CN113509962A - Preparation method of hairbrush-shaped nano silicon ball chiral catalyst with inner cavity and holes and product thereof - Google Patents
Preparation method of hairbrush-shaped nano silicon ball chiral catalyst with inner cavity and holes and product thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 239000004793 Polystyrene Substances 0.000 claims description 13
- 229920002223 polystyrene Polymers 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 235000021513 Cinchona Nutrition 0.000 claims description 5
- 241000157855 Cinchona Species 0.000 claims description 5
- 229930013930 alkaloid Natural products 0.000 claims description 5
- 150000003797 alkaloid derivatives Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- MJINPUKGRATQAC-UHFFFAOYSA-N triethoxy(prop-1-enyl)silane Chemical compound CCO[Si](OCC)(OCC)C=CC MJINPUKGRATQAC-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- HVVNJUAVDAZWCB-YFKPBYRVSA-N [(2s)-pyrrolidin-2-yl]methanol Chemical compound OC[C@@H]1CCCN1 HVVNJUAVDAZWCB-YFKPBYRVSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
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- 150000001408 amides Chemical class 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
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- 238000002156 mixing Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
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- 238000000034 method Methods 0.000 abstract description 4
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- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- -1 amide compound Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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Abstract
The invention relates to a preparation method of a hairbrush-shaped nano silicon ball chiral catalyst with a hole in an inner cavity and a product thereof, belonging to the field of functional polymer materials, wherein the hairbrush-shaped nano silicon ball chiral catalyst with a hole in an inner cavity is prepared by a hard template method, a hole template growth method and a suspension polymerization method, the size of the prepared silicon nano microsphere is 220nm, the inner cavity is 70-90nm, the hairbrush size is 18-15nm, and a large number of mesopores with the diameter of 5-50nm exist on the hole wall.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to a preparation method of a hairbrush-shaped nano silicon ball chiral catalyst with a hole in an inner cavity and a product thereof.
Background
Mesoporous hollow microspheres have received increasing attention and research due to their unique characteristics such as small density, large specific surface area, good thermal stability and surface permeability, and large internal space. The silicon mesoporous hollow microsphere is prepared by the synergistic polymerization of flexible carbon chains and rigid tetraethoxysilane to adjust the skeleton of the microsphere, so that the hardness of the microsphere is moderate. In addition, a large number of unpolymerized chain end active sites exist on the inner and outer surfaces of the microsphere, and good environments are provided for targeted slow release of medicines, immobilization of catalysts and the like. The chiral catalyst is attached to the inner surface and the outer surface of the mesoporous sphere to form a hairbrush shape, and can fully contact a catalyzed substrate in a large area, thereby achieving the effects of high efficiency, stability, environmental protection and the like.
In recent years, scholars at home and abroad make a lot of researches on brush-shaped mesoporous hollow microspheres, but the study focuses on adsorption type hollow microspheres, but because the stability is limited, the repeated use times are too few, and the application range of the microspheres is greatly reduced.
Therefore, further research needs to be carried out on the preparation method of the hairbrush-shaped nano silicon sphere chiral catalyst with the inner cavity and the product thereof.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a hairbrush-shaped nano silicon ball chiral catalyst with holes in the inner cavity, and another object of the present invention is to provide a hairbrush-shaped nano silicon ball chiral catalyst with holes in the inner cavity, which is prepared by the above method.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the preparation method of the brush-shaped nano silicon ball chiral catalyst with the inner cavity provided with the holes comprises the following steps:
(1) preparation of core-shell solids: adding polystyrene microspheres into an ethanol/polyvinyl alcohol aqueous solution, stirring to obtain a polystyrene nano microsphere suspension, dripping ammonia water to adjust the pH, adding a pore-foaming agent of cetyl trimethyl ammonium bromide under the protection of argon gas, dripping tetraethoxysilane, stirring uniformly, adding a polyvinyl alcohol aqueous solution, stirring to uniformly mix the solution, performing ultrasonic radiation, heating and stirring, centrifuging, washing, and airing to obtain a white powdery core-shell solid;
(2) preparing hollow porous nano silicon spheres: adding the core-shell solid prepared in the step (1) into deionized water, performing ultrasonic treatment, washing, placing in a muffle furnace, introducing nitrogen, and calcining to obtain hollow porous nano silicon spheres;
(3) preparing hollow porous nano silicon spheres with active double bonds on the surface: adding the hollow porous nano silicon spheres prepared in the step (2) into dehydrated THF (tetrahydrofuran) with argon replaced, dropwise adding propenyl triethoxysilane, and performing ultrasonic mixing to obtain hollow porous nano silicon spheres with activated double bonds on the surfaces;
(4) preparing a hairbrush-shaped nano silicon ball chiral catalyst with a hole in an inner cavity: and (3) dispersing the hollow porous nano silicon spheres with the active double bonds on the surfaces prepared in the step (3) in a mixed solvent of ethanol and water, dropwise adding an initiator potassium persulfate, then adding an ethanol solution of a chiral catalyst with the active double bonds, carrying out polymerization reaction at 60-100 ℃, centrifuging, washing and air drying to obtain the hairbrush-shaped porous nano silicon sphere chiral catalyst with the inner cavity.
Preferably, the mass-volume ratio of the ethyl orthosilicate, the polystyrene microspheres, the hexadecyl trimethyl ammonium bromide, the propenyl triethoxysilane, the potassium persulfate and the chiral catalyst with the activated double bonds is 100:55:12:36.4:4:3, and the mass-volume ratio of the mg: mg: mg: mg: mL.
Preferably, the mass-to-volume ratio of the polystyrene microspheres, the ethanol/polyvinyl alcohol aqueous solution and the polyvinyl alcohol aqueous solution in the step (1) is 10:1:3, mg: ml: ml; the pH is 10-12.
Preferably, the ethanol/polyvinyl alcohol aqueous solution is a mixed solution formed by ethanol and polyvinyl alcohol aqueous solution in a volume ratio of 1: 5; the mass fraction of the polyvinyl alcohol aqueous solution is 0.8%.
Preferably, the volume ratio of ethanol to water in the mixed solvent of ethanol and water in the step (4) is 10: 1; the chiral catalyst with the active double bond is one or more of cinchona alkaloid, amide or prolinol; the molar volume ratio of the chiral catalyst with the active double bonds to the ethanol is 3:100, and the mol: L.
2. The hairbrush-shaped nano silicon ball chiral catalyst with the inner cavity provided with the holes is prepared by the preparation method.
Preferably, the hairbrush-shaped nano silicon ball chiral catalyst with the inner cavity provided with the holes has the diameter size of 180-220nm, and the diameter of the inner hollow part is 70-90 nm; the size of the brush in the catalyst is 18-15 nm; the pore diameter of the pores in the catalyst is 5-50 nm.
The invention has the beneficial effects that: the invention discloses a preparation method of a hairbrush-shaped nano silicon ball chiral catalyst with a hole in an inner cavity, which is simple, and the prepared hairbrush-shaped nano silicon ball with a hole in an inner cavity has great effects on improving the specific surface area, exposing a catalytic site and improving the catalytic efficiency. The shape and the particle size of the hairbrush-shaped nano silicon ball chiral catalyst with the inner cavity and the holes are observed by a scanning and transmission electron microscope, and the aperture of the hairbrush-shaped nano silicon ball chiral catalyst with the inner cavity and the holes is measured by a nitrogen adsorption specific surface analyzer, so that a better verification result is obtained, wherein the diameter of the hairbrush-shaped nano silicon ball chiral catalyst with the inner cavity and the holes is 180-220nm, the diameter of the inner cavity is 70-90nm, the length of the hairbrush is 18-15nm, and the aperture of the holes is 5-50 nm.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a flow chart for the hydrolysis of ethyl orthosilicate in example 1;
FIG. 2 is a diagram showing the distribution of mesopores before and after removing cetyltrimethylammonium bromide from the brush-shaped nano-silica spheres with pores having inner cavities according to example 1, (a) before removing cetyltrimethylammonium bromide; (b) to remove cetyl trimethylammonium bromide.
FIG. 3 is a flow chart of the preparation of mesoporous hollow silica spheres with activated double bonds on the surface in example 1;
FIG. 4 is a chemical formula diagram of chiral catalysts with activated double bonds in examples, wherein (a), (b), (c) are chiral catalysts with activated double bonds in example 1, example 4 and example 5, respectively;
FIG. 5 is a structural diagram of a hairbrush-shaped nano silicon ball chiral catalyst with a hole in the inner cavity in example 1;
FIG. 6 is SEM image (a) and TEM image (b) of the hairbrush-shaped nano silicon sphere chiral catalyst with the inner cavity provided with the holes in the example 1;
FIG. 7 is an SEM of a hairbrush-shaped nanosilicon sphere chiral catalyst with holes in the inner cavity in the examples, wherein (a), (b), and (c) are the hairbrush-shaped nanosilicon sphere chiral catalysts with holes in the inner cavity in examples 1, 2, and 3, respectively;
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
The preparation of the hairbrush-shaped nano silicon sphere chiral catalyst with the inner cavity provided with the holes comprises the following steps:
(1) preparation of core-shell solids: adding 100mg of polystyrene microspheres into 10mL of 0.8% polyvinyl alcohol aqueous solution with the volume ratio of 1:5, stirring to obtain polystyrene nanoparticle suspension, adding ammonia water dropwise to adjust the pH to 11, adding 12mg of pore-forming agent hexadecyl trimethyl ammonium bromide under the protection of argon, adding 55mg of ethyl orthosilicate dropwise to hydrolyze the polystyrene nanoparticle suspension (wherein the flow chart of the hydrolysis of the ethyl orthosilicate is shown in figure 1), uniformly stirring, adding 30mL of 0.8% polyvinyl alcohol aqueous solution with the mass fraction, stirring at 800rpm for 4h to uniformly mix the solution, carrying out ultrasonic radiation for 5min, stirring at 60 ℃ for 24h, centrifuging at 12000rpm for 10min, washing with 5mL of deionized water for 3 times and 5mL of anhydrous ethanol for 2 times in sequence, and airing to obtain white powdery core-shell solid, wherein the core-shell solid takes the polystyrene microspheres as an inner core and silicon dioxide with active ethoxy functional groups as an outer shell (the mesoporous distribution chart is shown in figure 2) (ii) a
(2) Preparing hollow porous nano silicon spheres: adding the core-shell solid prepared in the step (1) into 20mL of deionized water, performing ultrasonic treatment for 5min, sequentially washing with 5mL of deionized water for 2 times and 5mL of ethanol for 2 times, placing the core-shell solid in a muffle furnace at 500 ℃ and introducing nitrogen to calcine for 4h, and removing the polystyrene microspheres and hexadecyl trimethyl ammonium bromide to obtain hollow porous nano silicon spheres (the mesoporous distribution diagram is shown as b in figure 2, and the diameter of the mesopores is 5-50 nm);
(3) preparing hollow porous nano silicon spheres with active double bonds on the surface: adding the hollow porous nano silicon spheres prepared in the step (2) into 50mL of dehydrated THF (tetrahydrofuran) with replaced argon, dropwise adding 36.4mg of propenyl triethoxysilane, and carrying out ultrasonic treatment for 30min to uniformly mix the spheres so as to obtain mesoporous hollow silicon spheres with active double bonds on the surfaces (the preparation flow chart is shown in figure 3);
(4) preparing a hairbrush-shaped nano silicon ball chiral catalyst with a hole in an inner cavity: dispersing the mesoporous hollow silicon spheres with the active double bonds on the surfaces prepared in the step (3) into a mixed solvent of ethanol and water with the volume ratio of 10:1, dropwise adding 4mg of initiator potassium persulfate, then adding 3mL of ethanol solution of cinchona alkaloid (the chemical structural formula of which is shown as a in the figure 4) with the concentration of 0.03mol/L, carrying out polymerization reaction at 90 ℃ for 24 hours, centrifuging, washing and air-drying to obtain the hairbrush-shaped chiral catalyst of the nano silicon spheres with the inner cavities and the holes (the structural diagram of which is shown in the figure 5).
In FIG. 6, a is an SEM picture of the hairbrush-shaped nano silicon sphere chiral catalyst with the hole in the inner cavity in example 1, and b in FIG. 6 is a TEM picture of the hairbrush-shaped nano silicon sphere chiral catalyst with the hole in the inner cavity in example 1. As shown in fig. 6(a), the hairbrush-shaped chiral catalyst with nano silicon spheres having holes in the inner cavities is spherical, and the surface of the silicon spheres is provided with hairbrushes; as shown in FIG. 6(b), the chiral catalyst of the hairbrush-shaped nano-silica sphere with a hole in the inner cavity has a diameter of 180-220nm, the inner hollow diameter of 70-90nm, and the length of the hairbrush is 18-15 nm.
Example 2
The preparation method is the same as that of the example 1 except that the pH value of the nano silicon sphere chiral catalyst with the hairbrush-shaped inner cavity and the hole is obtained by replacing the pH value of 11 with the pH value of 10 in the step (1) of the example 1 and replacing the polymerization reaction at 90 ℃ in the step (4) of the example 1 with the polymerization reaction at 60 ℃.
Example 3
The pH 11 in the step (1) of example 1 was changed to pH 12, the polymerization reaction at 90 ℃ in the step (4) of example 1 was changed to the polymerization reaction at 100 ℃, and the remaining preparation method was the same as that of example 1, thereby obtaining a hairbrush-like nano silica sphere chiral catalyst having a pore therein.
In FIG. 7, a, b and c are SEM images of hairbrush-shaped nano silicon sphere chiral catalysts with holes in inner cavities prepared in example 1, example 2 and example 3 respectively. As can be seen from FIG. 7, the chiral catalyst of the hairbrush-shaped nano silicon ball with the inner cavity and the hole can be prepared by polymerization reaction at 60-100 ℃ and the chiral catalyst has the diameter of 180-220nm, the inner hollow diameter of 70-90nm and the length of 18-15 nm.
Example 4
The cinchona alkaloid in the step (4) of the example 1 is replaced by an amide compound (the chemical structural formula is shown as b in a figure 4), and the other preparation methods are the same as the example 1, so that the hairbrush-shaped nano silicon sphere chiral catalyst with the inner cavity and the holes can be obtained.
Example 5
The cinchona alkaloid in the step (4) of the example 1 is replaced by prolinol (the chemical structural formula of which is shown as c in a figure 4), and the other preparation methods are the same as the example 1, so that the hairbrush-shaped nano silicon sphere chiral catalyst with the inner cavity provided with the holes can be obtained.
The hairbrush-shaped nano silicon ball chiral catalysts with holes and inner cavities prepared in the embodiments 2-5 have the performance of the hairbrush-shaped nano silicon ball chiral catalysts with holes and inner cavities prepared in the embodiment 1 through detection, the diameter size is 180-220nm, the diameter of the inner hollow part is 70-90nm, the length of the hairbrush is 18-15nm, and the aperture of the holes is 5-50 nm.
In conclusion, the invention discloses a preparation method of the hairbrush-shaped nano silicon ball chiral catalyst with the holes in the inner cavity, the preparation method is simple, and the prepared hairbrush-shaped nano silicon ball with the holes in the inner cavity has great effects on improving the specific surface area, exposing the catalytic sites and improving the catalytic efficiency. The shape and the particle size of the silicon spheres are observed by a scanning and transmission electron microscope, the aperture of the silicon spheres is measured by a nitrogen adsorption specific surface instrument, and a better verification result is obtained, wherein the diameter size of the brush-shaped nano silicon sphere chiral catalyst with the inner cavity provided with holes is 180-220nm, the diameter of the inner hollow part is 70-90nm, the length of the brush is 18-15nm, and the aperture of the holes is 5-50 nm.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (7)
1. The preparation method of the brush-shaped nano silicon ball chiral catalyst with the inner cavity provided with the holes is characterized by comprising the following steps of:
(1) preparation of core-shell solids: adding polystyrene microspheres into an ethanol/polyvinyl alcohol aqueous solution, stirring to obtain a polystyrene nano microsphere suspension, dripping ammonia water to adjust the pH, adding a pore-foaming agent of cetyl trimethyl ammonium bromide under the protection of argon gas, dripping tetraethoxysilane, stirring uniformly, adding a polyvinyl alcohol aqueous solution, stirring to uniformly mix the solution, performing ultrasonic radiation, heating and stirring, centrifuging, washing, and airing to obtain a white powdery core-shell solid;
(2) preparing hollow porous nano silicon spheres: adding the core-shell solid prepared in the step (1) into deionized water, performing ultrasonic treatment, washing, placing in a muffle furnace, introducing nitrogen, and calcining to obtain hollow porous nano silicon spheres;
(3) preparing hollow porous nano silicon spheres with active double bonds on the surface: adding the hollow porous nano silicon spheres prepared in the step (2) into anhydrous tetrahydrofuran which replaces argon, dropwise adding propenyl triethoxysilane, and performing ultrasonic mixing to obtain hollow porous nano silicon spheres with activated double bonds on the surfaces;
(4) preparing a hairbrush-shaped nano silicon ball chiral catalyst with a hole in an inner cavity: and (3) dispersing the hollow porous nano silicon spheres with the active double bonds on the surfaces prepared in the step (3) in a mixed solvent of ethanol and water, dropwise adding an initiator potassium persulfate, then adding an ethanol solution of a chiral catalyst with the active double bonds, carrying out polymerization reaction at 60-100 ℃, centrifuging, washing and air drying to obtain the hairbrush-shaped porous nano silicon sphere chiral catalyst with the inner cavity.
2. The preparation method of the hairbrush-shaped nano silicon ball chiral catalyst with the inner cavity provided with the holes as claimed in claim 1, wherein the mass-to-volume ratio of the tetraethoxysilane, the polystyrene microsphere, the hexadecyl trimethyl ammonium bromide, the propenyl triethoxysilane, the potassium persulfate and the chiral catalyst with the activated double bond is 100:55:12:36.4:4:3, mg: mg: mg: mg: mL respectively.
3. The preparation method of the brush-shaped nano silicon ball chiral catalyst with the inner cavity provided with the holes as claimed in claim 1, wherein the mass-to-volume ratio of the polystyrene microspheres, the ethanol/polyvinyl alcohol aqueous solution and the polyvinyl alcohol aqueous solution in the step (1) is 10:1:3, mg: ml: ml; the pH is 10-12.
4. The preparation method of the brush-shaped nano silicon ball chiral catalyst with the inner cavity provided with the holes as claimed in claim 3, is characterized in that: the ethanol/polyvinyl alcohol aqueous solution is a mixed solution formed by ethanol and polyvinyl alcohol aqueous solution in a volume ratio of 1: 5;
the mass fraction of the polyvinyl alcohol aqueous solution is 0.8%.
5. The preparation method of the brush-shaped nano silicon sphere chiral catalyst with the hole in the inner cavity as claimed in claim 1, wherein the volume ratio of ethanol to water in the mixed solvent of ethanol and water in the step (4) is 10: 1;
the chiral catalyst with the active double bond is one or more of cinchona alkaloid, amide or prolinol;
the molar volume ratio of the chiral catalyst with the active double bonds to the ethanol is 3:100, and the mol: L.
6. The hairbrush-shaped nano silicon sphere chiral catalyst with a hole in the inner cavity, prepared by the preparation method of any one of claims 1 to 5.
7. The brush-shaped chiral catalyst with nano-silica spheres having pores in the inner cavity as claimed in claim 6, wherein the diameter of the brush-shaped chiral catalyst with nano-silica spheres having pores in the inner cavity is 180-220nm, and the diameter of the inner hollow part is 70-90 nm; the length of a hairbrush in the catalyst is 18-15 nm; the pore diameter of the pores in the catalyst is 5-50 nm.
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| CN202110886107.0A CN113509962A (en) | 2021-08-03 | 2021-08-03 | Preparation method of hairbrush-shaped nano silicon ball chiral catalyst with inner cavity and holes and product thereof |
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| CN202110886107.0A CN113509962A (en) | 2021-08-03 | 2021-08-03 | Preparation method of hairbrush-shaped nano silicon ball chiral catalyst with inner cavity and holes and product thereof |
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| CN114380338A (en) * | 2022-01-25 | 2022-04-22 | 重庆邮电大学 | Preparation method of magnetic cobalt oxide mesoporous nanospheres, products and applications thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114380338A (en) * | 2022-01-25 | 2022-04-22 | 重庆邮电大学 | Preparation method of magnetic cobalt oxide mesoporous nanospheres, products and applications thereof |
| CN114380338B (en) * | 2022-01-25 | 2023-11-03 | 重庆邮电大学 | Preparation method of magnetic cobalt oxide mesoporous nanospheres, product and application thereof |
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Application publication date: 20211019 |