CN114804120A - Silicon dioxide micro-nano ball and preparation method and application thereof - Google Patents
Silicon dioxide micro-nano ball and 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 311
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 141
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011807 nanoball Substances 0.000 title claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000010419 fine particle Substances 0.000 claims abstract description 40
- 239000012798 spherical particle Substances 0.000 claims abstract description 32
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000012010 growth Effects 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 52
- 239000002105 nanoparticle Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000012071 phase Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002077 nanosphere Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- 230000001276 controlling effect Effects 0.000 claims description 14
- 239000004005 microsphere Substances 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000008346 aqueous phase Substances 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
- 230000009471 action Effects 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
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000013307 optical fiber Substances 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
- 230000004931 aggregating effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
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- 239000004576 sand Substances 0.000 claims description 2
- 230000001066 destructive effect Effects 0.000 claims 1
- 210000003371 toe Anatomy 0.000 claims 1
- 230000006911 nucleation Effects 0.000 abstract description 9
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- 238000001308 synthesis method Methods 0.000 abstract description 5
- 239000004038 photonic crystal Substances 0.000 description 15
- 239000011859 microparticle Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 239000000243 solution Substances 0.000 description 3
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- 229910021529 ammonia Inorganic materials 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- 239000010437 gem Substances 0.000 description 2
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- 229910001751 gemstone Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
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Images
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- 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
- C01P2004/51—Particles with a specific particle size distribution
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a silicon dioxide micro-nano ball and a preparation method and application thereof, which comprise two-phase synthesis of nano fine particles and control 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 nano fine particles, thereby ensuring the uniform and controllable nucleation and repeatedly synthesizing the uniform silicon dioxide fine particles in batches. The invention also utilizes the zero-order, one-time and more than one-time growth control method of the fine particles to separate the nucleation and the growth of the fine particles, thereby constructing a step-by-step customized synthesis method of the particle size of the silicon dioxide spherical particles. 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 particle size deviation is less than 2%. The method of the invention is convenient for enlarging the synthesis scale and has great commercial development value.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, relates to a silicon dioxide micro-nano ball and a preparation method and application thereof, and particularly relates to a silicon dioxide micro-nano ball with a customized particle size and a step-by-step synthesis method and application thereof.
Background
The silicon dioxide particles with regular appearance 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 biological toxicity, relatively simple preparation method, easy surface modification and the like. The silica particles can also be used as colloidal templates to construct core-shell, hollow, or 3D ordered pore structure materials. The monodisperse submicron silica microspheres are more common basic materials for assembling photonic crystals, and provide an effective way for manual preparation, scientific research and commercial development of the photonic crystals.
Photonic Crystals (PCs) originally are expensive natural gems, but the science of which began in 1987 when John and Yablonovitch proposed the concept of photonic crystals, respectively. PCs have photon forbidden band characteristics (similar to semiconductor electronic energy band), and thus are rapidly becoming the leading direction in the field of material research. The journal of the United states science 1999 lists it as one of ten scientific advances in the year. The purity of most natural photonic crystals is not high, so that the application development of the natural photonic crystals in the field of separation and analysis is limited. Therefore, there is a need to develop new methods for artificially manufacturing PCs to meet the development requirements of applications. The artificial photonic crystal not only has commercial value similar to natural gemstones, but also can be used for manufacturing novel lasers, lossless optical fibers, structural color pigments and the like, and can effectively adjust photon transmission, thereby having important scientific research value. In addition, in the field of analytical chemistry, photonic crystals can be used for sensing, optical enhancement, ultra-high performance separation, and the like. The application requirements push the rapid development of artificial preparation of photonic crystals, in particular to particle assembly preparation technology. However, how to prepare monodisperse and size-controllable silica micro-nanospheres is still a very challenging problem for artificial preparation of photonic crystals at present.
Admittedly, a large number of methods are available for preparing micro-nano silicon dioxide spheres, but the monodispersity and size controllability of the silicon dioxide micro-nano spheres prepared by the existing methods are not ideal. Therefore, it is desired to defineThe preparation of monodisperse silicon dioxide micro-nano particles with specific sizes is difficult to realize. Currently, the mainstream synthesis method of silica particles is 1968
The hydrolytic condensation method proposed by et al, abbreviated as
Method (J.colloid Interface Sci.1968,26, 62-69). In an alcohol medium, alkaline ammonia is used for catalyzing Tetraethoxysilane (TEOS) to hydrolyze and condense to prepare silicon dioxide micro-nano particles with the particle size of 0.05-2 mu m. The above method mainly adjusts the amount of ammonia and TEOS to control the particle size, but the size control is not accurate, and the monodispersity of the obtained particles is also poor because: in the process of preparing the silicon dioxide micro-and nano-particles by the method, the nucleation and growth processes appear in a staggered way, and the nucleation process is extremely sensitive to reaction conditions, so that the particle size controllability, the preparation repeatability and the reproducibility of the silicon dioxide micro-and nano-particles are poor. Through continuous exploration and improvement, the method is currently passed
The method can prepare monodisperse particles with the particle size of more than 300nm, but the particle size deviation of the obtained particles is still difficult to control to be less than 2-3%; when the method is adopted to prepare the silicon dioxide micro-and nano-particles with the particle size of less than 300nm, the particle size deviation can be further increased to 4-5% (J.Phys.chem.B 2003,107, 3400-3404). Based on the above technical defects, the preparation, popularization and application of PCs are severely restricted. Therefore, to assemble high quality PCs therefrom, or further separation of the resulting silica micro-and nanoparticles is required to homogenize the particles (chem. eng.j.2015,271, 128-134); or new assembly methods need to be developed (chem. Commun.2018,54, 13937-. This complicates the preparation process, prolongs the process, and increases the preparation cost.
At present, the methods for controlling and synthesizing the monodisperse silica particles are disclosed in the documents (J.colloid Interface Sci.2005,286,536-542, J.Eur.Ceram.Soc.1994,14,205-214) and the patent documents (such as publication numbers CN101993086A, CN104724713A), but the methods can not realize the precise control of the sizes of the micro-and nano-particles of the silica. Patent document CN104724713A discloses a method for controlling the particle size of silica microspheres, but the uniformity and reproducibility of the method are greatly different from expected ones, and it is necessary to calibrate or confirm the particle size of the prepared silica micro-or nano-particles by means of instruments such as dynamic light scattering and transmission electron microscopy, that is, it is practically impossible to realize the customized synthesis of the particle size of the silica micro-or nano-particles. Therefore, how to realize the synthesis of the monodisperse micro-and nano-silica particles with customized particle size, good uniformity and high reproducibility becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to improve the technical problem, the invention provides a preparation method of silicon dioxide micro-nano spheres, which comprises the following steps:
s1, controlled synthesis of silica nano fine particles;
s2, and controlling the growth of the silicon dioxide nanometer 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 30 nm; exemplary are 10nm, 15nm, 20nm, 25nm, 30 nm.
According to an embodiment of the present invention, in step S1:
the silica nanoparticles are prepared by a two-phase process comprising: and 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 the form of a solution. For example, the basic catalyst is first dissolved in water as an aqueous phase, and TEOS is dissolved in an organic solvent as an oil phase, and the aqueous phase and the oil phase form a two-phase interface after contacting each other.
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 not more than 50.0 mM. For example, 1 to 45 mM. Preferably 3 to 30 mM. Exemplary are 1.0mM, 2.0mM, 3.0mM, 4.4mM, 10.0mM, 15mM, 20mM, 25mM, 30mM, 35mM, 40mM, 45 mM.
In the invention, the concentration of the aqueous solution of the alkaline catalyst is a key regulation factor for synthesizing the silicon dioxide fine nanoparticles, and the excessive high concentration or the insufficient low concentration is not beneficial to preparing the nano silicon dioxide fine particles with uniform particle size. Meanwhile, the concentration of the aqueous solution of the basic catalyst is also a prerequisite for preparing the monodisperse silica particles with the target particle size by controlling the growth of fine particles.
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 selected from at least one of n-hexane, n-heptane, n-octane, cyclohexane, cycloheptane, and the like.
Preferably, the volume ratio of the TEOS to the organic solvent can 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 and 1: 10.
Preferably, the method further comprises the step of heating and stirring the separated water 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 50-80 ℃. More preferably 60 to 70 ℃. Exemplary are 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C. Further, the heating reaction time is not more than 30 h. Preferably 1-24 h, and is exemplified by 1h, 2h, 5h, 8h, 10h, 12h, 16h, 20h and 24 h.
Preferably, the stirring speed is 50-500 rpm, and the two-phase interface formed by the organic solvent and the water is not disturbed. More preferably 100 to 300rpm, and exemplified by 50rpm, 100rpm, 150rpm, 200rpm, 300rpm, 400rpm, and 500 rpm.
The TEOS can be promoted to uniformly diffuse from the oil phase into the water phase by stirring, and is hydrolyzed and aggregated at a certain speed under the action of an 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 the 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: the method comprises the step of regulating and controlling the dosage of the silicon dioxide nano fine particles prepared in the step S1 and TEOS according to the particle size of target silicon dioxide micro-nano spherical particles so as to prepare the silicon dioxide micro-nano spherical particles.
Preferably, the amount of the silica nanoparticles used is calculated from formula (1):
in the formula: d final And D seed Respectively representing the particle diameters of the target silicon dioxide micro-nano spherical particles and the silicon dioxide nano fine particles, and the unit is nm;
M TOES,seed a calculated value representing the amount of silica nanoparticles used in mmol;
M TEOS,added represents the preset addition of TEOS in mmol.
Preferably, in step S2, the amount of the silica nanoparticles is calculated according to the particle size of the target silica micro-and nanosphere particles, and then a mixed suspension of the silica nanoparticles is prepared. For example, the calculated silica nanoparticles are added to a previously prepared alcohol-water-ammonia water mixed solvent to prepare an alcohol-water-ammonia water mixed suspension of the 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 the 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, and a syringe pump. Further, the dropping speed of the TEOS is not more than 1.0mL/h, preferably 0.2-1 mL/h, and exemplarily 0.2mL/h, 0.4mL/h, 0.6mL/h, 0.7mL/h and 1.0 mL/h.
Preferably, the volume ratio of the water, the TEOS, the ammonia water and the 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 is exemplarily 1.7:2:1:15, 2.0:2:1:18, 2.8:2:2:20, 3.2:2:2:18, 4.0:2:3.0:19 and 6.2:2:3: 22. Within the above range defined by the invention, by adjusting and controlling the volume ratio of water, TEOS, ammonia water and ethanol, monodisperse micro-spheres and nanospheres of silicon dioxide with preset particle sizes can be obtained, and the particle size deviation of the target micro-spheres and nanospheres of silicon dioxide is less than 2%.
Preferably, in step S2, the controlled growth of the silica nanoparticles is performed under stirring conditions. For example, the rotation speed of the stirring is 50 to 1000rpm, preferably 100 to 800rpm, and exemplified by 50rpm, 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, 800rpm, and 1000 rpm.
Preferably, in step S2, the temperature for controlling the growth of the silica nanoparticles is not more than 50 ℃, for example, 15 to 50 ℃, exemplary 20 ℃, 30 ℃, 40 ℃, 50 ℃. Further, the growth time is not more than 24h, such as 2-24 h, exemplary 2h, 4h, 6h, 8h, 10h, 14h, 18h, 24 h.
Preferably, the number of controlled growths of the silica nanoparticles in step S2 may be zero, one, two or more.
Preferably, the method can be used for synthesizing 10-30 nm silicon dioxide spherical particles through zero-order growth.
Preferably, the method can be used for directionally synthesizing the silica spherical particles with the particle size of 10nm < silica particles less than or equal to 320nm through one-time growth. For example, the synthetic silica particles have a particle size of 50nm, 100nm, 150nm, 179nm, 254nm, 300nm, 324 nm.
Preferably, the method can be used for directionally synthesizing silicon dioxide spherical particles with the particle size of more than 320nm through more than one growth. More preferably, the particle size of the silicon dioxide spherical particles is 350-1000 nm. For example, the synthetic silica particles have a particle diameter of 550nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 935nm, or 1000 nm.
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 be by 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 the embodiment of the invention, the preparation method of the silicon dioxide micro-nano spheres comprises the following steps:
(1) two-phase synthesis of silica nanoparticles: dissolving an alkaline catalyst in water to serve as a bottom water phase; TEOS is dissolved in an organic solvent to be used as an oil phase and floats on a 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 aggregating into spherical particle dispersion liquid with the particle size of 10-30 nm under the action of an alkali catalyst;
(2) controlling growth of silica nanoparticles: calculating the use amount of the silica nano-fine particles on the basis of the particle size of the silica nano-fine particles prepared in the step (1) and the set TEOS (tetraethyl orthosilicate) use amount from the preset particle size of the silica nano-particles; dispersing the calculated silicon dioxide nano-fine particles into a mixed solvent of alcohol-water-ammonia water to form a mixed suspension of the silicon dioxide nano-fine particles; and then dropping TEOS with a set dosage into the mixed suspension, reacting under stirring, centrifuging, and washing to obtain the silicon dioxide micro-nano particles with the target particle size.
The invention also provides the silicon dioxide micro-nano spheres and nano-spheres prepared by the preparation method.
According to the embodiment of the invention, the particle size of the silicon dioxide micro-spheres and nano-spheres is 10-1000 nm. Preferably, the deviation of the particle size of the silicon dioxide micro-spheres and nano-spheres is less than 2%.
According to the embodiment of the invention, the silicon dioxide micro-spheres and nano-spheres are highly uniform monodisperse spherical particles. Preferably, the silica micro-nanospheres have a morphology substantially as shown in FIGS. 1-3.
The invention also provides the preparation method and/or the application of the silicon dioxide micro-spheres and nano-spheres in the fields of catalysis, chromatography, drug delivery, sensors, optical enhancement, ultrahigh-performance separation, lasers, lossless optical fibers, structural color pigments and the like.
The invention has the beneficial effects that:
(1) the invention adopts a two-step synthesis method, firstly, the silicon dioxide nano fine particles are prepared by a two-phase synthesis method; and then, the obtained silica nano fine particles are utilized to regulate and control the growth rate of the silica micro/nano spheres by regulating and controlling the dropping speed of TEOS. Therefore, the monodisperse silicon dioxide micro-nano spherical particles which are synthesized by the particle size customization are realized in stages and steps.
(2) In the preparation link of the silicon dioxide fine particles, the invention realizes the accurate regulation and control of the nucleation reaction rate of the silicon dioxide fine particles by adopting the two-phase nucleation reaction, thereby ensuring the uniform nucleation of the silicon dioxide fine particles, and thus, the silicon dioxide nano fine particles with narrower particle size distribution can be repeatedly prepared in batches.
(3) According to the method, the strategy of growing the silicon dioxide nano fine particles for zero, one or more times 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-spherical particles and the silicon dioxide nano-spherical particles can be reduced to be below 2%.
(4) The preparation method of the silicon dioxide micro-and nano-spherical particles has good reproducibility, can be used for large-scale production of the silicon dioxide micro-and nano-particles, and has higher commercial development value.
Drawings
FIG. 1 is a TEM image (left) and a corresponding particle size distribution diagram (right) of a monodisperse silica spherical particle having a particle size of 177nm, which is custom-synthesized in example 1 of the present invention.
FIG. 2 is a TEM image (left) and a corresponding particle size distribution diagram (right) of spherical particles of monodisperse silica having a particle size of 255nm, which were custom-synthesized in example 2 of the present invention.
FIG. 3 is a TEM image (left) and a corresponding particle size distribution diagram (right) of spherical monodisperse silica particles with a particle size of 935nm, which were custom-synthesized in example 3 of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The preparation method comprises the following steps of (1) customizing monodisperse spherical silica particles with the particle size of 177 nm:
(1) two-phase synthesis of silica nanoparticles: l-arginine (4.4mM) was uniformly dispersed in 7.0mL of water to form an aqueous phase, which was then purified according to V (TEOS): v (n-octane) ═ 1:5, and n-octane and TEOS were added in this order to form an oil phase, wherein V (aqueous phase): v (oil phase) ═ 7:1, reacting for 20 hours at a constant temperature of 70 ℃ and a stirring speed of 300rpm to obtain silicon dioxide nano-fine particle uniform dispersion liquid with the particle size of 22.6 nm;
(2) growth of silica nanoparticles: the amount of silica nanoparticles used was calculated according to the formula (1) based on the predetermined particle diameter of 177nm of the particles and the preset addition amount (8.96mmol) of TEOS:
as a result, 0.0187 mmol;
(3) according to the amount of the silicon dioxide nano fine particles calculated in the step (2), taking 175.9 microliter 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)), adding the dispersion liquid into a pre-prepared alcohol-water-ammonia water mixed solution, and uniformly mixing; finally, TEOS (2.0mL) was added dropwise to the above mixed system at a rate of 1.0mL/h using a syringe pump; in the reaction system, V (water), V (TEOS), V (ammonia water), V (ethanol), V (2.8: 2:2:20 are reacted at 30 ℃ for 10h at a stirring speed of 400rpm, and then centrifuged at 6500rpm for 10min, and the obtained product is washed to obtain silica particles with a target particle size.
Taking the monodisperse silica particles obtained in the step (3), and carrying out a Transmission Electron Microscope (TEM) test, wherein the result is shown in figure 1. The Image processing software Image J is used for randomly selecting 200 silicon dioxide particles from the TEM picture, and the particle size data of the silicon dioxide particles are measured, so that the following results can be obtained after statistics: the monodisperse silica particles prepared in this example had an average particle size of 179nm with a variation in particle size of 1.4%.
Example 2
Preparing monodisperse spherical silicon dioxide particles with the particle size of 255nm by customization, and comprising the following steps:
(1) two-phase synthesis of silica nanoparticles: uniformly dispersing DL-arginine (10.0mM) in 50.0mL of water to form an aqueous phase, then sequentially adding cyclohexane and TEOS according to V (TEOS): V (n-hexane): 1:2 to form an oil phase, wherein V (aqueous phase): V (oil phase): 7:1, and reacting at 60 ℃ at a stirring speed of 200rpm for 24 hours to obtain a silicon dioxide nano fine particle uniform dispersion liquid with the particle size of 18.7 nm;
(2) growth of silica nanoparticles: the amount of silica nanoparticles used was calculated according to formula (1) based on the predetermined particle size of the particles of 255nm and the preset addition amount of TEOS (8.96 mmol):
the result was 0.00353 mmol;
(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 amount of the silicon dioxide 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 (2.0mL) was added dropwise to the above mixed solution at a rate of 0.7mL/h using a peristaltic pump, and V (water): V (TEOS): V (ammonia water): V (ethanol): 3.2:2:2:18 in the reaction system, and reacted at 20 ℃ for 18h with a stirring speed of 600rpm, followed by centrifugation at 5000rpm for 10min and washing to obtain silica particles of the desired particle size.
Taking the monodisperse silica particles obtained in the step (3), and carrying out TEM test, wherein the result is shown in FIG. 2. The Image processing software Image J is used for randomly selecting 200 silicon dioxide particles from the TEM picture, and the particle size data of the silicon dioxide particles are measured, so that the following results can be obtained after statistics: the monodisperse silica particles obtained in this example had an average particle size of 254nm and a particle size deviation of 1.3%.
Example 3
Preparing monodisperse silicon dioxide spherical particles with the synthetic particle size of 935nm by the following steps:
(1) synthesis of 177nm silica spherical particles: dispersing the silica particles prepared in example 1 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 size of the particles, 935nm, and the preset addition amount of TEOS (8.96 mmol):
as a result, 0.0612 mmol;
(3) according to the using amount of 177nm spherical silicon dioxide particles obtained by calculation in the step (2), 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 using amount of TEOS in the step (1)), adding the dispersion liquid into an alcohol-water-ammonia water mixed solution prepared in advance according to a certain proportion, and uniformly mixing; finally, TEOS (2.0mL) was added dropwise to the above mixed system at a rate of 0.6mL/h using a peristaltic pump; in the reaction system, V (water), V (TEOS), V (ammonia water), V (ethanol), V (2: 2:2:22 are reacted at 50 ℃ for 24 hours at a stirring speed of 300rpm, centrifuged at 4000rpm for 10 minutes, and washed to obtain silica particles with the target particle size.
Taking the monodisperse silica obtained in the step (3), and carrying out TEM test, wherein the result is shown in FIG. 3. The Image processing software Image J is used for randomly selecting 200 silicon dioxide particles from the TEM picture, and the particle size data of the silicon dioxide particles are measured, so that the following results can be obtained after statistics: the monodisperse silica particles obtained in this example had an average particle size of 935nm and a particle size 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, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of silicon dioxide micro-nano balls is characterized by comprising the following steps:
s1, controlled synthesis of silica nano fine particles;
s2, and controlling the growth of the silicon dioxide nanometer fine particles.
Preferably, the particle size of the silica nanoparticles is 10 to 30nm, for example, 10 to 20nm, 20 to 30 nm.
2. The method of claim 1, wherein in step S1:
the silica nanoparticles are prepared by a two-phase process comprising: and 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 the form of a solution. For example, the basic catalyst is first dissolved in water as an aqueous phase, and TEOS is dissolved in an organic solvent as an oil phase, and the aqueous phase and the oil phase form a two-phase interface after contacting each other.
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 not more than 50.0 mM. For example, 1 to 45 mM. Preferably 3 to 30 mM.
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 selected from at least one of n-hexane, n-heptane, n-octane, cyclohexane, cycloheptane, and the like.
Preferably, the volume ratio of the TEOS to the organic solvent can be 1 (0.25-10). Preferably 1 (2-8).
3. The method according to claim 1 or 2, further comprising the step of heating and stirring the separated 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 50-80 ℃. More preferably 60 to 70 ℃. Further, the heating reaction time is not more than 30 h. Preferably 1-24 h.
Preferably, the rotation speed of the stirring is 50-500 rpm, and more preferably 100-300 rpm.
4. The production method according to any one of claims 1 to 3, wherein in step S2, the controlled growth of the silica nanoparticles: the method comprises the step of regulating and controlling the dosage of the silicon dioxide nano fine particles prepared in the step S1 and TEOS according to the particle size of target silicon dioxide micro-nano spherical particles so as to prepare the silicon dioxide micro-nano spherical particles.
Preferably, the amount of the silica nanoparticles used is calculated from formula (1):
in the formula: d final And D seed Respectively representing the particle diameters of the target silicon dioxide micro-nano spherical particles and the silicon dioxide nano fine particles, and the unit is nm;
M TOES,seed the calculated value representing the amount of the silica nanoparticles used is expressed in mmol;
M TEOS,added represents the preset addition of TEOS in mmol.
Preferably, in step S2, the amount of the silica nanoparticles is calculated according to the particle size of the target silica micro-and nanosphere particles, and then a mixed suspension of the silica nanoparticles is prepared. For example, the calculated silica nanoparticles are added to a previously prepared alcohol-water-ammonia water mixed solvent to prepare an alcohol-water-ammonia water mixed suspension of the 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 the 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, and a syringe pump. Further, the dropping speed of the TEOS is not more than 1.0mL/h, and preferably 0.2-1 mL/h.
Preferably, the volume ratio of the water, the TEOS, the ammonia water and the 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.
5. The method of any one of claims 1 to 4, wherein the controlled growth of the silica nanoparticles in step S2 is performed under stirring conditions. For example, the rotation speed of the stirring is 50 to 1000rpm, preferably 100 to 800 rpm.
Preferably, in step S2, the temperature for controlling the growth of the silica nanoparticles is not more than 50 ℃, for example, 15 to 50 ℃. Further, the growth time is not more than 24 hours, such as 2-24 hours.
6. The method of any one of claims 1 to 5, wherein the number of controlled growths of the silica nanoparticles in step S2 may be zero, one, two or more.
Preferably, the method can be used for synthesizing 10-30 nm silicon dioxide spherical particles through zero-order growth.
Preferably, the method can be used for directionally synthesizing the silica spherical particles with the particle size of 10nm < silica particles less than or equal to 320nm through one-time growth. .
Preferably, the method can be used for directionally synthesizing silicon dioxide spherical particles with the particle size of more than 320nm through more than one growth. More preferably, the particle size of the silicon dioxide spherical particles is 350-1000 nm.
7. The production method according to any one of claims 1 to 6, wherein in step S2, the production method further comprises a step of subjecting the reaction system to solid-liquid separation after the reaction is completed.
Preferably, the preparation method further comprises washing the reaction product obtained by solid-liquid separation.
8. The method of any one of claims 1 to 7, comprising the steps of:
(1) two-phase synthesis of silica nanoparticles: dissolving an alkaline catalyst in water to serve as a bottom water phase; TEOS is dissolved in an organic solvent to be used as an oil phase and floats on a 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 aggregating into spherical particle dispersion liquid with the particle size of 10-30 nm under the action of an alkali catalyst;
(2) controlling growth of silica nanoparticles: calculating the use amount of the silica nano-fine particles on the basis of the particle size of the silica nano-fine particles prepared in the step (1) and the set TEOS (tetraethyl orthosilicate) use amount from the preset particle size of the silica nano-particles; dispersing the calculated silicon dioxide nano-fine particles into a mixed solvent of alcohol-water-ammonia water to form a mixed suspension of the silicon dioxide nano-fine particles; and then dropping TEOS with a set dosage into the mixed suspension, reacting under the stirring condition, centrifuging and washing to obtain the silicon dioxide micro-nano particles with the target particle size.
9. A silica micro-or nanosphere prepared by the method of any of claims 1 to 8.
Preferably, the particle size of the silicon dioxide micro-spheres and nano-spheres is 10-1000 nm.
Preferably, the deviation of the particle sizes of the silicon dioxide micro-spheres and the silicon dioxide nano-spheres is less than 2%.
Preferably, the silicon dioxide micro-spheres and nano-spheres are highly uniform monodisperse spherical particles.
Preferably, the silica micro-nanospheres have a morphology substantially as shown in FIGS. 1-3.
10. Use of the preparation method of any one of claims 1 to 8 and/or the silica micro-, nanospheres of claim 9 in the fields of catalysis, chromatography, drug delivery, sensors, optical enhancement, ultra-high performance separation, lasers, non-destructive optical fibers, structured color pigments, and the like.
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