CN1556067A - Preparaton method of ordered macro porous inorganic oxide material - Google Patents
Preparaton method of ordered macro porous inorganic oxide material Download PDFInfo
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- CN1556067A CN1556067A CNA2004100156800A CN200410015680A CN1556067A CN 1556067 A CN1556067 A CN 1556067A CN A2004100156800 A CNA2004100156800 A CN A2004100156800A CN 200410015680 A CN200410015680 A CN 200410015680A CN 1556067 A CN1556067 A CN 1556067A
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Abstract
A process for preparing the ordered macroreticular inorganic oxide material includes sequentially and proportionally adding high-molecular polystyrene microbeads, solvent and precursor solution of inorganic substance to a glass container, stirring, gelating reaction, and removing high-molecular microbeads by high-temp calcining or dissolving in organic solvent.
Description
Technical field
The present invention relates to a kind of preparation method of ordered big hole inorganic oxide material, be specifically related to adopt the metal oxide of Prepared by Sol Gel Method macropore.Belong to chemistry and inorganic materials class technical field.
Background technology
According to the definition of International Union of Pure and Applied Chemistry(IUPAC) (IUPAC), macropore or grand hole material (macroporous materials) are meant the porous material of aperture greater than 50 nanometers.Because it is big that large pore material has the aperture, be evenly distributed, arrange characteristics such as orderly, in macromolecular catalysis, filter and parting material, aspect such as battery material and thermal resistance material has a wide range of applications, especially be in the orderly large pore material of submicron, be three-dimensional regular large pore material (3DOM, three-dimensionally orderedmacroporous), its size just in time with general visible light, infrared light, the number of wavelengths magnitude of UV-light is suitable, it can be used as the material of the photonic crystal with photon band gap characteristic, have a wide range of applications at photoelectron and optical communication field, become one of the research focus in material field in recent years.
In recent years, the large pore material that is widely studied has metal, inorganic oxide, chalcogenide, salt, polymkeric substance etc.Synthetic method commonly used has: miniature carving method, template etc.Wherein, the miniature carving method is suitable for the laboratory micropreparation to preparation condition requirement harshness very, is not suitable for large-scale production.Advantages such as template is simple because of it, cost is low, easy to operate become the most frequently used method.Domestic now when utilizing template to prepare large pore material, use settling process usually, method of evaporation, self-assembly method.And these methods need prepare high molecular template in advance, and then carry out the reaction of polymer template and precursor aqueous solution.Step is complicated, when preparation time is long, precondition is that the necessary volume of template for preparing is bigger, long-range order, the quality of template seriously influences last product, as be not long-range order on the formwork structure that obtains, the product hole wall structure will cave in the process that template is removed so, and can not get orderly grand hole material.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of ordered big hole inorganic oxide material is provided, operate simplyr, cost is low, the product pore structure is orderly, does not need to prepare template in advance and prolongs technological process.
For realizing such purpose, in the technical scheme of the present invention, adopt Prepared by Sol Gel Method inorganic oxide large pore material, comprise silicon oxide, titanium oxide and zirconic large pore material.At first be that body solution mixes by mass ratio 1: 10～20: 0.5～3 before the macromolecule polysterol microballoon, solvent, inorganics of 250 nanometers～2 micron with particle diameter, ageing at room temperature and dry after stirring, carry out aftertreatment then, adopt high-temperature calcination or adopt organic solvent (toluene) dissolution method, polymer microsphere is removed, can be prepared the inorganic oxide ordered big hole material of aperture from the hundreds of nanometer to several microns.
Preparation method of the present invention comprises following concrete steps:
1, the preparation of polymer microsphere: utilize the synthetic particle diameter of radical polymerization to be respectively the macromolecule polysterol microballoon of 250 nanometers to 2 micron.
2, reaction process: in Glass Containers, add the macromolecule polysterol microballoon successively, body solution before solvent and the inorganics, 1: 10～20: 0.5～3 mixing that the three press mass ratio, wherein solvent is the corresponding solvent of hydrolysate with the precursor aqueous solution of inorganics.Reaction solution is stirred, then said vesse is at room temperature placed naturally, to finish its gelation process.
3, aftertreatment: adopt high-temperature calcination to remove polymer microsphere, sample and Glass Containers are placed retort furnace, by 2 ℃ of/minute temperature programmings to 550 ℃ and constant temperature 3 hours; Perhaps adopt organic solvent toluene that polymer microsphere is dissolved, promptly get the ordered big hole inorganic oxide material of aperture from the hundreds of nanometer to several microns.
Body solution is tetraethoxy, isopropyl titanate or zirconium-n-propylate before the said inorganics of the present invention.
The said solvent of the present invention is the hydrolysate of the preceding body solution of inorganics of correspondence, is tetraethoxy as body solution before the inorganics, and then solvent is an ethanol, and the solvent of isopropyl titanate correspondence is a Virahol, and the solvent of zirconium-n-propylate correspondence is a n-propyl alcohol.
The present invention is owing to adopted the alcohol of corresponding hydrolyzate to make cosolvent, in the synthetic process, relaxed hydrolytic process, like this, polystyrene microsphere has time enough to carry out sedimentation, to obtain orderly template, its unique distinction is that the hydrolytic process of body solution before the inorganics and the ordered arrangement of high polymer micro balloons and the formation of template carries out simultaneously, so does not need at first to prepare orderly high polymer micro balloons template.And evidence can be regulated according to the particle diameter of microballoon, and the large pore material aperture that can prepare is from the submicron to the micron order.
The present invention has utilized the hydrolysis of precursor, and the carrying out of solgel reaction makes the present invention be applicable to the inorganics that those obtain by solgel reaction immediately, as silicon (Si), and titanium (Ti), the oxide compound of zirconium (Zr) and the oxide compound of other metal.The inventive method is simple to operate, preparation or the production time is short, cost is low, be suitable for preparing or the inorganic oxide scope of producing wide, the large pore material neat appearance of preparation, and the duct is orderly.
Description of drawings
Fig. 1 is the electron scanning micrograph enlarged view of the embodiment of the invention 1 resulting silicon oxide large pore material.
Fig. 2 is the electron scanning micrograph low power figure of the embodiment of the invention 1 resulting silicon oxide large pore material.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
1, the preparation of polymer microsphere: vinylbenzene, Polyvinylpyrolidone (PVP), ethanol and the deionized water of underpressure distillation are mixed in the there-necked flask, logical nitrogen 20 minutes also is warming up to 80 ℃ rapidly, add Diisopropyl azodicarboxylate (vinylbenzene, Polyvinylpyrolidone (PVP), ethanol, Diisopropyl azodicarboxylate and deionized water were pressed mass ratio 100: 6.7: 201: 1: 25.3) stirring reaction after 6 hours, use the sodium chloride solution breakdown of emulsion, filter and washing, product drying in the vacuum drying oven of room temperature obtained being about 2 microns polystyrene microsphere in 24 hours.
2, reaction process: 2 microns polystyrene microspheres, 0.05 gram, 0.5 gram ethanol and the 0.025 gram tetraethoxy of above-mentioned preparation are mixed in the flat Glass Containers, and stirring at room stopped to stir room temperature ageing 1 day after 2 hours.With vacuum drying oven with sample drying.
3, aftertreatment: with toluene with the dissolving of the polymer microsphere in the sample fully, and through repeatedly washing, the dry powder that obtains is the large pore material of silicon oxide in the baking oven.
The stereoscan photograph of the large pore material of resultant silicon-dioxide such as Fig. 1, the aperture of prepared as seen from Figure 1 macroporous silica is approximately 1.8～2 microns, and the hole is ordered arrangement.The low power stereoscan photograph of macroporous silica as shown in Figure 2; as can be seen from the figure; the block materials length of the macroporous silica of preparation can reach the millimeter level, thereby explanation can prepare the production of the grand hole material realization mass-producing of block by method of the present invention.
Embodiment 2:
1, the preparation of polymer microsphere: vinylbenzene, sodium lauryl sulphate and the deionized water of underpressure distillation are mixed in the there-necked flask, logical nitrogen 20 minutes also is warming up to 80 ℃ rapidly, (vinylbenzene, sodium lauryl sulphate, Potassium Persulphate and deionized water are 100: 0.1: 1 by mass ratio: 574) to add Potassium Persulphate, behind the stirring reaction 6 hours, obtain the emulsion first of the polystyrene microsphere of 250 nanometers; Is 100: 0.1: 1 with emulsion first, sodium lauryl sulphate, Potassium Persulphate and deionized water by mass ratio: 574, and react once by above-mentioned reaction conditions, obtain the emulsion second of the polystyrene microsphere of 500 nanometers; Is 100: 0.1: 1 with emulsion second, sodium lauryl sulphate, Potassium Persulphate and deionized water by mass ratio: 574 react once, obtain emulsion third.With sodium chloride solution breakdown of emulsion emulsion the third, filter also washing, product in the vacuum drying oven of room temperature dry 24 hours, the powder that obtains is 1 micron a polystyrene microsphere.
2, reaction process: 1 micron polystyrene microsphere, 0.05 gram, 1 gram Virahol and the 0.014 gram isopropyl titanate of above-mentioned preparation are mixed in the flat Glass Containers, and stirring at room stopped to stir room temperature ageing 1 day after 2 hours.With vacuum drying oven with sample drying.
3, aftertreatment: sample and Glass Containers are placed retort furnace, and by 2 ℃ of/minute temperature programmings to 550 ℃ and constant temperature 3 hours, the gained powder was the large pore material of titanium oxide.
Embodiment 3:
1, vinylbenzene, sodium lauryl sulphate, Potassium Persulphate and the deionized water with underpressure distillation is 100: 0.1: 1 by mass ratio: 574 are mixed in the there-necked flask, logical nitrogen 20 minutes also is warming up to 80 ℃ rapidly, behind the stirring reaction 6 hours, use the sodium chloride solution breakdown of emulsion, filter also washing, dry 24h obtains product in the vacuum drying oven of room temperature is the polystyrene microsphere of 250 nanometers.
2, reaction process: 250 nano pipe/polyhenylethylene microballoons, 0.05 gram, 1 gram n-propyl alcohol and the 0.15 gram zirconium-n-propylate of above-mentioned preparation are mixed in the flat Glass Containers, and stirring at room stopped to stir room temperature ageing 1 day after 2 hours.With vacuum drying oven with sample drying.
3, aftertreatment: sample and Glass Containers are placed retort furnace, and by 2 ℃ of/minute temperature programmings to 550 ℃ and constant temperature 3 hours, the gained powder was zirconic large pore material.
Claims (3)
1, a kind of preparation method of ordered big hole inorganic oxide material, it is characterized in that at first utilizing the synthetic particle diameter of radical polymerization to be respectively the macromolecule polysterol microballoon of 250 nanometers to 2 micron, in Glass Containers, add the macromolecule polysterol microballoon successively, the preceding body solution of solvent and inorganics, 1: 10～20: 0.5～3 mixing that the three presses mass ratio, wherein solvent is and the corresponding solvent of the hydrolysate of inorganics precursor aqueous solution, at room temperature place naturally after reaction solution stirred, finish gel, then container is placed retort furnace, by 2 ℃ of/minute temperature programmings to 550 ℃ and constant temperature 3 hours, remove polymer microsphere, perhaps adopt toluene that polymer microsphere is dissolved, promptly get the aperture from the hundreds of nanometer to several microns ordered big hole inorganic oxide materials that do not wait.
2, the preparation method of ordered big hole inorganic oxide material as claimed in claim 1 is characterized in that the preceding body solution of described inorganics is tetraethoxy, isopropyl titanate or zirconium-n-propylate.
3, the preparation method of ordered big hole inorganic oxide material as claimed in claim 2, the hydrolysate that it is characterized in that body solution before described solvent is for corresponding inorganics, body solution is tetraethoxy before the inorganics, then solvent is an ethanol, the solvent of isopropyl titanate correspondence is a Virahol, and the solvent of zirconium-n-propylate correspondence is a n-propyl alcohol.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410301C (en) * | 2006-02-21 | 2008-08-13 | 武汉化工学院 | Method for preparation of ordered porous conductive polymer by suction filtration / immersion method |
| CN101497067B (en) * | 2009-01-16 | 2011-11-09 | 北京航空航天大学 | Preparation method for assembling large-area ordered microsphere template by liquid level swirl method |
| CN102433170A (en) * | 2011-09-16 | 2012-05-02 | 太原理工大学 | Preparation method for ferrum-silicon complex desulfurizer |
| CN105413676A (en) * | 2015-11-06 | 2016-03-23 | 中国科学院山西煤炭化学研究所 | Method for preparing three-dimensional ordered macroporous V-Mg oxide materials and application thereof |
| CN108855008A (en) * | 2018-07-06 | 2018-11-23 | 常州大学 | A kind of preparation and its application of removal Cu (II) in water of 3D ordered big hole blotting chitosan film |
| CN111073403A (en) * | 2019-12-11 | 2020-04-28 | 胡莎 | High-temperature-resistant aging-resistant heat-insulating reflective coating |
| CN111574047A (en) * | 2020-05-25 | 2020-08-25 | 陕西科技大学 | Wide-color-gamut structural color glass and preparation method thereof |
| CN113135771A (en) * | 2021-05-14 | 2021-07-20 | 东南大学 | Multistage pore structure zirconium dioxide porous ceramic and preparation method thereof |
-
2004
- 2004-01-08 CN CNA2004100156800A patent/CN1556067A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410301C (en) * | 2006-02-21 | 2008-08-13 | 武汉化工学院 | Method for preparation of ordered porous conductive polymer by suction filtration / immersion method |
| CN101497067B (en) * | 2009-01-16 | 2011-11-09 | 北京航空航天大学 | Preparation method for assembling large-area ordered microsphere template by liquid level swirl method |
| CN102433170A (en) * | 2011-09-16 | 2012-05-02 | 太原理工大学 | Preparation method for ferrum-silicon complex desulfurizer |
| CN105413676A (en) * | 2015-11-06 | 2016-03-23 | 中国科学院山西煤炭化学研究所 | Method for preparing three-dimensional ordered macroporous V-Mg oxide materials and application thereof |
| CN108855008A (en) * | 2018-07-06 | 2018-11-23 | 常州大学 | A kind of preparation and its application of removal Cu (II) in water of 3D ordered big hole blotting chitosan film |
| CN111073403A (en) * | 2019-12-11 | 2020-04-28 | 胡莎 | High-temperature-resistant aging-resistant heat-insulating reflective coating |
| CN111574047A (en) * | 2020-05-25 | 2020-08-25 | 陕西科技大学 | Wide-color-gamut structural color glass and preparation method thereof |
| CN113135771A (en) * | 2021-05-14 | 2021-07-20 | 东南大学 | Multistage pore structure zirconium dioxide porous ceramic and preparation method thereof |
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