CN117361546A - Core-shell ratio adjustable preparation method of radial porous silica microspheres - Google Patents
Core-shell ratio adjustable preparation method of radial porous silica microspheres Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 239000012792 core layer Substances 0.000 claims description 4
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a preparation method of a radial porous silicon dioxide microsphere with adjustable core-shell ratio, which comprises the steps of adding a mixture of ethanol, water, a surfactant and a catalyst into a reaction container, adding a silicon source into the mixture under high-speed stirring, adding an organic solvent into the mixture at different intervals, reacting for several hours, cleaning and drying the obtained microsphere, calcining, and removing a template to obtain the radial porous silicon dioxide microsphere with good monodispersity, wherein the core-shell ratio of the porous silicon dioxide microsphere can be adjusted. The method can be used for preparing the silicon dioxide porous microsphere which has a core-shell structure and adjustable core-shell ratio, and the obtained porous silicon dioxide microsphere has extremely important application value in the aspects of biological medicine carrying, adsorption separation and energy catalysis.
Description
Technical Field
The invention relates to the field of preparation of silica microspheres, in particular to a preparation method with adjustable core-shell ratio of radial porous silica microspheres.
Background
The mesoporous silica microsphere has the attractive characteristics of multiple good performances, high specific surface area, large aperture, stable physical and chemical properties, easy surface functionalization and the like, and is widely applied to the aspects of biological medicine carrying, adsorption separation and energy catalysis.
In recent years, many researchers have begun to study silica microspheres having a core-shell structure. The three-dimensional dendritic silica microspheres having a core-shell structure were synthesized by an oil-water biphasic layering method using a method such as Shen Dengke (Nano Letters, biphase Stratification Approach to Three-Dimensional Dendritic Biodegradable Mesoporous Silica Nanospheres [ J ],2014,14 (2): 923-32.), and the pore size was adjusted by changing different hydrophobic solvents. Chinese patent application No. 202211703874.4 discloses a method for preparing monodisperse silica core-shell microspheres by a dual-template method, which comprises preparing solid silica microspheres by a template, and generating a shell layer on the surface of the solid silica microspheres by using a pore template. However, the prior synthesis of the silicon dioxide microsphere with the core-shell structure has the defects of complex pore size regulation and control steps, large or non-adjustable amount of the used organic solvent, and limitation of specific application of the silicon dioxide microsphere.
Disclosure of Invention
The invention provides a preparation method of a core-shell ratio of a radial porous silicon dioxide microsphere, which can control the core-shell ratio, the pore diameter and the specific surface area of the prepared silicon dioxide microsphere by changing the time interval of adding a silicon source and an organic solvent, wherein the specific surface area of the prepared silicon dioxide microsphere gradually increases along with the increase of time T1, and the pore diameter gradually decreases along with the increase of time T1.
The invention provides a preparation method with adjustable core-shell ratio of radial porous silica microspheres, which comprises the following specific steps:
the first step: adding a surfactant into a mixed solution of water, alcohol and a catalyst, stirring at a high speed to dissolve the surfactant completely, and adding a silicon source into the solution to obtain a mixed solution A;
and a second step of: after a certain time T1 after adding a silicon source, adding an organic solvent into the obtained mixed solution A, stirring at a high speed for a period of time T2, centrifuging, washing, freeze-drying and calcining the product to obtain the radial porous silicon dioxide microspheres with a core-shell structure, wherein the core-shell ratio of the silicon dioxide microspheres is regulated and controlled by changing the time T1, and the core-shell ratio is increased along with the increase of the time T1.
As a preferred scheme of the invention, in the step 1, the added surfactant is one of Cetyl Trimethyl Ammonium Bromide (CTAB), dodecyl Trimethyl Ammonium Bromide (DTAB), cetyl Trimethyl Ammonium Chloride (CTAC) and other quaternary ammonium salts, the mass percentage of the surfactant in the mixed solution A is 0.1-0.9%, the alcohol is one of methanol, ethanol, glycol and isopropanol, and the volume percentage of the alcohol in the mixed solution A is 30-40%.
As a preferable scheme of the invention, the catalyst in the step 1 is one or more of ammonia water, triethanolamine, triethylamine and diethylamine, and the volume percentage of the catalyst in the mixed solution A is 0.1-0.9%; the added silicon source is one of tetraethyl silicate, tetrapropyl silicate, silicon tetrachloride, silicon tetrafluoride, methyl silicon trichloride and sodium silicate, and the silicon source accounts for 1-9% of the volume of the mixed solution A.
As a preferable scheme of the invention, in the first step and the second step, the rotating speed of high-speed stirring is between 200 and 1000 r/min.
As a preferable scheme of the invention, in the second step, the organic solvent is one of toluene, xylene, trimethylbenzene, cyclohexane, normal hexane, cyclopentane, petroleum ether and heptane, and the addition volume of the organic solvent is 1-9% of the volume of the mixed solution A.
As a preferable scheme of the invention, in the second step, the time T1 is 0-360min.
As a preferable scheme of the invention, the time T2 is 60-480min.
As a preferable scheme of the invention, the calcination in the second step is to raise the temperature to 500-800 ℃ at a heating rate of 4+/-3 ℃/min, and keep the temperature for 120-480min, so as to remove the surfactant.
As a preferred scheme of the invention, the porous silica microspheres are radial porous microspheres, the size of the radial inner cores can be adjusted by adding the time interval between a silicon source and an organic solvent, and the inner cores of the radial porous silica microspheres account for 0-100% of the total and are continuously adjustable; the inner core of the radial porous silica microsphere is of a small mesoporous structure, and the outer shell is of a hierarchical mesoporous and macroporous structure; the particle size of the radial porous silica microspheres is between 100nm and 1000 nm.
According to the invention, by adjusting the time interval between the addition of the silicon source and the organic solvent, the radial porous silicon dioxide microspheres with different core-shell ratios can be obtained, and the prepared silicon dioxide microspheres have small mesoporous structures as the inner cores and hierarchical mesoporous and macroporous structures as the outer shells. The prepared silicon dioxide microsphere has unique advantages in the aspects of drug loading and release due to the different pore diameters.
Drawings
FIG. 1 is a TEM image of the sample obtained in example 1;
FIG. 2 is a TEM image of the sample obtained in example 2;
FIG. 3 is a TEM image of the sample obtained in example 3;
FIG. 4 is a TEM image of the sample obtained in example 4;
FIG. 5 is a TEM image of the sample obtained in example 5;
FIG. 6 is a TEM image of the sample obtained in example 6.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1
To a mixed solution of 39.56g of ethanol and 80g of water, 0.8g of CTAB and 0.6mL of ammonia water were added, and after mechanical stirring at 700r/min for 30min at normal temperature, 3.0mL of a mixed solution of TEOS and p-xylene was added thereto, i.e., the p-xylene addition time was 0min. Mechanical stirring was then continued for 2h at room temperature. And centrifuging, washing and freeze-drying the reacted solution, calcining the dried sample in a muffle furnace under the air atmosphere, heating to 600 ℃ at 1.5 ℃/min, preserving heat for 4 hours, and cooling to room temperature.
The radial porous silica microsphere with adjustable core-shell ratio can be obtained by the steps, the morphology of the radial porous silica microsphere is shown in the following figure 1, and the BET specific surface area is 543.18m 2 g -1 The average pore diameter was 5.66nm and the volume occupied by micropores was 21.54%.
Example 2
To a mixed solution of 39.56g of ethanol and 80g of water, 0.8g of CTAB and 0.6mL of ammonia water were added, and after mechanical stirring at 700r/min for 30min at normal temperature, 3.0mL of TEOS solution was added thereto, after 4min, 4.0mL of p-xylene solution was added thereto, and then mechanical stirring was continued at room temperature for 2h. And centrifuging, washing and freeze-drying the reacted solution, calcining the dried sample in a muffle furnace under the air atmosphere, heating to 600 ℃ at 1.5 ℃/min, preserving heat for 4 hours, and cooling to room temperature.
The radial porous silica microsphere with adjustable core-shell ratio can be obtained by the steps, the morphology is shown in the following figure 2, and the BET specific surface area is 749.10m 2 g -1 The average pore diameter was 4.84nm and the volume of micropores was 23.40%. The core and shell of the porous silica microsphere shown in fig. 2 are continuously and non-demarcating, and each large mesoporous in the shell layer is communicated with a small mesoporous in the core layer, and the pore wall of the large mesoporous is continuously and non-demarcating with the pore wall of the small mesoporous.
Example 3
To a mixed solution of 39.56g of ethanol and 80g of water, 0.8g of CTAB and 0.6mL of ammonia water were added, and after mechanical stirring at 700r/min for 30min at normal temperature, 3.0mL of TEOS solution was added thereto, after 16min, 4.0mL of p-xylene solution was added to the solution, and then mechanical stirring was continued at room temperature for 2h. And centrifuging, washing and freeze-drying the reacted solution, calcining the dried sample in a muffle furnace under the air atmosphere, heating to 600 ℃ at 1.5 ℃/min, preserving heat for 4 hours, and cooling to room temperature.
The radial porous silica microsphere with adjustable core-shell ratio can be obtained by the steps, the morphology is shown in the following figure 3, and the BET specific surface area is 800.34m 2 g -1 The average pore diameter was 3.48nm and the volume occupied by micropores was 46.50%. The core and shell of the porous silica microsphere shown in fig. 3 are continuously and non-demarcating, and each large mesoporous in the shell layer is communicated with a small mesoporous in the core layer, and the pore wall of the large mesoporous is continuously and non-demarcating with the pore wall of the small mesoporous.
Example 4
To a mixed solution of 39.56g of ethanol and 80g of water, 0.8g of CTAB and 0.6mL of ammonia water were added, and after mechanical stirring at 700r/min for 30min at normal temperature, 3.0mL of TEOS solution was added thereto, after 32min, 4.0mL of p-xylene solution was added to the solution, and then mechanical stirring was continued at room temperature for 2h. And centrifuging, washing and freeze-drying the reacted solution, calcining the dried sample in a muffle furnace under the air atmosphere, heating to 600 ℃ at 1.5 ℃/min, preserving heat for 4 hours, and cooling to room temperature.
The radial porous silica microsphere with adjustable core-shell ratio can be obtained by the steps, the morphology is shown in the following figure 4, and the BET specific surface area is 789.51m 2 g -1 The average pore diameter was 3.19nm and the volume of micropores was 51.02%. The core and shell of the porous silica microsphere shown in fig. 4 are continuously and non-demarcating, and each large mesoporous in the shell layer is communicated with a small mesoporous in the core layer, and the pore wall of the large mesoporous is continuously and non-demarcating with the pore wall of the small mesoporous.
Example 5
To a mixed solution of 39.56g of ethanol and 80g of water, 0.8g of CTAB and 0.6mL of ammonia water were added, and after mechanical stirring at 700r/min for 30min at normal temperature, 3.0mL of TEOS solution was added thereto, after 60min, 4.0mL of p-xylene solution was added thereto, and then mechanical stirring was continued at room temperature for 2h. And centrifuging, washing and freeze-drying the reacted solution, calcining the dried sample in a muffle furnace under the air atmosphere, heating to 600 ℃ at 1.5 ℃/min, preserving heat for 4 hours, and cooling to room temperature.
The radial porous silica microsphere with adjustable core-shell ratio can be obtained through the steps, the morphology is shown in the following figure 5, and the BET specific surface area is 790.57m 2 g -1 The average pore diameter was 2.63nm and the volume of micropores was 60.47%.
Example 6
To a mixed solution of 39.56g of ethanol and 80g of water, 0.8g of CTAB and 0.6mL of ammonia water were added, and after mechanical stirring at 700r/min for 30min at room temperature, 3.0mL of TEOS solution was added thereto, and then mechanical stirring was continued at room temperature for 2 hours. And centrifuging, washing and freeze-drying the reacted solution, calcining the dried sample in a muffle furnace under the air atmosphere, heating to 600 ℃ at 1.5 ℃/min, preserving heat for 4 hours, and cooling to room temperature.
The silica microsphere with the core-shell structure is not obtained through the steps, the morphology of the silica microsphere is shown in the following figure 6, and the BET specific surface area is 912.09m 2 g -1 The average pore diameter was 2.28nm and the volume occupied by micropores was 71.37%.
In summary, the porous silica microspheres obtained by the method are radial porous microspheres, the size of the radial inner cores can be adjusted by adding the time interval between the silicon source and the organic solvent, and the inner cores of the radial porous silica microspheres account for 0-100% of the total and are continuously adjustable; the inner core of the radial porous silica microsphere is of a small mesoporous structure, and the outer shell is of a hierarchical mesoporous and macroporous structure; the particle size of the radial porous silica microspheres is between 100nm and 1000 nm.
The foregoing examples are provided to illustrate the present invention and are described in more detail, but are not to be construed as limiting the scope of the invention. It should be noted that several variations and modifications can be made without departing from the inventive concept, which fall within the scope of the present invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
Claims (10)
1. The preparation method of the radial porous silica microsphere with adjustable core-shell ratio is characterized by comprising the following steps of:
the first step: adding a surfactant into a mixed solution of water, alcohol and a catalyst, stirring at a high speed to dissolve the surfactant completely, and adding a silicon source into the solution to obtain a mixed solution A;
and a second step of: after a certain time T1 after adding a silicon source, adding an organic solvent into the obtained mixed solution A, stirring at a high speed for a period of time T2, centrifuging, washing, freeze-drying and calcining the product to obtain the radial porous silicon dioxide microspheres with a core-shell structure, wherein the core-shell ratio of the silicon dioxide microspheres is regulated and controlled by changing the time T1, and the core-shell ratio is increased along with the increase of the time T1.
2. The method according to claim 1, wherein in the first step, the surfactant is one of cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB) and cetyltrimethylammonium chloride (CTAC), and the surfactant accounts for 0.1-0.9% by mass of the mixed solution a; the alcohol is one of methanol, ethanol, glycol and isopropanol, and the volume percentage of the alcohol in the mixed solution A is 30-40%.
3. The method according to claim 1, wherein in the first step, the catalyst is one or more of ammonia water, triethanolamine, triethylamine and diethylamine, and the volume percentage of the catalyst in the mixed solution A is 0.1-0.9%; the silicon source is one of tetraethyl silicate, tetrapropyl silicate, silicon tetrachloride, silicon tetrafluoride, methyl silicon trichloride and sodium silicate, and the silicon source accounts for 1-9% of the volume of the mixed solution A.
4. The method according to claim 1, wherein the high speed stirring speed in the first and second steps is between 200-1000 r/min.
5. The method according to claim 1, wherein in the second step, the organic solvent is one of toluene, xylene, trimethylbenzene, cyclohexane, n-hexane, cyclopentane, petroleum ether and heptane, and the addition volume of the organic solvent is 1% -9% of the volume of the mixed solution A.
6. The method according to claim 1, wherein in the second step, the time T1 is 0-360min and the time T2 is 60-480min.
7. The method according to claim 1, wherein in the second step, the calcination is performed by raising the temperature to 500-800 ℃ at a temperature raising rate of 4+ -3 ℃/min, and maintaining the temperature for 120-480min, thereby removing the surfactant.
8. The method according to claims 1-8, characterized in that: the porous silica microspheres are radial porous microspheres, the size of the radial inner cores can be adjusted by adding the time interval between a silicon source and an organic solvent, and the inner cores of the radial porous silica microspheres account for 0-100% of the total and are continuously adjustable; the inner core of the radial porous silica microsphere is of a small mesoporous structure, and the outer shell is of a hierarchical mesoporous and macroporous structure; the particle size of the radial porous silica microspheres is between 100nm and 1000 nm.
9. The method of claim 1, wherein the core and shell of the porous silica microsphere are continuously non-demarcating, and each of the large mesopores in the shell layer is in communication with the small mesopores in the core layer, and the walls of the large mesopores are continuously non-demarcating with the walls of the small mesopores.
10. The method according to claim 1, wherein in the second step, as the time T1 increases, the core fraction of the prepared silica microspheres gradually increases, and the average pore size of the porous silica microspheres gradually decreases as the time T1 increases.
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