CN102583400A - Preparation method for mesoporous silica hollow ball - Google Patents
Preparation method for mesoporous silica hollow ball Download PDFInfo
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- CN102583400A CN102583400A CN2012100175399A CN201210017539A CN102583400A CN 102583400 A CN102583400 A CN 102583400A CN 2012100175399 A CN2012100175399 A CN 2012100175399A CN 201210017539 A CN201210017539 A CN 201210017539A CN 102583400 A CN102583400 A CN 102583400A
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Abstract
The invention discloses a preparation method for a mesoporous silica hollow ball. The preparation method comprises the following steps: firstly, adding a surfactant and ammonia water in mixed solvent of alcohol and water; secondly, adding a silicon source, a silica precursor and a surfactant for assembling to form a silica primary product; thirdly, stirring the silica primary product in a raw solution to enable the silica and the surfactant to reorganize and grow to obtain the silica hollow ball; and finally, roasting to remove the surfactant and obtain a mesoporous silica hollow product. According to the preparation method disclosed by the invention, a sacrifice hard template or an emulsion template is not needed to be prefabricated; the preparation method has the characteristics of simple process flow, low cost and high yield; a porous canal of the silica hollow ball synthesized by the preparation method disclosed by the invention is vertical to the surface, so that the transmission of molecules and ions on two sides of a casing layer is facilitated; and the hollow ball used as an ultrasonic contrast agent or a medical carrier has huge potential in disease diagnosis and treatment and facilitates the application in the field of biomedicine.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous silicon oxide hollow ball, be specifically related to a kind of preparation method, belong to the preparation field of porous material with mesoporous silicon oxide hollow ball of vertical channel.
Background technology
Be that template synthetic mesoporous material has high specific surface area and pore volume, the aperture that homogeneous is adjustable, controlled excellent properties such as pattern with the tensio-active agent.Mesoporous material demonstrates huge potential using value at aspects such as support of the catalyst, chemical sensor, optics and delivery of drug.Through the control reaction conditions can synthesizing spherical, the mesoporous material of film, fiber and hollow structure.Wherein, the mesoporous silicon oxide hollow ball that has big cavity structure and a mesopore orbit has caused researchist's extensive concern.This is because the big cavity structure of mesoporous silicon oxide hollow ball can be used for the storage object molecule or as microreactor, its shell with mesopore orbit is that molecule or ionic transmission provide effective path simultaneously.Up-to-date result of study shows that the mesoporous silicon oxide hollow ball has broad application prospects in fields such as confinement catalysis, pharmaceutical carrier, electrode materials, acoustic contrast agents.At present, the compound method of mesoporous silicon oxide hollow ball mainly comprises two kinds, i.e. hard template method and soft template method.
Hard template method is meant class methods of making hollow structure template synthetic silica hollow ball with colloidal inorganic particle or high score bulbec, and the disclosed content of following patent application document and document all belongs to this method: application number is 201110069204.7 patent application document; Y.Zhu, E.Kockrick, T.Ikoma, N.Hanagata, S.Kaskel, Chem.Mater.2009,21,2547; H.Blas, M.Save, P.Pasetto, C.Boissiere, C.Sanchez, B.Charleux, Langmuir 2005,21, and 8180; F.J.Su á rez; M.Sevilla; S.
T.Vald é s-Sol í s, A.B.Fuertes, Chem.Mater.2007; 19,3096.This method at first will be synthesized the hollow structure template; Then the hollow structure template is joined in the solution that contains tensio-active agent and silicon source; At the assembling on hollow template surface, the silica shell that formation of deposits has mesoscopic structure, remove the hollow structure template through the method for etching, roasting at last and tensio-active agent promptly obtains the mesoporous silicon oxide hollow material through tensio-active agent and silicon-dioxide presoma.The process that hard template method prepares the mesoporous silicon oxide hollow ball is more loaded down with trivial details, cost is higher, is unfavorable for the development and utilization of Metaporous silicon dioxide material.
Soft template method is meant that with emulsion or bubble be the class methods that the hollow structure template prepares hollow silica ball.The advantage of this method is that building-up process is easy, and the disclosed content of following document belongs to this method: S.Schacht, Q.Huo, I.G.Voigt-Martin, G.D Stucky., F.Schuth, Science, 1996,273,768; J.Wang, Y.Xia, W.Wang, M.Poliskoff, R.Mokaya, J.Mater.Chem.2006,16,1751.Prepare the mesoporous silicon oxide hollow material with soft template method and do not need synthetic in advance colloidal particle or high score bulbec.But in soft template method prepares the process of hollow ball, often need use and have bigger toxic Three methyl Benzene and expensive tensio-active agent prepares emulsion oil droplets or bubble.Simultaneously, because emulsion or bubble template have thermodynamic instability, the pattern of the mesoporous silicon oxide hollow ball of employing soft template method preparation is not ideal enough, and the microballoon monodispersity is poor, and shell thickness is also inhomogeneous.In addition; Utilize the mesopore orbit of the mesoporous silicon oxide hollow ball of hard template and soft template method preparation often to be parallel to microsphere surface; The part duct is unordered; This is unfavorable for that molecule or ion enter into the inside of mesoporous silicon oxide hollow ball, have limited the application of hollow ball in fields such as support of the catalyst and medicine controlled releasings.
Summary of the invention
Goal of the invention: in order to overcome the deficiency that exists in the prior art, the present invention provides a kind of preparation method with mesoporous silicon oxide hollow ball of vertical channel.
Technical scheme: for realizing above-mentioned purpose; The preparation method of mesoporous silicon oxide hollow ball of the present invention; At first utilize collaborative assembling, the condensation in alcohol solution of silicon-dioxide presoma and tensio-active agent to form the elementary product of silicon-dioxide; And then, remove the mesoporous silicon oxide hollow ball that tensio-active agent promptly obtains having vertical channel through the method for roasting at last through the reorganization of the silicon-dioxide/tensio-active agent spontaneous formation hollow silica ball of growing.
The concrete synthesis step of mesoporous silicon oxide hollow ball of the present invention is following:
(1) tensio-active agent and ammoniacal liquor are joined in the mixed solvent of alcohol, water, the mass ratio of tensio-active agent, ammoniacal liquor, alcohol and water is 0.16: 0.1～1: 15～50: 20～80;
(2) the silicon source is joined in the gained solution, make that the concentration in silicon source is 0.005～0.05mg/ml, 10～50 ℃ of agitation conditions react the elementary product of silicon-dioxide that 5～30min obtains white down;
(3) with the elementary product of gained silicon-dioxide in original solution at 10～50 ℃, agitation condition is reaction 12～72h down;
(4) reaction product of step (3) gained is centrifugal, washing, drying; Behind 150～250 ℃ of roasting 5～7h again in 500～600 ℃ of roasting 5～7h, or directly with dried product in 500～600 ℃ of roasting 5～7h.
As preferably, described tensio-active agent is a kind of in Trimethyllaurylammonium bromide, TTAB, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, the palmityl trimethyl ammonium chloride.
Described silicon source is a kind of in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate or positive silicic acid four butyl esters.
Described alcohol is one or more in methyl alcohol, ethanol, n-propyl alcohol, the Virahol.
Described agitation condition is 200～1000 rev/mins.
The mesoporous silicon oxide hollow ball that adopts method for preparing to obtain, particle diameter is 100～1000nm, and this mesoporous silicon oxide hollow ball has the mesopore orbit perpendicular to the surface, and the aperture is 2.5～3.5nm; The specific surface area of mesoporous silicon oxide hollow ball is 800～2000m
2/ g.
Beneficial effect: compared with prior art, the preparation method of mesoporous silicon oxide hollow ball of the present invention has the following advantages:
1, the present invention is under the reaction conditions of gentleness, can the synthesizing mesoporous silicon dioxide hollow ball through simple technological process, and with low cost, lower, productive rate is high to equipment requirements;
2, in the preparation process, can regulate and control the size and the wall thickness of mesoporous silicon oxide hollow ball effectively through changing parameters such as pure water ratio, temperature of reaction;
3, in the preparation process, do not need synthesizing inorganic or organic filler work sacrifice template in advance, need not add organic solvent simultaneously yet and form emulsion, whole technological process is simple, has favorable industrial application prospect.
The mesoporous silicon oxide hollow ball that adopts preparation method of the present invention to make has the following advantages:
1, this mesoporous silicon oxide hollow ball has the size of homogeneous, big hollow structure, spheric pattern; Mesoporous aperture with high specific surface area and pore volume, homogeneous; Mesoporous silicon oxide hollow ball surface has abundant silicon hydroxyl, has good aqueous phase dispersibility ability and excellent biological compatibility; Make acoustic contrast agent or pharmaceutical carrier is used for medical diagnosis on disease and treatment has great potential with this hollow ball;
2, the mesopore orbit of this mesoporous silicon oxide hollow ball helps the load and the release of guest molecules such as medicine perpendicular to the surface, is specially adapted to drug carrier material; The meso-porous titanium dioxide hollow ball does not have crosslinked each other, helps the application at biomedical sector;
3, this mesoporous silicon oxide hollow ball surface is functionalized easily, utilizes the silane reagent that has groups such as amino, sulfydryl, epoxy that the surface is modified, and can obtain being modified with the mesoporous silicon oxide hollow ball of functional groups such as amino, sulfydryl, epoxy; The surface can connect various biologically active substances (like cell, antibody, antigen, enzyme or nucleic acid) after modifying.
Description of drawings
The transmission electron microscope photo of the elementary product of silicon-dioxide that Fig. 1 the present invention makes under the processing condition of embodiment 1;
The transmission electron microscope photo of the mesoporous silicon oxide hollow ball that Fig. 2 the present invention makes under the processing condition of embodiment 1;
The transmission electron microscope photo of the mesopore orbit of the mesoporous silicon oxide hollow ball that Fig. 3 the present invention makes under the processing condition of embodiment 1;
The transmission electron microscope photo of the mesoporous silicon oxide hollow ball that Fig. 4 the present invention makes under the processing condition of embodiment 2;
The transmission electron microscope photo of the mesoporous silicon oxide hollow ball that Fig. 5 the present invention makes under the processing condition of embodiment 3.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done explanation further.
The preparation method of mesoporous silicon oxide hollow ball of the present invention at first joins tensio-active agent and ammoniacal liquor in the mixed solvent of alcohol, water, adds the silicon source then, and silicon-dioxide presoma and tensio-active agent assembling, growth form the elementary product of silicon-dioxide; Continuation is stirred the elementary product of silicon-dioxide in original solution, silicon-dioxide and tensio-active agent are reorganized and then the acquisition hollow silica ball; At last, roasting is removed tensio-active agent and is obtained mesoporous silicon oxide hollow ball product.This preparation method does not need to prepare sacrificial hard template or emulsion template in advance, has the advantages that technological process is simple, with low cost, productive rate is high; The mesopore orbit of synthetic hollow silica ball helps the transmission in the shell both sides of molecule and ion perpendicular to the surface.
Embodiment of the present invention is following:
Embodiment 1:
(1) 0.16g cetyl trimethylammonium bromide and 1ml strong aqua (25-28%) are joined in the mixed solvent of 30ml ethanol and 56ml water;
(2) the positive tetraethyl orthosilicate of 1ml is joined in step (1) the gained solution, 35 ℃, 700rpm stirring reaction 10min obtains the elementary product of silicon-dioxide (referring to Fig. 1);
(3) with the elementary product of step (2) gained silicon-dioxide in original solution at 35 ℃, 700rpm stirs 12h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball.
(4) reaction product of step (3) gained is centrifugal, washing, drying; Behind 200 ℃ of roasting 6h,, obtain mesoporous silicon oxide hollow ball (referring to Fig. 2) again in 550 ℃ of roasting 6h.
The elementary product of silicon-dioxide that obtains has spherical morphology, does not form hollow structure as yet.The particle diameter of the mesoporous silicon oxide hollow ball that obtains is 500nm, has hollow structure, and shell thickness is 80～100nm; Mesopore orbit is perpendicular to hollow silica ball surface (referring to Fig. 3), and the aperture of mesoporous silicon oxide is 3.1nm; Specific surface area is 1233m
2/ g.
Embodiment 2:
(1) 0.16g cetyl trimethylammonium bromide and 1ml strong aqua (25-28%) are joined in the mixed solvent of 30ml ethanol and 50ml water;
(2) the positive tetraethyl orthosilicate of 1ml is joined in step (1) the gained solution, 35 ℃, 700rpm stirring reaction 10min obtains the elementary product of silicon-dioxide;
(3) with the elementary product of step (2) gained silicon-dioxide in original solution at 35 ℃, 700rpm stirs 24h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball.
(4) reaction product of step (3) gained is centrifugal, washing, drying; Behind 200 ℃ of roasting 6h,, obtain the mesoporous silicon oxide hollow ball again in 550 ℃ of roasting 6h.
The particle diameter of the mesoporous silicon oxide hollow ball that obtains is 700nm, and shell thickness is 150～170nm; Specific surface area is 1315m
2/ g; The aperture of mesoporous silicon oxide is 3.0nm.
Embodiment 3:
(1) 0.16g cetyl trimethylammonium bromide and 1ml strong aqua (25-28%) are joined in the mixed solvent of 30ml ethanol and 56ml water;
(2) the positive tetraethyl orthosilicate of 1ml is joined in step (1) the gained solution, 15 ℃, 700rpm stirring reaction 10min obtains the elementary product of silicon-dioxide;
(3) with the elementary product of step (2) gained silicon-dioxide in original solution at 15 ℃, 700rpm stirs 12h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball.
(4) reaction product of step (3) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6h, obtain the mesoporous silicon oxide hollow ball.
The particle diameter of the mesoporous silicon oxide hollow ball that obtains is 420nm, and shell thickness is 20～30nm; Specific surface area is 1011m
2/ g; The aperture of mesoporous silicon oxide is 3.0nm.
Embodiment 4:
(1) 0.16g cetyl trimethylammonium bromide and 1ml strong aqua (25-28%) are joined in the mixed solvent of 30ml Virahol and 56ml water;
(2) positive silicic acid four butyl esters of 2ml are joined in step (1) the gained solution, 35 ℃, 500rpm stirring reaction 10min obtains the elementary product of silicon-dioxide;
(3) with the elementary product of step (2) gained silicon-dioxide in original solution at 35 ℃, 500rpm stirs 12h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball.
(4) reaction product of step (3) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6h, obtain the mesoporous silicon oxide hollow ball.
The particle diameter of the mesoporous silicon oxide hollow ball that obtains is 500nm, and shell thickness is 80～90nm; Specific surface area is 1267m
2/ g; The aperture of mesoporous silicon oxide is 3.1nm.
Embodiment 5:
(1) 0.16g palmityl trimethyl ammonium chloride and 1ml strong aqua (25-28%) are joined in the mixed solvent of 30ml ethanol and 56ml water;
(2) the positive tetraethyl orthosilicate of 1ml is joined in step (1) the gained solution, 35 ℃, 700rpm stirring reaction 10min obtains the elementary product of silicon-dioxide;
(3) with the elementary product of step (2) gained silicon-dioxide in original solution at 35 ℃, 700rpm stirs 12h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball.
(4) reaction product of step (3) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6h, obtain the mesoporous silicon oxide hollow ball.
The particle diameter of the mesoporous silicon oxide hollow ball that obtains is 410nm, and shell thickness is 70nm; Specific surface area is 1526m
2/ g; The aperture of mesoporous silicon oxide is 3.2nm.
Embodiment 6:
(1) 0.16g TTAB and 2ml strong aqua (25-28%) are joined in the mixed solvent of 30ml ethanol and 56ml water;
(2) the positive tetraethyl orthosilicate of 1ml is joined in step (1) the gained solution, 35 ℃, 700rpm stirring reaction 30min obtains the elementary product of silicon-dioxide;
(3) with the elementary product of step (2) gained silicon-dioxide in original solution at 35 ℃, 700rpm stirs 24h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball.
(4) reaction product of step (3) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6h, obtain the mesoporous silicon oxide hollow ball.
The particle diameter of the mesoporous silicon oxide hollow ball that obtains is 550nm, and shell thickness is 70nm; Specific surface area is 1326m
2/ g; The aperture of mesoporous silicon oxide is 2.8nm.
Embodiment 7:
(1) 0.16g cetyl trimethylammonium bromide and 1ml strong aqua (25-28%) are joined in the mixed solvent of 28ml Virahol and 54ml water;
(2) the positive quanmethyl silicate of 1ml is joined in step (1) the gained solution, 35 ℃, 700rpm stirring reaction 10min obtains the elementary product of silicon-dioxide;
(3) with the elementary product of step (2) gained silicon-dioxide in original solution at 35 ℃, 700rpm stirs 48h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball.
(4) reaction product of step (3) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6h, obtain the mesoporous silicon oxide hollow ball.
The particle diameter of the mesoporous silicon oxide hollow ball that obtains is 500nm, and shell thickness is 80nm; Specific surface area is 1015m
2/ g; The aperture of mesoporous silicon oxide is 3.2nm.
Embodiment 8:
(1) 0.16g Trimethyllaurylammonium bromide and 0.1g ammoniacal liquor (0.44ml strong aqua (25-28%)) are joined in the mixed solvent of 15g methyl alcohol and 20g water;
(2) positive quanmethyl silicate is joined in step (1) the gained solution, make that the concentration of positive quanmethyl silicate is 0.005mg/ml, 10 ℃, 200rpm stirring reaction 5min obtains the elementary product of silicon-dioxide;
(3) with the elementary product of gained silicon-dioxide in original solution at 10 ℃, 200rpm stirs 12h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball;
(4) reaction product of step (3) gained is centrifugal, washing, drying; Behind 150 ℃ of roasting 5h,, obtain the mesoporous silicon oxide hollow ball again in 500 ℃ of roasting 5h.
The elementary product of silicon-dioxide that obtains has spherical morphology, does not form hollow structure as yet.The mesoporous silicon oxide hollow ball that obtains has hollow structure, and the hollow ball particle diameter is 106nm, and shell thickness is 10nm; Mesopore orbit is perpendicular to the hollow silica ball surface, and the aperture of mesoporous silicon oxide is 2.5nm; Specific surface area 813m
2/ g.
Embodiment 9:
(1) 0.16g TTAB and 0.5g ammoniacal liquor (2.2ml strong aqua (25-28%)) are joined in the mixed solvent of 35g ethanol and 50g water;
(2) positive tetraethyl orthosilicate is joined in step (1) the gained solution, make that the concentration of positive tetraethyl orthosilicate is 0.025mg/ml, 30 ℃, 600rpm stirring reaction 20min obtains the elementary product of silicon-dioxide;
(3) with the elementary product of gained silicon-dioxide in original solution at 30 ℃, 700rpm stirs 45h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball;
(4) reaction product of step (3) gained is centrifugal, washing, drying; Behind 200 ℃ of roasting 6h,, obtain the mesoporous silicon oxide hollow ball again in 500 ℃ of roasting 6h.
The elementary product of silicon-dioxide that obtains has spherical morphology, does not form hollow structure as yet.The mesoporous silicon oxide hollow ball that obtains has hollow structure, and the hollow ball particle diameter is 500nm, and shell thickness is 70nm; Mesopore orbit is perpendicular to the hollow silica ball surface, and the aperture of mesoporous silicon oxide is 2.9nm; Specific surface area 1052m
2/ g.
Embodiment 10:
(1) 0.16g octadecyl trimethylammonium bromide and 1g ammoniacal liquor (4.4ml strong aqua (25-28%)) are joined in the mixed solvent of 50g n-propyl alcohol and 80g water;
(2) positive silicic acid orthocarbonate is joined in step (1) the gained solution, make that the concentration of positive silicic acid orthocarbonate is 0.05mg/ml, 50 ℃, 700rpm stirring reaction 30min obtains the elementary product of silicon-dioxide;
(3) with the elementary product of gained silicon-dioxide in original solution at 50 ℃, 1000rpm stirs 72h, makes silicon-dioxide/tensio-active agent reorganize growth and obtains hollow silica ball;
(4) reaction product of step (3) gained is centrifugal, washing, drying; Directly with dried product in 500～600 ℃ of roasting 7h, finally obtain the mesoporous silicon oxide hollow ball.
The elementary product of silicon-dioxide that obtains has spherical morphology, does not form hollow structure as yet.The mesoporous silicon oxide hollow ball that obtains has hollow structure, and the hollow ball particle diameter is 989nm, and shell thickness is 145nm; Mesopore orbit is perpendicular to the hollow silica ball surface, and the aperture of mesoporous silicon oxide is 3.5nm; Specific surface area 1946m
2/ g.
The above only is a preferred implementation of the present invention; Be noted that for those skilled in the art; Under the prerequisite that does not break away from the principle of the invention, can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (6)
1. the preparation method of a mesoporous silicon oxide hollow ball is characterized in that comprising the steps:
(1) tensio-active agent and ammoniacal liquor are joined in the mixed solvent of alcohol, water, the mass ratio of tensio-active agent, ammoniacal liquor, alcohol and water is 0.16: 0.1～1: 15～50: 20～80;
(2) the silicon source is joined in step (1) the gained solution, make that the concentration in silicon source is 0.005～0.05mg/ml, reaction 5～30min generates the elementary product of white silicon-dioxide under 10～50 ℃, agitation condition;
(3) with the elementary product of gained silicon-dioxide in original solution under 10～50 ℃, agitation condition reaction 12～72h;
(4) reaction product of step (3) gained is centrifugal, washing, drying; Behind 150～250 ℃ of roasting 5～7h again in 500～600 ℃ of roasting 5～7h, or directly with dried product in 500～600 ℃ of roasting 5～7h, finally obtain the mesoporous silicon oxide hollow ball.
2. according to the preparation method of the said mesoporous silicon oxide hollow ball of claim 1, it is characterized in that: described tensio-active agent is a kind of in Trimethyllaurylammonium bromide, TTAB, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, the palmityl trimethyl ammonium chloride.
3. according to the preparation method of the said mesoporous silicon oxide hollow ball of claim 1, it is characterized in that: described silicon source is a kind of in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate or positive silicic acid four butyl esters.
4. according to the preparation method of the said mesoporous silicon oxide hollow ball of claim 1, it is characterized in that: described alcohol is one or more in methyl alcohol, ethanol, n-propyl alcohol, the Virahol.
5. according to the preparation method of the said mesoporous silicon oxide hollow ball of claim 1, it is characterized in that: described agitation condition is 200～1000 rev/mins.
6. mesoporous silicon oxide hollow ball that each said method of claim 1 to 5 prepares, it is characterized in that: this mesoporous silicon oxide hollow ball particle diameter is 100～1000nm; This mesoporous silicon oxide hollow ball has the mesopore orbit perpendicular to the surface, and the aperture is 2.5～3.5nm; The specific surface area of described mesoporous silicon oxide hollow ball is 800～2000m
2/ g.
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| CN105110343A (en) * | 2015-07-20 | 2015-12-02 | 清华大学 | Method for rapid preparation of monodisperse ordered mesoporous silicon oxide hollow sphere |
| CN107467613A (en) * | 2017-09-13 | 2017-12-15 | 浙江顶味食品有限公司 | A kind of Bio-sil microballoon and the application in meat flavor preparation |
| CN107827118A (en) * | 2017-11-24 | 2018-03-23 | 北京欧美中科学技术研究院 | A kind of preparation method of the adjustable mesoporous silica hollow ball of shell thickness |
| CN109160519A (en) * | 2018-09-14 | 2019-01-08 | 广东工业大学 | A kind of hollow mesoporous silica microsphere, hollow mesoporous silica microsphere load sun-screening agent and its preparation method and application |
| CN109675506A (en) * | 2018-12-27 | 2019-04-26 | 上海元颉新材料科技有限公司 | The structure mesoporous silicon oxide microsphere material of monodisperse hollow and its Dual Surfactants induce process for assembly preparing |
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2012
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105110343A (en) * | 2015-07-20 | 2015-12-02 | 清华大学 | Method for rapid preparation of monodisperse ordered mesoporous silicon oxide hollow sphere |
| CN105110343B (en) * | 2015-07-20 | 2017-02-01 | 清华大学 | Method for rapid preparation of monodisperse ordered mesoporous silicon oxide hollow sphere |
| CN107467613A (en) * | 2017-09-13 | 2017-12-15 | 浙江顶味食品有限公司 | A kind of Bio-sil microballoon and the application in meat flavor preparation |
| CN107467613B (en) * | 2017-09-13 | 2021-03-02 | 浙江顶味食品有限公司 | Porous silica gel microspheres and application thereof in preparation of meat flavor essence |
| CN107827118A (en) * | 2017-11-24 | 2018-03-23 | 北京欧美中科学技术研究院 | A kind of preparation method of the adjustable mesoporous silica hollow ball of shell thickness |
| CN109160519A (en) * | 2018-09-14 | 2019-01-08 | 广东工业大学 | A kind of hollow mesoporous silica microsphere, hollow mesoporous silica microsphere load sun-screening agent and its preparation method and application |
| CN109160519B (en) * | 2018-09-14 | 2022-03-04 | 广东工业大学 | Hollow mesoporous silica microsphere, sun-screening agent loaded on hollow mesoporous silica microsphere, and preparation method and application of sun-screening agent |
| CN109675506A (en) * | 2018-12-27 | 2019-04-26 | 上海元颉新材料科技有限公司 | The structure mesoporous silicon oxide microsphere material of monodisperse hollow and its Dual Surfactants induce process for assembly preparing |
| CN111317825A (en) * | 2020-03-06 | 2020-06-23 | 南京市江宁医院 | Regularly folded ultra-small-size large-pore inorganic silicon macromolecular drug carrier, and preparation method and application thereof |
| CN111317825B (en) * | 2020-03-06 | 2021-08-24 | 南京市江宁医院 | Regularly folded ultra-small-size large-pore inorganic silicon macromolecular drug carrier, and preparation method and application thereof |
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Application publication date: 20120718 |