CN101559952A - Method for preparing nanoscale mesoporous silica spheres - Google Patents
Method for preparing nanoscale mesoporous silica spheres Download PDFInfo
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- CN101559952A CN101559952A CNA200910027917XA CN200910027917A CN101559952A CN 101559952 A CN101559952 A CN 101559952A CN A200910027917X A CNA200910027917X A CN A200910027917XA CN 200910027917 A CN200910027917 A CN 200910027917A CN 101559952 A CN101559952 A CN 101559952A
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Abstract
The invention relates to a method for preparing nanoscale mesoporous silica spheres, and the method belongs to the technical field of preparation of inorganic porous materials. The invention specifically relates to the synthesis of a series of mesoporous silica with different sphere diameters. The method takes quaternary ammonium salt cationic surfactants with different carbon chain lengths, which are taken as template agents and adopts the sol-gel method for synthesis under alkaline conditions. The method is characterized in that mesoporous silica material particles are spherical, the sphere diameter is adjustable within the range of 40-400nm; the specific surface area is large, the particle size distribution is narrow; and the hole diameter is adjustable within the range of 1.9-4.0nm. The materials are widely applied in catalysis, separation, sensors, nano-reactors, optical materials and other aspects.
Description
Technical field
The invention belongs to the inorganic porous material preparation field, relate to the preparation of the mesoporous silica spheres of a series of nano-scales.Relate in particular to a kind of particle diameter regulation and control and preparation method of nanoscale mesoporous silica spheres.
Technical background
1992, U.S. Mobil company reported to be the method for template synthetic M41S series mesoporous silicon oxide under alkaline condition with the tensio-active agent.Such material has regular periodicity duct, highly homogeneous aperture, high specific surface area, good thermostability, make its in catalysis, absorption and separate, semi-conductor and fields such as opto-electronic device and transmitter have very high theoretical investigation and actual application value.But the particle size of traditional mesopore silicon oxide generally micron to centimetre between, and pattern heterogeneity, and these character have influenced the application of mesoporous material in some field to a great extent.
In materials chemistry, effectively the size of control material is the target that people pursue always.The nanoscale material has special surface and interface effect, small-size effect, quantum size effect and macro quanta tunnel effect etc.Having some special effects when the mesoporous material particle reaches nano-scale equally produces, for example, Kaifeng Lin (Journal of Catalysis, 2008,254,64-70) grade studies show that the Ti-MCM-41 of nano-scale shows than common Ti-MCM-41 better catalytic performance in the epoxidation catalyzed reaction of tetrahydrobenzene.In addition, the nano-scale mesoporous material has a wide range of applications at aspects such as biomacromolecule separation, chromatographic column packing material, medicinal slow release agent, micro semiconductor materials.
According to relevant patent and bibliographical information, the method that a variety of synthesizing mesoporous silicon dioxide balls have been arranged at present, the size of the mesoporous silica spheres that wherein most of method synthesizes micron to centimetre between, for example, Chinese patent CN1254436C has reported a kind of preparation method of mesopore molecular sieve of spherical narrow size distribution, the median size of this mesoporous ball is 2 μ m, and size distribution is between 1～4 μ m.The precedent that successfully synthesizes the nano-scale mesoporous silica spheres was also arranged both at home and abroad, for example, Stephen Mann (Adv.Mater.2001,13,649～652) etc. at room temperature make template with cetyl trimethylammonium bromide, tetraethoxy is done the silicon source, and having synthesized size distribution is the mesoporous silicon oxide of 15～100nm.But its size is non-adjustable, building-up process is complicated (needing repeatedly to change easy pH value in the building-up process), synthetic required time long (6 months).And can be adjustable in the nanoscale scope the diameter of mesoporous silica spheres, and the method for its narrow diameter distribution not be appeared in the newspapers as yet.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of nanoscale mesoporous silica spheres.Opened up a kind of new way of controlling the mesoporous silica spheres particle diameter.
Technical scheme of the present invention: be to be template with the quaternary cationics, in basic solution, synthetic by sol-gel method, and by changing synthesis condition, regulate and control the size of its nano-scale, thereby reach the modulation of diameter in the nanoscale scope of mesoporous silica spheres.The present invention also by changing the carbon chain lengths of cats product, changes the aperture of nano-scale mesoporous silica spheres, thereby reaches the regulation and control of aperture between 1.9～4nm.
Concrete technical scheme of the present invention is: a kind of preparation method of nanoscale mesoporous silica spheres, and its concrete steps are:
Quaternary cationics is joined in the alkaline solution as template, tensio-active agent is dissolved fully, be warming up to 30～90 ℃, add the silicon source; Keep temperature and stirring, after the white flocks to be generated, continue to stir 1～48 hour; Filter then, washing, normal temperature is dry down, and removed template method obtains product; Template: H wherein
2O: SiO
2: the mol ratio of alkali is 0.02～0.12: 420～1360: 1: 0.1～0.5.
The structural formula of described quaternary cationics is C
nH
2n+1N (CH
3)
3X, n=8～22 wherein, X=Cl or Br.Preferred described alkali is sodium hydroxide, potassium hydroxide, hydrated barta or ammoniacal liquor; Described silicon source is methyl silicate, tetraethoxy, positive silicic acid propyl ester, sodium metasilicate or silicon sol.
Preferred building-up process temperature of reaction is 50～85 ℃.The preferred building-up process reaction times is 1～10 hour.
Beneficial effect:
The present invention has synthesized the mesoporous silica spheres of a series of nano-scales.Its narrow diameter distribution, and particle diameter is adjustable between 40nm～400nm; The duct is regular, and the aperture is adjustable between 1.9～4nm.Being uniformly dispersed between the particle, is good nano-scale Metaporous silicon dioxide material, in Industrial Catalysis, and the separation of biomacromolecule, the packing material of chromatographic column, medicinal slow release agent, aspects such as micro semiconductor material have a wide range of applications.
Description of drawings
Fig. 1-a is the X-ray diffractogram (XRD) of embodiment 1 products obtained therefrom.
Fig. 1-b is the field emission Electronic Speculum figure (FE-SEM) of embodiment 1 products obtained therefrom.
Fig. 1-c is the high power transmission electron microscope picture (HRTEM) of embodiment 1 products obtained therefrom.
Fig. 1-d is the size distribution figure of embodiment 1 products obtained therefrom.
Fig. 2 is the FE-SEM figure of embodiment 5 products obtained therefroms.
Fig. 3 is the FE-SEM figure of embodiment 6 products obtained therefroms.
Fig. 4-a is the FE-SEM figure of embodiment 12 products obtained therefroms.
Fig. 4-b is the HRTEM figure of embodiment 12 products obtained therefroms.
Embodiment
[example 1]
1.0g cetyl trimethylammonium bromide (CTAB) is dissolved in the 192ml deionized water, stir to clarify, drip the NaOH solution of 1.0ml 1mol/L, under 80 ℃, stir above-mentioned solution, add the tetraethoxy of 5.68ml, keep above-mentioned condition, stirred 2 hours, and obtained containing the reaction solution of white precipitate.Then mixed solution is filtered, normal temperature is dry down, obtains the white solid powder, and powder is put into retort furnace under 550 ℃, earlier logical nitrogen roasting 1 hour, the blowing air roasting is 4 hours then, promptly obtains the mesoporous silicon oxide after the burn off template, analyzes test shows through XRD, HRSEM, BET, HRTEM, size distribution etc., its microscopic appearance is spherical, median size 49nm, particle size distribution range 40～55nm, specific surface are 803m
2/ g, the aperture is 2.2nm, its XRD, FE-SEM, HRTEM and size distribution be respectively as Fig. 1-a, 1-b, 1-c, 1-d.
[example 2]
With embodiment 1 operation, only change the amount of NaOH, drip the NaOH solution of 2.0ml 1mol/L, reaction gained sample average particle diameter is 180nm, specific surface is 747m
2/ g, the aperture is 2.6nm.
[example 3]
Reactant ratio and reaction conditions are changed into eight alkyl trimethyl ammonium bromides with embodiment 2 with template, and reaction gained sample average particle diameter is 380nm, and specific surface is: 971m
2/ g, the aperture is 1.9nm.
[example 4]
Reactant ratio and reaction conditions are changed into the eicosyl trimethylammonium bromide with embodiment 2 with template, and reaction gained sample average particle diameter is 40nm, and specific surface is: 670m
2/ g, the aperture is 4.0nm.
[example 5]
The amount of reaction conditions and other reactant is changed into 292ml with embodiment 2 with the water yield, and reaction gained sample average particle diameter is 140nm, and specific surface is: 900m
2/ g, the aperture is 2.8nm, its FE-SEM such as Fig. 2.
[example 6]
The amount of reaction conditions and other reactant is with embodiment 1, and CTAB changes into 0.8g with template, and reaction gained sample average particle diameter is 85nm, and specific surface is: 800m
2/ g, the aperture is 2.6nm, its FE-SEM such as Fig. 3.
[example 7]
The amount of reaction conditions and other reactant is changed into 3.68ml with embodiment 1 with the amount of tetraethoxy, and reaction gained sample average particle diameter is 120nm, and specific surface area is 795m
2/ g, the aperture is 2.6nm.
[example 8]
The amount of reaction conditions and other reactant is with embodiment 1, and it is 25% strong aqua that alkali source is changed into the 5ml massfraction, and reaction gained sample average particle diameter is 300nm, and specific surface is 750m
2/ g, the aperture is 2.7nm.
[example 9]
Reactant ratio and reaction conditions be with embodiment 2, and the sodium metasilicate of amount such as is changed in the silicon source, and reaction gained sample average particle diameter is 140nm, and specific surface area is 800m
2/ g, the aperture is 2.6nm.
[example 10]
Reactant ratio and other reaction conditionss be with embodiment 1, and the methyl silicate of amount such as is changed in the silicon source, and the median size of reaction gained sample is 80nm, and specific surface area is 731m
2/ g, the aperture is 2.6nm, its HRTEM, FE-SEM such as Fig. 4-a, 4-b.
[example 11]
Reactant ratio and other reaction conditionss be with embodiment 1, and the positive silicic acid propyl ester of amount such as is changed in the silicon source, and the median size of reaction gained sample is 40nm, and specific surface area is 970m
2/ g, the aperture is 2.6nm.
[example 12]
Reactant ratio and reaction conditions will extend to 10 hours the reaction times with embodiment 1, and reaction gained sample average particle diameter is 60nm, and specific surface area is 923m
2/ g, the aperture is 2.5nm.
[example 13]
Reactant ratio and other reaction conditions are with embodiment 2, and temperature of reaction becomes 40 ℃, and reaction gained sample average particle diameter is 150nm, and specific surface area is 786m
2/ g, the aperture is 2.7nm.
Claims (6)
1. the preparation method of a nanoscale mesoporous silica spheres, its concrete steps are:
Quaternary cationics is joined in the alkaline solution as template, tensio-active agent is dissolved fully, be warming up to 30～90 ℃, add the silicon source; Keep temperature and stirring, after the white flocks to be generated, continue to stir 1～48 hour; Filter then, washing, normal temperature is dry down, and removed template method obtains product; Template: H wherein
2O: SiO
2: the mol ratio of alkali is 0.02～0.12: 420～1360: 1: 0.1～0.5.
2. according to the described method of claim 1, the structural formula that it is characterized in that described quaternary cationics is C
nH
2n+1N (CH
3)
3X, n=8～22 wherein, X=Cl or Br.
3. according to the described method of claim 1, it is characterized in that described alkali is sodium hydroxide, potassium hydroxide, hydrated barta or ammoniacal liquor.
4. according to the described method of claim 1, it is characterized in that described silicon source is methyl silicate, tetraethoxy, positive silicic acid propyl ester, sodium metasilicate or silicon sol.
5. according to the described method of claim 1, it is characterized in that the building-up process temperature of reaction is 50～85 ℃.
6. according to the described method of claim 1, it is characterized in that the building-up process reaction times is 1～10 hour.
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| CN102732379A (en) * | 2012-04-23 | 2012-10-17 | 上海应用技术学院 | Temperature-sensitive capsules of silica-loaded essential oil, and preparation method thereof |
| CN103534208A (en) * | 2011-05-13 | 2014-01-22 | 默克专利有限公司 | Process for producing inorganic particulate material |
| CN104524587A (en) * | 2014-12-03 | 2015-04-22 | 上海交通大学 | Antibacterial drug system and preparation method thereof |
| CN104591194A (en) * | 2014-12-25 | 2015-05-06 | 中国建材国际工程集团有限公司 | Preparation method of controllable-particle-size monodisperse spherical nano SiO2 powder |
| CN105250239A (en) * | 2015-11-16 | 2016-01-20 | 遵义医学院 | Bilobalide nanometer controlled-release oral preparation and preparation method thereof |
| CN105731466A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A monodisperse nanometer mesoporous silica-titanium dioxide composite sphere and a synthetic method thereof |
| JP2017171509A (en) * | 2016-03-18 | 2017-09-28 | 株式会社豊田中央研究所 | Method for producing mesoporous silica nanoparticle |
| CN107915230A (en) * | 2017-11-30 | 2018-04-17 | 程桂平 | A kind of preparation method of nanometer particle |
| CN109650377A (en) * | 2019-01-30 | 2019-04-19 | 东华大学 | A method of mesoporous silicon dioxide modified carbon dots are prepared with hydro-thermal method |
| CN109705627A (en) * | 2019-01-30 | 2019-05-03 | 东华大学 | A method of mesoporous silicon dioxide modified carbon dots are prepared to be calcined method |
| CN109896528A (en) * | 2019-02-25 | 2019-06-18 | 华中科技大学 | Mesoporous silica nanospheres and preparation method thereof and the application in drug loading |
| CN110550638A (en) * | 2019-09-25 | 2019-12-10 | 东北大学 | Preparation method of monodisperse large-aperture mesoporous silica nanoparticles |
| US10577250B2 (en) | 2011-05-13 | 2020-03-03 | Merck Patent Gmbh | Process for producing of inorganic particulate material |
| CN111848097A (en) * | 2020-07-28 | 2020-10-30 | 安徽陆海石油助剂科技有限公司 | High-temperature high-density mud system for oil-based drilling fluid |
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2009
- 2009-05-13 CN CNA200910027917XA patent/CN101559952A/en active Pending
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| US10577250B2 (en) | 2011-05-13 | 2020-03-03 | Merck Patent Gmbh | Process for producing of inorganic particulate material |
| CN103534208A (en) * | 2011-05-13 | 2014-01-22 | 默克专利有限公司 | Process for producing inorganic particulate material |
| US9517268B2 (en) | 2011-05-13 | 2016-12-13 | Merck Patent Gmbh | Process for producing inorganic particulate material |
| CN102732379B (en) * | 2012-04-23 | 2013-08-14 | 上海应用技术学院 | Temperature-sensitive capsules of silica-loaded essential oil, and preparation method thereof |
| CN102732379A (en) * | 2012-04-23 | 2012-10-17 | 上海应用技术学院 | Temperature-sensitive capsules of silica-loaded essential oil, and preparation method thereof |
| CN104524587A (en) * | 2014-12-03 | 2015-04-22 | 上海交通大学 | Antibacterial drug system and preparation method thereof |
| CN105731466A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A monodisperse nanometer mesoporous silica-titanium dioxide composite sphere and a synthetic method thereof |
| CN104591194A (en) * | 2014-12-25 | 2015-05-06 | 中国建材国际工程集团有限公司 | Preparation method of controllable-particle-size monodisperse spherical nano SiO2 powder |
| CN105250239A (en) * | 2015-11-16 | 2016-01-20 | 遵义医学院 | Bilobalide nanometer controlled-release oral preparation and preparation method thereof |
| CN105250239B (en) * | 2015-11-16 | 2018-09-18 | 遵义医学院 | Ginkgolides nanometer delays controlled release oral dosage formulations and preparation method thereof |
| JP2017171509A (en) * | 2016-03-18 | 2017-09-28 | 株式会社豊田中央研究所 | Method for producing mesoporous silica nanoparticle |
| CN107915230A (en) * | 2017-11-30 | 2018-04-17 | 程桂平 | A kind of preparation method of nanometer particle |
| CN109650377A (en) * | 2019-01-30 | 2019-04-19 | 东华大学 | A method of mesoporous silicon dioxide modified carbon dots are prepared with hydro-thermal method |
| CN109705627A (en) * | 2019-01-30 | 2019-05-03 | 东华大学 | A method of mesoporous silicon dioxide modified carbon dots are prepared to be calcined method |
| CN109896528A (en) * | 2019-02-25 | 2019-06-18 | 华中科技大学 | Mesoporous silica nanospheres and preparation method thereof and the application in drug loading |
| CN109896528B (en) * | 2019-02-25 | 2021-02-02 | 华中科技大学 | Mesoporous silica nanosphere, preparation method thereof and application thereof in drug loading |
| CN110550638A (en) * | 2019-09-25 | 2019-12-10 | 东北大学 | Preparation method of monodisperse large-aperture mesoporous silica nanoparticles |
| CN111848097A (en) * | 2020-07-28 | 2020-10-30 | 安徽陆海石油助剂科技有限公司 | High-temperature high-density mud system for oil-based drilling fluid |
| CN111848097B (en) * | 2020-07-28 | 2022-04-12 | 安徽陆海石油助剂科技有限公司 | High-temperature high-density mud system for oil-based drilling fluid |
| CN117487515A (en) * | 2023-12-27 | 2024-02-02 | 甬江实验室 | Composite polishing abrasive particles with catalytic activity and preparation method thereof |
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Open date: 20091021 |