CN103833040A - Preparation methods of hollow mesoporous silicon oxide spheres and hollow mesoporous organosilicone spheres - Google Patents
Preparation methods of hollow mesoporous silicon oxide spheres and hollow mesoporous organosilicone spheres Download PDFInfo
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- CN103833040A CN103833040A CN201410042369.9A CN201410042369A CN103833040A CN 103833040 A CN103833040 A CN 103833040A CN 201410042369 A CN201410042369 A CN 201410042369A CN 103833040 A CN103833040 A CN 103833040A
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Abstract
The invention relates to preparation methods of hollow mesoporous silicon oxide spheres and a hollow mesoporous organosilicone spheres. According to the preparation methods, solid core/mesoporous shell silicon spheres with high dispersion and the uniform particle size are synthesized by adoption of a sol-gel method and a surfactant orientation method, and are then subjected to hydro-thermal treatment under acid conditions with the assistant of saline ions so as to remove the solid core and to maintain the complete shell, thus obtaining the hollow mesoporous silicon oxide/organosilicone spheres. The synthetic method is simple, feasible, mild in reactions, easy to control and regulate and is novel. The hollow mesoporous spheres have a wide application prospect in the fields of medicine transportation, adsorption, separation, catalysis, and the like.
Description
Technical field
The invention belongs to technical field of nano material, relate to a kind of novel preparation method of hollow mesopore silicon oxide/organosilicon ball.
Background technology
Since the scientist of Mobil company in 1992 synthesizes the mesoporous SiO of MCM-41 type
2since molecular sieve (Nature1992,359,710-712), mesoporous SiO
2material, owing to having high specific surface area, large pore volume, the pore passage structure of homogeneous, is widely used in the fields such as catalysis, absorption, separation and drug delivery.Wherein, hollow mesoporous SiO
2huge cavity structure has given carrier high load guest molecule amount, and the pore passage structure of homogeneous is beneficial to guest molecule and discharges slowly, and the multifunction that the outside surface that is easy to modify is carrier provides favourable condition.
Hollow mesoporous SiO
2the preparation method of ball is mainly divided into soft template method and hard template method two classes.Soft template, as micella or vesica etc., due to the complicacy of synthesis condition, makes the hollow mesoporous SiO synthesizing
2ball size, pattern and dispersiveness are difficult to control.Hard template, as PS ball, Fe
3o
4nanoparticle or SiO
2deng, because template is easily prepared, and pattern easy to control and dispersiveness, cause the extensive concern of scientists.Wherein, the silicon oxide etch chemistries that developed recently gets up adopts solid SiO
2ball is template, the mesoporous SiO of outer parcel
2shell, then adopts etching agent by solid SiO
2partial etching falls, this different lithographic method based on the different of nucleus shell structure rather than composition, and cost is low, pollution-free, simple, can be mass, and becomes the focus of research.
At present, the etching agent based on silicon oxide etch chemistries development mainly contains two kinds of alkaline etching agent and acid etch agent.Wherein, alkaline etchant is generally Na
2cO
3or ammoniacal liquor, because alkaline etching is removed SiO
2reaction be a reversible reaction,, at SiO
2when dissolving, also have SiO
2generation, material system by product prepared by this method is many, mutually impure.Acid etch agent is generally HF solution, and because HF is severe corrosive acid, reaction is violent, is difficult for finely regulating.
Summary of the invention
In the face of the problem that prior art exists, the present invention aims to provide a kind of method that new lithographic method prepares the mesoporous silicon sphere of control ball, and to solve, the reversible reaction existing in prior art is mutually impure, agglomeration seriously, react the problem such as violent, wayward.
At this, first, the invention provides a kind of preparation method of hollow mesopore silicon oxide spheres, comprising:
(1) adopt the synthetic solid silicon oxide ball of sol-gel method as solid core, then silicon source and tensio-active agent are coated on to the surface of described solid silicon oxide ball, centrifugation obtains having the double-deck silicon oxide ball of solid core and mesoporous shell structure;
(2) double-deck gained silicon oxide ball is dispersed in water, adds and contain inorganic salt and sour solution as etching reagent, at 100～250 ℃, hydrothermal treatment consists 5～30 hours is to remove described solid core; And
(3) calcine 4～8 hours to remove tensio-active agent at 500～600 ℃.
The salt ion auxiliary acid etching method of the bright exploration of method provided by the invention, method is simple, reaction temperature and, easy-regulating, method novelty, and there will not be that the reversible reaction existing in prior art is mutually impure, agglomeration is serious, react the problem such as violent, wayward.Material scatter prepared by method of the present invention is fine, and the specific surface area of the hollow mesopore silicon oxide spheres making is 600～1000m
2g
-1, pore volume is 1～4cm
3g
-1, aperture is 2～5nm, extremely the wide application prospect of tool.
Preferably, the mass ratio of described double-deck silicon oxide ball and described inorganic salt can be 1:(5～20), be preferably 1:(7～15);
The mol ratio of described inorganic salt and described acid can be 1:(0.6～6), be preferably 1:(1～4).
Preferably, step (2) can comprise:
Double-deck gained silicon oxide ball is dispersed in water to acquisition dispersion liquid, and the mass ratio of described double-deck silicon oxide ball and water can be 1:(70～90);
Adding volume is the water of 0.5～8 times of described dispersion liquid;
Add described inorganic salt or described acid, the concentration of described acid can be 0.02～0.2M; And
Be transferred to reactor hydrothermal treatment consists 5～30 hours at 100～250 ℃.
In the present invention, described silicon source can be methyl silicate, tetraethoxy, positive silicic acid propyl ester and/or butyl silicate.
The present invention also provides a kind of preparation method of hollow mesoporous organosilicon ball, comprising:
(1) adopt the synthetic solid silicon oxide ball of sol-gel method as solid core, then organosilicon source and tensio-active agent are coated on to the surface of described solid silicon oxide ball, centrifugation obtains having the double-deck organosilicon ball of solid core and mesoporous shell structure;
(2) double-deck gained organosilicon ball is dispersed in water, adds and contain inorganic salt and sour solution as etching reagent, at 100～250 ℃, hydrothermal treatment consists 5～30 hours is to remove described solid core; And
(3) calcine 4～8 hours to remove tensio-active agent at 500～600 ℃.
Preferably, the mass ratio of described double-deck organosilicon ball and described inorganic salt is 1:(6～18), be preferably 1:(8～15);
The mol ratio of described inorganic salt and described acid is 1:(2～12), be preferably 1:(2～9).
Preferably, step (2) can comprise:
Double-deck gained organosilicon ball is dispersed in water to acquisition dispersion liquid, and the mass ratio of described double-deck organosilicon ball and water is 1:(80～100);
Adding volume is the water of 0.5～8 times of described dispersion liquid;
Add described inorganic salt or described acid, the concentration of described acid is 0.02～0.2M; And
Be transferred to reactor hydrothermal treatment consists 5～30 hours at 100～250 ℃.
In the present invention, described organosilicon source can be two (triethoxyl silane) ethene, Isosorbide-5-Nitrae-bis-(triethoxy is silica-based) benzene and/or two (triethoxyl silane) ethane.
In the present invention, described inorganic salt can be NaCl, Na
2cO
3, Na
2sO
4, NaNO
3, NaHPO
4and Na
3pO
4in at least one.
In the present invention, described acid can be HCl, H
2sO
4, H
3pO
4, H
2cO
3, and HNO
3in at least one.
Accompanying drawing explanation
Fig. 1 (a) is the solid SiO of embodiment 1 gained
2transmission electron microscope (TEM) photo of core@mesopore silicon oxide shell; Fig. 1 (b) is transmission electron microscope (TEM) photo of the hollow mesopore silicon oxide spheres of embodiment 1 gained;
Fig. 2 is scanning electronic microscope (SEM) photo of the hollow mesopore silicon oxide spheres of embodiment 1 gained;
Fig. 3 (a) is the N of the hollow mesopore silicon oxide spheres of embodiment 1 gained
2adsorption/desorption isothermal curve;
Fig. 3 (b) is the corresponding graph of pore diameter distribution of hollow mesopore silicon oxide spheres of embodiment 1 gained;
Fig. 4 (a) is the solid SiO of embodiment 4 gained
2transmission electron microscope (TEM) photo of core@mesoporous organosilicon shell;
Fig. 4 (b) is transmission electron microscope (TEM) photo of the hollow mesoporous organosilicon ball of embodiment 4 gained;
Fig. 5 is scanning electronic microscope (SEM) photo of the hollow mesoporous organosilicon ball of embodiment 4 gained;
Fig. 6 is the element mapping figure (Si, O and C element) of the hollow mesoporous organosilicon ball of embodiment 4 gained;
Fig. 7 (a) is the N of the hollow mesoporous organosilicon ball of embodiment 4 gained
2adsorption/desorption isothermal curve;
Fig. 7 (b) is the corresponding graph of pore diameter distribution of hollow mesoporous organosilicon ball of embodiment 4 gained.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment and/or accompanying drawing are only for the present invention is described, and unrestricted the present invention.
The present invention adopts the etching of inorganic ion auxiliary acid to send the hollow mesopore silicon oxide/organosilicon ball of preparation., first add by sol-gel method the silicon ball that tensio-active agent guiding method synthesizes the solid core/mesoporous shell of high dispersing, uniform particle diameter; Remove solid core by hydrothermal treatment consists under the auxiliary acidic conditions of salt ion again and keep shell complete, obtained hollow type mesopore silicon oxide/organosilicon ball.The technical solution used in the present invention, comprises the following steps:
(1) prepare the silicon ball of the mesoporous shell structure of solid core@: can adopt the method for prior art report, for example Chinese patent, the synthetic solid SiO of sol-gel method of publication number CN 102060300B report
2ball is as solid core, then silicon source or organosilicon source and tensio-active agent are coated on to described solid SiO
2the surface of ball, obtains having the silicon ball of the mesoporous shell structure of solid core@, according to adopting the outer silicon ball for silicon oxide layer and silicone layer of difference making respectively of silicon source and organosilicon source.
As preferred version, described silicon source can be selected from least one in methyl silicate, tetraethoxy, positive silicic acid propyl ester and butyl silicate.
As preferred version, described organosilicon source can be selected from the one that has at least in two (triethoxyl silane) ethene, Isosorbide-5-Nitrae-bis-(triethoxy is silica-based) benzene and two (triethoxyl silane) ethane.
(2) the silicon ball of the mesoporous shell structure of gained solid core@is dispersed in water (preferably deionized water), adds and contain inorganic salt and sour solution as etching reagent, under hydrothermal condition, hydrothermal treatment consists is to remove solid core.Hydrothermal temperature can be 100～250 ℃, and the hydro-thermal time can be 5～30 hours.
Preferably, disperse (for example ultrasonic dispersion) to form dispersion liquid at 400-600mL in the silicon ball of the mesoporous shell structure of 5～7g solid core@.
Preferably, the silicon ball of the mesoporous shell structure of solid core@and the mass ratio of inorganic salt can be 1:(5～20), be preferably 1:(7～15); Inorganic salt and sour mol ratio can be 1:(0.6～12), be preferably 1:(1～9).
Preferably, inorganic salt can be NaCl, Na
2cO
3, Na
2sO
4, NaNO
3, NaHPO
4or Na
3pO
4in one or more.
Preferably, acid solution can be HCl solution, H
2sO
4solution, H
3pO
4solution, H
2cO
3solution or HNO
3one or more in solution, concentration can be 0.02～0.2M.
As a preferred example, above-mentioned steps (2) can comprise:
Scattered material solution (dispersion liquid) volume taking out is 5～20mL;
Adding volume is the deionized water of 0.5～8 times of dispersion liquid, for example, add the deionized water of 10-40mL;
Add 0.01～0.2g inorganic salt and 0.1～2mL concentration to can be the acid of 0.02～0.2M;
Be transferred to hydrothermal reaction kettle, under above-mentioned hydrothermal condition, process certain hour.
(3) the centrifugal rear deionized water wash of product 3 times, removes tensio-active agent for 4～8 hours 500～600 ℃ of calcinings after being dried.
Method of the present invention can be prepared a kind of mesopore silicon oxide/organosilicon ball of preparing high dispersing, high-specific surface area, large pore volume and homogeneous pore size distribution.The specific surface area of the hollow mesopore silicon oxide spheres that the present invention makes can be 600～1000m
2g
-1, pore volume can be 1～4cm
3g
-1, aperture can be 2～5nm.The specific surface area of the hollow mesoporous organosilicon ball that the present invention makes can be 600～900m
2g
-1, pore volume can be 0.1～2.3cm
3g
-1, aperture is 2～5.2nm.
The salt ion auxiliary acid etching method that the present invention explores, can solve that the reversible reaction existing in prior art is mutually impure, agglomeration is serious, react the problem such as violent, wayward; And preparation is simple, pollution-free, cost is low, efficiency is high, the not only hollow mesopore silicon oxide spheres of suitable preparation, and can prepare hollow mesoporous organosilicon ball, be a kind of pervasive method.The hollow mesoporous silicon sphere high dispersing that makes, specific surface area is high, pore volume is large, pore size distribution homogeneous, has and application prospect widely in fields such as drug delivery, absorption, separation and catalysis.
Further exemplify embodiment below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameter that following example is concrete etc. is only also an example in OK range, and those skilled in the art can be done in suitable scope and be selected by explanation herein, and do not really want to be defined in the below concrete numerical value of example.
Embodiment 1
Prepare solid SiO according to document (Chinese patent, publication number CN 102060300B)
2core@mesopore silicon oxide shell ball;
71.4mL dehydrated alcohol, the ammoniacal liquor of 10mL deionized water and 3.14mL mixes, and under 30 ℃ of conditions, stirs 30min; Add fast 6mL tetraethoxy, magnetic stirring 1h; After 5mL tetraethoxy and 2mL octadecyl Trimethoxy silane are evenly mixed, add rapidly above-mentioned solution, magnetic stirring lh, obtains the solid SiO of high dispersing after product is centrifugal
2core@mesopore silicon oxide shell ball;
Product after centrifugal is dispersed in 450mL deionized water, gets the scattered solution of 10mL, then adds 20mL deionized water, then adds the HCl solution of the 0.1M of 0.1g NaCl and 0.8mL; After stirring, under 200 ℃ of hydrothermal conditions, process 14h; The centrifugal rear deionized water wash of product 3 times is calcined 6h after dry and is removed tensio-active agent and make hollow mesopore silicon oxide spheres at 550 ℃.
Referring to Fig. 1 (a) and 1(b), it illustrates respectively the solid SiO that the present embodiment makes
2transmission electron microscope (TEM) photo of core@mesopore silicon oxide shell and hollow mesopore silicon oxide spheres, referring to Fig. 2, it illustrates scanning electronic microscope (SEM) photo of the hollow mesopore silicon oxide spheres that the present embodiment makes, therefrom visible, method of the present invention successfully etching solid SiO wherein
2core, pore volume is large, pore size distribution homogeneous.
Referring to Fig. 3 (a) and 1(b), it illustrates respectively the N of the hollow mesopore silicon oxide spheres that the present embodiment makes
2adsorption/desorption isothermal curve and corresponding graph of pore diameter distribution, show material have high specific surface and and pore volume, large hysteresis loop shows that material has large cavity structure and ink doleiform pore passage structure.
Embodiment 2
First obtain solid SiO according to the synthesis technique of embodiment 1
2core@mesopore silicon oxide shell ball.Centrifugal rear scattered solution, gets 10mL solution, then adds 20mL deionized water, then adds the HCl solution of the 0.12M of 0.07g NaCl and 0.8mL.Subsequent disposal is as embodiment 1.
Embodiment 3
First obtain solid SiO according to the synthesis technique of embodiment 1
2core@mesopore silicon oxide shell ball.Centrifugal rear scattered solution, gets 10mL solution, then adds 20mL deionized water, then adds the HCl solution of the 0.08M of 0.1g NaCl and 0.15mL.Subsequent disposal is as embodiment 1.
Embodiment 4
Prepare solid SiO according to document (Chinese patent, publication number CN102060300B)
2core@mesopore silicon oxide shell ball;
71.4mL dehydrated alcohol, the ammoniacal liquor of 10mL deionized water and 3.14mL mixes, and under 30 ℃ of conditions, stirs 30min; Add fast 6mL tetraethoxy, magnetic stirring 1h; By 5mL1, two (triethoxy the is silica-based) benzene of 4-and 2mL hexadecyl trimethoxy brometo de amonio add rapidly above-mentioned solution after evenly mixing, and magnetic stirring lh obtains the solid SiO of high dispersing after product is centrifugal
2core@mesoporous organosilicon shell ball;
Product after centrifugal is dispersed in 500mL deionized water, gets the scattered solution of 10mL, then adds 20mL deionized water, then adds 0.08g Na
2sO
4h with the 0.1M of 1.2mL
2sO
4solution; After stirring, under 200 ℃ of hydrothermal conditions, process 14h; The centrifugal rear deionized water wash of product 3 times is calcined 6h after dry and is removed tensio-active agent and make hollow mesoporous organosilicon ball at 550 ℃.
Referring to Fig. 4 (a) and 4(b), it illustrates respectively the solid SiO that the present embodiment makes
2transmission electron microscope (TEM) photo of core@mesoporous organosilicon shell and hollow mesoporous organosilicon ball, referring to Fig. 5, it illustrates scanning electronic microscope (SEM) photo of the hollow mesoporous organosilicon ball that the present embodiment makes, therefrom visible, method of the present invention successfully etching solid SiO wherein
2core, pore volume is large, pore size distribution homogeneous.
Referring to Fig. 6, its illustrate hollow mesoporous organosilicon ball that the present embodiment makes element mapping figure (Si, O and C element), therefrom visible, the successful preparation of mesoporous organosilicon shell.
Referring to Fig. 7 (a) and 7(b), it illustrates respectively the N of the hollow mesoporous organosilicon ball that the present embodiment makes
2adsorption/desorption isothermal curve and corresponding graph of pore diameter distribution, show that material has high specific surface area and the aperture structure of homogeneous.
First obtain solid SiO according to the synthesis technique of embodiment 2
2core@mesoporous organosilicon shell ball.Centrifugal rear scattered solution, gets 10mL solution, then adds 20mL deionized water, then adds 0.12g Na
2sO
4h with the 0.1M of 0.6mL
2sO
4solution.Subsequent disposal is as embodiment 4.
Embodiment 6
First obtain solid SiO according to the synthesis technique of embodiment 2
2core@mesoporous organosilicon shell ball.Centrifugal rear scattered solution, gets 10mL solution, then adds 20mL deionized water, then adds 0.08g Na
2sO
4h with the 0.15M of 1.6mL
2sO
4solution.Subsequent disposal is as embodiment 4.
Industrial applicability: preparation is simple for method of the present invention, pollution-free, cost is low, efficiency is high, the not only hollow mesopore silicon oxide spheres of suitable preparation, and can prepare hollow mesoporous organosilicon ball, be a kind of pervasive method.The hollow mesoporous silicon sphere high dispersing that makes, specific surface area is high, pore volume is large, pore size distribution homogeneous, has and application prospect widely in fields such as drug delivery, absorption, separation and catalysis.
Claims (10)
1. a preparation method for hollow mesopore silicon oxide spheres, is characterized in that, comprising:
(1) adopt the synthetic solid silicon oxide ball of sol-gel method as solid core, then silicon source and tensio-active agent are coated on to the surface of described solid silicon oxide ball, centrifugation obtains having the double-deck silicon oxide ball of solid core and mesoporous shell structure;
(2) double-deck gained silicon oxide ball is dispersed in water, adds and contain inorganic salt and sour solution as etching reagent, at 100～250 ℃, hydrothermal treatment consists 5～30 hours is to remove described solid core; And
(3) calcine 4～8 hours to remove tensio-active agent at 500～600 ℃.
2. preparation method according to claim 1, is characterized in that,
The mass ratio of described double-deck silicon oxide ball and described inorganic salt is 1:(5～20), be preferably 1:(7～15);
The mol ratio of described inorganic salt and described acid is 1:(0.6 ~ 6), be preferably 1:(1～4).
3. preparation method according to claim 1 and 2, is characterized in that, step (2) comprising:
Double-deck gained silicon oxide ball is dispersed in water to acquisition dispersion liquid, and the mass ratio of described double-deck silicon oxide ball and water is 1:(70～90);
Adding volume is the water of 0.5～8 times of described dispersion liquid;
Add described inorganic salt or described acid, the concentration of described acid is 0.02～0.2 M; And
Be transferred to reactor hydrothermal treatment consists 5～30 hours at 100～250 ℃.
4. according to the preparation method described in any one in claims 1 to 3, it is characterized in that, described silicon source is methyl silicate, tetraethoxy, positive silicic acid propyl ester and/or butyl silicate.
5. a preparation method for hollow mesoporous organosilicon ball, is characterized in that, comprising:
(1) adopt the synthetic solid silicon oxide ball of sol-gel method as solid core, then organosilicon source and tensio-active agent are coated on to the surface of described solid silicon oxide ball, centrifugation obtains having the double-deck organosilicon ball of solid core and mesoporous shell structure;
(2) double-deck gained organosilicon ball is dispersed in water, adds and contain inorganic salt and sour solution as etching reagent, at 100～250 ℃, hydrothermal treatment consists 5～30 hours is to remove described solid core; And
(3) calcine 4～8 hours to remove tensio-active agent at 500～600 ℃.
6. preparation method according to claim 5, is characterized in that,
The mass ratio of described double-deck organosilicon ball and described inorganic salt is 1:(6～18), be preferably 1:(8～15);
The mol ratio of described inorganic salt and described acid is 1:(2～12), be preferably 1:(2～9).
7. according to the preparation method described in claim 5 or 6, it is characterized in that, step (2) comprising:
Double-deck gained organosilicon ball is dispersed in water to acquisition dispersion liquid, and the mass ratio of described double-deck organosilicon ball and water is 1:(80～100);
Adding volume is the water of 0.5～8 times of described dispersion liquid;
Add described inorganic salt or described acid, the concentration of described acid is 0.02～0.2 M; And
Be transferred to reactor hydrothermal treatment consists 5～30 hours at 100～250 ℃.
8. according to the preparation method described in any one in claim 5 to 7, it is characterized in that, described organosilicon source is two (triethoxyl silane) ethene, Isosorbide-5-Nitrae-bis-(triethoxy is silica-based) benzene and/or two (triethoxyl silane) ethane.
9. according to the preparation method described in any one in claim 1 to 8, it is characterized in that, described inorganic salt are NaCl, Na
2cO
3, Na
2sO
4, NaNO
3, NaHPO
4and Na
3pO
4in at least one.
10. according to the preparation method described in any one in claim 1 to 9, it is characterized in that, described acid is HCl, H
2sO
4, H
3pO
4, H
2cO
3, and HNO
3in at least one.
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| CN106000246A (en) * | 2016-05-18 | 2016-10-12 | 中国科学院上海光学精密机械研究所 | Mesoporous organosilica hollow nanoparticles with asymmetric morphology and synthetic method of mesoporous organosilica hollow nanoparticles |
| CN107019802A (en) * | 2017-03-22 | 2017-08-08 | 南京邮电大学 | A kind of flexible hollow mesoporous organic silicon oxide nanometer capsule material and preparation method |
| CN113745491A (en) * | 2021-08-10 | 2021-12-03 | 扬州大学 | SnO with double-wall hollow sphere structure2@ C material and preparation method thereof |
| CN113745491B (en) * | 2021-08-10 | 2022-11-29 | 扬州大学 | SnO with double-wall hollow ball structure 2 @ C material and preparation method thereof |
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