CN102020283A - Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter - Google Patents
Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter Download PDFInfo
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- CN102020283A CN102020283A CN 201010588100 CN201010588100A CN102020283A CN 102020283 A CN102020283 A CN 102020283A CN 201010588100 CN201010588100 CN 201010588100 CN 201010588100 A CN201010588100 A CN 201010588100A CN 102020283 A CN102020283 A CN 102020283A
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Abstract
The invention relates to a preparation method of a silicon dioxide nano hollow sphere with an adjustable inner diameter. The method is characterized by comprising the followings steps: (1) adding phenyl trimethoxy silane with the concentration of 0.04-0.08mol/L into an aqueous solution containing nitric acid with the concentration of 0.005-0.008mol/L, and carrying out hydrolysis in a warm water bath at the temperature of 60-80 DEG C for 0.5-4min, wherein the volume ratio of the phenyl trimethoxy silane to the water solution containing nitric acid is 25:1-30:1; and (2) adding ammonia water with the mol concentration of 0.85-2.6mol/L, continuing to react for 1-3h while stirring in the warm water bath at the temperature of 60-80 DEG C, and then, washing and drying products, wherein the volume ratio of the ammonia water to the phenyl trimethoxy silane is 8:1-10:1. Compared with the prior art, the invention has the advantages that the invention does not need a template, other conditions such as temperature and the like in the reaction process can be controlled easily, and the reaction time is very short, thus the preparation process is simple and time-saving; and massive silicon dioxide hollow spheres with different inner diameters and shell thicknesses can be synthesized as required by changing different reaction conditions.
Description
Technical field
The present invention relates to a kind of preparation method of hollow ball, relate in particular to a kind of preparation method of silica nanometer hollow ball, belong to technical field of nano material.
Background technology
The inorganic nano hollow granule has that density is low, specific surface is big, mechanicalness and Heat stability is good, have characteristics such as surperficial permeability, and these unique character make them have in fields such as catalysis, coating, matrix material, medicine and fillers widely and use.And nano-hollow silicon-dioxide purifies, adsorbs, separates at water owing to it, and the unique application of aspects such as medical science, catalysis obtains broad research in recent years.For example, because the porousness of silica sphere, many in recent years scholars are devoted to study the porous silicon adsorbent, and wait used as the heavy duty metal ion adsorbent and to eliminate environmental pollution.Moreover because silicon-dioxide has unique hydroxyapatite structure, at the support that medically can be used as regenerating tissues, it is connected just with cell sclerous tissues can carry out tissue repair.And because of silicon-dioxide has good and other materials consistency,, medicine nontoxic, harmless to human body be advantage such as release easily, composite hollow ball useful as drug transmission systems such as the silica-magnetic material of nucleocapsid structure.
The method of existing preparation hollow silica ball has many, as organic template, surfactant templates method, layer-layer self-assembly method etc., wherein, open source literature about the organic formwork method can be with reference to " Acta PhySico-Chimica Sinica " 2008,24 (3): " is template synthetic silica nano-hollow ball with the negatively charged ion polypeptide " that Li Li grain husk etc. is shown (359-363), mention in the document, with 3 one aminopropyl trimethoxysilane (APMS) and tetraethoxy (TEOS) is the silicon source, and polyglutamic acid sodium is the template for preparing hollow ball; But open " a kind of nano-silicon dioxide hollow sphere material and preparation method thereof " (publication number: CN101343065A) of the Chinese invention patent application of the open source literature application reference of relevant surfactant templates method numbers 200810042501.0.
Above-mentioned these methods need be used template mostly, thereby make synthesis step more numerous and diverse, and are consuming time longer, generally need to select suitable chemical agent dissolves or under certain high temperature the combustion decomposition template can obtain hollow structure.And there is easily shortcoming such as reunite, particle diameter differs, time-consuming, effort, reaction conditions are wayward in varying degrees in the hollow silica ball that makes with these methods.
Some scholars select suitable polyelectrolyte to form the spheric aggregate in poor solvent in recent years, with this aggregate is matrix, in conjunction with classical stober method, the growth of control silicon-dioxide, synthetic internal diameter, the hollow silica ball that wall thickness is controlled, adjustable of having obtained.
More advanced preparation technology can also referenced patent number is Chinese invention patent " a kind of preparation method of the hollow silica ball " (grant number: CN100494057C) of ZL200610096601.2, the colloid that this patent adopts polyelectrolyte to form in alcoholic solvent is the matrix of silicon source precursor hydrolytic polymerization, prepare hollow silica ball, prepare hollow silica ball in this way and need not to prepare template in advance and use tensio-active agent, the simple relatively and particle diameter homogeneous and controllable, better dispersed of method.
Summary of the invention
Technical problem to be solved by this invention is the preparation method that the silica nanometer hollow ball that a kind of technical process is simple and internal diameter is adjustable is provided at the above-mentioned state of the art.
Another technical problem to be solved by this invention provides the preparation method of the silica nanometer hollow ball that a kind of preparation cycle is short and internal diameter is adjustable.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the preparation method of the silica nanometer hollow ball that a kind of internal diameter is adjustable is characterized in that comprising the steps:
1. the phenyltrimethoxysila,e of 0.04～0.08mol/L joins in the aqueous solution that contains 0.005～0.008mol/L nitric acid, and in 60～80 ℃ warm water bath hydrolysis 0.5～4min; Wherein, the volume ratio of phenyltrimethoxysila,e and salpeter solution is 25: 1～30: 1;
2. add the ammoniacal liquor that concentration is 0.85～2.6mol/L, stir 60～80 ℃ warm water baths and continue reaction 1～3h, then to product wash, drying treatment, wherein, ammoniacal liquor and phenyltrimethoxysila,e volume ratio are 8: 1～10: 1.
The volume ratio that is phenyltrimethoxysila,e described in step 1. and salpeter solution is 25.6: 1, and 2. described ammoniacal liquor of step and phenyltrimethoxysila,e volume ratio are 8.7: 1.
As the best, the phenyltrimethoxysila,e concentration of step described in 1. is 0.06mol/L.
As the best, the bath temperature of step described in 1. is 60 ℃.
As the best, the speed that step stirs described in 2. is 260rpm.
As the best, the ammonia concn of step described in 2. is controlled at 1.40mol/L.
Compared with prior art, the invention has the advantages that: the present invention not only need not to use template, and other conditions such as temperature are more easy to control in the reaction process, reaction times is very short, therefore preparation process is simple, save time, by changing the hollow silica ball that different reaction conditionss can synthesize different inner diameters size and outer casing thickness on demand in a large number, wherein hydrolysis time is a key factor, regulate hydrolysis time and can obtain wall thickness and the different hollow ball of internal diameter size, in addition, change the concentration of phenyltrimethoxysila,e, concentration of nitric acid, temperature of reaction etc. are also to its hollowness, and wall thickness and internal diameter size are influential.The hollow silica ball particle diameter that adopts this method to make is 300～800nm, and internal diameter is 100～500nm.
Description of drawings
Fig. 1 is the transmission electron microscope photo of hollow silica ball among the embodiment 1.
Fig. 2 is the electron scanning micrograph of hollow silica ball among the embodiment 1.
Fig. 3 is the isothermal adsorption desorption graphic representation of hollow silica ball among the embodiment 1.
Fig. 4 is the transmission electron microscope photo of hollow silica ball among the embodiment 2.
Fig. 5 is the transmission electron microscope photo of hollow silica ball among the embodiment 3.
Fig. 6 is the transmission electron microscope photo of hollow silica ball among the embodiment 4.
The transmission electron microscope photo of hollow silica ball when Fig. 7 is 80 ℃ for bath temperature.
Fig. 8 is the transmission electron microscope photo of hollow silica ball among the embodiment 5.
Fig. 9 is the transmission electron microscope photo of hollow silica ball among the embodiment 6.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1:
A. phenyltrimethoxysila,e hydrolysis under acidic conditions: get a there-necked flask, add 45ul again
0.0066mol/L be put in behind the nitric acid in 60 ℃ the warm water bath, add 1.15ml 0.06mol/L PTMS then, this mixture stirs 4min with the speed of 260rpm/min;
B. continue reaction 1h under alkaline condition: add the ammoniacal liquor of 10ml 1.4mol/L, solution originally becomes the milk look immediately, continues stirred solution 1h it is fully reacted;
C. the particle that obtains separates under rotating speed 3500r/min with whizzer and water and ethanol are washed several times, and dry 2h in 80 ℃ of following vacuum drying ovens obtains off-white powder shape solid.
The XRD figure spectrum analysis shows that the product that obtains is a silicon-dioxide, but the not obvious product that shows in peak is an amorphous structure, and non-crystal structure.
As shown in Figure 1, transmission electron microscope (TEM) photo by hollow silica ball can observe, and the silicon-dioxide that embodiment 1 makes is spherical in shape and be hollow structure, the product good dispersity, and particle diameter is even, the about 180nm of internal diameter, the about 380nm of wall thickness.
As shown in Figure 2, the scanning electronic microscope of hollow silica ball (SEM) photo shows, the silica spheres surface smoother that embodiment 1 makes.
Sample is carried out the specific surface area test result obtain, the BET specific surface area of the hollow silica ball that this embodiment makes is 18.9913m
2/ g, the Langmuir specific surface area data is 27.6057m
2/ g.The size average out to 300nm of the hollow silica ball that this embodiment makes.
Embodiment 2:
Operation is with embodiment 1, keep the consumption of other experiment conditions and reactant constant, the concentration that changes phenyltrimethoxysila,e (PTMS) is 0.04mol/L, can observe by transmission electron microscope (TEM) photo: the hollow silicon dioxide particle diameter that makes during for 0.04mol/L when the concentration of PTMS and pore size is inhomogeneous and wall is thicker.
Embodiment 3:
Operation is with embodiment 1, keep the consumption of other experiment conditions and reactant constant, the concentration that changes phenyltrimethoxysila,e (PTMS) is 0.08mol/L, and can observe by transmission electron microscope (TEM) photo: the ball hollowness that obtains is bad, and internal diameter is less.
Therefore when being 0.06mol/L, PTMS concentration just can obtain the uniform hollow silica ball of particle diameter and pore size as preferably having only.
Embodiment 4:
Operation is with embodiment 1, keep the consumption of other experiment conditions and reactant constant, the amount that only adds ammoniacal liquor changes 6ml into, can be observed by transmission electron microscope (TEM) photo: the size of particles that obtains during for 6ml when the amount that adds ammoniacal liquor is more even but ball that hollow internal diameter is less, and also having minority is the flaky netted hollow ball of similar lemon.
Keep the consumption of other experiment conditions and reactant constant, the particle that obtains when the amount that adds ammoniacal liquor is followed successively by 14ml, 18ml presents more and more irregular shape, and the edge of particle thickens.(more and more fuzzyyer)
Therefore just can obtain particle diameter when preferably having only the 10ml of adding ammoniacal liquor and pore size is even, and the hollow silica ball of regular shape.
When control reaction temperature was followed successively by 60 ℃, 70 ℃, 80 ℃, the consumption of other each experiment conditions and reactant was all constant, can be observed the hollow ball internal diameter that obtains by transmission electron microscope (TEM) photo and diminished gradually.Therefore the bath temperature as preferred whole experiment is the best with 60 ℃.
Embodiment 5:
Operation is with embodiment 1, keep the consumption of other experiment conditions and reactant constant, only the hydrolysis time of step a changes 2min among the embodiment 1, can be observed the size of gained particle and hollowness by transmission electron microscope (TEM) photo compares with the particle that embodiment 1 obtains considerable change is all arranged, the hollow silica ball diameter that obtains is about 550nm, internal diameter is about 300nm, illustrates that the hydrolysis time that changes step a can control the size and the hollowness of particle.
Embodiment 6:
Operation is with embodiment 1, keep the consumption of other experiment conditions and reactant constant, only the hydrolysis time of step a changes 1min among the embodiment 1, big or small the comparing with the particle that embodiment 1,5 obtains with outer casing thickness of internal diameter that can be observed the gained particle by transmission electron microscope (TEM) photo all has considerable change, the hollow silica ball diameter that this embodiment obtains is about 800nm, and internal diameter is about 500nm.The particle that these three different hydrolysis times of comparison obtain can find that along with phenyltrimethoxysila,e hydrolysis time under acidic conditions shortens, the particle that obtains increases gradually.
Claims (6)
1. the preparation method of the adjustable silica nanometer hollow ball of an internal diameter is characterized in that comprising the steps:
1. the phenyltrimethoxysila,e of 0.04～0.08mol/L joins in the aqueous solution that contains 0.005～0.008mol/L nitric acid, and in 60～80 ℃ warm water bath hydrolysis 0.5～4min; Wherein, the volume ratio of phenyltrimethoxysila,e and salpeter solution is 25: 1～30: 1;
2. add the ammoniacal liquor that concentration is 0.85～2.6mol/L, stir 60～80 ℃ warm water baths and continue reaction 1～3h, then to product wash, drying treatment, wherein, ammoniacal liquor and phenyltrimethoxysila,e volume ratio are 8: 1～10: 1.
2. preparation method according to claim 1, the volume ratio that it is characterized in that phenyltrimethoxysila,e described in step is 1. and salpeter solution is 25.6: 1,2. described ammoniacal liquor of step and phenyltrimethoxysila,e volume ratio are 8.7: 1.
3. preparation method according to claim 1 is characterized in that the phenyltrimethoxysila,e concentration described in step 1. is 0.06mol/L.
4. preparation method according to claim 3 is characterized in that the bath temperature described in step 1. is 60 ℃.
5. preparation method according to claim 4 is characterized in that the speed that stirs described in step 2. is 260rpm.
6. preparation method according to claim 5 is characterized in that the ammonia concn described in step 2. is controlled at 1.40mol/L.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150021896A (en) * | 2013-08-21 | 2015-03-03 | (주)석경에이티 | Hollow silica particles, method of manufacturing the same, composition including the same and sheet with inner cavities |
| WO2015182878A1 (en) * | 2014-05-30 | 2015-12-03 | (주)석경에이티 | Method for manufacturing hollow silica particles, hollow silica particles, and composition and thermal insulation sheet comprising same |
| KR20150139233A (en) * | 2014-06-03 | 2015-12-11 | 한양대학교 산학협력단 | manufacturing method of hollow/rattle/raspberry/mesoporous type silica particles by a selective etching process |
| JP2017501099A (en) * | 2014-05-30 | 2017-01-12 | スギュン アット カンパニー リミテッド | Method for producing hollow silica particles, hollow silica particles, composition containing them, and heat insulating sheet |
| CN112156730A (en) * | 2020-08-25 | 2021-01-01 | 安徽壹石通材料科技股份有限公司 | Preparation method of high-purity monodisperse porous silicon oxide spheres |
| CN113264534A (en) * | 2021-06-21 | 2021-08-17 | 江苏辉迈粉体科技有限公司 | Preparation method of silicon dioxide hollow microspheres |
| KR20210153227A (en) * | 2020-06-10 | 2021-12-17 | 주식회사 케이씨텍 | Manufacturing method of hollow silica particles and hollow silica particles manufactured using the same |
| US11242256B2 (en) | 2018-06-01 | 2022-02-08 | Imam Abdulrahman Bin Faisal University | Multi-stage calcination method for making hollow silica spheres |
-
2010
- 2010-12-03 CN CN 201010588100 patent/CN102020283A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《Chemical Communications》 20030613 Hoe Jin Hah et al Simple preparation of monodisperse hollow silica particles without using templates 1712页-1713页 1-6 , * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101724603B1 (en) * | 2013-08-21 | 2017-04-07 | (주)석경에이티 | Hollow silica particles, method of manufacturing the same, composition including the same and sheet with inner cavities |
| KR20150021896A (en) * | 2013-08-21 | 2015-03-03 | (주)석경에이티 | Hollow silica particles, method of manufacturing the same, composition including the same and sheet with inner cavities |
| WO2015182878A1 (en) * | 2014-05-30 | 2015-12-03 | (주)석경에이티 | Method for manufacturing hollow silica particles, hollow silica particles, and composition and thermal insulation sheet comprising same |
| KR101790553B1 (en) * | 2014-05-30 | 2017-10-26 | (주)석경에이티 | Process for production of hollow silica particles, hollow silica particles, and composition and insulation sheet which contain same |
| JP2017501099A (en) * | 2014-05-30 | 2017-01-12 | スギュン アット カンパニー リミテッド | Method for producing hollow silica particles, hollow silica particles, composition containing them, and heat insulating sheet |
| US20170073237A1 (en) * | 2014-05-30 | 2017-03-16 | Sukgyung At Co., Ltd . | Method for manufacturing hollow silica particles, hollow silica particles, and composition and thermal insulation sheet comprising same |
| KR101598696B1 (en) * | 2014-06-03 | 2016-02-29 | 한양대학교 산학협력단 | manufacturing method of hollow/rattle/raspberry/mesoporous type silica particles by a selective etching process |
| KR20150139233A (en) * | 2014-06-03 | 2015-12-11 | 한양대학교 산학협력단 | manufacturing method of hollow/rattle/raspberry/mesoporous type silica particles by a selective etching process |
| US11242256B2 (en) | 2018-06-01 | 2022-02-08 | Imam Abdulrahman Bin Faisal University | Multi-stage calcination method for making hollow silica spheres |
| KR20210153227A (en) * | 2020-06-10 | 2021-12-17 | 주식회사 케이씨텍 | Manufacturing method of hollow silica particles and hollow silica particles manufactured using the same |
| KR102479902B1 (en) | 2020-06-10 | 2022-12-21 | 주식회사 케이씨텍 | Manufacturing method of hollow silica particles and hollow silica particles manufactured using the same |
| CN112156730A (en) * | 2020-08-25 | 2021-01-01 | 安徽壹石通材料科技股份有限公司 | Preparation method of high-purity monodisperse porous silicon oxide spheres |
| CN112156730B (en) * | 2020-08-25 | 2022-05-03 | 安徽壹石通材料科技股份有限公司 | Preparation method of high-purity monodisperse porous silicon oxide spheres |
| CN113264534A (en) * | 2021-06-21 | 2021-08-17 | 江苏辉迈粉体科技有限公司 | Preparation method of silicon dioxide hollow microspheres |
| CN113264534B (en) * | 2021-06-21 | 2022-10-25 | 江苏辉迈粉体科技有限公司 | Preparation method of silicon dioxide hollow microspheres |
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Application publication date: 20110420 |