CN104445215A - Preparation method of hollow silicon dioxide nanomaterial - Google Patents
Preparation method of hollow silicon dioxide nanomaterial Download PDFInfo
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- CN104445215A CN104445215A CN201410614977.2A CN201410614977A CN104445215A CN 104445215 A CN104445215 A CN 104445215A CN 201410614977 A CN201410614977 A CN 201410614977A CN 104445215 A CN104445215 A CN 104445215A
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- nano material
- nanomaterial
- carbon ball
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 5
- 238000000034 method Methods 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000003756 stirring Methods 0.000 claims description 17
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract 3
- 229910052682 stishovite Inorganic materials 0.000 abstract 3
- 229910052905 tridymite Inorganic materials 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002077 nanosphere Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 241000143432 Daldinia concentrica Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- -1 methoxyl group Chemical group 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention relates to a preparation method of a hollow silicon dioxide nanomaterial. According to the preparation method, with carbon nanospheres as a hard template, tetraethoxysilane (TEOS) as a silicon source, water as a solvent and cetyl trimethyl ammonium bromide (CTAB) as a structure-directing agent, the hollow SiO2 nanomaterial which is even in appearance and folded in surface can be formed after residual organic matters such as carbon spheres and CTAB are removed by use of subsequent heat treatment. A TEM picture indicates that the SiO2 nanomaterial prepared by use of the method has a hollow structure and is about 20 nanometers in wall thickness and about 200 nanometers in grain size. The hollow SiO2 nanomaterial prepared by use of the method has potential application prospect in the fields such as biomedicine.
Description
Technical field
The present invention relates to a kind of preparation method of hollow silica nano material.
Background technology
Along with the development of nanotechnology, nano material has been widely used in multiple fields such as catalysis, biomedicine and fine chemistry industry.Wherein, nano silicon (SiO
2) as one of extremely important New Inorganic Materials, because it has many unrivaled advantages such as particle diameter is adjustable, specific surface area is high, dispersing property is good and structural stability is high and abundance, with low cost, there is very important effect in various fields.
At present, about the material of the special appearance on different nanostructure and nano-scale, as nano particle, nano wire, nanotube and nanometer rod etc., be widely studied.Wherein, hollow porous nanometer structure is one of focus of studying of people always.With traditional Si O
2material is compared, this kind of material has porous and hollow dual structure characteristic, not only density is lower, specific surface area is larger, and have unique advantage such as good biocompatibility, stable skeleton structure, higher porosity and easy modification, therefore all have important application in fields such as chemistry, biological and Materials science, as catalysis, absorption and be separated, drug delivery etc.In recent years, multiple preparation hollow porous SiO
2method, comprise sol-gel method, template, microemulsion method and hydrothermal synthesis method etc., be in the news.Wherein, template (soft template and hard template method) is one of important method of nano materials, and technology is comparatively ripe.Soft template method utilizes tensio-active agent, micella or polymer vesicle etc. as Flexible formwork assembly to prepare SiO
2hollow porous material, but the SiO that the method is obtained
2material shape is irregular, particle diameter is uneven and shell is easily damaged.Organic solvent used easily causes environmental pollution, and productive rate is low, is not suitable for scale operation.And hard template method mainly utilizes its space confinement effect and the pattern, size, structure etc. of structure-directing effect to material to carry out effective cutting.Compared with additive method, it is workable that hard template method prepares nano material, more accurate to the regulation and control of product, obtained good product dispersibility.
Given this, the present invention is with the pyrogenically prepared Nano carbon balls of glucose for hard template, and water is solvent, and tetraethoxy is silicon source, by simple low temperature hydrolysis process, prepares hollow sphere monox nanometer material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of hollow silica nano material, the hollow SiO that present method can obtain pattern rule, there is fold on uniform particle diameter, surface
2nano material.
For achieving the above object, the present invention by the following technical solutions:
A preparation method for hollow silica nano material, is characterized in that the concrete steps of the method are:
A. be dissolved in 0.20 ~ 0.50 mol/L ethanolic soln by obtained carbon ball, then add 3-aminopropyl triethoxysilane, stirring at normal temperature 2 h obtains mixing solutions; Wherein, the mass ratio of 3-aminopropyl triethoxysilane and carbon ball is 0.00125 ~ 0.002:1;
B. in step a gained mixing solutions, a certain amount of tetraethoxy and ammoniacal liquor (25 ~ 28 wt%) is added, adjust ph to 11 ~ 12, centrifugation after stirring at normal temperature 12 h; Wherein, the mass ratio of tetraethoxy and carbon ball is 0.0018 ~ 0.0025:1;
C. be dissolved in deionized water by step b products therefrom, add cetyl trimethylammonium bromide, and adjust ph is 9 ~ 10, stirs, and dropwise adds tetraethoxy, 55 ° of C stir 2 h; After having reacted, reactant is taken out, through the step such as centrifugal, washing, oven dry of routine, and in 550 ° of C air atmospheres, calcine 6 h, obtain hollow-sphere silica nano material prepared by the present invention; Wherein, the mass ratio of cetyl trimethylammonium bromide and TEOS is 0.20 ~ 1.0:1.
In present invention process process, first hydrothermal method is adopted to prepare particle diameter at about 180 nm, pattern is homogeneous and the carbon ball of good dispersity is hard template, then the dealcoholysis polycondensation utilizing the methoxyl group in the hydroxyl on carbon ball surface and APTES to occur carries out organic decoration to gained carbon ball, then in the alkaline environment provided at ammoniacal liquor, the SiO that a small amount of TEOS hydrolysis generates
2nanoparticle in the surface growth of carbon ball, thus forms the unbodied SiO of one deck
2thin layer.Subsequently, in the alkaline condition of sodium hydroxide or ammoniacal liquor, after the TEOS that adds continue hydrolysis, by the structure-directing effect of Surfactant CTAB, further at amorphous Si O
2surface growth, finally roasting 6 h in retort furnace 550 ° of C air atmospheres, after removing carbon template, CTAB and residual organic impurity, obtains the SiO of hollow porous
2nano material.
Compared with prior art, the technology of the present invention has following remarkable advantage: reaction temperature of the present invention and, obtained product has low density, pattern and structure-controllable, and to be uniformly dispersed and the advantage such as easily to be modified in surface, in addition, the cavity that ball interior is huge is conducive to storage and the transport of material, therefore there is potential biomedical applications prospect, can be used for the controllable release etc. of medicine.
Accompanying drawing explanation
Fig. 1 is the TEM photo of gained hollow silica nano material in the embodiment of the present invention 1.
Fig. 2 is the SEM photo of gained hollow silica nano material in the embodiment of the present invention 1.
Fig. 3 is the FT-IR spectrogram of gained hollow silica nano material in the embodiment of the present invention 1.
Embodiment
All embodiments all operate by the operation steps of technique scheme.Carbon ball its preparation method used in the present invention refers to
crystEngComm,2012,14,3793-3801.
Embodiment 1
A. first carbon ball is produced by existing known technology: take 1.98 g glucose with electronic balance and add 20 mL deionized water for ultrasonic to dissolving, be poured in the band teflon-lined autoclave of 100 mL, 6 h are reacted under 180 ° of C conditions, after having reacted, product is taken out from reactor, carry out centrifugal, washing with ethanol and deionized water, and dry under 60 ° of C, obtain the carbon ball that the pattern of particle diameter 180 about nm is homogeneous;
B. the carbon ball getting 50 mg obtained is dissolved in 20 mL ethanol, then adds 100 μ L 3-aminopropyl triethoxysilane (APTES), stirring at normal temperature 2 h;
C. in above-mentioned solution, add 100 μ L tetraethoxys (TEOS) and 250 μ L ammoniacal liquor (NH
3h
2o, 25 ~ 28 wt%), centrifugal after stirring at normal temperature 12 h;
D. be dissolved in 18 mL deionized waters by the product after centrifugal, add 0.0364 g cetyl trimethylammonium bromide (CTAB), then after adding 0.9 mL 0.001M NaOH, stir, dropwise add 200 μ L TEOS, 55 ° of C stir 2 h;
E., after having reacted, product is taken out, with deionized water and ethanol repetitive scrubbing, centrifugal after, product is dried under 60 ° of C, finally be placed in retort furnace air atmosphere, 550 ° of C calcine 6 h, obtain hollow-sphere silica nano material prepared by the present invention.
The product of gained is carried out physical property sign, and its partial results as shown in drawings.Resulting materials is hollow spheres structure, and wall thickness is about 20 nm, particle diameter 200 about nm, and surface irregularity, has a lot of folds.
Embodiment 2: the preparation process of the present embodiment is substantially identical with embodiment with step, and difference is b step:
The carbon ball getting 50 mg obtained is dissolved in 20 mL ethanol, does not add 3-aminopropyl triethoxysilane (APTES), stirring at normal temperature 2 h.
Acquired results and embodiment 1 topographical difference are comparatively large, and can not form complete hollow ball structure, surface folding is many, reunites comparatively serious.
Embodiment 3
Preparation process and the step of the present embodiment are substantially the same manner as Example 1, and difference is Step d:
Product after centrifugal is dissolved in 18 mL deionized waters, then after adding 0.9 mL 0.001M NaOH, stirs, dropwise add 200 μ L TEOS, stir 2 h; Do not add cetyl trimethylammonium bromide (CTAB).
Acquired results and embodiment 1 topographical difference are comparatively large, and product is the uneven solid silica ball of particle diameter.
Embodiment 4
Preparation process and the step of the present embodiment are substantially the same manner as Example 1, and difference is Step d:
Product after centrifugal is dissolved in 18 mL deionized waters, adds 0.0364 g cetyl trimethylammonium bromide (CTAB), then add 0.9 mL 0.001M NH
3h
2after O, stir, dropwise add 200 μ L TEOS, 55 ° of C stir 2 h;
Acquired results and embodiment 1 pattern slightly difference, SiO
2the surface folding of shell is more obvious.
See accompanying drawing, Fig. 1 is transmission electron microscope (TEM) picture of the embodiment of the present invention 1 gained hollow silica nano material.Tem analysis: adopt Jeol Ltd. JEOL-200CX type transmission electron microscope observation material morphology.As can be seen from TEM picture, the hollow silica nano material that the present invention obtains, globosity is complete, surface folding porous, its particle diameter at about 200 nm, particle diameter and wall thickness homogeneous controlled.
See accompanying drawing, Fig. 2 is the embodiment of the present invention 1 gained spherical hollow SiO
2scanning electron microscope (SEM) picture of nano material.Sem analysis: adopt NEC company JSM-6700F type emission scan electron microscope observation material morphology.As can be seen from SEM picture, the hollow SiO that the present invention obtains
2nano material is regular spherical particle, consistent with TEM result.
See accompanying drawing, Fig. 3 is the embodiment of the present invention 1 gained spherical hollow SiO
2the infrared absorpting light spectra (Fourier transform infrared spectrometer, FT-IR) of nano material.FT-IR analyzes: the infrared absorption spectrum adopting the AVATAR 370 type Fourier transform infrared spectrometer test sample of Thermo Nicolet company, carry out infrared drying to sample before test, adopt KBr pressed disc technique, spectrogram test specification is 400 ~ 4000 cm
-1.As we know from the figure, 1066 cm
-1absorption belong to Si-O-Si antisymmetric stretching vibration peak, 808 cm
-1the peak at place is Si-O key symmetrical stretching vibration peak, proves that products therefrom is SiO
2material.
Claims (1)
1. a preparation method for hollow silica nano material, is characterized in that the concrete steps of the method are:
A. be dissolved in 0.20 ~ 0.50 mol/L ethanolic soln by obtained carbon ball, then add 3-aminopropyl triethoxysilane, stirring at normal temperature 2 h obtains mixing solutions; Wherein, the mass ratio of 3-aminopropyl triethoxysilane and carbon ball is 0.00125 ~ 0.002:1;
A. in step a gained mixing solutions, a certain amount of tetraethoxy and ammoniacal liquor (25 ~ 28 wt%) is added, adjust ph to 11 ~ 12, centrifugation after stirring at normal temperature 12 h; Wherein, the mass ratio of tetraethoxy and carbon ball is 0.0018 ~ 0.0025:1;
B. be dissolved in deionized water by step b products therefrom, add cetyl trimethylammonium bromide, and adjust ph is 9 ~ 10, stirs, and dropwise adds tetraethoxy, 55 ° of C stir 2 h; After having reacted, reactant is taken out, through the step such as centrifugal, washing, oven dry of routine, and in 550 ° of C air atmospheres, calcine 6 h, obtain hollow-sphere silica nano material prepared by the present invention; Wherein, the mass ratio of cetyl trimethylammonium bromide and TEOS is 0.20 ~ 1.0:1.
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|---|---|---|---|
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| CN104445215B CN104445215B (en) | 2016-11-16 |
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| CN106009428A (en) * | 2016-05-13 | 2016-10-12 | 电子科技大学 | Silicon dioxide filled PTFE composite and preparing method thereof |
| CN106044788A (en) * | 2016-05-26 | 2016-10-26 | 齐鲁工业大学 | Nanometer material with controllable particle sizes and silicon dioxide hollow spheres and method for preparing nanometer material |
| CN106145121A (en) * | 2016-06-25 | 2016-11-23 | 上海大学 | Hollow that double silicon sources guide and sandwich hollow silica mesoporous material and synthetic method thereof |
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| CN112744818B (en) * | 2019-10-30 | 2022-08-12 | 中国石油化工股份有限公司 | Carbon-silicon oxide compound and preparation method thereof |
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| 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 |
| CN112903761A (en) * | 2021-01-19 | 2021-06-04 | 重庆大学 | Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof |
| CN112903761B (en) * | 2021-01-19 | 2022-09-23 | 重庆大学 | Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof |
| CN113428867A (en) * | 2021-07-15 | 2021-09-24 | 深圳先进技术研究院 | Hollow silicon dioxide spherical particle and preparation method and application thereof |
| CN114572989A (en) * | 2022-05-06 | 2022-06-03 | 北洋研创(天津)科技有限公司 | Silicon dioxide nanosheet and preparation method and laminated structure thereof |
| CN114572989B (en) * | 2022-05-06 | 2022-09-16 | 北洋研创(天津)科技有限公司 | Silicon dioxide nanosheet and preparation method and laminated structure thereof |
| CN116462218A (en) * | 2023-03-13 | 2023-07-21 | 上海林海生态技术股份有限公司 | White nano calcium carbonate and preparation method thereof |
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