CN104587471A - Functional hollow mesoporous SiO2 nanometer composite material and preparation method thereof - Google Patents
Functional hollow mesoporous SiO2 nanometer composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a functional hollow mesoporous SiO2 nanometer composite material and a preparation method thereof. The preparation method of the invention is characterized by comprising the following steps: (1) preparing hollow ordered mesoporous nanometer materials of even particle diameters and fine dispersibilities by combined use of a co-precipitation method and a sol-gel method; (2) using CTAB as surfactant to enable formation of an ordered mesoporous silicon dioxide layer so that not only a larger surface area for leading in a large number of functional micellae is provided, but also larger pore diameters for absorbing and packaging biomolecules are provided; (3) synthesizing hollow ordered mesoporous structural nanometer composite materials of various sizes by altering reactant qualities and crystal growth time. The method of the invention has simple and easy experimentation and the experimental method is easy for manufacturing and promotion. According to the invention, the functional hollow mesoporous SiO2 nanometer composite material of the invention emits strong conversion fluorescence under 980nm stimulating luminesce so that the functional hollow mesoporous SiO2 nanometer composite material can be used in detections of drug slow-release process and curative effect.
Description
Technical field
What the present invention relates to is a kind of nano composite material, the present invention also relates to a kind of preparation method of nano composite material.Relate in particular to a kind of Y
2o
3: the coated hollow mesoporous SiO of Yb, Er
2nano composite material and preparation method thereof.
Background technology
To control medicament slow release be most important and one of the research field having most captivation, and for controlling medicament storage capacity and its release rate, carrier is most critical.Last decade, this research has obtained great raising, and in drug controlled release system, a large amount of organic systems has carried out certain scientific experiments research as new drug carrier, such as micelle, liposomes and polymer.But they have various use limitation, such as poor heat stability and chemical stability, fast decoupled etc. in immune system.
Have large surface area, the mesoporous material of ordered mesopore structure is one of most important carrier material, not only aperture and pore volume have adjustability, and the surface nature of modification is also conducive to bioactive molecule and is embedded in structure, for the diffusion after these molecules provides passage.Hollow mesoporous silica spheres has high memory capacity due to hollow-core construction on the one hand, and on the other hand, the hollow ball having mesoporous layer, compared with traditional solid layer hollow ball, presents good advantage in extensive diffusion and transport.In addition Metaporous silicon dioxide material has good biocompatibility, stable selectivity and nontoxic, and it can be degraded to Si (OH) in health
4, Si (OH)
4excrete by kidney, therefore hollow mesoporous silicon oxide receives increasing attention in medicament slow release, and is widely used as adjuvant in pharmaceutical technology.At Progress in Biochemistry and Biophysics magazine, within 2013, the 40th phase the 10th scrolling code is 1014 ~ 1022, be entitled as the preparation of the mesoporous silicon-dioxide-substrate medicine-carried system described in multifunctional nano drug delivery system progress one literary composition based on mesoporous silicon oxide, but it exists the problems such as particle diameter is uneven, dispersibility is bad, limit its application in pharmaceutical technology.
Summary of the invention
An object of the present invention is to provide a kind of hollow mesoporous SiO of functionalization with uniform particle sizes, favorable dispersibility
2nano composite material; Two of object of the present invention is to provide the hollow mesoporous SiO of a kind of functionalization
2the preparation method of nano composite material.
The hollow mesoporous SiO of functionalization of the present invention
2the chemical expression of nano composite material is:
Y
2O
3:Yb,Er@mSiO
2
The hollow mesoporous SiO of functionalization of the present invention
2the preparation method of nano composite material is:
(1) hydro-thermal method is adopted to prepare carbon ball: to be dissolved in by 3g ~ 8g glucose in 30mL ~ 32mL water, join in reactor, 5h ~ 8h is reacted at 160 DEG C ~ 180 DEG C, after reaction terminates, naturally cool to room temperature, respectively wash once with water and dehydrated alcohol, dry 4h ~ 12h at 60 DEG C ~ 80 DEG C, obtain carbon ball;
(2) coprecipitation coating fluorescent powder presoma is utilized on carbon ball surface: by 0.05g ~ 0.2g carbon ball ultrasonic 10min in 25mL ~ 30mL water, add 1840 μ L 0.5mol/L Yttrium trinitrates, 200 μ L 0.1mol/L Ytterbium(III) nitrate .s and 200 μ L 0.05mol/L Nitrate Solution successively, add 3.0g ~ 4.0g carbamide again, 2h ~ 8h is reacted in the water-bath of 75 DEG C ~ 95 DEG C, reaction terminates to carry out centrifugalize, washing and drying to product afterwards, obtain the nucleocapsid structure powder at carbon ball Surface coating subcarbonate, be expressed as C@Y (OH) CO
3: Yb, Er;
(3) sol-gel process is utilized to prepare hollow-core construction meso-porous nano composite: the nucleocapsid structure powder of 0.05g ~ 0.2g carbon ball Surface coating subcarbonate, ultrasonic agitation 10min in 20mL ~ 25mL water, add 50mL ~ 70mL water, 50mL ~ 70mL dehydrated alcohol, 0.8mL ~ 1.2mL strong aqua ammonia and 0.2g ~ 0.4g cetyl trimethyl ammonium bromide successively, finally dropwise drip 100 μ L ~ 200 μ L ethyl orthosilicates, centrifugal after vigorous stirring 5h under room temperature ~ 7h, washing also drying, obtain the presoma of composite, be expressed as C@Y (OH) CO
3: Yb, Er@mSiO
2– CTAB, roasting 3h in 800 DEG C of Muffle furnaces, obtains Y
2o
3: the coated hollow mesoporous SiO of Yb, Er
2nano composite material, is expressed as Y
2o
3: Yb, Er@mSiO
2.
The present invention can also comprise:
1, the reaction temperature of described hydro-thermal method is 180 DEG C, and the response time is 5h.
2, described coprecipitation is at carbon ball template Surface coating fluorescent material presoma, and 0.1g carbon ball is ultrasonic in 25mL water.
3, described sol-gel process prepares hollow-core construction meso-porous nano composite, 0.05g precursor powder, ultrasonic agitation 10min in 20mLmL water, add 60mL water, 60 dehydrated alcohol, 1mL strong aqua ammonia and 0.2g cetyl trimethyl ammonium bromide successively, finally dropwise drip 170 μ L ethyl orthosilicates, vigorous stirring 6h under room temperature.
The advantage that the present invention has is:
The present invention adopts coprecipitation and sol-gal process to combine the Y preparing hollow shell structure
2o
3: Yb, Er@mSiO
2nano composite material.This composite inner has cavity structure, can be used for storing high amount of drug molecule.Material surface has one deck meso-porous titanium dioxide silicon layer, the internal cavities of material and external environment condition can be made to be communicated with one another by mesopore orbit, can realize inside and outside mass exchange.In addition, mesoporous silicon oxide duct itself also can store high amount of drug molecule, is a kind of good slow releasing carrier of medication material.Under 980nm exciting light, send strong up-conversion fluorescence, can be used for the detection of medicament slow release process and curative effect.All can not produce toxic products environmental protection in actual production process, and raw material is cheap, production process is simple, is easy to actual production.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram before and after sample roasting;
Fig. 2 A is TEM photo and the HRTEM photo of carbon ball;
Fig. 2 B is C@Y (OH) CO
3: the TEM photo of Yb, Er and HRTEM photo;
Fig. 2 C is C@Y (OH) CO
3: Yb, Er@mSiO
2the TEM photo of – CTAB and HRTEM photo;
Fig. 2 D is hollow Y
2o
3: the TEM photo of Yb, Er and HRTEM photo;
Fig. 2 E is hollow Y
2o
3: Yb, Er@mSiO
2tEM photo and HRTEM photo;
Fig. 2 F is hollow Y
2o
3: Yb, Er@mSiO
2the HRTEM photo of sample;
Fig. 3 A is Y
2o
3: the adsorption/desorption isotherms of Yb, Er;
Fig. 3 B is hollow Y
2o
3: Yb, Er@mSiO
2adsorption/desorption isotherms;
Fig. 4 A is Y
2o
3: the pore size distribution curve of Yb, Er;
Fig. 4 B is hollow Y
2o
3: Yb, Er@mSiO
2pore size distribution curve;
Fig. 5 A is hollow Y
2o
3: the Up-conversion emission spectrogram of Yb, Er;
Fig. 5 B is hollow Y
2o
3: Yb, Er@mSiO
2up-conversion emission spectrogram;
Fig. 6 is hollow Y
2o
3: Yb, Er@mSiO
2the elution profiles of – DOX sample.
Detailed description of the invention
For a better understanding of the present invention, below by embodiment, the present invention will be described in more detail.
Embodiment 1:
(1) Hydrothermal Synthesis carbon ball template agent is adopted.Accurately taking 3g glucose is dissolved in 30mL distilled water, rapid stirring forms supernatant liquid, then transfer in the sealable politef reactor of 40mL respectively, baking oven reactor being placed in simultaneously 160 DEG C again reacts 5h, reaction terminates rear reactor and naturally cools to room temperature, obtains black and purple product.Respectively wash once with distilled water and dehydrated alcohol, dry more than 4h at 60 DEG C.
(2) adopt coprecipitation at carbon ball template Surface coating fluorescent material presoma.Specific experiment step is as follows: the carbon ball of precise 0.05g, and ultrasonic disperse is in 25mL distilled water.Then Y (the NO of 0.5mol/L is added successively
3)
3, 0.1mol/L Yb (NO
3)
3with the Er (NO of 0.05mol/L
3)
3the each 1840 μ L of solution, 200 μ L and 200 μ L, then add 3.0g carbamide.Said mixture is proceeded to reacting by heating 2h in the water-bath of 75 DEG C.Reaction terminates to carry out centrifugalize, washing and drying to product afterwards.
(3) precise 0.05g C@Y (OH) CO3:Yb, Er powder, and ultrasonic disperse is in 20mL distilled water, carries out Quick mechanical stirring.Meanwhile, add 70mL distilled water, 50mL dehydrated alcohol, 0.8mL strong aqua ammonia and 0.3g cetyl trimethyl ammonium bromide (CTAB) successively, last slowly dropping 100 μ L ethyl orthosilicates.Centrifugal after vigorous stirring 5h under room temperature, washing also drying, obtains the presoma of composite, is expressed as C@Y (OH) CO3:Yb, Er@mSiO2 – CTAB.By above-mentioned presoma roasting 3h in 800 DEG C of Muffle furnaces, on high-temperature roasting removable carbon ball template, formation, conversion nano crystalline substance also removes mesoporous template, the multi-functional mesoporous nano composite material of final acquisition hollow-core construction.
Embodiment 2:
(1) Hydrothermal Synthesis carbon ball template agent is adopted.Accurately taking 8g glucose is dissolved in 32mL distilled water, rapid stirring forms supernatant liquid, then transfer in the sealable politef reactor of 40mL respectively, baking oven reactor being placed in simultaneously 180 DEG C again reacts 8h, reaction terminates rear reactor and naturally cools to room temperature, obtains black and purple product.Respectively wash once with distilled water and dehydrated alcohol, at 60 DEG C, dry 10h.
(2) adopt coprecipitation at carbon ball template Surface coating fluorescent material presoma.Specific experiment step is as follows: the carbon ball of precise 0.05g, and ultrasonic disperse is in 25mL distilled water.Then Y (the NO of 0.5mol/L is added successively
3)
3, 0.1mol/L Yb (NO
3)
3with the Er (NO of 0.05mol/L
3)
3the each 1840 μ L of solution, 200 μ L and 200 μ L, then add 4.0g carbamide.Said mixture is proceeded to reacting by heating 8h in the water-bath of 95 DEG C.Reaction terminates to carry out centrifugalize, washing and drying to product afterwards.
(3) adopt sol-gel process at C@Y (OH) CO
3: Yb, Er Surface coating meso-porous titanium dioxide silicon layer, the multi-functional mesoporous nano composite material of preparation hollow-core construction.Specific experiment content is as follows: precise 0.2g C@Y (OH) CO
3: Yb, Er powder, and ultrasonic disperse is in 25mL distilled water, carries out Quick mechanical stirring.Meanwhile, add 50mL distilled water, 70mL dehydrated alcohol, 1.2mL strong aqua ammonia and 0.4g cetyl trimethyl ammonium bromide (CTAB) successively, last slowly dropping 200 μ L ethyl orthosilicates.Centrifugal after vigorous stirring 7h under room temperature, washing also drying, obtains the presoma of composite.By above-mentioned presoma roasting 3h in 800 DEG C of Muffle furnaces, on high-temperature roasting removable carbon ball template, formation, conversion nano crystalline substance also removes mesoporous template, the multi-functional mesoporous nano composite material of final acquisition hollow-core construction.
Embodiment 3:
(1) Hydrothermal Synthesis carbon ball template agent is adopted.Accurately taking 4g glucose is dissolved in 30mL distilled water, rapid stirring forms supernatant liquid, then transfer in the sealable politef reactor of 40mL respectively, baking oven reactor being placed in simultaneously 180 DEG C again reacts 5h, reaction terminates rear reactor and naturally cools to room temperature, obtains black and purple product.Respectively wash once with distilled water and dehydrated alcohol, dry more than 4h at 60 DEG C.
(2) adopt coprecipitation at carbon ball template Surface coating fluorescent material presoma.Specific experiment step is as follows: the carbon ball of precise 0.1g, and ultrasonic disperse is in 25mL distilled water.Then Y (the NO of 0.5mol/L is added successively
3)
3, 0.1mol/L Yb (NO
3)
3with the Er (NO of 0.05mol/L
3)
3the each 1840 μ L of solution, 200 μ L and 200 μ L, then add 3.0g carbamide.Said mixture is proceeded to reacting by heating 4h in the water-bath of 90 DEG C.Reaction terminates to carry out centrifugalize, washing and drying to product afterwards.
(3) adopt sol-gel process at C@Y (OH) CO
3: Yb, Er Surface coating meso-porous titanium dioxide silicon layer, the multi-functional mesoporous nano composite material of preparation hollow-core construction.Specific experiment content is as follows: precise 0.05g C@Y (OH) CO
3: Yb, Er powder, and ultrasonic disperse is in 20mL distilled water, carries out Quick mechanical stirring.Meanwhile, add 60mL distilled water, 60mL dehydrated alcohol, 1mL strong aqua ammonia and 0.2g cetyl trimethyl ammonium bromide (CTAB) successively, last slowly dropping 170 μ L ethyl orthosilicates.Centrifugal after vigorous stirring 6h under room temperature, washing also drying, obtains the presoma of composite, is expressed as C@Y (OH) CO
3: Yb, Er@mSiO
2– CTAB.By above-mentioned presoma roasting 3h in 800 DEG C of Muffle furnaces, on high-temperature roasting removable carbon ball template, formation, conversion nano crystalline substance also removes mesoporous template, the multi-functional mesoporous nano composite material of final acquisition hollow-core construction.
For embodiment 3, a series of sign (XRD, TEM, EDS, N are carried out to the sample of preparation
2absorption and UCL spectrum) and analysis with proved invent successfully synthesized Y
2o
3: the coated hollow mesoporous SiO of Yb, Er
2nano composite material.Fig. 1 is the Wide angle X-ray diffraction figure of sample, JCPDS 25 – 1011 is standard card; Wherein, in Fig. 1, A is sample C@Y (OH) CO before roasting
3: Yb, Er@mSiO
2the Wide angle X-ray diffraction figure of – CTAB; In Fig. 1, B is hollow Y after roasting
2o
3: Yb, Er@mSiO
2x-ray diffractogram.Can be determined to be unformed phase mutually before roasting by figure.In Fig. 1, in B, we can see in 2 θ=29.2 °, 33.4 °, and there are four sharp-pointed peaks at 48.5 ° and 57 ° of places, are Y
2o
3characteristic peak, and Y
2o
3the relative intensity position that them are compared by standard X-ray diffraction card (JCPDS No.25-1011) is consistent with diffraction locations, under 800 DEG C of conditions, the powder body of roasting does not have dephasign generation as can be seen here, in 2 θ=22, ° place, can be attributed to unformed SiO herein
2characteristic peak (JCPDS 29 – 0085).It can be said that bright SiO
2successfully be coated to powder surface, and 2 θ=29.2 °, 33.4 °, 48.5 ° and 57 ° four sharp-pointed peaks show SiO
2the coated crystal structure on powder body do not affect.
Fig. 2 A, Fig. 2 B, Fig. 2 C, Fig. 2 D, Fig. 2 E are respectively carbon ball, C@Y (OH) CO
3: Yb, Er, C@Y (OH) CO
3: Yb, Er@mSiO
2– CTAB, hollow Y
2o
3: Yb, Er, hollow Y
2o
3: Yb, Er@mSiO
2the TEM photo of sample; Fig. 2 F is hollow Y
2o
3: Yb, Er@mSiO
2the HRTEM photo of sample.From Fig. 2 A, the particle size distribution that we can see carbon ball is still relatively more uniform, and its particle diameter substantially at 200 about nm, and also agglomeration does not occur the while that the pattern of carbon ball being also relatively good.From Fig. 2 B, we can see that the microsphere after coating fluorescent powder presoma is obviously larger.Fig. 2 C is C@Y (OH) CO
3: Yb, Er@mSiO
2the TEM photo of-CTAB sample, slightly increases compared to Fig. 2 B microsphere size, and we can observe and be with the darker shell of one deck color at the outer of ball simultaneously.Compared to Fig. 2 B and Fig. 2 C, we can observe carbon ball and are removed Fig. 2 D and 2E, and can observe the pore structure of sample.From Fig. 2 D, we can see the nucleocapsid structure of sample clearly, the shell that the peripheral color of ball is more shallow be coated after SiO
2shell, the thickness of shell is approximately 20nm.These all show SiO above
2successfully be coated on powder surface, this is consistent with the characterization result of XRD.
Fig. 3 A is Y
2o
3: the adsorption/desorption isotherms of Yb, Er, Fig. 3 B is hollow Y
2o
3: Yb, Er@mSiO
2adsorption/desorption isotherms.In figure, we can see, at P/P
0the half interval contour of=0.9 and 1.0 has obvious hop, and hollow Y is described
2o
3: Yb, Er sample is pore structure material.Fig. 3 B is hollow Y
2o
3: Yb, Er@mSiO
2the adsorption/desorption isotherms of sample is H1 type hysteresis loop according to IUPCA (international theory and chemical combined meeting) curve, at P/P
0the half interval contour of=0.9 to 1.0 has obvious hop to be shown to be the IV type isothermal line of mesoporous material.
Fig. 4 A is Y
2o
3: the pore size distribution curve of Yb, Er, Fig. 4 B is hollow Y
2o
3: Yb, Er@mSiO
2pore size distribution curve.We can see, at coating mesoporous SiO
2the average pore size of sample is at about 24nm before, and coating mesoporous SiO
2the average pore size of sample is obviously reduced to about 4nm afterwards, visible coating mesoporous SiO
2composite is afterwards suitable as the carrier of drug conveying and release.
Fig. 5 A and Fig. 5 B is respectively hollow Y
2o
3: Yb, Er and hollow Y
2o
3: Yb, Er@mSiO
2the Up-conversion emission spectrogram of sample.Under the exciting of 980nm laser instrument, the sample stronger green glow of display and red emission.Hollow Y can be seen from Fig. 5 A
2o
3: there are three different Er in Yb, Er sample
3+characteristic emission peak, results from Er during green emission between 520nm to 538nm and between 540nm and 560nm
3+'s
2h
11/2arrive
4i
15/2with
4s
3/2arrive
4i1
5/2transition, the red emission between 640nm to 680nm be due to
4f
9/2arrive
4i
15/2transition.Namely under 980nm excites, Er
3+ground state electron be excited to by absorption photon
4i
11/2energy level, is energized into further at absorption second photon
4f
7/2energy level, this energy level is positioned at visible region, Er
3+arrived by phonon damping process nonradiative relaxation fast
2h
11/2with
4s
3/2energy level, produces
2h
11/2arrive
4i
15/2with
4s
3/2arrive
4i1
15/2green emission, the further relaxation of electronic energy, layout arrives
4f
9/2energy level, produces
4f
9/2arrive
4i
15/2red emission.Fig. 5 B is hollow Y
2o
3: Yb, Er@mSiO
2the upper conversion emission spectra of sample, from figure, we can see that this is coated Si O except the intensity of emission peak is by significantly reducing outer figure without any change
2cause.
Finally again the sustained release performance of material resistant cancer drug DOX is studied, determines its drug carrying ability.Fig. 6 is hollow Y
2o
3: Yb, Er@mSiO
2the elution profiles of – DOX sample.I.e. amycin (DOX) release amount of medicine graph of a relation in time.From figure, my door can be seen at the rate of release of experiment incipient stage DOX quite fast, within 5 hours, just releases 80% of total amount, after 9 hours, burst size reaches 93%, the burst size of 12 hours completes substantially, and the rate of release in 1-5 hour stage is very fast, and rate of release afterwards reduces gradually.The rate of release of incipient stage drug molecule DOX, than very fast, can think that part DOX molecule is at mesoporous SiO
2shell, to periphery, does not that is also load to carrier inside, is also likely due to SiO
2mesoporous middle part DOX drug molecule is more weak with the molecular force of mesoporous interior surface, first this part drug molecule can enter into PBF buffer solution, and the comparatively strong rate of release by contrast of the drug molecule DOX of another part and mesoporous interior surface molecular force is just slow.From the total amount discharged, we can see has 0.6mg drug molecule DOX to reprint on carrier, although the 2.5mg drug molecule DOX used compared to experiment is somewhat few, but as a whole, our the composite specific surface area of synthesis is larger, and the mesopore orbit of applicable drug molecule delivery size, therefore, meso-porous titanium dioxide silicon composite (the hollow Y with the fluorescent functional of hollow-core construction of the prepared synthesis of experiment
2o
3: Yb, Er@mSiO
2) be the carrier that is suitable as drug conveying.The meso-hole structure of silicon dioxide combines with the fluorescence property of rare earth by prepared composite, large pore volume and bigger serface, be applicable to loading high amount of drug molecule and good medicament slow release performance, can be used for drug delivery system, and fluorescence property can be used to carry out tracing detection to it, at biomedical sector, there is very large application potential.
Claims (6)
1. the hollow mesoporous SiO of functionalization
2nano composite material, is characterized in that having following structure:
Y
2O
3:Yb,Er@mSiO
2。
2. the hollow mesoporous SiO of functionalization
2the preparation method of nano composite material, is characterized in that:
(1) hydro-thermal method is adopted to prepare carbon ball: to be dissolved in by 3g ~ 8g glucose in 30mL ~ 32mL water, join in reactor, 5h ~ 8h is reacted at 160 DEG C ~ 180 DEG C, after reaction terminates, naturally cool to room temperature, respectively wash once with water and dehydrated alcohol, dry 4h ~ 12h at 60 DEG C ~ 80 DEG C, obtain carbon ball;
(2) coprecipitation coating fluorescent powder presoma is utilized on carbon ball surface: by 0.05g ~ 0.2g carbon ball ultrasonic 10min in 25mL ~ 30mL water, add 1840 μ L 0.5mol/L Yttrium trinitrates, 200 μ L 0.1mol/L Ytterbium(III) nitrate .s and 200 μ L 0.05mol/L Nitrate Solution successively, add 3.0g ~ 4.0g carbamide again, 2h ~ 8h is reacted in the water-bath of 75 DEG C ~ 95 DEG C, reaction terminates to carry out centrifugalize, washing and drying to product afterwards, obtain the nucleocapsid structure powder at carbon ball Surface coating subcarbonate, be expressed as C@Y (OH) CO
3: Yb, Er;
(3) sol-gel process is utilized to prepare hollow-core construction meso-porous nano composite: the nucleocapsid structure powder of 0.05g ~ 0.2g carbon ball Surface coating subcarbonate, ultrasonic agitation 10min in 20mL ~ 25mL water, add 50mL ~ 70mL water, 50mL ~ 70mL dehydrated alcohol, 0.8mL ~ 1.2mL strong aqua ammonia and 0.2g ~ 0.4g cetyl trimethyl ammonium bromide successively, finally dropwise drip 100 μ L ~ 200 μ L ethyl orthosilicates, centrifugal after vigorous stirring 5h under room temperature ~ 7h, washing also drying, obtain the presoma of composite, be expressed as C@Y (OH) CO
3: Yb, Er@mSiO
2– CTAB, roasting 3h in 800 DEG C of Muffle furnaces, obtains Y
2o
3: the coated hollow mesoporous SiO of Yb, Er
2nano composite material, is expressed as Y
2o
3: Yb, Er@mSiO
2.
3. the hollow mesoporous SiO of functionalization according to claim 2
2the preparation method of nano composite material, is characterized in that: the reaction temperature of described hydro-thermal method is 180 DEG C, and the response time is 5h.
4. the hollow mesoporous SiO of the functionalization according to Claims 2 or 3
2the preparation method of nano composite material, is characterized in that: 0.1g carbon ball, ultrasonic in 25mL water.
5. the hollow mesoporous SiO of the functionalization according to Claims 2 or 3
2the preparation method of nano composite material, it is characterized in that: the nucleocapsid structure powder of 0.05g carbon ball Surface coating subcarbonate, ultrasonic agitation 10min in 20mL water, add 60mL water, 60 dehydrated alcohol, 1mL strong aqua ammonia and 0.2g cetyl trimethyl ammonium bromide successively, finally dropwise drip 170 μ L ethyl orthosilicates, vigorous stirring 6h under room temperature.
6. the hollow mesoporous SiO of functionalization according to claim 4
2the preparation method of nano composite material, it is characterized in that: the nucleocapsid structure powder of 0.05g carbon ball Surface coating subcarbonate, ultrasonic agitation 10min in 20mLmL water, add 60mL water, 60 dehydrated alcohol, 1mL strong aqua ammonia and 0.2g cetyl trimethyl ammonium bromide successively, finally dropwise drip 170 μ L ethyl orthosilicates, vigorous stirring 6h under room temperature.
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| CN105699331B (en) * | 2016-04-06 | 2018-08-07 | 清华大学深圳研究生院 | A kind of optical waveguide sensing chip and preparation method thereof and application |
| CN108619115A (en) * | 2018-06-29 | 2018-10-09 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of multi-functional hollow mesoporous SiO2The preparation method of nanocomposite |
| CN109967123A (en) * | 2019-03-07 | 2019-07-05 | 中国科学院化学研究所 | A kind of hollow Nano robot and preparation method thereof and the application as antioxidant |
| CN109967123B (en) * | 2019-03-07 | 2020-06-09 | 中国科学院化学研究所 | Hollow nano robot, preparation method thereof and application of hollow nano robot as antioxidant |
| CN110354805A (en) * | 2019-07-29 | 2019-10-22 | 江西师范大学 | A kind of P-6 type basic yttrium carbonate/carbon composite and its preparation method and application |
| CN110354805B (en) * | 2019-07-29 | 2022-08-30 | 江西师范大学 | P-6 type basic yttrium carbonate/carbon composite material and preparation method and application thereof |
| CN113896206A (en) * | 2021-11-18 | 2022-01-07 | 中国农业科学院兰州兽医研究所 | Hollow mesoporous silicon nano-microsphere and preparation method and application thereof |
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