CN114804120B - Silicon dioxide micro-nanospheres, preparation method and application thereof - Google Patents
Silicon dioxide micro-nanospheres, preparation method and application thereof 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 295
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 132
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002077 nanosphere Substances 0.000 title claims description 29
- 239000002245 particle Substances 0.000 claims abstract description 96
- 239000010419 fine particle Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000012010 growth Effects 0.000 claims abstract description 27
- 239000012798 spherical particle Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 239000004005 microsphere Substances 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 46
- 239000002105 nanoparticle Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 11
- 230000001276 controlling effect Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ODKSFYDXXFIFQN-UHFFFAOYSA-N Arginine Chemical compound OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 244000282866 Euchlaena mexicana Species 0.000 claims description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 229940110377 dl- arginine Drugs 0.000 claims description 3
- 238000012377 drug delivery Methods 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- ODKSFYDXXFIFQN-SCSAIBSYSA-N D-arginine Chemical compound OC(=O)[C@H](N)CCCNC(N)=N ODKSFYDXXFIFQN-SCSAIBSYSA-N 0.000 claims description 2
- 229930028154 D-arginine Natural products 0.000 claims description 2
- 229930064664 L-arginine Natural products 0.000 claims description 2
- 235000014852 L-arginine Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- HXCHRJMJMALFHP-UHFFFAOYSA-N azanium;ethanol;hydroxide Chemical compound N.O.CCO HXCHRJMJMALFHP-UHFFFAOYSA-N 0.000 claims 4
- 230000004931 aggregating effect Effects 0.000 claims 1
- 210000003371 toe Anatomy 0.000 claims 1
- 230000006911 nucleation Effects 0.000 abstract description 9
- 238000010899 nucleation Methods 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 27
- 239000004038 photonic crystal Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010437 gem Substances 0.000 description 2
- 229910001751 gemstone Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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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
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- 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
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- C01P2004/51—Particles with a specific particle size distribution
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- 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
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- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Biotechnology (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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- Silicon Compounds (AREA)
Abstract
The invention discloses a silicon dioxide microsphere and a preparation method and application thereof, comprising two-phase synthesis of nanometer fine particles and controlled growth of the fine particles. The monodisperse silicon dioxide micro-nano spherical particles prepared by the method have the advantages of narrow particle size distribution, high uniformity, expected size and the like. The invention adopts a two-phase reaction system to regulate and control the nucleation reaction rate of the nanometer fine particles, thereby ensuring that the nucleation is uniform and controllable and synthesizing the uniform silicon dioxide fine particles in batches and repeatedly. The invention also utilizes the zero-order, one-time and more control growth method of the fine particles to separate the nucleation and growth of the fine particles, thereby constructing the method for customizing and synthesizing the particle size of the spherical silica particles step by step. The method can be used for conveniently synthesizing the monodisperse silicon dioxide spherical particles with the preset particle size of 10-1000 nm, and the deviation of the particle size is less than 2%. The method of the invention is convenient for enlarging the synthesis scale and has huge commercial development value.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, relates to a silicon dioxide microsphere and a preparation method and application thereof, and in particular relates to a silicon dioxide microsphere and a silicon dioxide nanosphere with customized particle size and a stepwise synthesis method and application thereof.
Background
The silica particles with regular morphology and uniform particle size are widely applied to the fields of catalysis, chromatography, drug delivery, sensor development and the like due to the advantages of good stability, low biotoxicity, relatively simple preparation method, easy surface modification and the like. Silica particles can also be used as colloidal templates to build core-shell, hollow or 3D ordered pore structure materials. The monodisperse submicron silicon dioxide microsphere is a common base material for assembling the photonic crystal, and provides an effective way for artificial preparation, scientific research and commercial development of the photonic crystal.
Photonic Crystals (PCs) were originally an expensive natural precious stone, but human beings scientifically recognized photonic crystals began in 1987, and John and Yablonovith respectively proposed the concept of photonic crystals. PCs are rapidly becoming the leading edge of the field of materials research due to their photonic band gap characteristics (similar to semiconductor electronic energy bands). Journal of science in the united states of america in 1999 listed it as one of ten scientific advances in the current year. The natural photonic crystal has low purity in the vast majority, so that the application development of the natural photonic crystal in the field of separation analysis is limited. Therefore, there is a need to develop new methods for artificially manufacturing PCs to meet the application development requirements. The artificial photon crystal has commercial value similar to natural precious stone, can be used for manufacturing novel lasers, lossless optical fibers, structural color pigments and the like, and can effectively regulate photon propagation, so that the artificial photon crystal has important scientific research value. In addition, in the analytical chemistry field, photonic crystals can be used for sensing, optical enhancement, ultra-high performance separations, and the like. The application requirements promote the rapid development of the technology for manually preparing the photonic crystal, in particular to the particle assembly preparation. However, how to prepare monodisperse and controllable-size silica microspheres and nanospheres is still a very challenging task for the artificial preparation of photonic crystals at present.
Indeed, a large number of methods are available for preparing micro-nano silica spheres, but the monodispersity and the size controllability of the silica micro-nano spheres prepared by the prior methods are not ideal. Therefore, it is difficult to customize monodisperse silica micro-and nano-particles of a specific size. Currently, the main synthesis method of silica particles is 1968The hydrolysis condensation method proposed by et al is abbreviated as->Method (J.colloid Interface Sci.1968,26, 62-69). In alcohol medium, basic ammonia is used to catalyze hydrolysis and condensation of Tetraethoxysilane (TEOS) to prepare silicon dioxide micro-nano particles with the particle size of 0.05-2 mu m. The method is mainly realized by adjusting the use of ammonia and TEOSThe amount to achieve regulation of particle size, but the size control is not accurate and the monodispersity of the resulting particles is also poor, because: in the process of preparing the silicon dioxide micro-nano particles by the method, nucleation and growth processes are staggered, and the nucleation process is extremely sensitive to reaction conditions, so that the controllability of the particle sizes of the silicon dioxide micro-nano particles and the silicon dioxide nano particles, the preparation repeatability and the reproducibility are poor. Through continuous exploration and improvement, the traditional method is that ∈10 is adopted at present>Monodisperse particles with the particle size of more than 300nm can be prepared by the method, but the particle size deviation of the particles is still difficult to control to be less than 2-3%; when the method is used for preparing the silicon dioxide micro-nano particles with the particle diameter below 300nm, the particle diameter deviation is further increased to 4-5% (J.Phys.chem.B 2003,107,3400-3404). Based on the technical defects, the preparation and popularization and application of PCs are severely restricted. Thus, if high quality PCs are to be assembled therefrom, or the resulting silica micro-and nanoparticles need to be further separated to homogenize the particles (chem. Eng. J.2015,271, 128-134); or a new assembly method needs to be developed (chem. Commun.2018,54, 13937-13940). This complicates the preparation process, prolongs the process, and increases the preparation cost.
Currently, methods for controlled synthesis of monodisperse silica particles are disclosed in various documents (J.colloid Interface Sci.2005,286,536-542, J.Eur. Ceram. Soc.1994,14,205-214) and patent documents (such as publication No. CN101993086A, CN 104724713A), but none of the above methods can achieve precise control of silica micro-and nanoparticle sizes. Patent document with publication number of CN104724713A discloses a method capable of well controlling particle size of silica microspheres, but uniformity and reproducibility of the method are greatly different from expected ones, and particle sizes of prepared silica micro-nano particles are calibrated or confirmed by means of instruments such as dynamic light scattering and transmission electron microscopy, namely custom synthesis of the particle sizes of the silica micro-nano particles cannot be realized in practice. Therefore, how to realize the custom synthesis of the particle size, the monodisperse silica micro-nano particles with good uniformity and high reproducibility becomes a technical problem to be solved.
Disclosure of Invention
In order to improve the technical problems, the invention provides a preparation method of silica micro-nanospheres and nanospheres, which comprises the following steps:
s1, controlling synthesis of silica nano fine particles;
s2, controlling growth of the silicon dioxide nano-fine particles.
According to an embodiment of the present invention, the silica nanoparticles have a particle diameter of 10 to 30nm, for example 10 to 20nm, 20 to 30nm; exemplary are 10nm, 15nm, 20nm, 25nm, 30nm.
According to an embodiment of the present invention, in step S1:
the silica nanoparticles are prepared by a two-phase method, comprising: and (3) reacting the alkaline catalyst with TEOS to obtain the nano fine particle silicon dioxide.
Preferably, the basic catalyst and TEOS are both added to the reaction system in solution. For example, the basic catalyst is first dissolved in water as the aqueous phase, and TEOS is dissolved in an organic solvent as the oil phase, and the aqueous phase and the oil phase form a two-phase interface after contact.
Preferably, the basic catalyst may be selected from one, two or three of L-arginine, D-arginine and DL-arginine.
Preferably, the concentration of the aqueous alkaline catalyst solution is no more than 50.0mM. For example, 1 to 45mM. Preferably 3 to 30mM. Exemplary are 1.0mM, 2.0mM, 3.0mM, 4.4mM, 10.0mM, 15mM, 20mM, 25mM, 30mM, 35mM, 40mM, 45mM.
In the invention, the concentration of the alkaline catalyst aqueous solution is a key regulating factor for synthesizing the silica nano-fine particles, and the concentration of the alkaline catalyst aqueous solution is too high or too low, which is unfavorable for preparing the nano-silica fine particles with uniform particle size. Meanwhile, the concentration of the aqueous alkaline catalyst solution is also a prerequisite for the growth-controlled fine particles to prepare monodisperse silica particles of the target particle diameter.
Preferably, the organic solvent is a non-polar solvent having a density less than water and being immiscible with water. For example, the organic solvent may be at least one selected from n-hexane, n-heptane, n-octane, cyclohexane, cycloheptane, and the like.
Preferably, the volume ratio of TEOS to organic solvent may be 1 (0.25-10). Preferably 1 (2-8), and exemplary are 1:0.25, 1:0.5, 1:1, 1:2, 1:3, 1:5, 1:8, 1:10.
Preferably, the method further comprises the step of heating and stirring the layered aqueous phase and oil phase. For example, the heating means may be at least one of an oil bath, a water bath, an air bath, a sand bath, a metal bath, and an electric heating jacket.
Preferably, the temperature of the heating reaction is 50 to 80 ℃. More preferably 60 to 70 ℃. Exemplary is 50 ℃, 60 ℃, 70 ℃, 80 ℃. Further, the heating reaction time is not more than 30 hours. Preferably 1 to 24h, and exemplified by 1h, 2h, 5h, 8h, 10h, 12h, 16h, 20h, 24h.
Preferably, the stirring speed is 50-500 rpm, which is limited by not disturbing the two-phase interface formed by the organic solvent and water. More preferably 100 to 300rpm, and exemplary are 50rpm, 100rpm, 150rpm, 200rpm, 300rpm, 400rpm, 500rpm.
The stirring can promote TEOS to uniformly diffuse from the oil phase into the water phase, and hydrolyze and aggregate at a certain speed under the action of the alkaline catalyst to form spherical particle dispersion liquid with the particle size of 10-30 nm. In the invention, the two-phase interface formed by the organic solvent and water can be used for effectively regulating and controlling the nucleation reaction rate of the silicon dioxide nano-fine particles.
According to an embodiment of the present invention, in step S2, the controlled growth of the silica nanoparticles: according to the particle size of target silicon dioxide micro-nano spherical particles, the silicon dioxide micro-nano spherical particles are prepared by regulating and controlling the dosage of the silicon dioxide nano fine particles prepared in the step S1 and TEOS.
Preferably, the amount of the silica nanoparticles is calculated from formula (1):
wherein: d (D) final And D seed The particle size of the target silicon dioxide micro-nano sphere particles and the particle size of the silicon dioxide nano fine particles are respectively expressed in nm;
M TOES,seed a calculated value representing the amount of silica nanoparticles in mmol;
M TEOS,added the preset addition amount of TEOS is expressed in mmol.
Preferably, in step S2, the amount of the silica nanoparticles is calculated according to the particle diameters of the target silica micro-nano spherical particles, and then a mixed suspension of the silica nanoparticles is prepared. For example, the calculated silica nanoparticles are added to a pre-formulated alcohol-water-ammonia water mixed solvent to prepare an alcohol-water-ammonia water mixed suspension of silica nanoparticles. Preferably, the alcohol is ethanol.
Preferably, in step S2, the TEOS is added dropwise to the alcohol-water-ammonia water mixed suspension of silica nanoparticles. For example, the TEOS may be added by at least one of a constant pressure dropping funnel, a constant flow pump, a peristaltic pump, a syringe pump, etc. Further, the TEOS has a dropping speed of not more than 1.0mL/h, preferably 0.2 to 1mL/h, and exemplary is 0.2mL/h, 0.4mL/h, 0.6mL/h, 0.7mL/h, 1.0mL/h.
Preferably, the volume ratio of the water, TEOS, ammonia water and ethanol is (1.7-6.2): 2 (1.0-3.0): (15-22), preferably (2.0-4.0): 2 (1.0-3.0): 18-20), and the exemplary ratio is 1.7:2:1:15, 2.0:2:1:18, 2.8:2:20, 3.2:2:18, 4.0:2:3.0:19, and 6.2:2:3:22. Within the above range defined by the invention, the monodispersed silica micro-spheres and nanospheres with preset particle sizes can be obtained by regulating and controlling the volume ratio of water, TEOS, ammonia water and ethanol, and the deviation of the particle sizes of the target silica micro-spheres and nanospheres is less than 2%.
Preferably, in step S2, the controlled growth of the silica nanoparticles is performed under stirring conditions. For example, the stirring speed is 50 to 1000rpm, preferably 100 to 800rpm, and exemplary are 50rpm, 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, 800rpm, 1000rpm.
Preferably, in step S2, the temperature of controlled growth of the silica nanoparticles is not more than 50 ℃, for example 15-50 ℃, and exemplified by 20 ℃, 30 ℃, 40 ℃, 50 ℃. Further, the time for the growth is not more than 24 hours, for example, 2 to 24 hours, and is exemplified by 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 14 hours, 18 hours, 24 hours.
Preferably, in step S2, the controlled number of growth times of the silica nanoparticles may be zero times, one time, two times or more.
Preferably, spherical particles of silica of 10 to 30nm can be synthesized by zero-order growth.
Preferably, spherical silica particles having a particle size of 10nm < 320nm can be directionally synthesized by one-time growth. For example, the synthetic silica particles have a particle size of 50nm, 100nm, 150nm, 179nm, 254nm, 300nm, 324nm.
Preferably, more than one growth can be used to orient the synthetic silica spherical particles with particle size not less than 320 nm. More preferably spherical silica particles having a particle diameter of 350 to 1000nm. For example, the synthetic silica particles have a particle size of 550nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 935nm, 1000nm.
Preferably, in step S2, the preparation method further includes a step of performing solid-liquid separation on the reaction system after the reaction is completed. For example, the solid-liquid separation may employ means known in the art, such as centrifugation.
According to an embodiment of the present invention, the preparation method further comprises washing the reaction product obtained by the solid-liquid separation.
According to an embodiment of the invention, the preparation method of the silica micro-nanospheres comprises the following steps:
(1) Two-phase synthesis of silica nanoparticles: dissolving an alkaline catalyst in water to form a bottom water phase; dissolving TEOS in organic solvent to obtain oil phase, and floating on the water phase; heating and stirring the water phase to promote TEOS to uniformly diffuse from the oil phase into the water phase, and hydrolyzing to obtain spherical particle dispersion liquid with the particle size of 10-30 nm under the action of an alkali catalyst;
(2) Controlled growth of silica nanoparticles: calculating the amount of the silica nano fine particles based on the particle size of the silica nano fine particles prepared in the step (1) and the set TEOS amount from the preset particle size of the silica nano particles; dispersing the calculated silica nano fine particles in a mixed solvent of alcohol-water-ammonia water to form a mixed suspension of the silica nano fine particles; and then dripping the set amount of TEOS into the mixed suspension, reacting under stirring, centrifuging and washing to obtain the silica micro-nano particles with the target particle size.
The invention also provides the silicon dioxide micro-nanospheres prepared by the preparation method.
According to the embodiment of the invention, the particle size of the silicon dioxide micro-nanospheres is 10-1000 nm. Preferably, the particle size deviation of the silica micro-nano spheres is less than 2%.
According to an embodiment of the invention, the silica micro-nanospheres are highly uniform monodisperse spherical particles. Preferably, the silica micro-nanospheres have a morphology substantially as shown in figures 1-3.
The invention also provides the preparation method and/or the application of the silica micro-nanospheres in the fields of catalysis, chromatography, drug delivery, sensors, optical enhancement, ultra-high performance separation, lasers, lossless optical fibers, structural color pigments and the like.
The invention has the beneficial effects that:
(1) According to the invention, through a two-step synthesis method, firstly, silica nano fine particles are prepared through a two-phase synthesis method; and then regulating the growth rate of the silica micro-nanospheres by regulating the dropping speed of TEOS by utilizing the obtained silica nano-fine particles. Thus, the monodisperse silicon dioxide micro-nano spherical particles with custom-synthesized particle size are realized in stages and steps.
(2) In the preparation link of the silica fine particles, the precise regulation and control of the nucleation reaction rate of the silica fine particles is realized by adopting the two-phase nucleation reaction, so that the uniform nucleation of the silica fine particles is ensured, and the silica nano fine particles with narrower particle size distribution can be prepared in batches and repeatedly.
(3) According to the invention, the strategy of zero-order, one-time or more than one-time growth of the silicon dioxide nano-fine particles is adopted, and the controlled growth of the silicon dioxide nano-fine particles is separated from the controllable preparation of the nano-fine particles, so that the monodisperse silicon dioxide spherical particles with the particle size of 10-1000 nm can be customized and synthesized, and the particle size deviation of the silicon dioxide micro-nano spherical particles can be reduced to below 2%.
(4) The preparation method of the silica micro-nano spherical particles has good reproducibility, can be used for large-scale production of the silica micro-nano particles, and has higher commercial development value.
Drawings
FIG. 1 is a TEM image (left) and corresponding particle size distribution (right) of monodisperse spherical silica particles of 177nm particle size custom made according to example 1 of the present invention.
FIG. 2 is a TEM image (left) and corresponding particle size distribution (right) of monodisperse spherical silica particles of particle size 255nm custom made according to example 2 of the present invention.
FIG. 3 is a TEM image (left) and corresponding particle size distribution (right) of monodisperse spherical silica particles of particle size 935nm custom-made according to example 3 of the invention.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
The steps of customizing the monodisperse silica spherical particles with the particle size of 177nm are as follows:
(1) Two-phase synthesis of silica nanoparticles: l-arginine (4.4 mM) was homogeneously dispersed in 7.0mL of water to form an aqueous phase, followed by V (TEOS): v (n-octane) =1:5, n-octane and TEOS are added sequentially to form an oil phase, where V (water phase): v (oil phase) =7: 1, reacting for 20 hours at a stirring speed of 300rpm under the constant temperature condition of 70 ℃ to obtain a silica nano fine particle uniform dispersion liquid with the particle size of 22.6 nm;
(2) Growth of silica nanoparticles: according to the preset particle diameter 177nm of the particles and the preset addition amount (8.96 mmol) of TEOS, the dosage of the silicon dioxide nanometer fine particles is calculated according to a formula (1):
the result was 0.0187mmol;
(3) Taking 175.9 mu L of the dispersion liquid obtained in the step (1) according to the dosage of the silica nano fine particles calculated in the step (2) (the concentration of the dispersion liquid is calculated by the molar dosage of TEOS in the step (1)), adding the dispersion liquid into a pre-prepared alcohol-water-ammonia water mixed solution, and uniformly mixing; finally, TEOS (2.0 mL) is dripped into the mixed system at the speed of 1.0mL/h by using a syringe pump; v (water): V (TEOS): V (ammonia water): V (ethanol) =2.8:2:2:20 in the reaction system, and reacting for 10 hours at 30 ℃ at a stirring speed of 400rpm, and then centrifuging for 10 minutes at 6500rpm, and washing to obtain the silica particles with the target particle size.
And (3) taking the monodisperse silicon dioxide particles obtained in the step (3), and carrying out a Transmission Electron Microscope (TEM) test, wherein the result is shown in figure 1. 200 silica particles were randomly selected from the TEM Image using Image processing software Image J, and the particle size data were measured and statistically determined to be: the monodisperse silica particles obtained in this example had an average particle diameter of 179nm and a deviation in particle diameter of 1.4%.
Example 2
The preparation method comprises the following steps of:
(1) Two-phase synthesis of silica nanoparticles: uniformly dispersing DL-arginine (10.0 mM) in 50.0mL of water to form a water phase, then sequentially adding cyclohexane and TEOS according to V (TEOS): V (n-hexane) =1:2 to form an oil phase, wherein V (water phase): V (oil phase) =7:1, and reacting at 60 ℃ for 24 hours at a stirring speed of 200rpm to obtain a uniform dispersion of silica nano-particles with the particle size of 18.7 nm;
(2) Growth of silica nanoparticles: according to the predetermined particle diameter of 255nm of the particles and the predetermined addition amount (8.96 mmol) of TEOS, the amount of the silica nano fine particles can be calculated according to the formula (1):
as a result, 0.00353mmol;
(3) Taking 163.4 mu L of the dispersion liquid obtained in the step (1) (the concentration of the dispersion liquid is calculated by the molar amount of TEOS in the step (1)) according to the dosage of the silica nano fine particles calculated in the step (2), adding the dispersion liquid into a pre-prepared alcohol-water-ammonia water mixed solution, and uniformly mixing; finally, TEOS (2.0 mL) was added dropwise to the above mixed solution at a rate of 0.7mL/h by means of a peristaltic pump, V (water): V (TEOS): V (ammonia): V (ethanol) =3.2:2:2:18 in the reaction system, and reacted at 20℃for 18 hours at a stirring speed of 600rpm, and then centrifuged at 5000rpm for 10min, followed by washing to obtain silica particles of the target particle diameter.
The monodisperse silica particles obtained in step (3) were subjected to TEM test, and the results are shown in FIG. 2. 200 silica particles were randomly selected from the TEM Image using Image processing software Image J, and the particle size data were measured and statistically determined to be: the monodisperse silica particles obtained in this example had an average particle diameter of 254nm and a deviation in particle diameter of 1.3%.
Example 3
The steps of customizing the monodisperse silica spherical particles with the particle size of 935nm are as follows:
(1) Synthesis of 177nm silica spherical particles: the silica particles prepared in example 1 were dispersed in 10mL of ethanol to form a dispersion;
(2) Secondary growth of 177nm silica spherical particles: the amount of 177nm spherical silica particles was calculated according to formula (1) based on the predetermined particle diameter 935nm of the particles and the preset addition amount (8.96 mmol) of TEOS:
as a result, 0.0612mmol;
(3) Taking 69.0 mu L of the dispersion liquid obtained in the step (1) (the concentration of the dispersion liquid is calculated by the molar amount of TEOS in the step (1)) according to the dosage of 177nm silicon dioxide spherical particles calculated in the step (2), adding the dispersion liquid into an alcohol-water-ammonia water mixed solution with a certain proportion, and uniformly mixing; finally, dropwise adding TEOS (2.0 mL) into the mixed system at a speed of 0.6mL/h by using a peristaltic pump; v (water): V (TEOS): V (ammonia water): V (ethanol) =2:2:2:22 in the reaction system, reacting at 50 ℃ for 24 hours at a stirring speed of 300rpm, centrifuging at 4000rpm for 10min, and washing to obtain silica particles with target particle size.
The monodisperse silica obtained in the step (3) was subjected to a TEM test, and the result is shown in FIG. 3. 200 silica particles were randomly selected from the TEM Image using Image processing software Image J, and the particle size data were measured and statistically determined to be: the monodisperse silica particles obtained in this example had an average particle diameter of 935nm and a particle diameter deviation of 1.4%.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The preparation method of the silicon dioxide micro-nanospheres is characterized by comprising the following steps:
s1, controlling synthesis of silica nano fine particles; the silica nanoparticles are prepared by a two-phase method, comprising: respectively dissolving an alkaline catalyst in water to serve as a bottom water phase, dissolving TEOS in an organic solvent to serve as an oil phase, floating on the water phase, heating and stirring the water phase to promote the TEOS to diffuse from the oil phase into the water phase, and hydrolyzing and aggregating the TEOS into spherical particle dispersion liquid with the particle size of 10-30 nm under the action of the alkaline catalyst;
the alkaline catalyst is selected from one, two or three of L-arginine, D-arginine and DL-arginine; the concentration of the alkaline catalyst aqueous solution is 3-30 mM;
s2, controlling growth of the silicon dioxide nano fine particles: according to the particle size of target silicon dioxide micro-nano sphere particles, the silicon dioxide micro-nano sphere particles are prepared by regulating and controlling the dosage of the silicon dioxide nano fine particles prepared in the step S1 and TEOS;
the amount of the silica nanoparticles is calculated from formula (1):
wherein: d (D) final And D seed The particle size of the target silicon dioxide micro-nano sphere particles and the particle size of the silicon dioxide nano fine particles are respectively expressed in nm;
M TOES,seed a calculated value representing the amount of silica nanoparticles in mmol;
M TEOS,added the preset addition amount of TEOS is expressed in mmol; the particle size of the silica nano fine particles is 10-30 nm;
the controlled number of growth times of the silica nanoparticles is zero, one, two or more times;
the method is used for synthesizing spherical silica particles with the diameter of 10-30 nm through zero-order growth;
the method is used for directionally synthesizing silicon dioxide spherical particles with the particle size of 10nm < silicon dioxide particles less than or equal to 320nm through primary growth;
growing silicon dioxide spherical particles with the grain diameter of 350-1000 nm for directional synthesis through more than two times;
the particle size of the silicon dioxide micro-spheres and the nano-spheres is 10-1000 nm;
the particle diameter deviation of the silicon dioxide micro-nano spheres is less than 2%;
the silicon dioxide micro-spheres and the silicon dioxide nanospheres are spherical particles with high uniformity and single dispersion.
2. The method of claim 1, wherein in step S1:
the organic solvent is at least one selected from n-hexane, n-heptane, n-octane, cyclohexane and cycloheptane;
and/or the volume ratio of TEOS to the organic solvent is 1 (0.25-10).
3. The preparation method according to claim 1, wherein the temperature of the heating reaction is 50-80 ℃, and the time of the heating reaction is 1-24 hours;
and/or the stirring speed is 50-500 rpm.
4. A method according to any one of claims 1 to 3, wherein in step S2, the amount of silica nanoparticles is calculated based on the particle size of the target silica micro-nanosphere particles, and then a mixed suspension of silica nanoparticles is prepared.
5. The method according to claim 4, wherein the ethanol-water-ammonia water mixed suspension of the silica nanoparticles is prepared by adding the calculated silica nanoparticles to a pre-formulated ethanol-water-ammonia water mixed solvent.
6. The preparation method of claim 5, wherein in step S2, TEOS is added into the ethanol-water-ammonia water mixed suspension of the silica nano fine particles in a dropwise manner, and the volume ratio of water, TEOS, ammonia water and ethanol is (1.7-6.2): 2 (1.0-3.0): 15-22.
7. The preparation method of claim 6, wherein the TEOS is added by at least one of a constant pressure dropping funnel, a constant flow pump, a peristaltic pump and a syringe pump;
and/or the dripping speed of TEOS is 0.2-1 mL/h.
8. The preparation method according to claim 1, wherein in step S2, the controlled growth of the silica nanoparticles is performed under stirring conditions;
and/or the stirring speed is 50-1000 rpm;
and/or in the step S2, the temperature of the silicon dioxide nano-fine particles for controlling the growth is 15-50 ℃, and the time for growing is 2-24 hours.
9. The method according to any one of claims 1 to 3, wherein in step S2, the method further comprises a step of performing solid-liquid separation on the reaction system after the reaction is completed;
and/or, the preparation method further comprises washing the reaction product obtained by solid-liquid separation.
10. The method of preparing as claimed in claim 9, comprising the steps of:
(1) Two-phase synthesis of silica nanoparticles: dissolving an alkaline catalyst in water to form a bottom water phase; dissolving TEOS in organic solvent to obtain oil phase, and floating on the water phase; heating and stirring the water phase to promote TEOS to uniformly diffuse from the oil phase into the water phase, and hydrolyzing and gathering spherical particle dispersion liquid with the particle size of 10-30 nm under the action of an alkali catalyst;
(2) Controlled growth of silica nanoparticles: calculating the amount of the silica nano fine particles based on the particle size of the silica nano fine particles prepared in the step (1) and the set TEOS amount from the preset particle size of the silica nano particles; dispersing the calculated silica nano fine particles in a mixed solvent of ethanol-water-ammonia water to form a mixed suspension of the silica nano fine particles; and then dripping the set amount of TEOS into the mixed suspension, reacting under the stirring condition, centrifuging and washing to obtain the silica micro-nano particles with the target particle size.
11. Silica micro-nanospheres produced by the production process of any one of claims 1 to 10;
and/or the particle size of the silicon dioxide microspheres is 10-1000 nm;
and/or, the particle diameter deviation of the silicon dioxide micro-spheres is less than 2%;
and/or the silicon dioxide micro-spheres and nano-spheres are high-uniformity monodisperse spherical particles.
12. Use of the silica micro-nanospheres prepared by the preparation method of any one of claims 1-10 and/or the silica micro-nanospheres of claim 11 in the fields of catalysis, chromatography, drug delivery, sensors, optical enhancement, ultra-high performance separations, lasers, structural color pigments.
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