CN102070148A - 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 PDFInfo
- Publication number
- CN102070148A CN102070148A CN200910073248XA CN200910073248A CN102070148A CN 102070148 A CN102070148 A CN 102070148A CN 200910073248X A CN200910073248X A CN 200910073248XA CN 200910073248 A CN200910073248 A CN 200910073248A CN 102070148 A CN102070148 A CN 102070148A
- Authority
- CN
- China
- Prior art keywords
- silicon oxide
- mesopore silicon
- mcm
- molar ratio
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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
Technical field:
The present invention relates to a kind of inorganic materials preparation and biomacromolecule and separate Application Areas, 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 are subjected to certain limitation.
1998, (S.Inagaki such as Inagaki, et al, Stud.Surf.Sci.Catal., 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.Unger in 1997 etc. (K.K.Unger, et al, Adv.Mater., 1997,9:254-257) by means of improved
Method (
Et al, 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 main drawback of this method is the particle size of the product that obtains and 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, and is therefore 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 biological enzyme, and be absorption or appendix to the single creature enzyme, up to the present rarely have report for the absorption or the appendix of two or more biological enzyme.
Summary of the invention
The purpose of this invention is to provide synthetic 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 by following technical scheme:
The synthetic 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 represents template, x is molar ratio 0.05≤x≤0.25 of template and silicon oxide (SiO2), 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 by 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 after refluxing 6～12 hours under 60-80 ℃.
Monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic 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, obtains clear soln under stirring condition; With following gel proportioning xR: yOH-: zH2O is mixed with initial gel reaction thing, wherein R represents template, and x is molar ratio 0.05≤x≤0.25 of template and silicon oxide sio 2, and 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 decided on the type of used aminoalkoxy silane.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 by 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 after refluxing 6～12 hours under 60-80 ℃.
The synthetic 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 represents template, 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 by 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 after refluxing 6～12 hours under 60-80 ℃.
Monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic 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 represents template, 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 decided on the type of used aminoalkoxy silane.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 by 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 after refluxing 6～12 hours under 60-80 ℃.
Described monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic 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 synthetic method, described alkali source is sodium hydroxide or ammoniacal liquor, is preferably sodium hydroxide.
Described monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic method, described crystallization temperature is controlled at 120 ℃ and is advisable.
Described monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic method, the aperture of described mesopore silicon oxide spheres, can pass through to use the mixture of alkyl trimethyl amine bromide, alkyltrimethyl ammonium chloride and segmented copolymer 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, provide possibility for sharp separation organic macromolecule and biomacromolecule 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 the support of the catalyst in the fluidized-bed reactor, is applied to the catalytic pyrolysis and the mass industrialized production CNT (carbon nano-tube) 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:
Synthetic 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 reactor 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 the silicon oxide ball fragmentation, crossing 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 alkyl trimethyl amine bromide tensio-active agent in mesoporous, place retort furnace by 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 synthetic 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, 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 the amorphous silicon oxide ball that 3 grams have inhomogeneous size distribution again, and at room temperature stirred 30 minutes, transfer in the reactor 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 the silicon oxide ball fragmentation, crossing 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 alkyl trimethyl amine bromide tensio-active agent in mesoporous, with the dried powder of the gained mode by solution extraction, the used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon at 60-80 ℃ after refluxing 6 hours down.
Embodiment 3:
Second step, the former powder of the product of above-mentioned gained is removed alkyl trimethyl amine bromide tensio-active agent in mesoporous, with the dried powder of gained mode by solution extraction, the used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon after refluxing 6 hours under 60-80 ℃, table 1 is listed in d value and specific surface area, pore volume and the aperture of its XRD analysis.
Embodiment 4:
Second step, the former powder of the product of above-mentioned gained is removed alkyl trimethyl amine bromide tensio-active agent in mesoporous, with the dried powder of gained mode by solution extraction, the used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon after refluxing 6 hours under 60-80 ℃, table 1 is listed in d value and specific surface area, pore volume and the aperture of its XRD analysis.
Embodiment 5:
Second step, the former powder of the product of above-mentioned gained is removed alkyl trimethyl amine bromide tensio-active agent in mesoporous, with the dried powder of gained mode by solution extraction, the used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon after refluxing 6 hours under 60-80 ℃, table 1 is listed in d value and specific surface area, pore volume and the aperture of its XRD analysis.
Embodiment 6:
Second step, the former powder of the product of above-mentioned gained is removed alkyl trimethyl amine bromide tensio-active agent in mesoporous, with the dried powder of gained mode by solution extraction, the used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon after refluxing 6 hours under 60-80 ℃, table 1 is listed in d value and specific surface area, pore volume and the aperture of its XRD analysis.
Embodiment 7:
Second step, the former powder of the product of above-mentioned gained is removed alkyl trimethyl amine bromide tensio-active agent in mesoporous, with the dried powder of the gained mode by solution extraction, the used acid ethanol solution of the mode of described solution extraction obtains the mesopore silicon oxide microballoon at 60-80 ℃ after refluxing 6 hours down.
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 stand-by;
(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 mutually with the solution of the first step gained, at 21 ℃, under changeing, stirred 30 minutes per minute 200, centrifugation 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 10:
Embodiment 11:
The pore structure feature of sample after processing of table 1 different condition and the roasting
Claims (9)
1. the synthetic method of a monodisperse micron level spherical mesopore silicon oxide MCM-41, it is characterized in that: the first step prepares 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 represents template, x is molar ratio 0.05≤x≤0.25 of template and silicon oxide (SiO2), 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 by 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 after refluxing 6～12 hours under 60-80 ℃.
2. monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic method, it is characterized in that: 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, obtains clear soln under stirring condition; With following gel proportioning xR: yOH-: zH2O is mixed with initial gel reaction thing, wherein R represents template, and x is molar ratio 0.05≤x≤0.25 of template and silicon oxide sio 2, and 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 decided on the type of used aminoalkoxy silane.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 by 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 after refluxing 6～12 hours under 60-80 ℃.
3. the synthetic method of monodisperse micron level spherical mesopore silicon oxide MCM-41 according to claim 1 is characterized in that: the first step prepares 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 represents template, 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 by 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 after refluxing 6～12 hours under 60-80 ℃.
4. monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic method according to claim 2 is characterized in that: the first step prepares 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 represents template, 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 decided on the type of used aminoalkoxy silane.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 by 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 after refluxing 6～12 hours under 60-80 ℃.
5. according to claim 1,2,3 or 4 described monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic methods, it is characterized in that: 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.
6. according to claim 1,2,3 or 4 described monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic methods, it is characterized in that: described alkali source is sodium hydroxide or ammoniacal liquor, is preferably sodium hydroxide.
7. according to claim 1,2,3 or 4 described monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic methods, it is characterized in that: described crystallization temperature is controlled at 120 ℃ and is advisable.
8. according to claim 1,2,3 or 4 described monodisperse micron level spherical mesopore silicon oxide MCM-41 synthetic methods, it is characterized in that: the aperture of described mesopore silicon oxide spheres, can pass through to use the mixture of alkyl trimethyl amine bromide, alkyltrimethyl ammonium chloride and segmented copolymer 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.
9. according to the application of claim 1,2,3 or 4 described monodisperse micron level spherical mesopore silicon oxide MCM-41, it is characterized in that: 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910073248XA CN102070148B (en) | 2009-11-23 | 2009-11-23 | Synthesis method and application of mono-disperse micron-scale spherical mesoporous silicon oxide MCM-41 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910073248XA CN102070148B (en) | 2009-11-23 | 2009-11-23 | Synthesis method and application of mono-disperse micron-scale spherical mesoporous silicon oxide MCM-41 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102070148A true CN102070148A (en) | 2011-05-25 |
| CN102070148B CN102070148B (en) | 2012-11-07 |
Family
ID=44028935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910073248XA Expired - Fee Related CN102070148B (en) | 2009-11-23 | 2009-11-23 | Synthesis method and application of mono-disperse micron-scale spherical mesoporous silicon oxide MCM-41 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102070148B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336411A (en) * | 2011-06-27 | 2012-02-01 | 长春理工大学 | Spherical MCM-41 molecular sieve with particle size more than 400 nanometers, and synthesis method for the same |
| CN102976350A (en) * | 2012-12-12 | 2013-03-20 | 天津大学 | Method for synthesizing monodisperse MCM-41 molecular sieves with two particle size distribution ranges by one-step process |
| CN103285908A (en) * | 2013-06-21 | 2013-09-11 | 黑龙江大学 | Co-SBA-16 mesoporous molecule sieve synthesis method |
| CN103601201A (en) * | 2013-11-19 | 2014-02-26 | 哈尔滨理工大学 | Monodispersed mesoporous silica nanoparticles and synthetic method thereof |
| CN103990177A (en) * | 2014-04-29 | 2014-08-20 | 东华大学 | Preparation method for mesoporous-silicon medicine-carrying system modified by bone-morphogenetic-protein active polypeptide |
| CN104010970A (en) * | 2011-12-01 | 2014-08-27 | 赛默电子制造有限公司 | Porous particles for liquid chromatography and processes for the preparation thereof |
| CN107128948A (en) * | 2017-05-09 | 2017-09-05 | 西安工程大学 | A kind of mesopore molecular sieve MCM 41 preparation method |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390784A (en) * | 2002-07-30 | 2003-01-15 | 复旦大学 | Process for synthesizing macroreticular SiO2 molecular sieve containing sequential mesopores |
| CN1994879A (en) * | 2006-11-29 | 2007-07-11 | 南开大学 | Process for preparing mesopore silica dioxide hollow sphere |
-
2009
- 2009-11-23 CN CN200910073248XA patent/CN102070148B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336411A (en) * | 2011-06-27 | 2012-02-01 | 长春理工大学 | Spherical MCM-41 molecular sieve with particle size more than 400 nanometers, and synthesis method for the same |
| US10493428B2 (en) | 2011-12-01 | 2019-12-03 | Thermo Electron Manufacturing Limited | Porous particles for liquid chromatography and processes for the preparation thereof |
| CN104010970A (en) * | 2011-12-01 | 2014-08-27 | 赛默电子制造有限公司 | Porous particles for liquid chromatography and processes for the preparation thereof |
| CN102976350A (en) * | 2012-12-12 | 2013-03-20 | 天津大学 | Method for synthesizing monodisperse MCM-41 molecular sieves with two particle size distribution ranges by one-step process |
| 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 |
| CN103285908B (en) * | 2013-06-21 | 2015-06-03 | 黑龙江大学 | Method for Co-SBA-16 mesoporous molecule sieve for direct hydroxylation synthesis for phenol |
| CN103285908A (en) * | 2013-06-21 | 2013-09-11 | 黑龙江大学 | Co-SBA-16 mesoporous molecule sieve synthesis method |
| CN103601201A (en) * | 2013-11-19 | 2014-02-26 | 哈尔滨理工大学 | Monodispersed mesoporous silica nanoparticles and synthetic method thereof |
| CN103601201B (en) * | 2013-11-19 | 2015-09-23 | 哈尔滨理工大学 | Monodisperse mesoporous monox nanometer particle and synthetic method thereof |
| CN103990177A (en) * | 2014-04-29 | 2014-08-20 | 东华大学 | Preparation method for mesoporous-silicon medicine-carrying system modified by bone-morphogenetic-protein active polypeptide |
| CN107128948A (en) * | 2017-05-09 | 2017-09-05 | 西安工程大学 | A kind of mesopore molecular sieve MCM 41 preparation method |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102070148B (en) | 2012-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102070148B (en) | Synthesis method and application of mono-disperse micron-scale spherical mesoporous silicon oxide MCM-41 | |
| Yeh et al. | Synthesis of hollow silica spheres with mesostructured shell using cationic− anionic-neutral block copolymer ternary surfactants | |
| Manzano et al. | Studies on MCM-41 mesoporous silica for drug delivery: effect of particle morphology and amine functionalization | |
| Shao et al. | Effective adsorption and separation of lysozyme with PAA-modified Fe3O4@ silica core/shell microspheres | |
| Roosen et al. | Shaping of alginate–silica hybrid materials into microspheres through vibrating-nozzle technology and their use for the recovery of neodymium from aqueous solutions | |
| Ulu et al. | Chloro-modified magnetic Fe 3 O 4@ MCM-41 core–shell nanoparticles for L-asparaginase immobilization with improved catalytic activity, reusability, and storage stability | |
| González-Delgado et al. | β-galactosidase covalent immobilization over large-pore mesoporous silica supports for the production of high galacto-oligosaccharides (GOS) | |
| CN102381715B (en) | Large-pore-wall cage-shaped silica hollow sphere and preparation method thereof | |
| CN101786639B (en) | Mesoporous silicon dioxide molecular sieve and preparation method thereof | |
| CN106044788A (en) | Nanometer material with controllable particle sizes and silicon dioxide hollow spheres and method for preparing nanometer material | |
| JPH06505911A (en) | Substances with aggregates | |
| Zhang et al. | Crucial factors affecting the physicochemical properties of sol–gel produced Fe 3 O 4@ SiO 2–NH 2 core–shell nanomaterials | |
| CN106745007B (en) | A kind of multi-stage porous mesoporous organosilicon ball and preparation method thereof | |
| Zhang et al. | Magnetic mesoporous microspheres modified with hyperbranched amine for the immobilization of penicillin G acylase | |
| Li et al. | Design of flexible dendrimer-grafted flower-like magnetic microcarriers for penicillin G acylase immobilization | |
| Pang et al. | Esterification of oleic acid with methanol by immobilized lipase on wrinkled silica nanoparticles with highly ordered, radially oriented mesochannels | |
| Wan et al. | A novel mesoporous nanocarrier: Integrating hollow magnetic fibrous silica with PAMAM into a single nanocomposite for enzyme immobilization | |
| EP1165201B1 (en) | Particulate material for fluidised bed purification of bio-macromolecules such as plasmid dna, chromosomal dna, rna, viral dna, bacteria and viruses | |
| Motevalizadeh et al. | Polyacrolein/mesoporous silica nanocomposite: Synthesis, thermal stability and covalent lipase immobilization | |
| CN102515173A (en) | Method for preparing mesoporous SBA-15 unstuck micro spheres | |
| Wang et al. | Preparation of amine-functionalized mesoporous magnetic colloidal nanocrystal clusters for glucoamylase immobilization | |
| Ribeiro et al. | Immobilization of the enzyme invertase in SBA-15 with surfaces functionalized by different organic compounds | |
| Knežević‐Jugović et al. | An approach for the improved immobilization of penicillin G acylase onto macroporous poly (glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) as a potential industrial biocatalyst | |
| Li et al. | Combined membrane emulsification with biomimetic mineralization: Designing and constructing novel organic-inorganic hybrid microspheres for enzyme immobilization | |
| Kim et al. | Releasing properties of proteins on SBA-15 spherical nanoparticles functionalized with aminosilanes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121107 Termination date: 20151123 |