CN110255573A - A kind of preparation method and application method of silicon dioxide nanosphere - Google Patents
A kind of preparation method and application method of silicon dioxide nanosphere Download PDFInfo
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Abstract
The object of the present invention is to provide a kind of preparation method and application methods of silicon dioxide nanosphere, a kind of preparation method of silicon dioxide nanosphere, using ethyl orthosilicate as silicon source, using double template octadecyltrimethylammonium chloride and tri-n-octyl methyl ammonium chloride as perforating agent, triethylamine is catalyst, hydrophobic organic solvent and water are two-phase system, monodispersed silicon dioxide nanosphere is prepared by sol-gel process, then template is removed by high-temperature calcination, prepares monodisperse silica nanosphere.The silicon dioxide nanosphere of preparation has large specific surface area, larger radioactivity meso-hole structure, to large biological molecule volume containing the sample with higher, to overcome the problems, such as that existing preparation method intermediary pore size is smaller and material is easy to reunite.
Description
Technical field
The present invention relates to a kind of preparation method and application methods of silicon dioxide nanosphere.
Background technique
Metaporous silicon dioxide material, in absorption, is separated, is urged since it is with biggish specific surface area and adsorption capacity
The fields such as change all have a wide range of applications.Especially in the application of Nano medication conveyer system, mesoporous silica nano-particle
Have become the excellent substitute of traditional organic emulsion or liposome.However, mesoporous silicon oxide used in drug delivery process
It is typically limited to molecular drug, because the aperture of prepared mesoporous silica nano-particle is smaller (5 nm of <).But with
Biomedical development, some macromolecular drugs (such as proteins and peptides) be increasingly used in the various diseases of the mankind
Treatment.Therefore, preparing the mesoporous silicon dioxide nano microballoon with large specific surface area and larger aperture has potentially
Application value.
The method for preparing mesoporous silicon dioxide nano microballoon at present is also more mature, and what is be most widely used is soft template
Method.As long as this method passes through sol-gel process using cationic surfactant as template (CN200810202772.8)
The nano silica microsphere with ordered mesopore structure is prepared, this method is more convenient quick, but prepares the aperture of material
Generally less than 3 nm.Bimodulus version method (CN104787768 A) developed in recent years improves material to a certain extent
Aperture, aperture size can reach 6 nm, and keep opening meso-hole structure, but when this method prepares mesoporous microsphere is easily sent out
It is raw to reunite, it needs to be reacted under especially low concentration, should not be mass produced.In order to further increase mesoporous silicon oxide
Aperture size, developed high molecule polymer template (P123, F123 etc.), equally prepared in sol-gel system
Silicon dioxide nanosphere of the aperture within the scope of 6-9 nm, this method operating process is also relatively simple, but with polyphosphazene polymer
Closing object is the surface that the mesoporous channel that template prepares is generally parallel to core microballoon, and this arrangement reduces materials in absorption
Effective ratio area, reduce the adsorption efficiency of material, increase absorption cost.
The nanometer with high specific surface area and larger meso-hole structure is prepared in oil water two phase system using bimodulus version method
Silicon dioxide microsphere, while guaranteeing has larger meso-hole structure, specific surface area also with higher can be improved effectively
Volume containing the sample of the material in absorption, is particularly suitable for the absorption to large biological molecule.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application method of silicon dioxide nanosphere, the dioxies of preparation
SiClx nanosphere has large specific surface area, larger radioactivity meso-hole structure, to large biological molecule volume containing the sample with higher,
To overcome the problems, such as that existing preparation method intermediary pore size is smaller and material is easy to reunite.
The present invention realizes that process is as follows: a kind of preparation method of silicon dioxide nanosphere, using ethyl orthosilicate as silicon source,
Using double template octadecyltrimethylammonium chloride and tri-n-octyl methyl ammonium chloride as perforating agent, triethylamine is catalyst, hydrophobic
Property organic solvent and water be two-phase system, monodispersed silicon dioxide nanosphere is prepared by sol-gel process, then
Template is removed by high-temperature calcination, prepares monodisperse silica nanosphere.
Double template hexadecyltrimethylammonium chloride and tri-n-octyl methyl ammonium chloride are added to the water dissolution, it is completely molten
The hydrophobic organic solvent for being dispersed with ethyl orthosilicate is added to reaction system after solution, catalyst of triethylamine is then added,
It is continuously stirred at 60 DEG C~80 DEG C, after reaction, cleaning product is dry by gained cleaning product, then will be after drying
Sample is placed in Muffle furnace, calcines 8 hours~14 hours at 550 DEG C~700 DEG C to get micro- to silica nanometer
Ball.
The molar ratio 1: 0.1~1: 1 of template hexadecyltrimethylammonium chloride and tri-n-octyl methyl ammonium chloride.
The molar ratio of triethylamine and ethyl orthosilicate is 1: 9.After catalyst of triethylamine is added, at 60 DEG C~80 DEG C
Under continuously stir 10 hours~15 hours, mixing speed be the rpm of 100 rpm~300；By gained cleaning product 90
DEG C~110 DEG C at dry 13 hours.
The molar ratio 4: 1 of hexadecyltrimethylammonium chloride and tri-n-octyl methyl ammonium chloride, triethylamine and positive silicic acid second
The molar ratio of ester is 1: 9；After catalyst of triethylamine is added, continuously stirred at 60 DEG C 12 hours, mixing speed is
The rpm of 100 rpm~300, the cleaning product by way of centrifugation, by gained cleaning product, drying 13 is small at 100 DEG C
When, the sample after drying is placed in Muffle furnace, is calcined 13 hours at 600 DEG C.
The hydrophobic organic solvent for being dispersed with ethyl orthosilicate is hexamethylene, toluene, tridecane, the 18 non-poles such as dilute
At least one of property organic solvent.
The application method of the silicon dioxide nanosphere of preparation, the silicon dioxide microsphere of preparation is through octadecyl trichlorosilane alkane
It is modified, large biological molecule can be adsorbed.
Octadecyl trichlorosilane alkane is to the method for modifying of silicon dioxide microsphere, first to the silicon dioxide microsphere of preparation into
Row acid processing, microballoon is distributed in the hydrochloric acid of 6 mol/L, is flowed back 4 hours at 125 DEG C, naturally cold after reaction
But, then with distilled water, for cleaning product to neutrality, the product after washing is 14 hours dry at 120 DEG C, then will repeatedly
Silicon dioxide microsphere after drying is distributed in dry toluene, octadecyl trichlorosilane alkane is added, then in 123 °C of oil baths
Middle reflux 12 hours；After the reaction was completed, it is filtered, is successively washed respectively with dry toluene, acetone and methanol, 100
°C dry 13 hours.
Preparation method of the invention combines double-template method and Two Liquid Phases method, using ethyl orthosilicate as silicon source, hybrid guided mode
Plate agent is perforating agent, and triethylamine is catalyst, is prepared out by Two Liquid Phases method with high-specific surface area and larger meso-hole structure
Full porous silicon dioxide nano microballoon, such as the silicon dioxide microsphere specific surface area of preparation are 589.5 m2·g-1When average pore size be
18.4 nm.Preparation method of the invention is by adjusting the proportion of mixed templates come the aperture of controlled material, porosity and grain
Diameter can be realized the controllability in material particle size and aperture in a certain range.Organic phase in double liquid phase system is able to enter
Increase the partial size of surfactant micellar inside surfactant, it is final to realize further increasing for material mesopore size.Its
Secondary, the hydrolytic condensation process of ethyl orthosilicate only carries out at the interface of water phase and an oil phase in double liquid phase system, can effectively control in this way
The rate for making reaction, avoids secondary nucleation and agglomeration traits, improves the monodispersity of material.Two Liquid Phases and water in the application
Oily two-phase refers to water and organic solvent.
The silicon dioxide nanosphere of high-specific surface area prepared by the present invention and larger meso-hole structure can be applied to biological big
The absorption of molecule, specifically that the mesoporous silicon dioxide micro-sphere of preparation is modified through octadecyl trichlorosilane alkane (ODS), static state is inhaled
Its in adhesion test test is 325.6 mg/g to the maximal absorptive capacity of large biological molecule BSA.Mesoporous dioxy prepared by the present invention
SiClx nanosphere, while guaranteeing biggish aperture size, and specific surface area with higher, it is particularly suitable for biological big
The absorption of molecule can effectively improve material volume containing the sample.
Beneficial effects of the present invention:
1, the present invention is prepared using double-template method with larger meso-hole structure and high specific surface area in double liquid phase system
Full porous nano silica microballoon, establishes a kind of new method for preparing high-specific surface area macroporous silica nanosphere,
Obtained nanosphere has good monodispersity.The preparation method simple process, easy to spread and amplification；
2, the aperture size of nano silica microsphere, tricaprylmethyl chlorination are adjusted by changing the ratio of mixed templates
The molar ratio of ammonium and hexadecyltrimethylammonium chloride from 0.1: 1~when increasing to 1: 1, aperture size is presented first increase after
Reduced trend realizes that aperture is adjustable within the scope of 2.4 ~ 18.4 nm, but the partial size of silicon dioxide microsphere is with trioctylphosphine first
The increase of ammonium chloride molar ratio and increase, realize silicon dioxide microsphere average grain diameter can within the scope of 29 ~ 130.5 nm
Control；
3, the mesoporous silicon dioxide nano microballoon prepared by the present invention has larger while guaranteeing biggish meso-hole structure
Specific surface area, material can be effectively improved to the adsorbance of large biological molecule；
5, the mesoporous silicon dioxide micro-sphere of the method for the present invention preparation has the monodispersity of height, and preparation process is simple, condition temperature
With easily controllable and amplification.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of meso-porous nano silicon dioxide microsphere prepared by the present invention；
Fig. 2 is the transmission electron microscope picture of meso-porous nano silicon dioxide microsphere prepared by the present invention；
Fig. 3 is the graph of pore diameter distribution of meso-porous nano silicon dioxide microsphere prepared by the present invention；
Fig. 4 is the N2 absorption De contamination isollaothermic chart of meso-porous nano silicon dioxide microsphere prepared by the present invention；
Adsorption curve of the modified meso-porous nano silicon dioxide microsphere of Fig. 5 to BSA.
Specific embodiment
Below by way of example, the invention will be further described.
One, the preparation of the mesoporous silicon dioxide nano microballoon of high-specific surface area.
A kind of preparation method of silicon dioxide nanosphere, using ethyl orthosilicate as silicon source, with double template octadecyl
Trimethyl ammonium chloride and tri-n-octyl methyl ammonium chloride are perforating agent, and triethylamine is catalyst, and hydrophobic organic solvent and water are two
Phase system prepares monodispersed silicon dioxide nanosphere by sol-gel process, then removes mould by high-temperature calcination
Monodisperse silica nanosphere is prepared in plate agent.
Embodiment 1
A kind of preparation method of silicon dioxide nanosphere: weighing 1.3 g TCMAC respectively and 10.7 g CTAC are distributed to
In 120 mL water, 8 mL ethyl orthosilicates and 32 mL 1- octadecylenes are then added reaction system after mixing, 150
It is reacted 10 minutes under rpm, the triethylamine of 0.4 g of addition, mechanical stirring 12 hours at 60 DEG C.After reaction, it mixes
Solution is closed to be centrifuged 20 minutes at 10000 rpm.Then by obtained precipitating with ethyl alcohol centrifuge washing 3 times, 100 DEG C
Lower drying 13 hours, drying are moved back into Muffle furnace, are calcined 13 hours at 600 DEG C.Monodisperse mesoporous nanometer can be obtained
Silicon dioxide microsphere.Material is characterized using aperture and specific surface area analysis instrument, average pore size is 4.7 nm, compares table
Area is 667.2 m2·g-1, porosity is 0.81 cm3·g-1.Pass through the average grain diameter of dynamic light scattering test material
For 29 nm.
Embodiment 2
A kind of preparation method of silicon dioxide nanosphere: weighing 2.8 g TCMAC respectively and 9.2 g CTAC are distributed to
In 120 mL water, 8 mL ethyl orthosilicates and 32 mL 1- octadecylenes are then added reaction system after mixing, 150
It is reacted 10 minutes under rpm, the triethylamine of 0.4 g of addition, mechanical stirring 12 hours at 60 DEG C.After reaction, it mixes
Solution is closed to be centrifuged 20 minutes at 10000 rpm.Then by obtained precipitating with ethyl alcohol centrifuge washing 3 times, 100 DEG C
Lower drying 13 hours, drying are moved back into Muffle furnace, are calcined 13 hours at 600 DEG C.Monodisperse mesoporous nanometer can be obtained
Silicon dioxide microsphere.Material is characterized using aperture and specific surface area analysis instrument, average pore size is 7.5 nm, compares table
Area is 658.5 m2·g-1, porosity is 0.27 cm3·g-1.Pass through the average grain diameter of dynamic light scattering test material
For 56.3 nm.
Embodiment 3
A kind of preparation method of silicon dioxide nanosphere: 4.5 g TCMAC and 7.5g CTAC are weighed respectively and are distributed to
In 120 mL water, 8 mL ethyl orthosilicates and 32 mL 1- octadecylenes are then added reaction system after mixing, 150
It is reacted 10 minutes under rpm, the triethylamine of 0.4 g of addition, mechanical stirring 12 hours at 60 DEG C.After reaction, it mixes
Solution is closed to be centrifuged 20 minutes at 10000 rpm.Then by obtained precipitating with ethyl alcohol centrifuge washing 3 times, 100 DEG C
Lower drying 13 hours, drying are moved back into Muffle furnace, are calcined 13 hours at 600 DEG C.Monodisperse mesoporous nanometer can be obtained
Silicon dioxide microsphere.Material is characterized using aperture and specific surface area analysis instrument, average pore size is 18.4 nm, compares table
Area is 589.5 m2·g-1, porosity is 1.27 cm3·g-1.Pass through the average grain diameter of dynamic light scattering test material
For 82.9 nm.Material morphology is shown in Fig. 1 and Fig. 2, and pore-size distribution and specific surface area are shown in Fig. 3 and Fig. 4 respectively.
Embodiment 4
A kind of preparation method of silicon dioxide nanosphere: weighing 5.8 g TCMAC respectively and 6.2 g CTAC are distributed to
In 120 mL water, 8 mL ethyl orthosilicates and 32 mL 1- octadecylenes are then added reaction system after mixing, 150
It is reacted 10 minutes under rpm, the triethylamine of 0.4 g of addition, mechanical stirring 12 hours at 60 DEG C.After reaction, it mixes
Solution is closed to be centrifuged 20 minutes at 10000 rpm.Then by obtained precipitating with ethyl alcohol centrifuge washing 3 times, 100 DEG C
Lower drying 13 hours, drying are moved back into Muffle furnace, are calcined 13 hours at 600 DEG C.Monodisperse mesoporous nanometer can be obtained
Silicon dioxide microsphere.Material is characterized using aperture and specific surface area analysis instrument, average pore size is 2.4 nm, compares table
Area is 719.1 m2·g-1, porosity is 0.46 cm3·g-1.Pass through the average grain diameter of dynamic light scattering test material
For 106.3 nm.
Embodiment 5
A kind of preparation method of silicon dioxide nanosphere: weighing 6.6 g TCMAC respectively and 5.4 g CTAC are distributed to
In 120 mL water, 8 mL ethyl orthosilicates and 32 mL 1- octadecylenes are then added reaction system after mixing, 150
It is reacted 10 minutes under rpm, the triethylamine of 0.4 g of addition, mechanical stirring 12 hours at 60 DEG C.After reaction, it mixes
Solution is closed to be centrifuged 20 minutes at 10000 rpm.Then by obtained precipitating with ethyl alcohol centrifuge washing 3 times, 100 DEG C
Lower drying 13 hours, drying are moved back into Muffle furnace, are calcined 13 hours at 600 DEG C.Monodisperse mesoporous nanometer can be obtained
Silicon dioxide microsphere.Material is characterized using aperture and specific surface area analysis instrument, average pore size is 2.3 nm, compares table
Area is 619.8 m2·g-1, porosity is 0.36 cm3·g-1.Pass through the average grain diameter of dynamic light scattering test material
For 130.5 nm.
Embodiment 6
A kind of preparation method of silicon dioxide nanosphere: 4.5 g TCMAC and 7.5g CTAC are weighed respectively and are distributed to
In 120 mL water, reaction system, 150 rpm are then added in 8 mL ethyl orthosilicates and 32 mL toluene after mixing
Lower reaction 10 minutes, is added the triethylamine of 0.4 g, mechanical stirring 12 hours at 60 DEG C.After reaction, it mixes molten
Liquid is centrifuged 20 minutes at 10000 rpm.Then obtained precipitating is done at ethyl alcohol centrifuge washing 3 times, 100 DEG C
Dry 13 hours, drying was moved back into Muffle furnace, was calcined 13 hours at 600 DEG C.Monodisperse mesoporous nano-silica can be obtained
SiClx microballoon.Average grain diameter by dynamic light scattering test material is 83 nm.Utilize aperture and specific surface area analysis instrument
Material is characterized, average pore size is 13.2 nm, and specific surface area is 612.5 m2·g-1, porosity 1.31
cm3·g-1。
Embodiment 7
A kind of preparation method of silicon dioxide nanosphere: 4.5 g TCMAC and 7.5g CTAC are weighed respectively and are distributed to
In 120 mL water, reaction system, 150 rpm are then added in 8 mL ethyl orthosilicates and 32 mL hexamethylenes after mixing
Lower reaction 10 minutes, is added the triethylamine of 0.4 g, mechanical stirring 12 hours at 60 DEG C.After reaction, it mixes molten
Liquid is centrifuged 20 minutes at 10000 rpm.Then obtained precipitating is done at ethyl alcohol centrifuge washing 3 times, 100 DEG C
Dry 13 hours, drying was moved back into Muffle furnace, was calcined 13 hours at 600 DEG C.Monodisperse mesoporous nano-silica can be obtained
SiClx microballoon.Average grain diameter by dynamic light scattering test material is 82.5 nm.Utilize aperture and specific surface area analysis
Instrument characterizes material, and average pore size is 7.2 nm, and specific surface area is 622.3 m2·g-1, porosity 1.37
cm3·g-1。
The preparation method of silicon dioxide nanosphere can also be by the operation of following embodiment:
Embodiment 8
A kind of preparation method of silicon dioxide nanosphere: 5.5 g TCMAC and 7.5g CTAC are weighed respectively and are distributed to
In 120 mL water, reaction system, 100 rpm are then added in 8 mL ethyl orthosilicates and 32 mL tridecanes after mixing
Lower reaction 10 minutes, is added the triethylamine of 0.4 g, mechanical stirring 10 hours at 80 DEG C.After reaction, it mixes molten
Liquid is centrifuged 20 minutes at 10000 rpm.Then by the drying at ethyl alcohol centrifuge washing 3 times, 90 DEG C of obtained precipitating
13 hours, drying was moved back into Muffle furnace, was calcined 14 hours at 550 DEG C.Monodisperse mesoporous nanometer titanium dioxide can be obtained
Silicon microballoon.
Embodiment 9
A kind of preparation method of silicon dioxide nanosphere: weighing 5 g TCMAC respectively and 7 g CTAC are distributed to 120
In mL water, 8 mL ethyl orthosilicates and 32 mL hexamethylenes are then added reaction system after mixing, under 300 rpm
It reacts 10 minutes, the triethylamine of 0.4 g of addition, mechanical stirring 15 hours at 70 DEG C.After reaction, mixed solution
It is centrifuged 20 minutes at 10000 rpm.Then by the drying at ethyl alcohol centrifuge washing 4 times, 110 DEG C of obtained precipitating
13 hours, drying was moved back into Muffle furnace, calcines 8 hours at 700 DEG C, monodisperse mesoporous nano silica can be obtained
Microballoon.
Embodiment 10
A kind of preparation method of silicon dioxide nanosphere: weighing 4 g TCMAC respectively and 8 g CTAC are distributed to 120
In mL water, reaction system, 200 rpm are then added in 8 mL ethyl orthosilicates and 32 mL 1- octadecylenes after mixing
Lower reaction 13 minutes, is added the triethylamine of 0.4 g, mechanical stirring 12 hours at 70 DEG C.After reaction, it mixes molten
Liquid is centrifuged 20 minutes at 10000 rpm.Then obtained precipitating is done at ethyl alcohol centrifuge washing 4 times, 110 DEG C
Dry 13 hours, drying was moved back into Muffle furnace, calcines 10 hours at 650 DEG C, monodisperse mesoporous nano-silica can be obtained
SiClx microballoon.
Two, application of the high-specific surface area macroporous silica nanosphere in large biological molecule BSA absorption
(1) C18 modifies meso-porous titanium dioxide silicon matrix
Acid processing activation is carried out to nano silica microsphere first, to improve the silicone hydroxyl density on silicon dioxide microsphere surface.
Microballoon is distributed to first in the hydrochloric acid of 6 mol/L, is flowed back 4 hours at 125 DEG C, after reaction natural cooling, then with steaming
For cleaning product to neutrality, the product after washing is 14 hours dry at 120 DEG C repeatedly for distilled water.Next to silicon dioxide microsphere
Surface has carried out C18 (octadecyl trimethyl silane) and has been modified, and the silicon dioxide microsphere after weighing 1 g drying is distributed to nothing
In water-toluene, 1 mL octadecyl trichlorosilane alkane is added, is then warming up to 123 DEG C and flows back 12 hours.After the reaction was completed,
It is filtered with G5 sand core funnel, successively respectively with 50 mL dry toluenes, acetone and methanol are washed, 100 DEG C of dryings
13 hours.
(2) C18 modifies mesoporous silicon oxide to the absorption property of BSA
Mesoporous silicon oxide after weighing 50 mg C18 modification is added in 100 mL centrifuge tubes, and 35 mL, 500 ug/ is added
ML BSA protein solution and 15 mL acetonitriles, are put into constant-temperature table concussion, take out centrifugation sampling at regular intervals, take every time
Then 1.5 mL coloring agents are added in 0.5 mL of sample.Its concentration, Detection wavelength are tested using ultraviolet specrophotometer are as follows: 595
nm.Adsorbance is calculated by formula 1.
(1)q t For mesoporous silicon oxide to BSA in adsorbance (mg/g) sometime,C 0 WithCeRespectively BSA's
Concentration (mg/L) after initial concentration and adsorption equilibrium,VIt is the volume (L) of solution,mIt is the quality of mesoporous silicon oxide
(g).Test result is shown in that Fig. 5, maximal absorptive capacity are 325.6 mg/g.
Sample time such as following table table 1:
Table 1
What has been described above is only a preferred embodiment of the present invention, it is noted that for those skilled in the art, not
It is detached under the premise of general idea of the present invention, several changes and improvements can also be made, these also should be considered as protection of the invention
Range.
Claims (9)
1. a kind of preparation method of silicon dioxide nanosphere, it is characterised in that: using ethyl orthosilicate as silicon source, with double template
Octadecyltrimethylammonium chloride and tri-n-octyl methyl ammonium chloride are perforating agent, and triethylamine is catalyst, hydrophobic organic solvent
It is two-phase system with water, monodispersed silicon dioxide nanosphere is prepared by sol-gel process, is then forged by high temperature
Burn off removes template, prepares monodisperse silica nanosphere.
2. the preparation method of silicon dioxide nanosphere according to claim 1, it is characterised in that: by double template 16
Alkyl trimethyl ammonium chloride and tri-n-octyl methyl ammonium chloride are added to the water dissolution, and ethyl orthosilicate will be dispersed with after being completely dissolved
Hydrophobic organic solvent be added to reaction system, catalyst of triethylamine is then added, is continuously stirred at 60 DEG C~80 DEG C
It mixes, after reaction, cleaning product is dry by gained cleaning product, the sample after drying is then placed in Muffle furnace,
8 hours~14 hours are calcined at 550 DEG C~700 DEG C to get silicon dioxide nanosphere is arrived.
3. the preparation method of silicon dioxide nanosphere according to claim 2, it is characterised in that: template cetyl
The molar ratio 1: 0.1~1: 1 of trimethyl ammonium chloride and trimethyloctyl ammonium chloride.
4. the preparation method of silicon dioxide nanosphere according to claim 2, it is characterised in that: triethylamine and positive silicic acid
The molar ratio of ethyl ester is 1: 9.
5. the preparation method of silicon dioxide nanosphere according to claim 2, it is characterised in that: three second of catalyst is added
It after amine, is continuously stirred at 60 DEG C~80 DEG C 10 hours~15 hours, mixing speed is 100 rpm~300
rpm；Gained cleaning product is 13 hours dry at 90 DEG C~110 DEG C.
6. the preparation method of the silicon dioxide nanosphere according to claim 2, it is characterised in that: cetyl front three
The molar ratio of the molar ratio 4: 1 of ammonium chloride and tri-n-octyl methyl ammonium chloride, triethylamine and ethyl orthosilicate is 1: 9；
After catalyst of triethylamine is added, being continuously stirred at 60 DEG C 12 hours, mixing speed is the rpm of 100 rpm~300,
The cleaning product by way of centrifugation, gained cleaning product is 13 hours dry at 100 DEG C, by the sample after drying
It is placed in Muffle furnace, is calcined 13 hours at 600 DEG C.
7. the preparation method of silicon dioxide nanosphere according to claim 1, it is characterised in that: described to be dispersed with positive silicon
The hydrophobic organic solvent of acetoacetic ester is hexamethylene, toluene, tridecane, at least one in 18 non-polar organic solvents such as dilute
Kind.
8. the application method of the silicon dioxide nanosphere prepared according to claim 1, it is characterised in that: the silica of preparation
Microballoon is modified through octadecyl trichlorosilane alkane, can adsorb to large biological molecule.
9. according to the application method of silicon dioxide nanosphere prepared by claim 8, it is characterised in that: octadecyl trichlorosilane
Alkane is to carry out sour processing to the silicon dioxide microsphere of preparation first, microballoon is distributed to the method for modifying of silicon dioxide microsphere
In the hydrochloric acid of 6 mol/L, flow back 4 hours at 125 DEG C, natural cooling, is then washed with distilled water repeatedly after reaction
Product is to neutrality, and the product after washing is 14 hours dry at 120 DEG C, then by the silicon dioxide microsphere after drying point
It is scattered in dry toluene, octadecyl trichlorosilane alkane is added, then flows back 12 hours in 123 °C of oil baths；Reaction is completed
Afterwards, filtered, successively washed respectively with dry toluene, acetone and methanol, 100 °C drying 13 hours.
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