CN105836750A - Preparation method of magnetic nano-silica hollow spheres - Google Patents
Preparation method of magnetic nano-silica hollow spheres Download PDFInfo
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- CN105836750A CN105836750A CN201610251955.3A CN201610251955A CN105836750A CN 105836750 A CN105836750 A CN 105836750A CN 201610251955 A CN201610251955 A CN 201610251955A CN 105836750 A CN105836750 A CN 105836750A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/124—Preparation of adsorbing porous silica not in gel form and not finely divided, i.e. silicon skeletons, by acidic treatment of siliceous materials
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—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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- 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
- C01P2004/34—Spheres hollow
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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Abstract
The invention discloses a preparation method of magnetic nano-silica hollow spheres. According to the preparation method, magnetic silica nanoparticles are synthesized by taking high-paramagnetism oily ferroferric oxide as a core and cheap tetraethyl orthosilicate as a silicon source through a miniemulsion method, and the simple chemical treatment is carried out to remove partial ferroferric oxide, so as to form magnetic silica hollow spheres. The silica hollow spheres prepared by virtue of the preparation method have good dispersibility and stability, are uniform in size and relatively small in particle sizes and are not obviously agglomerated; and furthermore, the preparation method is simple, the operability is relatively good, and the particle sizes can be controlled within 40nm-60nm.
Description
Technical field
The present invention relates to the preparation method of a kind of hollow silica ball, be specifically related to a kind of nano magnetic silica empty
The preparation method of bulbus cordis, belongs to inorganic silicon field of material preparation.
Background technology
Use the nano ferriferrous oxide particle with superparamagnetism as the core of compound particle, the magnetic two prepared
The advantages such as silicon oxide nanoparticle has thermally and chemically stability, and bio-compatibility is good.By simple method so that answer
Close particle and become hollow granule, it is also possible to make particle keep magnetic, it is simple to recycle.Therefore, nano magnetic silica is empty
Bulbus cordis can be widely used on the fields such as chemical detection, biological medicine, environmental improvement.
According to the literature, synthesizing nano magnetic hollow silica ball has a lot of method, but typically mainly uses template
Synthetic method, template can first be coated on ferroso-ferric oxide, and then silicon dioxide on the Surface coating of template, with heating
Method or the method for solvent corrosion obtain nano magnetic silica hollow ball.It is said that in general, synthetic silica is main
Use sol-gel and the method for miniemulsion.The silicon dioxide particle diameter that the method for collosol and gel is synthesized is relatively big, but synthesis
Time shorter, and Yield compari@is big, and the magnetic silica particle diameter of miniemulsion method synthesis is less, good dispersion, and grain
Footpath can control, but generated time is longer, and yield also ratio is relatively low.By the method for miniemulsion, the nanoparticle being synthesized, two
Silicon oxide is to present stratiform to be wrapped on ferroso-ferric oxide, by simple chemical treatment, removes the four of the interior part of compound particle
Fe 3 O can obtain nano magnetic silica hollow ball, by changing consumption and the acid of solvent of oiliness ferroso-ferric oxide
Basicity, it is also possible to control boring degree and the magnetic of hollow granule.After magnetic silica is made hollow ball, internal
Hollow-core construction significantly increase the using effect of silicon dioxide, environmental improvement can increase silicon dioxide and absorb and have
The amount of machine thing, in biological medicine, can increase the drug loading of medicine, and, magnetic silica hollow ball is also with necessarily
Magnetic, under the effect of externally-applied magnetic field, i.e. can be able to recycle again with displacement to the position specified.
Zhu et al. ((Zhu Y, Fang Y, Kaskel S. Folate-Conjugated Fe3O4@SiO2 Hollow
Mesoporous Spheres for Targeted Anticancer Drug Delivery[J]. Journal of
Physical Chemistry C, 2010,114 (39): 16382-16388.) method) using sol-gel, by system in advance
The ferroso-ferric oxide of standby carbon parcel, as magnetic core, wraps up silicon dioxide on carbon ball surface, in 550 degree of calcinings, removes carbon-coating,
To hollow magnetic silica.Yang et al. (Yang L, Guo Y, Zhan W, et al. One-pot synthesis
of aldehyde-functionalized mesoporous silica-Fe 3 O 4 nanocomposites for
immobilization of penicillin G acylase[J]. Microporous & Mesoporous
Materials, 2014,197 (5): 1-7.) with the addition polymers of Pluronic P123(polypropylene glycol with oxirane) conduct
Template, is first coated on ferroso-ferric oxide, then at the Surface coating silicon dioxide of template, the most in ethanol, and 80 degree of backflows
Remove removing template, obtain hollow silicon dioxide.Above method is when preparing hollow silica ball, and employing is all template
Method, cope match-plate pattern to be added, template to be removed, complex steps, operation easier is relatively big, and particle diameter is between 100-200nm.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of nano magnetic silica hollow ball.
The technical solution realizing the object of the invention is: the preparation method of a kind of nano magnetic silica hollow ball,
Use oiliness nano ferriferrous oxide as magnetic core, with tetraethyl orthosilicate as silicon source, prepare magnetic silica, then
Remove part ferroso-ferric oxide and obtain nano magnetic silica hollow ball, specifically include following steps:
(1) oiliness ferroso-ferric oxide is joined in solvent, ultrasonic disperse；
(2) add triton x-100, hexanol and water, continue ultrasonic disperse；
(3) it is subsequently added silicon source and strong aqua ammonia, reacts under room temperature；
(4) sample obtained is carried out acid treatment.
In step (1), described oiliness ferroso-ferric oxide particle diameter is 5-15nm, and solvent is hexamethylene, and oiliness four aoxidizes three
Ferrum concentration 150-450mg/L in a solvent；The ultrasonic disperse time is more than 30min.
In step (2), the volume integral of described triton x-100, hexanol and water is than for 6:6:1；Oiliness four aoxidizes three
Ferrum is 5:3 mg/ ml with the amount ratio of triton x-100；The continuation ultrasonic disperse time is more than 30min.
In step (3), silicon source is tetraethyl orthosilicate, and oiliness ferroso-ferric oxide is 1:40 mg/ μ with the amount ratio in silicon source
L；Strong aqua ammonia is 7:4 with the volume ratio in silicon source；Response time is more than 24 hours.
In step (4), acid is 55-58wt% dust technology；The temperature of acid treatment is 60-80 DEG C, and the acid treatment time is that 6-18 is little
Time.
Compared with prior art, the invention have the advantage that
(1) preparation method is simple: the present invention need not use template, it is only necessary to removes compound particle interior section ferroso-ferric oxide
Can be obtained by nano magnetic silica hollow ball, method simple practical, operability is preferable, and size controlling is at 40-60nm
Between.
(2) preparation cost is relatively low: the most inexpensively, cost is relatively low for the reagent cost of material used by the present invention.
(3) environmental friendliness: the present invention does not has any poisonous and hazardous material, and whole anti-response environment is the most harmless.
(4) performance is good: product prepared by the present invention may be uniformly dispersed in aqueous solution, and good dispersion, size is equal
One, particle diameter is less, good stability, does not occur significantly reuniting.
(5) purity is higher: the product obtained after reaction all presents obvious hollow-core construction.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the nano magnetic silica hollow ball of embodiment 1.
Fig. 2 is the transmission electron microscope picture of the nano magnetic silica hollow ball of embodiment 2.
Detailed description of the invention
Embodiment 1: weigh 10mg oiliness ferroso-ferric oxide, is scattered in 40mL hexamethylene, after ultrasonic 10min, adds 6mL
Triton x-100,6mL hexanol, 1mL water, the ultrasonic 1h of room temperature, it is then slowly added to 400 μ L tetraethyl orthosilicates, ultrasonic 1h
After, adding 0.7mL ammonia, after normal-temperature reaction 24h, under the rotating speed of 10000 revs/min, centrifugation is collected, then 70
1mL nitric acid, reacting by heating 6 hours, centrifugal collection is added under degree Celsius.The transmission of the nano magnetic silica hollow ball of preparation
Electronic Speculum figure as it is shown in figure 1, nano-particles size is homogeneous, size controlling between 40-60nm, good dispersion.
Embodiment 2: weigh 10mg oiliness ferroso-ferric oxide, is scattered in 40mL hexamethylene, after ultrasonic 10min, adds 6mL
Triton x-100,6mL hexanol, 1mL water, the ultrasonic 1h of room temperature, it is then slowly added to 400 μ L tetraethyl orthosilicates, ultrasonic 1h
After, adding 0.7mL ammonia, after normal-temperature reaction 24h, under the rotating speed of 10000 revs/min, centrifugation is collected, then 70
2mL nitric acid, reacting by heating 12 hours, centrifugal collection is added under degree Celsius.Nano magnetic silica hollow ball saturating of preparation
Radio mirror figure is as shown in Figure 2.
Embodiment 3: weigh 10mg oiliness ferroso-ferric oxide, is scattered in 40mL hexamethylene, after ultrasonic 10min, adds 6mL
Triton x-100,6mL hexanol, 1mL water, the ultrasonic 1h of room temperature, it is then slowly added to 400 μ L tetraethyl orthosilicates, ultrasonic 1h
After, adding 0.7mL ammonia, after normal-temperature reaction 24h, under the rotating speed of 10000 revs/min, centrifugation is collected, then 70
3mL nitric acid, reacting by heating 18 hours, centrifugal collection is added under degree Celsius.
Claims (5)
1. the preparation method of a nano magnetic silica hollow ball, it is characterised in that specifically include following steps:
(1) oiliness ferroso-ferric oxide is joined in solvent, ultrasonic disperse；
(2) add triton x-100, hexanol and water, continue ultrasonic disperse；
(3) it is subsequently added silicon source and strong aqua ammonia, reacts under room temperature；
(4) sample obtained is carried out acid treatment.
2. the preparation method of nano magnetic silica hollow ball as claimed in claim 1, it is characterised in that in step (1),
Described oiliness ferroso-ferric oxide particle diameter is 5-15nm, and solvent is hexamethylene, oiliness ferroso-ferric oxide concentration in a solvent
150-450mg/L；The ultrasonic disperse time is more than 30min.
3. the preparation method of nano magnetic silica hollow ball as claimed in claim 1, it is characterised in that in step (2),
The volume integral of described triton x-100, hexanol and water is than for 6:6:1；Oiliness ferroso-ferric oxide and the use of triton x-100
Amount ratio is 5:3 mg/ ml；The continuation ultrasonic disperse time is more than 30min.
4. the preparation method of nano magnetic silica hollow ball as claimed in claim 1, it is characterised in that in step (3),
Silicon source is tetraethyl orthosilicate, and oiliness ferroso-ferric oxide is 1:40 mg/ μ L with the amount ratio in silicon source；Strong aqua ammonia and the body in silicon source
Long-pending ratio is 7:4；Response time is more than 24 hours.
5. the preparation method of nano magnetic silica hollow ball as claimed in claim 1, it is characterised in that in step (4),
Acid is 55-58wt% dust technology；The temperature of acid treatment is 60-80 DEG C, and the acid treatment time is 6-18 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111394002A (en) * | 2020-03-27 | 2020-07-10 | 宁波华显智能科技有限公司 | Transparent display film containing silicon dioxide hollow spheres and preparation method and application thereof |
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| CN1421455A (en) * | 2002-12-11 | 2003-06-04 | 湖南大学 | Fast DNA extracting and purifying process with shell magnetic nanoscale particle of aminated silica |
| CN101687632A (en) * | 2008-01-10 | 2010-03-31 | 延世大学校产学协力团 | Porous hollow silica n anop articles, preparation method of the silica nanoparticles, and drug carriers and pharmaceutical composition comprising the silica nanoparticles |
| CN101716348A (en) * | 2009-12-07 | 2010-06-02 | 江南大学 | Construction and application of gold-magnetic nanoparticle-based medicament carrying platform |
| KR20120008929A (en) * | 2010-07-21 | 2012-02-01 | 주식회사 나노스페이스 | Preparation of hollow-type metal oxide particle |
| CN102500296A (en) * | 2011-11-04 | 2012-06-20 | 同济大学 | Preparation method for mesoporous silicon oxide hollow microspheres with magnetic nanoparticles embedded in shell layers |
| CN102633265A (en) * | 2012-03-29 | 2012-08-15 | 中国科学院山西煤炭化学研究所 | Preparation method for controllable hollow mesoporous silicon dioxide nanospheres |
| CN104188985A (en) * | 2014-09-11 | 2014-12-10 | 天津市职业大学 | Method for preparing targeted controlled release aspirin powder |
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2016
- 2016-04-21 CN CN201610251955.3A patent/CN105836750A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1421455A (en) * | 2002-12-11 | 2003-06-04 | 湖南大学 | Fast DNA extracting and purifying process with shell magnetic nanoscale particle of aminated silica |
| CN101687632A (en) * | 2008-01-10 | 2010-03-31 | 延世大学校产学协力团 | Porous hollow silica n anop articles, preparation method of the silica nanoparticles, and drug carriers and pharmaceutical composition comprising the silica nanoparticles |
| CN101716348A (en) * | 2009-12-07 | 2010-06-02 | 江南大学 | Construction and application of gold-magnetic nanoparticle-based medicament carrying platform |
| KR20120008929A (en) * | 2010-07-21 | 2012-02-01 | 주식회사 나노스페이스 | Preparation of hollow-type metal oxide particle |
| CN102500296A (en) * | 2011-11-04 | 2012-06-20 | 同济大学 | Preparation method for mesoporous silicon oxide hollow microspheres with magnetic nanoparticles embedded in shell layers |
| CN102633265A (en) * | 2012-03-29 | 2012-08-15 | 中国科学院山西煤炭化学研究所 | Preparation method for controllable hollow mesoporous silicon dioxide nanospheres |
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Non-Patent Citations (1)
| Title |
|---|
| 孙鹏飞等: "生物相容性Fe3O4@SiO2纳米粒子的合成与性能", 《中国组织工程研究与临床康复》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111394002A (en) * | 2020-03-27 | 2020-07-10 | 宁波华显智能科技有限公司 | Transparent display film containing silicon dioxide hollow spheres and preparation method and application thereof |
| CN111394002B (en) * | 2020-03-27 | 2022-04-05 | 宁波华显智能科技有限公司 | Transparent display film containing silicon dioxide hollow spheres and preparation method and application thereof |
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