CN105731537A - Method of preparing hollow mesoporous zirconium dioxide through sol-gel protective method - Google Patents
Method of preparing hollow mesoporous zirconium dioxide through sol-gel protective method Download PDFInfo
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Abstract
The invention discloses a method of preparing hollow mesoporous zirconium dioxide through a sol-gel protective method. The method includes the steps of: 1) synthesis of mono-dispersed silicon dioxide microsphere seeds through a Stober method: adding a certain amount of TEOS to a solvent system comprising alcohol, water and ammonia water at the reaction temperature of 30 DEG C to obtain the mono-dispersed silicon dioxide microsphere seeds; 2) dispersing the mono-dispersed silicon dioxide microsphere seeds in an alcohol system, adding a certain amount of a mesoporous agent, water and a zirconium source at the reaction temperature of 30 DEG C, performing centrifugation, and washing and aging the mixture and adding a certain amount of a template agent to prepare mono-dispersed mesoporous SiO2@ZrO2 microspheres; 3) at the reaction temperature of 30 DEG C, placing the microspheres in the system comprising alcohol, water and ammonia water through the sol-gel protective method, adding a certain amount of TEOS, centrifugally washing, drying and calcining the mixture to prepare mono-dispersed SiO2@ZrO2@SiO2 microspheres; and 4) dispersing the microspheres in a sodium hydroxide water solution, stirring the mixture to remove the cores to obtain the mono-dispersed hollow mesoporous zirconium dioxide microspheres. The hollow mesoporous zirconium dioxide, as an excellent nano container, is used for adsorbing and pH-controllably releasing a corrosion inhibitor to inhibit corrosion.
Description
Technical field
The invention belongs to spherical powder body manufacture of materials technical field, particularly relate to a kind of method preparing hollow mesoporous ZrO 2 with sol-gel Protection Code.
Background technology
Comprehensive literature is reported, hollow microsphere all has important application at numerous areas such as chemistry, biology and materials, as being used for preparing (medicine, pigment, cosmetics, ink etc.) control release capsule, electricity component, light filler, catalyst and carrier, separation material, deadener etc..
Mesoporous material is a kind of aperture new material with huge surface area and three-dimensional open-framework between micropore and macropore.The research and development of mesoporous material is all significant for theoretical research and actual production.It has the excellent specific property that other porous material does not have: have the pore passage structure of high-sequential；The single distribution in aperture, and aperture size can change at relative broad range；Mesoporous various shapes, hole wall composition and character controllable；High thermal stability and hydrothermal stability can be obtained by optimum synthesis condition.Its tempting part also resides in it in catalysis, absorption, the potential using value in many fields such as separation and optical, electrical, magnetic.
Zirconium dioxide (ZrO2) there is excellent heat-resisting, corrosion-resistant, abrasion resistance properties, it it is one of the most resistant to elevated temperatures oxide, its fusing point is up to 2680 DEG C, come for iron and steel smelting as refractory material, melt glass very early, be used as thermal barrier coating, inorganic separating film, electronic ceramics, High temperature ion conductor, oxygen concentration analysis device etc. as functional material again subsequently.In recent decades, ZrO2Itself has caused the extensive concern of people as catalyst and as catalyst carrier.But the zirconium dioxide poor heat stability of routine, specific surface are little, hole is less-developed, the defects such as pore size change is irregular, limit the performance of its premium properties.The nanoscale effect of zirconium dioxide and meso-hole structure effect being combined, developing meso-porous nano zirconium dioxide is the optimal path solving the problems referred to above.Although the method preparing Zirconium dioxide powder at present is a lot, but is respectively arranged with its limitation, the method preparing hollow mesoporous ZrO 2 microsphere then needs further to probe into.
Li Peng etc. are respectively with cetyl trimethylammonium bromide, triethanolamine, and yeast is template, zirconium oxychloride is inorganic zirconium source, with ammonia for precipitant, prepare mesoporous ZrO 2 by coprecipitation and calcination method, but its complex process severe reaction conditions does not have particularly strong repeatability.
Song Xiuqin etc. are with sucrose (C12H22O11) for template, with ZrOCl2 8H2O for zirconium source, utilize the sedimentation method to synthesize Tetragonal mesoporous ZrO 2.
ShaohengTang, XiaoqingHuang et al. are with SiO2Nano microsphere is masterplate, and zirconium-n-butylate is zirconium source, and hard template method prepares hollow mesoporous ZrO 2 nano material, but the meso-porous titanium dioxide zirconia material that the method is prepared is very easily broken, and microsphere its stability thin especially for the big wall of cavity is worse.
Summary of the invention
In view of the deficiencies in the prior art, the present invention provides a kind of with low cost, the preparation method of the hollow mesoporous ZrO 2 microsphere that method is easy.The characteristic of this method is in that the hollow mesoporous ZrO 2 nano material prepared with sol-gel Protection Code is more stable, non-friable.
For reaching above-mentioned purpose, the preparation method of hollow mesoporous ZrO 2 microsphere provided by the invention is:
The first step: under the reaction temperature of 20 DEG C～30 DEG C, in alcohol, water and aqueous ammonia solvent system, when with the mixing speed of 300rpm, stirring a certain amount of tetraethyl orthosilicate of addition (TEOS) obtains monodisperse silica microspheres seed, wherein, in dicyandiamide solution, the volume ratio of alcohol, water and ammonia is 3:2:1～21:5:1；TEOS and ammonia volume ratio be 1:6～2:1；
Second step: adopt hard template method by dropwise dripping zirconium source and mesoporous dose in monodispersed silicon dioxide microsphere, be dispersed in water after eccentric cleaning and add template more wherein, stirring, obtain monodispersed mesoporous SiO after eccentric cleaning2ZrO2Microsphere, wherein, zirconium source is (3～8) with the volume ratio of the mesoporous dose of amount added: 1, and the volume ratio of the TEOS addition of zirconium source and the first step is 1:(4～6), the volume ratio in the quality of template and zirconium source is 0.15:(1～1.5) g/mL；
3rd step: under the reaction temperature of 20 DEG C～30 DEG C; utilize sol-gel Protection Code that above-mentioned microsphere is placed in alcohol; in water and ammonia-water systems, after stirring 30min, add a certain amount of TEOS; stirring 8h; centrifugal, water and ethanol clean successively, and drying and calcining obtains monodispersed SiO2ZrO2SiO2 microsphere; wherein, in dicyandiamide solution, the volume ratio of alcohol, water and ammonia is 15:1:1～21:5:1；The volume ratio of TEOS and ammonia is 1:1～2:1；
4th step: be dispersed in NaOH aqueous solution by microsphere obtained above, stirring 8h removes the SiO of ectonexine2Obtain hollow mesoporous ZrO 2 microsphere.
The zirconium source of cladding titanium dioxide zirconium layer can be zirconium nitrate, basic zirconium chloride, Zirconium tetrachloride., zirconyl nitrate or zirconium-n-butylate, it is preferable that zirconium-n-butylate.
Selected template is polyvinylpyrrolidone (PVP), and mesoporous dose is polyoxyethylene laurel ether (Brij30).
Compared with prior art, the invention have the characteristics that
(1) the hollow mesoporous ZrO 2 microsphere being obtained by reacting has regular appearance, and the size of cavity and the wall thickness of microsphere are adjustable, and the firm feature such as not broken, the breakable problem existed in the research before solving significantly.
(2) this hollow mesoporous ZrO 2 can suppress corrosion as the absorption for corrosion inhibiter of the good nano container and PH controllable release.
Accompanying drawing explanation
Fig. 1 is particle diameter about 100nm, the TEM figure of the hollow mesoporous ZrO 2 microsphere of wall thickness 45nm.
Fig. 2 is particle diameter about 300nm, the TEM figure of the hollow mesoporous ZrO 2 microsphere of wall thickness 23nm.
Fig. 3 is particle diameter about 500nm, the TEM figure of the hollow mesoporous ZrO 2 microsphere of wall thickness 31nm.
Detailed description of the invention
Embodiment 1:44mL ethanol, 2mL ammonia, 9mL water is 30 DEG C of temperature, under the speed conditions of 300rpm, after stirring 30min, adds 4mLTEOS, reacts 8h, centrifugal, and water obtains the monodispersed SiO of about 100nm after ethanol purge2Microsphere；Product is scattered in 180mL ethanol, 30 DEG C of temperature, under the speed conditions of 400rpm, adds 0.3mLBrij30,0.3mL water and 1.3mL zirconium-n-butylate, reacts 8h, and centrifugal, washing, product is scattered in 40mL water, ageing 12h；Product is scattered in 80mL water, adds 0.15gPVP under 400rpm rotating speed, centrifugal after reaction 24h, ethanol purge；Appeal product is scattered in 44mL ethanol, 2mL ammonia, and 9mL water is 30 DEG C of temperature, under the speed conditions of 300rpm, after stirring 30min, adds 4mLTEOS, reacts 8h, centrifugal, and water obtains monodispersed SiO after ethanol purge2ZrO2SiO2Microgranule；600 DEG C of calcining 5h；By the aqueous solution of above-mentioned product NaOH except core, centrifugal, clean, obtain monodispersed hollow mesoporous ZrO 2 microsphere (Fig. 1) of particle diameter about 100nm after drying；
Embodiment 2:75mL ethanol, 5.13mL ammonia, 8mL water is 30 DEG C of temperature, under the speed conditions of 300rpm, after stirring 30min, adds 6mLTEOS, reacts 8h, centrifugal, and water obtains the monodispersed SiO of about 300nm after ethanol purge2Microsphere；Product is scattered in 180mL ethanol, 30 DEG C of temperature, under the speed conditions of 400rpm, adds 0.5mLBrij30,0.5mL water and 1.5mL zirconium-n-butylate, reacts 8h, and centrifugal, washing, product is scattered in 40mL water, ageing 12h；Product is scattered in 80mL water, adds 0.15gPVP under 400rpm rotating speed, centrifugal after reaction 24h, ethanol purge；Appeal product is scattered in 75mL ethanol, 5.13mL ammonia, and 8mL water is 30 DEG C of temperature, under the speed conditions of 300rpm, after stirring 30min, adds 6mLTEOS, reacts 8h, centrifugal, and water obtains monodispersed SiO after ethanol purge2ZrO2SiO2Microgranule；600 DEG C of calcining 5h；By the aqueous solution of above-mentioned product NaOH except core, centrifugal, clean, obtain monodispersed hollow mesoporous ZrO 2 microsphere (Fig. 2) of particle diameter about 300nm after drying；
Embodiment 3:91mL ethanol, 32.5mL ammonia, 30 DEG C of temperature, under the speed conditions of 300rpm, after stirring 30min, add 5.5mLTEOS, react 1h, centrifugal, water, obtain the monodispersed SiO of about 500nm after ethanol purge2Microsphere；Product is scattered in 175mL ethanol, 30 DEG C of temperature, under the speed conditions of 400rpm, adds 0.13mLBrij30,0.13mL water and 1.0mL zirconium-n-butylate, reacts 8h, and centrifugal, washing, product is scattered in 40mL water, ageing 12h；Product is scattered in 80mL water, adds 0.15gPVP under 400rpm rotating speed, centrifugal after reaction 24h, ethanol purge；Appeal product is scattered in 75mL ethanol, 5.13mL ammonia, and 8mL water is 30 DEG C of temperature, under the speed conditions of 300rpm, after stirring 30min, adds 3mLTEOS, reacts 8h, centrifugal, and water obtains monodispersed SiO after ethanol purge2ZrO2SiO2Microgranule；600 DEG C of calcining 5h；By the aqueous solution of above-mentioned product NaOH except core, centrifugal, clean, obtain monodispersed hollow mesoporous ZrO 2 microsphere (Fig. 3) of particle diameter about 500nm after drying.
Fig. 1 to Fig. 3 respectively particle diameter is 100nm, 300nm, Electronic Speculum (TEM) figure of the hollow mesoporous ZrO 2 of 500nm, its pattern is similar, Stability Analysis of Structures, but the microgranule of different-grain diameter is different for the adsorbance of different size of inhibitor molecular, the amount of the absorption inhibitor molecular that particle diameter is big is many, and the amount of the absorption corrosion inhibiter that particle diameter is little is few.
Embodiment 4: equivalent weighs 200mgL-histidine three groups and is dissolved in 5mL deionized water respectively, it is 100nm by three groups of solution are separately added into 40mg cavity diameter, 300nm, the hollow mesoporous ZrO 2 microsphere of 500nm, after stirring 48 hours, by microsphere respectively at PH=2,7, the buffer solution of 10 carries out the release of inhibitor molecular L-Histidine, by the change of ultraviolet visualization burst size and rate of release.
Effect data
Following table be embodiment 4 different particle diameter situations under the comparison of maximal absorptive capacity
When following table is embodiment 4 same particle diameter difference PH, (cavity inside diameter is the hollow mesoporous ZrO 2 of 300nm in the comparison of rate of release
| PH | 2 | 7 | 10 |
| Rate of release ug/min | 15 | 5 | 9 |
。
Claims (6)
1. the method preparing hollow mesoporous ZrO 2 with sol-gel Protection Code, it is characterised in that comprise the steps:
The first step: under the reaction temperature of 20 DEG C～30 DEG C, in alcohol, water and aqueous ammonia solvent system, when with the mixing speed of 300rpm, stirring addition tetraethyl orthosilicate obtains monodisperse silica microspheres seed；
Second step: adopt hard template method by dropwise dripping zirconium source and mesoporous dose in monodispersed silicon dioxide microsphere, be dispersed in water after eccentric cleaning and add template more wherein, stirring, obtain monodispersed mesoporous SiO after eccentric cleaning2ZrO2Microsphere；
3rd step: under the reaction temperature of 20 DEG C～30 DEG C, utilizes sol-gel Protection Code that above-mentioned microsphere is placed in alcohol, water and in ammonia-water systems; after stirring 30min, add a certain amount of tetraethyl orthosilicate, stir 8h; centrifugal, water and ethanol clean successively, and drying and calcining obtains monodispersed SiO2ZrO2SiO2Microsphere；
4th step: be dispersed in NaOH aqueous solution by microsphere obtained above, stirring 8h removes the SiO of ectonexine2Obtain hollow mesoporous ZrO 2 microsphere.
2. the method preparing hollow mesoporous ZrO 2 with sol-gel Protection Code as claimed in claim 1, it is characterised in that in the first step, in described dicyandiamide solution, the volume ratio of alcohol, water and ammonia is 3:2:1～21:5:1；Tetraethyl orthosilicate and ammonia volume ratio be 1:6～2:1.
3. the method as claimed in claim 1 preparing hollow mesoporous ZrO 2 with sol-gel Protection Code, it is characterised in that in second step, described zirconium source is zirconium nitrate, basic zirconium chloride, Zirconium tetrachloride., zirconyl nitrate or in zirconium-n-butylate one or more；The volume ratio of zirconium source and the mesoporous dose of amount added is (3～8): 1, the volume ratio of the tetraethyl orthosilicate addition of zirconium source and the first step is 1:(4～6), the volume ratio in the quality of template and zirconium source is 0.15:(1～1.5) g/mL.
4. the method preparing hollow mesoporous ZrO 2 with sol-gel Protection Code as claimed in claim 1, it is characterised in that zirconium source is zirconium-n-butylate.
5. the method preparing hollow mesoporous ZrO 2 with sol-gel Protection Code as claimed in claim 1, it is characterised in that in second step, selected template is polyvinylpyrrolidone, and mesoporous dose is polyoxyethylene laurel ether.
6. the method preparing hollow mesoporous ZrO 2 with sol-gel Protection Code as claimed in claim 1, it is characterised in that in the 3rd step, in described dicyandiamide solution, the volume ratio of alcohol, water and ammonia is 15:1:1～21:5:1；The volume ratio of tetraethyl orthosilicate and ammonia is 1:1～2:1.
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Cited By (12)
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| CN106214665A (en) * | 2016-08-25 | 2016-12-14 | 南京理工大学 | A kind of intellectual drug transmission system based on hollow mesoporous ZrO 2 Nano microsphere and preparation method thereof |
| CN107511125A (en) * | 2017-09-06 | 2017-12-26 | 南京理工大学 | Load the preparation method of hollow Nano hydrous zirconium oxide(HZO) grade polymer drops |
| CN107556865A (en) * | 2017-08-22 | 2018-01-09 | 哈尔滨工程大学 | The preparation method of Mg alloy surface selfreparing erosion shield |
| CN107768061A (en) * | 2017-01-06 | 2018-03-06 | 华侨大学 | A kind of preparation method of bag silicon nanoscale magnetic bead |
| CN108102447A (en) * | 2017-11-25 | 2018-06-01 | 浙江大学 | A kind of preparation method and its usage of silica doped modified protective coating |
| CN109607554A (en) * | 2019-01-23 | 2019-04-12 | 天津医科大学 | The preparation method of macroporous silica nanoparticle |
| CN113337210A (en) * | 2021-05-28 | 2021-09-03 | 上海应用技术大学 | Corrosion inhibitor-loaded pH-responsive silicon dioxide nano container composite silane film and preparation and application thereof |
| CN113499766A (en) * | 2021-06-30 | 2021-10-15 | 南京工业大学 | Preparation method of mesoporous bimetal solid base catalyst for synthesizing DMC |
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| CN116062791A (en) * | 2023-01-29 | 2023-05-05 | 宁波卿甬新材料科技有限公司 | Preparation method of mesoporous zirconia nano particles |
| CN117430121A (en) * | 2023-10-23 | 2024-01-23 | 博路天成新能源科技有限公司 | Silica microsphere manufacturing process based on Stober method |
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| CN106214665A (en) * | 2016-08-25 | 2016-12-14 | 南京理工大学 | A kind of intellectual drug transmission system based on hollow mesoporous ZrO 2 Nano microsphere and preparation method thereof |
| CN107768061A (en) * | 2017-01-06 | 2018-03-06 | 华侨大学 | A kind of preparation method of bag silicon nanoscale magnetic bead |
| CN107768061B (en) * | 2017-01-06 | 2019-08-23 | 华侨大学 | A kind of preparation method of packet silicon nanoscale magnetic bead |
| CN107556865A (en) * | 2017-08-22 | 2018-01-09 | 哈尔滨工程大学 | The preparation method of Mg alloy surface selfreparing erosion shield |
| CN107511125A (en) * | 2017-09-06 | 2017-12-26 | 南京理工大学 | Load the preparation method of hollow Nano hydrous zirconium oxide(HZO) grade polymer drops |
| CN108102447A (en) * | 2017-11-25 | 2018-06-01 | 浙江大学 | A kind of preparation method and its usage of silica doped modified protective coating |
| CN108102447B (en) * | 2017-11-25 | 2020-01-10 | 浙江大学 | Preparation method and application of silica-doped modified protective coating |
| CN109607554B (en) * | 2019-01-23 | 2021-11-02 | 天津医科大学 | Preparation method of microporous mesoporous silica nanoparticles |
| CN109607554A (en) * | 2019-01-23 | 2019-04-12 | 天津医科大学 | The preparation method of macroporous silica nanoparticle |
| CN113337210A (en) * | 2021-05-28 | 2021-09-03 | 上海应用技术大学 | Corrosion inhibitor-loaded pH-responsive silicon dioxide nano container composite silane film and preparation and application thereof |
| CN113499766A (en) * | 2021-06-30 | 2021-10-15 | 南京工业大学 | Preparation method of mesoporous bimetal solid base catalyst for synthesizing DMC |
| CN114619793A (en) * | 2021-11-23 | 2022-06-14 | 浙江画之都文化创意有限公司 | Method for making glass-imitated double-layer decorative picture |
| CN114619793B (en) * | 2021-11-23 | 2023-03-03 | 浙江画之都文化创意有限公司 | Method for making glass-imitated double-layer decorative picture |
| CN115322557A (en) * | 2022-08-15 | 2022-11-11 | 马鞍山市申龙涂料有限公司 | Fireproof organic foam heat-insulating material and production method thereof |
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| CN116062791B (en) * | 2023-01-29 | 2023-12-19 | 宁波卿甬新材料科技有限公司 | Preparation method of mesoporous zirconia nano particles |
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Application publication date: 20160706 |