CN1167616C - Process for preparing mesoporous SiO2 microparticles material - Google Patents
Process for preparing mesoporous SiO2 microparticles material Download PDFInfo
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- CN1167616C CN1167616C CNB011451629A CN01145162A CN1167616C CN 1167616 C CN1167616 C CN 1167616C CN B011451629 A CNB011451629 A CN B011451629A CN 01145162 A CN01145162 A CN 01145162A CN 1167616 C CN1167616 C CN 1167616C
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Abstract
The present invention discloses a preparation method of a silicon dioxide mesoporous fine particle. 2 to 9 portions of silicon dioxide is added to 10 to 18 portions of 30 to 40% sodium hydroxide solution or potassium hydroxide solution to prepare water soluble silicate collosol; 10 to 40 portions of low molecular organic solvent is added, and is uniformly mixed with 2 to 10 portions of surface active agent as a template to prepare inorganic salt collosol containing a template; 10 to 20 portions of 30 to 40% inorganic acid salt solution is added to 10 to 40 portions of the low molecular organic solvent, and is uniformly mixed with 2 to 10 portions of surface active agent; all the inorganic salt collosol containing templates are add, stirred, made stand at room temperature for 2 to 48 hours, filtered, washed with water, or washed with alcohol for 3 to 5 times for the elimination of templates, dried at 80 to 180 DEG C to prepare the silicon dioxide mesoporous fine particle. The preparation method has the advantages of low cost, simple preparation process, etc.
Description
Technical field
The invention belongs to and relate to a kind of silicon oxide.
Background technology
It is in the ascendant that template prepares the research that contains regular mesopore (mostly being hexagonal mesoporous) material at present, and the preparation system is varied, is used for aspects such as mechanism research, mesoporous photovoltaic effect, magnetic effect, hole wall modification and adsorption catalysis research more.Mould plate technique is because of the biomineralization process, and is subjected to people's attention more and more.It should be noted that in the biomineralization pattern that inorganic species nucleation, growth, distortion depend on the pre-assembling of organic molecule, and guide nucleation and process of growth.From the bionics angle, people utilize solid geometry effect, the self-assembly effect of surfactant molecule, can form micella spherical, bar-shaped, ellipsoid shaped in lower concentration (more than the CMC); Then can form the double-deck mesomorphic phase of La, L in higher concentration (10 times more than the CMC)
3The sponge phase, and then can form accumulation hexagonal liquid crystal phase more closely, by the interaction between polar head and the inorganic species, make the gelation on template of inorganic species, have the novel material of the different sight schema structures that are situated between in order to preparation.
Mould plate technique occupies important status always in the research of molecular sieve synthetic.In the previous micro porous molecular sieve building-up process with ion (as Ca
2+) as template, and they are present in the specific position of the basket structure (as the β cage) of framework of molecular sieve structure, become integral part important in the molecular sieve, and they had both played the effect of the electric charge in the balance lattice, played the expansion duct simultaneously again.
1992, Mobil company scientists (Kresge C T, Leonowicz M E, Roth W J et al.Orderedmesoporous molecular sieves synthesized by a liquid-crystal template mechanism.Nature, 1992, research work 359:710.) makes molecular template technology such as template prepare mesopore molecular sieve research to be able to flourish.Subsequently, liquid crystal templated (KresgeCT, LeonowiczME, RothWJetal.Ordered mesoporous molecularsieves synthesized by a liquid-crystal template mechanism.Nature, 1992,359:710; Attard G S, Clyde J C, Goltner C G.Liquid-crystalline phases as templates for thesynthesis of mesoporous silica.Nature, 1995,378:366-368.), emulsion template (ImhofA, PineK.Ordered macroporous materials by emulsion templating.Nature, 1997,389:948-951.), and even bacterium template (Davis S, Burkett S, Mendelson N et al.Bacterial templating Of orderedmacrostructures in silica and silica-surfactant mesophases.Nature, 1997,385:420-423.) wait mould plate technique to be used widely.
In the above-mentioned technology, the microvoid structure that obtains by the ion template, by liquid crystal templated what obtain is hexagonal mesoporous structure, what obtained by emulsion template is the regular spherical pore passage structure, and what obtained by the bacterium template is bacterium shape pore structure.Its weak point of above-mentioned technology is that cost is higher, the manufacturing process complexity.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide a kind of with low cost, manufacturing process simply prepares the method that inside has the mesoporous SiO 2 microparticles material of laminate structure.
Technical scheme of the present invention is summarized as follows:
(1) weight percent that 2-9 weight part silicon-dioxide is joined the 10-18 weight part is in the sodium hydroxide or potassium hydroxide solution of 30-40%, make water-soluble silicate colloidal sol, add 10-40 weight part low mass molecule alcohol or ether again, with the rapping plate effect tensio-active agent 2-10 weight part mix, make the inorganic salt colloidal sol that contains template;
(2) get one of ammonium sulfate that weight percent concentration is 30-40%, ammonium nitrate, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, the 10-20 weight part, add described low mass molecule alcohol or ether 10-40 weight part, mix with described tensio-active agent 2-10 weight part, add all described inorganic salt colloidal sol that contains template, stir, room temperature left standstill 2-48 hour, suction filtration, water or washing with alcohol 3-5 time, remove template,, make the mesoporous SiO 2 microparticles material that inside has laminate structure through 80-180 ℃ of drying.
Silicon-dioxide proposed by the invention is preferably 6 weight parts.
Low mass molecule alcohol proposed by the invention or ether are one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, and the parts by weight of adding are 15 parts.
Tensio-active agent proposed by the invention is one of lauryl amine, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, and the parts by weight of adding are 5 parts.
The present invention is the silicon source with the soluble silicate, is template with suitable tensio-active agent, prepares mesoporous particulate.Tensio-active agent both provided the La bilayer liquid crystal templated (inner formword claims " formpiston " again) for the silicate sol particle forms mesoporous particulate in preparation microvoid structure process, provided " exterior sheathing " for mesoporous particulate forms again.The particulate that makes, inside have layered mesoporous structure.See Fig. 1.
Adopt the prepared mesoporous particulate of the present invention, carry out x ray diffraction spectrogram and show, see Fig. 2, three diffraction peaks at little angle have characterized this mesoporous particulate and have had special mesoscopic structure, be i.e. the nanostructure of long-range order, as calculated, the interlamellar spacing of this nanostructure is 3.7nm.Electron microscope observation shows that the median size of particulate is between the 70-300nm.
The mesoporous SiO 2 microparticles material that adopts the prepared inside of the present invention to have laminate structure with silver salt dipping, drying, after the thermal treatment, forms silicon-dioxide/silver-colored composite antibacterial material.
The inside that utilizes the present invention to make has the mesoporous SiO 2 microparticles material of laminate structure, and it is with low cost, and raw material is easy to get, and is easy and simple to handle.
Description of drawings
Fig. 1 is a yin, yang template model synoptic diagram.
Fig. 2 is the X-ray diffraction spectrogram of microparticle material sample.
Embodiment
The present invention will be further described below in conjunction with embodiment.
In the following embodiments, all umbers and per-cent are all by weight.
1. 6 parts of silicon-dioxide are joined in 16 part 37.5% the sodium hydroxide or potassium hydroxide solution, boil, form water glass or potassium silicate colloidal sol, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, mixing in the lump of 5 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, room temperature is placed.
In 16 parts of concentration are 37.5% ammoniumsulphate soln, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, one of 5 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, and mix, the water glass that contains template or the potassium silicate solution that prepare are evenly added wherein, stir simultaneously.Room temperature was placed 12 hours, and suction filtration, water or ethanol are washed 4 times, and 80 ℃ of dryings promptly get inner mesoporous SiO 2 microparticles material with laminate structure.
2. 2 parts of silicon-dioxide are joined in 16 part 37.5% the sodium hydroxide or potassium hydroxide solution, boil, form water glass or potassium silicate colloidal sol, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, mixing in the lump of 5 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, room temperature is placed.
In 16 parts of concentration are 37.5% ammoniumsulphate soln, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, one of 5 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, and mix, the water glass that contains template or the potassium silicate solution that prepare are evenly added wherein, stir simultaneously.Room temperature was placed 12 hours, and suction filtration, water or ethanol are washed 4 times, and 80 ℃ of dryings promptly get inner mesoporous SiO 2 microparticles material with laminate structure.
3. 9 parts of silicon-dioxide are joined in 16 part 37.5% the sodium hydroxide or potassium hydroxide solution, boil, form water glass or potassium silicate colloidal sol, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, mixing in the lump of 5 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, room temperature is placed.
In 16 parts of concentration are 37.5% ammoniumsulphate soln, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, one of 5 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, and mix, the water glass that contains template or the potassium silicate solution that prepare are evenly added wherein, stir simultaneously.Room temperature was placed 12 hours, and suction filtration, water or ethanol are washed 4 times, and 80 ℃ of dryings promptly get inner mesoporous SiO 2 microparticles material with laminate structure.
4. 6 parts of silicon-dioxide are joined in 16 part 37.5% the sodium hydroxide or potassium hydroxide solution, boil, form water glass or potassium silicate colloidal sol, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, mixing in the lump of 2 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, room temperature is placed.
16 parts of concentration is in 37.5% the ammoniumsulphate soln, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, one of 2 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, and mix, the water glass that contains template or the potassium silicate solution that prepare are evenly added wherein, stir simultaneously.Room temperature was placed 12 hours, and suction filtration, water or ethanol are washed 4 times, and 80 ℃ of dryings promptly get inner mesoporous SiO 2 microparticles material with laminate structure.
5. 6 parts of silicon-dioxide are joined in 16 part 37.5% the sodium hydroxide or potassium hydroxide solution, boil, form water glass or potassium silicate colloidal sol, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, mixing in the lump of 10 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, room temperature is placed.
In 16 parts of concentration are 37.5% ammoniumsulphate soln, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, one of in 10 parts of lauryl amines, sodium laurylsulfonate, the palmityl trimethyl ammonium chloride, and mix, the water glass that contains template or the potassium silicate solution that prepare are evenly added wherein, stir simultaneously.Room temperature was placed 12 hours, and suction filtration, water or ethanol are washed 4 times, and 80 ℃ of dryings promptly get inner mesoporous SiO 2 microparticles material with laminate structure.
6. 6 parts of silicon-dioxide are joined in 16 part 37.5% the sodium hydroxide or potassium hydroxide solution, boil, form water glass or potassium silicate colloidal sol, one of add 15 parts of low mass molecule alcohols or ether: in methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, the ethylene glycol ethyl ether, mixing in the lump of 5 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, room temperature is placed.
In 16 parts of concentration are 37.5% ammoniumsulphate soln, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, one of 5 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, and mix, the water glass that contains template or the potassium silicate solution that prepare are evenly added wherein, stir simultaneously.Room temperature was placed 12 hours, and suction filtration, water or ethanol are washed 3 times, and 120 ℃ of dryings promptly get inner mesoporous SiO 2 microparticles material with laminate structure.
7. 6 parts of silicon-dioxide are joined in 16 part 37.5% the sodium hydroxide or potassium hydroxide solution, boil, form water glass or potassium silicate colloidal sol, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, mixing in the lump of 5 parts of lauryl amines, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, room temperature is placed.
In 16 parts of concentration are 37.5% ammoniumsulphate soln, add 15 parts of low mass molecule alcohols or ether: one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, one of in 5 parts of lauryl amines, sodium laurylsulfonate, the palmityl trimethyl ammonium chloride, and mix, the water glass that contains template or the potassium silicate solution that prepare are evenly added wherein, stir simultaneously.Room temperature was placed 12 hours, and suction filtration, water or ethanol are washed 4 times, and 180 ℃ of dryings promptly get inner mesoporous SiO 2 microparticles material with laminate structure.
Claims (4)
1. one kind prepares the method that inside has the mesoporous SiO 2 microparticles material of laminate structure, it is characterized in that it comprises the steps:
(1) weight percent that 2-9 weight part silicon-dioxide is joined the 10-18 weight part is in the sodium hydroxide or potassium hydroxide solution of 30-40%, make water-soluble silicate colloidal sol, add 10-40 weight part low mass molecule alcohol or ether again, with the rapping plate effect tensio-active agent 2-10 weight part mix, make the inorganic salt colloidal sol that contains template;
(2) get one of ammonium sulfate that weight percent concentration is 30-40%, ammonium nitrate, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, the 10-20 weight part, add described low mass molecule alcohol or ether 10-40 weight part, mix with described tensio-active agent 2-10 weight part, add all described inorganic salt colloidal sol that contains template, stir, room temperature left standstill 2-48 hour, suction filtration, water or washing with alcohol 3-5 time, remove template,, make the mesoporous SiO 2 microparticles material that inside has laminate structure through 80-180 ℃ of drying.
2, a kind of method that inside has the mesoporous SiO 2 microparticles material of laminate structure for preparing according to claim 1 is characterized in that described silicon-dioxide is 6 weight parts.
3, a kind of method that inside has the mesoporous SiO 2 microparticles material of laminate structure for preparing according to claim 1, it is characterized in that described low mass molecule alcohol or ether are one of methyl alcohol, ethanol, Virahol, propyl carbinol, methyl ethyl ether, ether, ethylene glycol ethyl ether, the parts by weight of adding are 15 parts.
4, a kind of method that inside has the mesoporous SiO 2 microparticles material of laminate structure for preparing according to claim 1, it is characterized in that described tensio-active agent is one of lauryl amine, sodium laurylsulfonate, palmityl trimethyl ammonium chloride, the parts by weight of adding are 5 parts.
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| CNB011451629A CN1167616C (en) | 2001-12-31 | 2001-12-31 | Process for preparing mesoporous SiO2 microparticles material |
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| KR101102115B1 (en) * | 2004-07-08 | 2012-01-02 | 닛키 쇼쿠바이카세이 가부시키가이샤 | Process for producing fine silica-based particle, coating composition for coating film formation, and base with coating film |
| KR100921185B1 (en) | 2007-11-09 | 2009-10-13 | 학교법인 함주학원 | A production method of porous silica |
| CN101555044B (en) * | 2009-03-25 | 2011-04-20 | 吴帅 | Method for softening hardwater by taking river-sand as raw material |
| CN101973554B (en) * | 2010-09-16 | 2012-10-31 | 昆明理工大学 | Method for preparing mesoporous silica material |
| CN102583404A (en) * | 2012-03-15 | 2012-07-18 | 天津大学 | Mesoporous silicon dioxide nanometer particle and preparation method |
| CN102774844B (en) * | 2012-08-03 | 2015-04-15 | 西安文理学院 | Method for preparing dual acid type ordered cage mesoporous silica |
| KR102071364B1 (en) * | 2018-06-01 | 2020-01-31 | 전주대학교 산학협력단 | Biomass Fly Ash as an Alternative Approach for Synthesis of Amorphous Silica Nanoparticles with High Surface Area and Method of Manufacturing |
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