CN102275936B - Preparation method of mesoporous spherical Sio2 nanoparticles - Google Patents
Preparation method of mesoporous spherical Sio2 nanoparticles Download PDFInfo
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- CN102275936B CN102275936B CN201110153544A CN201110153544A CN102275936B CN 102275936 B CN102275936 B CN 102275936B CN 201110153544 A CN201110153544 A CN 201110153544A CN 201110153544 A CN201110153544 A CN 201110153544A CN 102275936 B CN102275936 B CN 102275936B
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Abstract
The invention discloses a preparation method of mesoporous spherical Sio2 nanoparticles. The template agent used in the method is cetyl trimethyl p-methyl benzene sulfonate, the alkali source used in the method is a binary mixture comprising organic micro-molecular amine and inorganic base, the silica source used in the method is tetra alkyl silicate ester, and the molar ratio of cetyl trimethyl p-methyl benzene sulfonate to organic base to inorganic base to water is 1 to 0.03-0.06 to 0.5-2 to 0.01-0.35 to 80-500. By regulating the molar ratio of organic base to inorganic base, the particle size can be effectively controlled within 50-1000 nm. Compared with the prior art, the method disclosed in the invention has the most significant advantages that using cetyl trimethyl p-methyl benzene sulfonate as the template molecule can greatly reduce the dosage of surfactant, and regulating the molar ratio of the diacidic base can effectively regulate the final particle size. The method has the advantages of simple processing, short cycle, low cost, and good repeatability, and is an environmental friendly synthetic method.
Description
Technical field
The present invention relates to a kind of preparation method of nano-spherical mesoporous molecular sieve, relate in particular to the preparation method of the silicon-based mesoporous molecular sieve nano particle that a kind of particle size can modulation.
Background technology
Mesopore silicon dioxide nano material is a kind of novel inorganic nano material with high-specific surface area, large pore volume, pattern and controllable size, and it has caused extensive concern in the applied research of Materials science, biological medicine, environmental protection, field of biosensors in recent years.The main synthesis strategy of current synthesizing mesoporous silicon dioxide nano particle (MSN) comprising: use single CTAB cats product (Angew. Chem. Int. Ed., 2002,2151; 2317.), early stage what react, through a large amount of water dilutions; Cancellation particle growth; Thereby prepared the mesoporous silica nano-particle of size, but particle shape is irregular, and the yardstick very heterogeneity that distributes less than 100 nm; Through improved St ber method (J. Phys. Chem. B 2004,108,20122.), can prepare highly monodispersed mesoporous SiO as the cosurfactant of CTAB cats product with ethanol
2Nano particle, but size is often greater than 100 nm; Bein is through using trolamine (TEAH
3) replace mineral alkali and can synthesize meter ruler cun less than 200 nm mesoporous nano-grains (Adv. Funct. Mater. 2007,17,605.), but trolamine (TEAH
3) consumption very big, and need just can obtain final particle through ultracentrifugal way; Kuroda has reported that recently a new synthesis strategy comes preparation size less than the mesoporous SiO of 50nm
2Nano particle, but the molar ratio of CTAB/TMOS greater than 0.5, the high and tensio-active agent of synthetic cost will could be removed (Chem. Commu., 2009,5094.) through complicated dialysis process; Chinese patent CN1923684A utilizes sarcosyl to make template, is co-structured directed agents with (3-aminopropyl) Trimethoxy silane, synthesized big or small evenly, the SiO of controllable size
2Nano particle, higher but the synthetic cost compares; The synthesis strategy of mixed templates can be used for synthetic highly monodispersed mesoporous nano-grain equally, but the expensive price limit of tensio-active agent its use (SCI, 2011,32,560.) widely.Visible from above-mentioned report, existing compound method existence condition is harsh, cost is high, pollution is big and be unfavorable for shortcoming such as scale operation.Therefore researching and developing new synthetic technology is current mesoporous SiO
2The top priority of nano particle basis research.
Summary of the invention
The object of the present invention is to provide a kind of fast, low-cost, pollute little mesoporous SiO
2The green technology of preparing of nano particle synthetic.
A kind of preparation method of mesoporous silica spheres shape nano particle is characterized in that this method is that CTATos is that template, organic bases and mineral alkali are that alkali source, tetraalkyl silicon ester are that silicon source, deionized water are that the water source is as raw material with cetyl trimethyl p-methyl benzenesulfonic acid salt; The mole of raw material consists of the silicon source: cetyl trimethyl p-methyl benzenesulfonic acid salt: organic bases: mineral alkali: water=1:0.03～0.06:0.5～2:0.01～0.35:80～500; Concrete preparation may further comprise the steps:
Earlier be mixed in deionized water, alkali source, template in the reaction vessel successively; 80 ℃ of constant temperature are stirred to the solution clarification, then the silicon source are joined rapidly in the middle of the mixing solutions, and 80 ℃ of constant temperature continue to stir 2 hours; Directly product is filtered, washs and drying behind the cool to room temperature; Use roasting or acid-treated method with the removal of surfactant in the duct, obtain mesoporous silica spheres shape nano particle, particulate is of a size of 50～1000nm; Wherein: said tetraalkyl silicon ester is tetramethoxy silicon ester (TMOS) or tetraethoxy silicon ester (TEOS); Said organic bases is Monoethanolamine MEA BASF (EA H), diethylolamine (BEA H
2) or trolamine (TEAH
3); Mineral alkali is 28～30% ammoniacal liquor, sodium hydroxide or Pottasium Hydroxide; Said roasting is 550 ℃ of following roastings 5 hours; S.t. is that the HCl ethanolic soln with 1M at room temperature stirred 1 hour.
Cetyl trimethyl p-methyl benzenesulfonic acid salt used in the present invention (CTATos) cats product comes from the Merck chemical reagents corporation of Germany; Other reagent is domestic commercially available.
The present invention compares with prior preparation method has following advantage:
⑴, the present invention can reduce tensio-active agent (CTATos)/Si mol ratio to 0.03, have reduced synthetic cost, have reduced environmental pollution.Because the tensio-active agent in the system by 100% utilization, filters, the foam that has no in the middle of the washing process produces, greatly simplified the operation steps that sample reclaims in addition.
⑵ the synthesis strategy of, two alkaline process promptly can realize that to the relative molar ratio of mineral alkali the size of nano particle is effectively regulated and control through changing in the synthetic system organic bases 50 ~ 1000nm scope in.
, from the characterization result of product, the product regular shape that the present invention obtains, aperture homogeneous, the surface-area of sample reaches 934m
2/ g, pore volume are 2.57ml/g, and the aperture is 2.7nm.
⑷ the mother liquor of, filtered and recycled can directly be used to have the mesoporous SiO of large-size
2Synthesizing of nano particle.
⑸ the tensio-active agent in, the mesopore orbit was removed through one step of way of direct pickling and high-temperature roasting.
⑹, sample can obtain through the way of direct suction filtration, have saved loaded down with trivial details steps such as high speed centrifugation sedimentation.
⑺, the sample way through simple supersound process can be distributed in the middle of water, the ethanol isopolarity protonated solvent, obtains high stability colloidal solution.
Description of drawings
Fig. 1 is the mesoporous SiO of synthetic of the present invention
2The ESEM of nano particle (SEM) figure;
Fig. 2 is the mesoporous SiO of synthetic of the present invention
2High-resolution projection Electronic Speculum (TEM) figure of nano particle.
Embodiment
Through embodiment the present invention is described further below, its purpose only is better to understand research contents of the present invention and unrestricted protection scope of the present invention.
At first 2.74g cetyl trimethyl p-methyl benzenesulfonic acid salt (CTATos) is joined the trolamine (TEAH that contains 144ml deionized water, 0.04g sodium hydroxide (NaOH) and 14.92g
3) beaker in, 80 ℃ of constant temperature stir 1 hour to the solution becomes clarification, then 20.83g tetraethoxy silicon ester (TEOS) are joined rapidly in this beaker, 80 ℃ of constant temperature continue to stir 2 hours, obtain white precipitate, the mole of this mixture consists of SiO
2: CTATos:TEAH
3: NaOH:H
2O=1:0.06:1:0.01:80; To obtain the direct suction filtration of mixture, washing, oven dry, obtain mesoporous SiO
2Nano particle, productive rate 95%, median size 60 nm.Utilize high-temperature roasting or acid-treated method can a step that the removal of surfactant in the duct is specifically put method is following: the directly roasting 6 hours in 550 ℃ of muffle furnaces of the former powder of (1) 1.0g; (2) the former powder of 1.0g is in the ethanol solution hydrochloride of 40ml 1M, and stirring at room 1 hour is filtered, washs, dried.Finally obtain particulate specific surface area 934m
2/ g, 2.57ml/g, aperture 2.7nm.
Embodiment 2
At first 2.74g cetyl trimethyl p-methyl benzenesulfonic acid salt (CTATos) is joined and contain 144ml deionized water, 14.92g trolamine (TEAH
3) and the beaker of 0.20gNaOH mixing solutions in; 80 ℃ of constant temperature stir 1 hour to the solution becomes clarification, then 20.83g tetraethoxy silicon ester (TEOS) are joined rapidly in this beaker, and 80 ℃ of constant temperature continue to stir 2 hours; Obtain white precipitate, the mole of this mixture consists of SiO
2: CTATos:TEAH
3: NaOH:H
2O=1:0.06:1:0.05:80; To obtain the direct suction filtration of mixture, washing, oven dry, obtain mesoporous SiO
2Nano particle, productive rate 95%, median size 180 nm.Change NaOH to TEAH
3Molar ratio, can obtain the mesoporous silica nano-particle of varying particle size, basicity is high more, the particulate size is big more.
Embodiment 3
At first 2.74g cetyl trimethyl p-methyl benzenesulfonic acid salt (CTATos) is joined and contain 144ml deionized water, 1.4gNaOH and 14.92g trolamine (TEAH
3) in the beaker of mixing solutions, 80
oC constant temperature stirs 1 hour to the solution becomes clarification, then 20.83g tetraethoxy silicon ester (TEOS) is joined in this beaker 80 rapidly
oC constant temperature continues to stir 2 hours, obtains white precipitate, and the mole of this mixture consists of SiO
2: CTATos:TEAH
3: NaOH:H
2O=1:0.06:1:0.35:80; To obtain the direct suction filtration of mixture, washing, oven dry, obtain mesoporous SiO
2Nano particle, productive rate 95%, median size 800 nm.
Embodiment 4
Remove with Monoethanolamine MEA BASF (EAH) and replace the trolamine (TEAH among the embodiment 1
3) outside, other preparation condition is all identical with embodiment 1, obtains mesoporous SiO
2The nano particle median size is 60 nm.
Embodiment 5
Remove with diethylolamine (BEAH
2) replace the trolamine (TEAH among the embodiment 1
3) outside, other preparation condition is all identical with embodiment 1, obtains mesoporous SiO
2The nano particle median size is 60 nm.
Embodiment 6
Except that with the NaOH among 28 ~ 30% aqueous ammonia to replace embodiment 2, other preparation condition is all identical with embodiment 2, obtains mesoporous SiO
2The nano particle median size is 100 nm.
Embodiment 7
Except that the NaOH that replaces with Pottasium Hydroxide among the embodiment 2, other preparation condition is all identical with embodiment 2, obtains mesoporous SiO
2The nano particle median size is 160 nm.
Embodiment 8
Except that the tetraethoxy silicon ester (TEOS) that replaces with tetramethoxy silicon ester (TMOS) among the embodiment 1, other preparation condition is all identical with embodiment 1, obtains mesoporous SiO
2The nano particle median size is 40 nm.
Claims (1)
1. the preparation method of a mesoporous silica spheres shape nano particle is characterized in that this method is that template, organic bases and mineral alkali are that alkali source, tetraalkyl silicon ester are that silicon source, deionized water are that the water source is as raw material with cetyl trimethyl p-methyl benzenesulfonic acid salt; The mole of raw material consists of the silicon source: cetyl trimethyl p-methyl benzenesulfonic acid salt: organic bases: mineral alkali: water=1:0.03～0.06:0.5～2:0.01～0.35:80～500; Concrete preparation may further comprise the steps:
Earlier be mixed in deionized water, alkali source, template in the reaction vessel successively; 80 ℃ of constant temperature are stirred to the solution clarification, then the silicon source are joined rapidly in the middle of the mixing solutions, and 80 ℃ of constant temperature continue to stir 2 hours; Directly product is filtered, washs and drying behind the cool to room temperature; Use roasting or acid-treated method with the removal of surfactant in the duct, obtain mesoporous silica spheres shape nano particle, particulate is of a size of 50～1000nm; Wherein: said tetraalkyl silicon ester is tetramethoxy-silicane or tetraethoxysilane; Said organic bases is Monoethanolamine MEA BASF, diethylolamine or trolamine; Mineral alkali is 28～30% ammoniacal liquor, sodium hydroxide or Pottasium Hydroxide; Said roasting is 550 ℃ of following roastings 5 hours; S.t. is that the HCl ethanolic soln with 1M at room temperature stirred 1 hour.
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| CN102557051B (en) * | 2012-01-04 | 2013-11-27 | 复旦大学 | Method for preparing hollow mesocellular silica nanometer particles based on polymer formwork |
| CN102718225A (en) * | 2012-07-18 | 2012-10-10 | 中国人民解放军***南京总医院 | Preparation method of ordered mesoporous silica microspheres with hollow structures |
| CN103539135B (en) * | 2013-10-24 | 2015-07-08 | 华东师范大学 | Preparation method of mesoporous silica suspension with stable colloidal state |
| CN103613101B (en) * | 2013-10-31 | 2016-01-20 | 华东师范大学 | A kind of preparation method with dendroid pore passage structure mesoporous silicon oxide shape nanometer ball |
| CN103641122B (en) * | 2013-11-15 | 2015-08-19 | 华东师范大学 | A kind of preparation method of multistage mesoporous silica nano-particle |
| CN103663478B (en) * | 2013-11-20 | 2016-05-04 | 华东师范大学 | A kind of preparation method of dendroid pore passage structure mesoporous spherical nano Sio 2 particle |
| CN107381579A (en) * | 2017-06-28 | 2017-11-24 | 华东师范大学 | A kind of preparation method of mesoporous spherical nano Sio 2 particle |
| CN108484258A (en) * | 2018-04-03 | 2018-09-04 | 金华市野泉园艺技术有限公司 | The preparation method of Hibiscus hamabo composite fertilizer |
| CN113797226B (en) * | 2021-09-14 | 2023-09-19 | 华东师范大学 | Ammonia borane/silicon sphere/mesoporous silica nano composite particle, preparation and application thereof |
| CN114468353A (en) * | 2022-03-01 | 2022-05-13 | 湖北中烟工业有限责任公司 | Thermosensitive response essence slow-release microcapsule and preparation method and application thereof |
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Non-Patent Citations (1)
| Title |
|---|
| Kun Zhang et al.Novel synthesis and molecularly scaled surface hydrophobicity control of colloidal mesoporous silica.《Microporous and Mesoporous Materials》.2011,(第143期),P402左侧栏第2段-P403右侧栏第2段. * |
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