CN1341550A - Preparation method of silicon oxide nano pore molecular sieve film - Google Patents
Preparation method of silicon oxide nano pore molecular sieve film Download PDFInfo
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- CN1341550A CN1341550A CN 01126472 CN01126472A CN1341550A CN 1341550 A CN1341550 A CN 1341550A CN 01126472 CN01126472 CN 01126472 CN 01126472 A CN01126472 A CN 01126472A CN 1341550 A CN1341550 A CN 1341550A
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Abstract
The preparation method of silicon oxide nanometer porous molecular sieve film is characterized by adopting mixed non-ionic surfactant as structural guide agent, mixing the prehydrolyzed inorganic precursor, surfactant, volatile non-aqueous solvent, proper quantity of water and hydrochloric acid, stirring them and making them produce reaction, then utilizing quick volatilization of solvent and utilizing sol-gel and liquid crystal template self-assembling process to form 2-D and 3-D high-ordered organic-inorganic composite silicon oxide film material. After the film material is undergone the processes of ageing, high-temp. calcination or ethyl alcohol extraction to remove surfactant, it can be formed into the silicon oxide molecular sieve film with large specific surface and high porosity. Said invented silicon oxide molecular sieve film possesses ectensive application in the fields of separation, catalysis and sensor, etc.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to the preparation method of a kind of degree of order height, silicon oxide nano pore molecular sieve film that specific surface area is big.
Technical background
With amphiphilic (hydrophilic, oleophylic) molecule is structure directing agent and the synthesizing ordered mano-porous material of template, and extremely important influence is arranged on materialogy.This important discovery, it is higher to have introduced a kind of specific surface for scientific circles and industry member, duct homogeneous, and the orderly type material of dimension.This material can be designed to certain pattern, as film, thin slice, fiber, ball, polyhedron etc.Wherein nano-porous thin film material purposes in laboratory and industrial production is the most extensive, because its specific surface area is big, the surface is easy to modify, and duct one dimension or three-dimensional communication have a good application prospect in many-sides such as separation, sensing, catalysis.Yet at present as the commonplace silicon oxide nano pore thin-film material of application, preparation method's more complicated, structurally ordered degree is not high, influences its range of application.
Summary of the invention
The objective of the invention is to propose a kind of simple, easy preparation method of row, the silicon oxide nano pore molecular sieve film being convenient to promote, and big by thin-film material degree of order height, the specific surface of this method preparation, thereby its range of application is wider.
The preparation method of the silicon oxide nano pore molecular sieve film that the present invention proposes, adopting nonionogenic tenside is the solvent of structure directing agent and non-aqueous reaction system, concrete steps are as follows: at first will mix nonionogenic tenside (is structure directing agent, be called for short SDA) be dissolved in the non-aqueous volatile solvent, the mass ratio of SDA and solvent (being the SDA/ solvent) is 0.05～0.15, the silicon source is dissolved in contains small amount of hydrochloric acid (HCl) and water (H simultaneously
2O) in the same non-aqueous volatile solvent, make silicon sol, silicon source, HCl, H
2The mass ratio of O and solvent (also being silicon source/solvent, hydrochloric acid/solvent, water/solvent) is respectively: 0.2～0.4,0.005～0.6,0～0.18; Then above-mentioned two kinds of solution are mixed, stir, utilize solvent evaporates,, form the organic-inorganic composite film material of bidimensional and three-dimensional high-sequential through colloidal sol, gel and liquid crystal templated self assembling process; Mould material is after wearing out, and tensio-active agent is removed in high-temperature roasting or ethanol extracting again, promptly gets the silicon oxide molecular sieve thin film that specific surface area is big, porosity is high.
The present invention adopts acidic catalyst, relies on the hydrolytic polycondensation in silicon source, and the liquid crystal templated effect that mixes nonionogenic tenside forms the bidimensional and the three-D nano material of high-sequential.Wherein methyl silicate (TMOS), tetraethoxy (TEOS) can be selected in the silicon source, just silicic acid propyl ester (TPOS), butyl silicate (TBOS) is a kind of, generally selects TEOS for use.Mix nonionogenic tenside can select for use mix Pluronic series with Brij series, mixes Polyglycol serial and Brij series, mixed polyoxyethylene alkylamine and Tetronic series or mixed polyoxyethylene alkylamine and Triton series etc.Here, back two kinds of mixed systems also can prepare orderly microporous membrane material.Solvent adopts lower boiling, high polar non-aqueous reaction system, as ethanol, tetrahydrofuran (THF), acetonitrile, or its mixture.It is 1～2 relatively good that the pH value of reaction mother liquor is controlled to be.
Among the present invention, when removing tensio-active agent employing high-temperature roasting, maturing temperature generally is higher than 450 ℃, and comparatively suitable temperature is 500～550 ℃, and keeps under this temperature 5～8 hours.Perhaps adopt the alcohol reflux extracting to remove tensio-active agent and product is got final product in drying at room temperature.
Mix the use of nonionogenic tenside among the present invention, can obtain than single surfactant system better experiment results commonly used in the world, comprise the structurally ordered degree that has improved mano-porous material, cause changing mutually and the formation of novel material, micropore district etc. is reduced in the aperture.And, the suitable proportioning of mixed surfactant can be regulated the structure of thin-film material, (for example, mixing nonionogenic tenside B50-6600 and Brij35 mass ratio is 7: 3 o'clock, and material is a three-dimensional cubic structure can to cause changing mutually or reducing on the contrary the structurally ordered property of material in the time of too much; When B50-6600 and Brij35 mass ratio were 7: 7, material was the bidimensional hexagonal structure.)。The effect of anhydrous solvent not only can be controlled hydrolysis, the polycondensation speed in silicon source, and has created favourable condition for the solvent evaporates film forming; The acidity of reaction mother liquor has very significant effects to the structurally ordered property of material, and the present invention controls suitable pH value can guarantee quality of materials and preparation cycle.The aperture of the silicon oxide nano pore molecular sieve film material that is made by the present invention can be regulated and control to 10 nanometers in 1.4 nanometers, and specific surface can be up to 860m
2/ g, pore volume can be up to 1.4cm
3/ g, mould material are bidimensional hexagonal structure or three-dimensional cubic structure.This molecular sieve film material can be easy " plating " in the various substrates of different curvature, substrate can comprise sheet glass, silicon chip, sheet mica and plastics etc.
The present invention is not only applicable to thin-film material, but also is applicable to other mano-porous materials that utilize solvent evaporates and template self-assembly to obtain such as preparation thin slice, fiber.The inventive method is simple, and the combined coefficient height, and prepared silicon oxide film performance is more improved, and can expand its range of application greatly, especially is widely used at aspects such as separation, catalysis, transmitters.
The specific embodiment
Embodiment 1:
Pluronics P123 (EO with the certain mass ratio20PO
70EO
20) and Brij35 (C12EO
23) be dissolved in the absolute ethyl alcohol, in addition with TEOS, H2O, 2MHCl, ethanol mix according to a certain ratio, preparation SiO2Colloidal sol. Separately Stir after two hours and mix, mixed liquor continues to stir 1 hour, is transferred to then in the culture dish, dries film forming. 2 After-5 days film is taken out, in 100 ℃ of lower hydro-thermals one day. Then product is placed the Muffle furnace Program to be warming up to 550 ℃, and this roasting temperature 5 hours; Or in ethanol, reflux and remove surfactant. Female in the culture dish The quality proportioning of liquid raw material is as follows: P123: Brij35: TEOS: 2MCl: H2O: ethanol=1.0: 0.3: 2.08: 0.1: 0.9: 15. This membrane material of the analyses such as PXRD, BET and TEM test proof is high-quality two The silicon oxide film material of dimension hexagonal structure (space group is p6mm). The specific area of material is 780m2/ g, pore volume are 1.2cm3/ g, the aperture is 7.8 nanometers.
Embodiment 2:
Pluronics F127 (EO with the certain mass ratio106PO
70EO
106) and Brij78 (C16EO
20) be dissolved in the absolute ethyl alcohol, in addition with TMOS, H2O, 2M HCl, ethanol mix according to a certain ratio, preparation SiO2Colloidal sol. Separately Stir after two hours and mix, mixed liquor continues to stir 1 hour, is transferred to then in the culture dish, dries film forming. 2-After 5 days film is taken out, in 100 ℃ of lower hydro-thermals one day. Then product is placed 550 ℃ of lower roastings 5.5 of Muffle furnace Hour; Or in ethanol, reflux and remove surfactant. The quality proportioning of mother liquor raw material is as follows in the culture dish: F127: Brij78: TMOS: 2MCl: H2O: ethanol=0.7: 0.1: 1.52: 0.1: 0.9: 15. PXRD, This membrane material of the analysis such as BET and TEM test proof is high-quality three-dimensional cubic structure (space group is Im-3m) The silicon oxide film material. The specific area of material is 620m2/ g, pore volume are 1.0cm3/ g, the aperture is 6.3 to receive Rice.
Embodiment 3:
Polyglycol B50-6600 (EO with the certain mass ratio39BO
47EO
39) be dissolved in the absolute ethyl alcohol with Brij35, in addition with TEOS, H2O, 2M HCl, ethanol mix according to a certain ratio, preparation SiO2Colloidal sol. Stir separately Mix after two hours, mixed liquor continues to stir 1 hour, is transferred to then in the culture dish, dries film forming. 2-5 days After film is taken out, in 100 ℃ of lower hydro-thermals one day. Then product is placed 550 ℃ of lower roastings of Muffle furnace 5 hours; Or in ethanol, reflux and remove surfactant. The quality proportioning of mother liquor raw material is as follows in the culture dish: B50-6600: Brij35: TEOS: 2MCl: H2O: ethanol=0.7: 0.3: 2.08: 0.1: 0.9: 15. PXRD, This membrane material of the analysis such as BET and TEM test proof is high-quality three-dimensional cubic structure (space group is Im-3m) The silicon oxide film material. The specific area of material is 650m2/ g, pore volume are 1.1cm3/ g, the aperture is 9.2 to receive Rice.
Embodiment 4:
Polyglycol B50-6600 and the Brij35 of certain mass ratio are dissolved in the absolute ethyl alcohol, in addition with TEOS, H2O, 2M HCl, ethanol mix according to a certain ratio, preparation SiO2Colloidal sol. Stir separately after two hours and mix, mixed Close liquid and continue to stir 1 hour, be transferred to then in the culture dish, dry film forming. After 2-5 days film is taken out, in 100 ℃ of lower hydro-thermals one day. Then product is placed 550 ℃ of lower roastings of Muffle furnace 5 hours; Or in ethanol, reflux Remove surfactant. The quality proportioning of mother liquor raw material is as follows in the culture dish: B50-6600: Brij35: TEOS: 2MCl: H2O: ethanol=0.7: 0.7: 2.08: 0.1: 0.9: 15. PXRD, BET and TEM five equilibrium Analysing this membrane material of test proof is the silicon oxide film material of high-quality bidimensional hexagonal structure (space group is p6mm) Material. The specific area of material is 860m2/ g, pore volume are 1.4cm3/ g, the aperture is 7.8 nanometers.
Embodiment 5:
Polyglycol B50-1500 (EO with the certain mass ratio75BO
45) be dissolved in the absolute ethyl alcohol with Brij35, in addition with TEOS, H2O, 2M HCl, ethanol mix according to a certain ratio, preparation SiO2Colloidal sol. Stir separately two little The time after mix, mixed liquor continue to stir 1 hour, was transferred to then in the culture dish, dried film forming. Will after 2-5 days Film took out, in 100 ℃ of lower hydro-thermals one day. Then product is placed 550 ℃ of lower roastings of Muffle furnace 5 hours; Or Reflux in the ethanol and remove surfactant. The quality proportioning of mother liquor raw material is as follows in the culture dish: B50-1500: Brij35: TEOS: 2MCl: H2O: ethanol=0.7: 0.2: 2.08: 0.15: 0.9: 15. PXRD, This membrane material of the analysis such as BET and TEM test proof is high-quality bidimensional hexagonal structure (space group is p6mm) The silicon oxide film material. The specific area of material is 690m2/ g, pore volume are 1.1cm3/ g, the aperture is 5.9 to receive Rice.
Embodiment 6:
With 0.8 gram polyoxyethylene alkyl amine (H (C2H
4O)
x(R)N(C
2H
4O)
yH (x+y＞5)) surfactant and 0.2 gram Triton-100 are dissolved in 10 gram acetonitrile (CH3CN) in, and the method for mentioning by former examples configuration Ludox, Then two kinds of solution are mixed, be transferred to and evaporate into membranoid substance in the culture dish, directly place horse not without hydro-thermal In the stove in 550 ℃ of lower roastings to remove surfactant. Mother liquor quality proportioning is as follows: surfactant: TEOS: 2MHCl: H2O∶CH
3CN=1: 2.08: 0.1: 0.9: 15. PXRD and BET analytical test proof material Material is the poromerics of bidimensional hexagonal structure. The specific area of material is 780m2/ g, pore volume are 0.9cm3/ g, the hole The footpath is 1.4 nanometers.
Embodiment 7:
With 0.8 gram polyoxyethylene alkyl amine (H (C2H
4O)
x(R)N(C
2H
4O)
yH (x+y＞5)) surfactant with 0.2 gram Tergital TMN6 is dissolved in the 10 gram oxolanes (THF), and disposes silicon by the method that former examples are mentioned Colloidal sol mixes two kinds of solution then, is transferred to and evaporates into membranoid substance in the culture dish, directly puts without hydro-thermal In Muffle furnace in 550 ℃ of lower roastings to remove surfactant. Mother liquor quality proportioning is as follows: surfactant: TEOS: 2MHCl: H2O: THF=1: 2.08: 0.1: 0.9: 15. PXRD and BET analytical test Testimonial material is the poromerics of bidimensional hexagonal structure. The specific area of material is 720m2/ g, pore volume are 0.8 cm3/ g, the aperture is 1.5 nanometers.
Claims (7)
1, a kind of preparation method of silicon oxide nano pore molecular sieve film, it is characterized in that adopting the mixing nonionogenic tenside is that structure directing agent and non-aqueous system are solvent, concrete steps are as follows: at first will mix nonionogenic tenside and be dissolved in the non-aqueous volatile solvent, the mass ratio of SDA and solvent is 0.05～0.15, the silicon source is dissolved in the same non-aqueous volatile solvent that contains small amount of hydrochloric acid and water simultaneously, get silicon sol, the mass ratio of silicon source, hydrochloric acid, water and solvent is respectively: 0.2～0.4,0.005～0.6,0～0.18; Then above-mentioned two kinds of solution are mixed, stir, utilize solvent evaporates,, form the organic-inorganic composite film material of bidimensional and three-dimensional high-sequential through colloidal sol, gel and liquid crystal templated self assembling process; Mould material is after wearing out, and tensio-active agent is removed in high-temperature roasting or ethanol extracting again.
2, the preparation method of silicon oxide nano pore molecular sieve film according to claim 1 is characterized in that methyl silicate, tetraethoxy can be selected in used silicon source, just silicic acid propyl ester, butyl silicate is a kind of.
3, the preparation method of silicon oxide nano pore molecular sieve film according to claim 1, it is characterized in that said mixing nonionogenic tenside can be selected for use mixes Pluronic series and Brij series, mixes a kind of of Polyglycol serial and Brij series, mixed polyoxyethylene alkylamine and Tetronic series, mixed polyoxyethylene alkylamine and Triton series.
4, the preparation method of silicon oxide nano pore molecular sieve film according to claim 1 is characterized in that said solvent is lower boiling, high polar non-aqueous system: ethanol, tetrahydrofuran (THF), acetonitrile, or its mixture.
5, the preparation method of silicon oxide nano pore molecular sieve film according to claim 1 is characterized in that the pH value of reaction solution is controlled to be 1～2.
6, the preparation method of silicon oxide nano pore molecular sieve film according to claim 1, the maturing temperature that it is characterized in that removing tensio-active agent is 500～550 ℃.
7, the preparation method of silicon oxide nano pore molecular sieve film according to claim 1, it is characterized in that this molecular sieve film easily " plating " in the various substrates of different curvature.
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| CN1329113C (en) * | 2004-07-30 | 2007-08-01 | 中国科学院大连化学物理研究所 | Method of preparing adsorbent of heavy metal ion |
| CN100480205C (en) * | 2002-09-17 | 2009-04-22 | 3M创新有限公司 | Surfactant mediated porous metal oxide film |
| CN100558628C (en) * | 2005-12-27 | 2009-11-11 | 北京大学 | Si base membrane nanometer pore canal and preparation method thereof |
| CN102167398A (en) * | 2011-03-16 | 2011-08-31 | 奇瑞汽车股份有限公司 | Preparation method of normal-temperature-cured titanium dioxide sol |
| CN101691207B (en) * | 2009-09-28 | 2012-03-21 | 中山大学 | Method for preparing micro-nano structure |
| CN101863121B (en) * | 2009-04-14 | 2012-09-05 | 杨庆理 | Nano-pore membrane and manufacturing method |
| CN102992339A (en) * | 2011-09-15 | 2013-03-27 | 华东理工大学 | Solvent volatilization self-assembly method used for preparing multistage-channel SAPO-34 and SAPO-18 molecular sieves |
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| CN100480205C (en) * | 2002-09-17 | 2009-04-22 | 3M创新有限公司 | Surfactant mediated porous metal oxide film |
| CN1329113C (en) * | 2004-07-30 | 2007-08-01 | 中国科学院大连化学物理研究所 | Method of preparing adsorbent of heavy metal ion |
| CN100558628C (en) * | 2005-12-27 | 2009-11-11 | 北京大学 | Si base membrane nanometer pore canal and preparation method thereof |
| CN101863121B (en) * | 2009-04-14 | 2012-09-05 | 杨庆理 | Nano-pore membrane and manufacturing method |
| CN101691207B (en) * | 2009-09-28 | 2012-03-21 | 中山大学 | Method for preparing micro-nano structure |
| CN102167398A (en) * | 2011-03-16 | 2011-08-31 | 奇瑞汽车股份有限公司 | Preparation method of normal-temperature-cured titanium dioxide sol |
| CN102992339A (en) * | 2011-09-15 | 2013-03-27 | 华东理工大学 | Solvent volatilization self-assembly method used for preparing multistage-channel SAPO-34 and SAPO-18 molecular sieves |
| CN105408102A (en) * | 2013-06-28 | 2016-03-16 | 哈佛学院院长及董事 | High-surface area functional material coated structures |
| CN105408102B (en) * | 2013-06-28 | 2019-10-22 | 哈佛学院院长及董事 | The functional material coated structure of high surface area |
| CN104844014A (en) * | 2015-05-06 | 2015-08-19 | 浙江大学 | Silicon dioxide mesoporous thin film based insulating glass and production method thereof |
| CN106045330A (en) * | 2016-05-27 | 2016-10-26 | 浙江大学 | Preparation method of mesoporous SiO2 film and products and application of mesoporous SiO2 film |
| CN106045330B (en) * | 2016-05-27 | 2019-02-26 | 浙江大学 | A kind of mesoporous SiO2Preparation method of film and products thereof and application |
| CN114768552A (en) * | 2022-04-11 | 2022-07-22 | 重庆工程职业技术学院 | Preparation method of silicon nanopore oil-water separation film and oil-water separator |
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| CN115613012A (en) * | 2022-09-22 | 2023-01-17 | 辽宁师范大学 | Preparation method of patterned thin film |
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