation and biomacromolecule separating application field, be specifically related to a kind of monodisperse micron level spherical mesopore silicon oxide MCM-41 micro-sphere material and preparation method thereof and separate the application of aspect as biomacromolecule with it.
Background technology
1992, Mobil company has synthesized mesopore silicon oxide molecular sieve M41S, and (U.S.Patent 5057296,1991; U.S.Patent 5098684,1992); This molecular sieve has high specific surface area and thermostability; Arrange in order in the duct, pore size is adjustable; Be with a wide range of applications at aspects such as catalysis, biocatalysis, chromatogram, transmitter and controlled delivery of pharmaceutical agents releases, since report, received much concern always; It generally is the product that is formed by random particle packing that the investigator of Mobil company has synthesized mesopore silicon oxide molecular sieve M41S; Therefore the product pattern is being required than higher Application Areas; For example aspects such as chromatogram, photoelectron and controlled delivery of pharmaceutical agents release receive certain limitation.
1998; (S.Inagaki, et al, Stud.Surf.Sci.Catal. such as Inagaki; 1998; 117:65-76) the first step has been synthesized mesopore silicon oxide molecular sieve M41S with Mobil company and has been applied to the stratographic filler, and he finds this material because tiny particle, random pattern and relatively poor physical strength is not suitable for the filling of chromatographic column.Since then, the control of mesoporous material pattern just becomes the focus of numerous studies person's research.(K.K.Unger such as Unger in 1997; Et al; Adv.Mater.; 1997; 9:254-257) by means of method (
Figure G200910073248XD00012
the et al of improved
Figure G200910073248XD00011
; J.Colloid Interface Sci.; 1968,26:62-69) synthesize spherical mesopore silicon oxide MCM-41, and successfully it is applied to the separation of organic macromolecule as efficient liquid phase chromatographic stuffing with spherical pattern.But the particle size of the product that the main drawback of this method is to obtain is generally less than 2 μ m, also needs the mesoporous condition that forms mutually of the specific silicon oxide-tensio-active agent of system's modulation, just can obtain the globular meso pore silicon oxide material.
(T.Martin such as Martin in 2002; Et al; Angew.Chem.Int.Ed.; 2002,41:2590-2592) pseudo-lattice synthetic thought (Pseudomorphic transformation) is incorporated in macrobead (＞5 μ m) mesopore silicon oxide MCM-41 synthetic of controllable appearance, the spherical mesopore silicon oxide MCM-41 of synthetic successfully is applied to the separation of organic macromolecule in the high-efficient liquid phase chromatogram HPLC.They find that the amount of alkali source and the water yield are to keep the key factor of granule-morphology in the preparation process of material; And employed amorphous silicon oxide ball must have the uniform grain sizes distribution in their method, and they do not inquire into the possibility of the spherical mesopore silicon oxide MCM-41 with wide particle diameter distribution.
In view of silica material is being safe aspect food and the medical applications, the simultaneous oxidation silicon face has a large amount of surface silanol groups that the anchor point of further finishing can be provided, so especially noticeable aspect the biology separation.Meso pore silicon oxide material is applied to the separation field of biomacromolecule and reports less; The great majority report concentrates on the appendix and the absorption aspect of enzyme; And be absorption or the appendix to the single creature enzyme, up to the present rarely have report for the absorption or the appendix of two or more enzyme.
Summary of the invention
The purpose of this invention is to provide compound method and application that a kind of single dispersion has the micron level spherical mesopore silicon oxide MCM-41 material of wide particle diameter distribution
Above-mentioned purpose realizes through following technical scheme:
The compound method of monodisperse micron level spherical mesopore silicon oxide MCM-41, the first step prepare the uniform mesopore silicon oxide microballoon of size distribution; Alkyl trimethyl amine bromide tensio-active agent and sodium hydroxide or the inorganic alkali source of ammoniacal liquor is soluble in water, under stirring condition, obtain clear soln; With following gel proportioning xR: yOH-: zH2O is mixed with initial gel reaction thing; Wherein R representation template agent; X is molar ratio 0.05≤x≤0.25 of template and silicon oxide (SiO2), and y is molar ratio 0.1≤y≤0.5 of OH-and SiO2, and z is molar ratio 10≤z≤150 of water and SiO2; Add the uniform amorphous silicon oxide ball of size distribution, its size is 5-500 μ m, and at room temperature stirs 15-45 minute; Mixture moves in the crystallizing kettle, descends static crystallization 2-24 hour at 110-120 ℃; The solid product that obtains obtains the former powder of product through separation, drying;
Second step; Remove the alkyl trimethyl amine bromide tensio-active agent in mesoporous; Also can be the mode of solution extraction with the dried powder of gained through roasting method, and described maturing temperature is 500～800 ℃, and roasting time is to obtain the mesopore silicon oxide microballoon after 6～8 hours; The used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6～12 hours.
Monodisperse micron level spherical mesopore silicon oxide MCM-41 compound method; It is soluble in water with alkyltrimethyl ammonium chloride tensio-active agent and sodium hydroxide or the inorganic alkali source of ammoniacal liquor that the first step prepares mesopore silicon oxide microballoon that wide particle diameter distributes, under stirring condition, obtains clear soln; With following gel proportioning xR: yOH-: zH2O is mixed with initial gel reaction thing; Wherein R representation template agent, x is molar ratio 0.05≤x≤0.25 of template and silicon oxide sio 2, y is molar ratio 0.1≤y≤0.5 of OH-and SiO2;, z is molar ratio 10≤z≤150 of water and SiO2; Add the uneven amorphous silicon oxide ball of size distribution, its size is 5-500 μ m, adds aminoalkoxy silane pattern adjusting control agent, and add-on is looked the type of used aminoalkoxy silane and decided.And at room temperature stirred 15-45 minute; Mixture moves in the crystallizing kettle, descends static crystallization 2-24 hour at 110-120 ℃; The solid product that obtains obtains the former powder of product through separation, drying;
Second step; Remove the alkyl trimethyl amine bromide tensio-active agent in mesoporous; Also can be the mode of solution extraction with the dried powder of gained through roasting method, and described maturing temperature is 500～800 ℃, and roasting time is to obtain the mesopore silicon oxide microballoon after 6～8 hours; The used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6～12 hours.
The compound method of monodisperse micron level spherical mesopore silicon oxide MCM-41, the first step prepare the uniform mesopore silicon oxide microballoon of size distribution; Alkyl trimethyl amine bromide tensio-active agent and sodium hydroxide or the inorganic alkali source of ammoniacal liquor is soluble in water, under stirring condition, obtain clear soln; With following gel proportioning xR: yOH-: zH2O is mixed with initial gel reaction thing; Wherein R representation template agent; X is molar ratio 0.1≤x≤0.2 of template and silicon oxide sio 2, and y is molar ratio 0.2≤y≤0.3 of OH-and SiO2, and z is molar ratio 20≤y≤80 of water and SiO2; Add the uniform amorphous silicon oxide ball of size distribution, its size is 5-500 μ m, and at room temperature stirs 15-45 minute; Mixture moves in the crystallizing kettle, descends static crystallization 2-24 hour at 110-120 ℃; The solid product that obtains obtains the former powder of product through separation, drying;
Second step; Remove the alkyl trimethyl amine bromide tensio-active agent in mesoporous; Also can be the mode of solution extraction with the dried powder of gained through roasting method, and described maturing temperature is 500～800 ℃, and roasting time is to obtain the mesopore silicon oxide microballoon after 6～8 hours; The used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6～12 hours.
Monodisperse micron level spherical mesopore silicon oxide MCM-41 compound method, the first step prepare the mesopore silicon oxide microballoon that wide particle diameter distributes; Alkyltrimethyl ammonium chloride tensio-active agent and sodium hydroxide or the inorganic alkali source of ammoniacal liquor is soluble in water, under stirring condition, obtain clear soln; With following gel proportioning xR: yOH-: zH2O is mixed with initial gel reaction thing; Wherein R representation template agent; X is molar ratio 0.1≤x≤0.2 of template and silicon oxide sio 2, and y is molar ratio 0.2≤y≤0.3 of OH-and SiO2, and z is molar ratio 20≤y≤80 of water and SiO2; Add the uneven amorphous silicon oxide ball of size distribution, its size is 5-500 μ m, adds aminoalkoxy silane pattern adjusting control agent, and add-on is looked the type of used aminoalkoxy silane and decided.And at room temperature stirred 15-45 minute; Mixture moves in the crystallizing kettle, descends static crystallization 2-24 hour at 110-120 ℃; The solid product that obtains obtains the former powder of product through separation, drying;
Second step; Remove the alkyl trimethyl amine bromide tensio-active agent in mesoporous; Also can be the mode of solution extraction with the dried powder of gained through roasting method, and described maturing temperature is 500～800 ℃, and roasting time is to obtain the mesopore silicon oxide microballoon after 6～8 hours; The used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6～12 hours.
Described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound method; Described tensio-active agent is a cats product, and described tensio-active agent is the mixture of alkyl trimethyl amine bromide, alkyltrimethyl ammonium chloride and alkyl trimethyl amine bromide or alkyltrimethyl ammonium chloride and triblock copolymer; Alkyl in described alkyltrimethyl ammonium chloride or the alkyl trimethyl amine bromide can be hexadecyl, octadecyl, eicosyl.
Described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound method, described alkali source is sodium hydroxide or ammoniacal liquor, is preferably sodium hydroxide.
Described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound method, described crystallization temperature is controlled at 120 ℃ and is advisable.
Described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound method; The aperture of described mesopore silicon oxide spheres; The mixture that can pass through to use alkyl trimethyl amine bromide, alkyltrimethyl ammonium chloride and segmented copolymer is as structure directing agent; Also can use the alkyl trimethyl amine bromide as structure directing agent, sym-trimethylbenzene, normal hexane are realized as expanding agent.
The application of described monodisperse micron level spherical mesopore silicon oxide MCM-41; Described this meso pore silicon oxide material as carrier of separating to egg albumen N,O-Diacetylmuramidase Hen egg white lysozyme and bovine serum albumin Bovine serum albumin, the application of two kinds of proteinic competitive adsorption separation of BSA aspect.
Beneficial effect of the present invention:
1. the present invention can synthesize the monodisperse mesoporous MCM-41 material of micron level spherical, the range of application of having widened mesoporous MCM-41 to a great extent easily.
2. the monodisperse mesoporous MCM-41 of the uniform micron level spherical of synthetic particle size distribution of the present invention can be used as the filler of liquid chromatography; Since its particle during than Datong District granule interior have adjustable mesopore orbit; Can largely reduce bed layer pressure falls; Can be applicable to separating of organic macromolecule and biomacromolecule, for sharp separation organic macromolecule and biomacromolecule possibility is provided simultaneously.
3. the monodisperse mesoporous MCM-41 of micron level spherical of the wide size-grade distribution of synthetic of the present invention can be used as catalyzer or support of the catalyst in the fluidized-bed reactor, is applied to the catalytic pyrolysis and the mass industrialized production CNT of organic macromolecule.
4. the adding of tensio-active agent of the present invention mainly is as the meso-hole structure template; In reaction, pass through assembling effect to the silicate ion of various polymerization states; Make the silicon oxide ball of generation have orderly meso-hole structure, thereby help the further application of material.
Description of drawings:
Fig. 1 is the figure of the mesopore silicon oxide microballoon XRD of the embodiment of the invention 1
Fig. 2 is the nitrogen physisorption isothermal chart of the mesopore silicon oxide microballoon of the embodiment of the invention 1
Fig. 3 is the sem photograph of the mesopore silicon oxide microballoon of the embodiment of the invention 1
Fig. 4 is the transmission electron microscope picture of the mesopore silicon oxide microballoon of the embodiment of the invention 1
Fig. 5 is the X-ray diffractogram of the mesopore silicon oxide microballoon of the embodiment of the invention 3
Fig. 6 is the nitrogen physisorption isothermal chart of the mesopore silicon oxide microballoon of the embodiment of the invention 3
Fig. 7 is the sem photograph of the mesopore silicon oxide microballoon of the embodiment of the invention 3
Fig. 8 is the transmission electron microscope picture of the mesopore silicon oxide microballoon of the embodiment of the invention 3
Fig. 9 is the grain size distribution curve of the mesopore silicon oxide microballoon of the embodiment of the invention 3
Figure 10 is 1,4 and 6 pairs of egg albumen N,O-Diacetylmuramidases of the embodiment of the invention and two kinds of proteinic competitive adsorption figure of bovine serum albumin.
Embodiment:
Embodiment 1:
Compound method and the application of a kind of monodisperse micron level spherical mesopore silicon oxide MCM-41, the first step prepares the mesopore silicon oxide microballoon; Alkyl trimethyl amine bromide tensio-active agent 1.82 grams and inorganic alkali source 0.5 gram of sodium hydroxide are dissolved in the 18 gram water, and the dissolving back is stirred and was obtained clear soln in 1 hour; Add 3 gram amorphous silicon oxide balls, its size is 5-500 μ m, and size distribution is even, and at room temperature stirs 30 minutes; Transfer in the reaction kettle that has liner 120 ℃ of following crystallization 6 hours then; The dissolving and the original position redeposition balance of the disruptive oxidation silicon of crystallization excessive temperature meeting; Cause silicon oxide ball broken, the mistake low temperature can not produce mesoporous uniformly in silicon oxide ball, after cooling and the washing; 100 ℃ of dryings obtain the former powder of product;
Second step; The former powder of the product of above-mentioned gained is removed the alkyl trimethyl amine bromide tensio-active agent in mesoporous; Place retort furnace through roasting method the dried powder of gained, described maturing temperature is 500 ℃, and roasting time is to obtain the mesopore silicon oxide microballoon after 6～8 hours.
Embodiment 2:
Monodisperse micron level spherical mesopore silicon oxide MCM-41 compound method, the first step prepares the mesopore silicon oxide microballoon: alkyltrimethyl ammonium chloride tensio-active agent 1.82 grams and inorganic alkali source 0.5 gram of sodium hydroxide are dissolved in the 18 gram water, and stirred 1 hour the dissolving back; Add 0.555 gram aminoalkoxy silane pattern adjusting control agent APTS then; Continue to stir after 30 minutes, add 3 grams again and have the amorphous silicon oxide ball of inhomogeneous size distribution, and at room temperature stirred 30 minutes; Transfer in the reaction kettle that has liner 120 ℃ of following crystallization 6 hours then; The dissolving and the original position redeposition balance of the disruptive oxidation silicon of crystallization excessive temperature meeting cause silicon oxide ball broken, cross low temperature and can not in silicon oxide ball, produce mesoporous uniformly; After cooling and the washing, 100 ℃ of dryings obtain the former powder of product;
Second step; The former powder of the product of above-mentioned gained is removed the alkyl trimethyl amine bromide tensio-active agent in mesoporous; With the dried powder of the gained mode through solution extraction, the used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6 hours.
Embodiment 3:
Embodiment 2 described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound methods, described preparation mesopore silicon oxide microballoon: alkyltrimethyl ammonium chloride tensio-active agent 1.82 grams and inorganic alkali source 0.5 gram of sodium hydroxide are dissolved in the 18 gram water, and stirred 1 hour the dissolving back; Add 1.11 gram aminoalkoxy silane pattern adjusting control agent APTS then; Continue to stir after 30 minutes, add 3 grams again and have the amorphous silicon oxide ball of inhomogeneous size distribution, and at room temperature stirred 30 minutes; Transfer in the reaction kettle that has liner 120 ℃ of following crystallization 6 hours then; The dissolving and the original position redeposition balance of the disruptive oxidation silicon of crystallization excessive temperature meeting cause silicon oxide ball broken, cross low temperature and can not in silicon oxide ball, produce mesoporous uniformly; After cooling and the washing, 100 ℃ of dryings obtain the former powder of product;
Second step; The former powder of the product of above-mentioned gained is removed the alkyl trimethyl amine bromide tensio-active agent in mesoporous; With the dried powder of gained mode through solution extraction; The used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6 hours, table 1 is listed in d value and specific surface area, pore volume and the aperture of its XRD analysis.
Embodiment 4:
Embodiment 2 described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound methods, described preparation mesopore silicon oxide microballoon: alkyltrimethyl ammonium chloride tensio-active agent 1.82 grams and inorganic alkali source 0.5 gram of sodium hydroxide are dissolved in the 18 gram water, and stirred 1 hour the dissolving back; Add 2.22 gram aminoalkoxy silane pattern adjusting control agent APTS then; Continue to stir after 30 minutes, add 3 grams again and have the amorphous silicon oxide ball of inhomogeneous size distribution, and at room temperature stirred 30 minutes; Transfer in the reaction kettle that has liner 120 ℃ of following crystallization 6 hours then; The dissolving and the original position redeposition balance of the disruptive oxidation silicon of crystallization excessive temperature meeting cause silicon oxide ball broken, cross low temperature and can not in silicon oxide ball, produce mesoporous uniformly; After cooling and the washing, 100 ℃ of dryings obtain the former powder of product;
Second step; The former powder of the product of above-mentioned gained is removed the alkyl trimethyl amine bromide tensio-active agent in mesoporous; With the dried powder of gained mode through solution extraction; The used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6 hours, table 1 is listed in d value and specific surface area, pore volume and the aperture of its XRD analysis.
Embodiment 5:
Embodiment 2 described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound methods, described preparation mesopore silicon oxide microballoon: alkyltrimethyl ammonium chloride tensio-active agent 1.82 grams and inorganic alkali source 0.5 gram of sodium hydroxide are dissolved in the 18 gram water, and stirred 1 hour the dissolving back; Add 3.33 gram aminoalkoxy silane pattern adjusting control agent APTS then; Continue to stir after 30 minutes, add 3 grams again and have the amorphous silicon oxide ball of inhomogeneous size distribution, and at room temperature stirred 30 minutes; Transfer in the reaction kettle that has liner 120 ℃ of following crystallization 6 hours then; The dissolving and the original position redeposition balance of the disruptive oxidation silicon of crystallization excessive temperature meeting cause silicon oxide ball broken, cross low temperature and can not in silicon oxide ball, produce mesoporous uniformly; After cooling and the washing, 100 ℃ of dryings obtain the former powder of product;
Second step; The former powder of the product of above-mentioned gained is removed the alkyl trimethyl amine bromide tensio-active agent in mesoporous; With the dried powder of gained mode through solution extraction; The used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6 hours, table 1 is listed in d value and specific surface area, pore volume and the aperture of its XRD analysis.
Embodiment 6:
Embodiment 2 described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound methods, described preparation mesopore silicon oxide microballoon: alkyltrimethyl ammonium chloride tensio-active agent 1.82 grams and inorganic alkali source 0.5 gram of sodium hydroxide are dissolved in the 18 gram water, and stirred 1 hour the dissolving back; Add 4.44 gram aminoalkoxy silane pattern adjusting control agent APTS then; Continue to stir after 30 minutes, add 3 grams again and have the amorphous silicon oxide ball of inhomogeneous size distribution, and at room temperature stirred 30 minutes; Transfer in the reaction kettle that has liner 120 ℃ of following crystallization 6 hours then; The dissolving and the original position redeposition balance of the disruptive oxidation silicon of crystallization excessive temperature meeting cause silicon oxide ball broken, cross low temperature and can not in silicon oxide ball, produce mesoporous uniformly; After cooling and the washing, 100 ℃ of dryings obtain the former powder of product;
Second step; The former powder of the product of above-mentioned gained is removed the alkyl trimethyl amine bromide tensio-active agent in mesoporous; With the dried powder of gained mode through solution extraction; The used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6 hours, table 1 is listed in d value and specific surface area, pore volume and the aperture of its XRD analysis.
Embodiment 7:
Embodiment 2 described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound methods, described preparation mesopore silicon oxide microballoon: alkyltrimethyl ammonium chloride tensio-active agent 1.82 grams and inorganic alkali source 0.5 gram of sodium hydroxide are dissolved in the 36 gram water, and stirred 1 hour the dissolving back; Add 0.555 gram aminoalkoxy silane pattern adjusting control agent APTS then; Continue to stir after 30 minutes, add 3 grams again and have the amorphous silicon oxide ball of inhomogeneous size distribution, and at room temperature stirred 30 minutes; Transfer in the reaction kettle that has liner 120 ℃ of following crystallization 6 hours then; The dissolving and the original position redeposition balance of the disruptive oxidation silicon of crystallization excessive temperature meeting cause silicon oxide ball broken, cross low temperature and can not in silicon oxide ball, produce mesoporous uniformly; After cooling and the washing, 100 ℃ of dryings obtain the former powder of product;
Second step; The former powder of the product of above-mentioned gained is removed the alkyl trimethyl amine bromide tensio-active agent in mesoporous; With the dried powder of the gained mode through solution extraction, the used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6 hours.
Embodiment 8:
The application of embodiment 1 or 2 described monodisperse micron level spherical mesopore silicon oxide MCM-41, (1) is dispersed in 1 milliliter of 50 mmole/rise in the Tris buffered soln with 1mg egg albumen N,O-Diacetylmuramidase and two kinds of protein of 1mg bovine serum albumin, and is for use;
(2) sample with embodiment 1-7 places 90-120 ℃ of baking oven activation 12 hours;
(3) the mesopore silicon oxide microballoon that obtains in second step is mixed with the solution of the first step gained mutually; At 21 ℃;, stirred 30 minutes PM 200 under changeing; Spinning goes out the solid in the solution then, uses remaining egg albumen N,O-Diacetylmuramidase and two kinds of protein concns of bovine serum albumin in the reverse high-performance liquid chromatogram determination solution;
(4) use separation factor come quantitatively characterizing silicon oxide microsphere material as carrier of separating to egg albumen N,O-Diacetylmuramidase and two kinds of isolating abilities of proteinic competitive adsorption of bovine serum albumin, separation factor=| the amount (mg) of the bovine serum albumin of the amount (mg) of the egg albumen N,O-Diacetylmuramidase of absorption-absorption | amount (mg) x100% of/gross protein that adsorbs
Embodiment 9:
Embodiment 2 or 4 described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound methods when the silicon oxide ball size distribution of described use is even, needn't be introduced pattern adjusting control agent aminoalkoxy silane; If usefulness is the uneven silicon oxide ball of size distribution; This must add pattern adjusting control agent aminoalkoxy silane (3-TSL 8330 or 3-(2-amino-ethyl) TSL 8330); The molar ratio of itself and silicon oxide is 0-0.4; Optimum proportion is looked the type of used aminoalkoxy silane and is decided, and is generally 0.1.Amount hour has fragment to exist in the product that is obtained, and measures when excessive, can cause the amorphous silicon oxide ball can not change mesopore silicon oxide spheres into.Churning time is preferably 30-45 minute under the room temperature, and the length of this step churning time is also relevant with the size of silicon oxide ball simultaneously.The main effect of pattern adjusting control agent aminoalkoxy silane is; At the amorphous silicon oxide spherolite that uses when directly being inhomogeneous; Participate in silicate ion polycondensation under the help of tensio-active agent that dissolving generates, so that the dissolution rate of silicon oxide and polycondensation speed reach balance.Simultaneously at mesopore orbit inwall grappling amido functional group, for later functionalized application provides the basis.
Embodiment 10:
Embodiment 1,2,3 or 4 described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound methods, described alkali source is sodium hydroxide and ammoniacal liquor, is preferably sodium hydroxide; The main effect of described alkali source is to make the dissolving of amorphous silicon oxide ball, generates silicate ion, and polycondensation becomes mesopore silicon oxide under the help of tensio-active agent.Adjust the consumption of alkali source suitably, make the dissolution rate of silicon oxide and in-situ polycondensation speed reach balance, and then can not change the spherical pattern of silicon oxide ball, obtain having the silicon oxide microsphere of meso-hole structure.
Embodiment 11:
Embodiment 1,2,3 or 4 described monodisperse micron level spherical mesopore silicon oxide MCM-41 compound methods; The aperture of described mesopore silicon oxide spheres; Can through use alkyl trimethyl amine bromide, alkyltrimethyl ammonium chloride and segmented copolymer, mixture as structure directing agent; Also can use the alkyl trimethyl amine bromide as structure directing agent, sym-trimethylbenzene, normal hexane are realized as expanding agent; The aperture maximum adjustable changes to 10 nanometers.
The pore structure characteristic of sample after processing of table 1 different condition and the roasting
Figure G200910073248XD00121

Claims (2)

1. The compound method of a kind of monodisperse micron level spherical mesopore silicon oxide MCM-41 is characterized in that: the first step prepares the mesopore silicon oxide microballoon; Alkyl trimethyl amine bromide tensio-active agent 1.82 grams and inorganic alkali source 0.5 gram of sodium hydroxide are dissolved in the 18 gram water, and the dissolving back is stirred and was obtained clear soln in 1 hour; Add 3 gram amorphous silicon oxide balls, its size is 5-500 μ m, and size distribution is even, and at room temperature stirs 30 minutes; Transfer in the reaction kettle that has liner 120 ℃ of following crystallization 6 hours then; The dissolving and the original position redeposition balance of the disruptive oxidation silicon of crystallization excessive temperature meeting; Cause silicon oxide ball broken, the mistake low temperature can not produce mesoporous uniformly in silicon oxide ball, after cooling and the washing; 100 ℃ of dryings obtain the former powder of product;
second step; The former powder of the product of above-mentioned gained is removed the alkyl trimethyl amine bromide tensio-active agent in mesoporous; Place retort furnace to pass through roasting method the dried powder of gained; Described maturing temperature is 500 ℃, and roasting time is to obtain the mesopore silicon oxide microballoon after 6～8 hours.
2. A kind of monodisperse micron level spherical mesopore silicon oxide MCM-41 compound method, it is characterized in that: the first step prepares the mesopore silicon oxide microballoon: alkyltrimethyl ammonium chloride tensio-active agent 1.82 grams and inorganic alkali source 0.5 gram of sodium hydroxide are dissolved in the 18 gram water, and stirred 1 hour the dissolving back; Add 0.555 gram aminoalkoxy silane pattern adjusting control agent APTS then; Continue to stir after 30 minutes, add 3 grams again and have the amorphous silicon oxide ball of inhomogeneous size distribution, and at room temperature stirred 30 minutes; Transfer in the reaction kettle that has liner 120 ℃ of following crystallization 6 hours then; The dissolving and the original position redeposition balance of the disruptive oxidation silicon of crystallization excessive temperature meeting cause silicon oxide ball broken, cross low temperature and can not in silicon oxide ball, produce mesoporous uniformly; After cooling and the washing, 100 ℃ of dryings obtain the former powder of product;
second step; The former powder of the product of above-mentioned gained is removed the alkyl trimethyl amine bromide tensio-active agent in mesoporous; With the dried powder of the gained mode through solution extraction, the used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon 60-80 ℃ of refluxed after 6 hours.
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CN102976350B (en) * 2012-12-12 2014-05-21 天津大学 Method for synthesizing monodisperse MCM-41 molecular sieves with two particle size distribution ranges by one-step process
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CN107551999A (en) * 2017-09-25 2018-01-09 江苏苏通碳纤维有限公司 The preparation method of activated carbon fiber-loaded ordered mesoporous silicon dioxide composite material
CN111847460A (en) * 2020-07-15 2020-10-30 南昌大学 Method for synthesizing mesoporous silica MCM-41 by using organic silicon waste residues

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