CN101274246B - Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon - Google Patents
Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon Download PDFInfo
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- CN101274246B CN101274246B CN2007101731112A CN200710173111A CN101274246B CN 101274246 B CN101274246 B CN 101274246B CN 2007101731112 A CN2007101731112 A CN 2007101731112A CN 200710173111 A CN200710173111 A CN 200710173111A CN 101274246 B CN101274246 B CN 101274246B
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Abstract
The invention provides a method for preparing an SiO2/TiO2 hollow microsphere by a sol-gel method. The method is mainly characterized in that cation polystyrene microsphere (PS) is used as a formwork;ethyl silicate and butyl titanate are respectively used as raw material and diluted ammonia is taken as regulator of pH value; a multi-layer organic-inorganic hybrid composite microsphere is obtainedby the sol-gel reaction under the temperature of 70-80 DEG C. Formwork particle of the obtained deposition is removed by a calcining process to obtain the SiO2/ TiO2 hollow microsphere. By changing the consistency of reactant, content of surfactant and calcining temperature, the SiO2/ TiO2 hollow microsphere with different spherical shell thickness, density and grain size can be obtained. The hollow microsphere prepared by the method has high photo-catalytic activity, overcomes the shortage that existing preparation method of hollow microsphere can only prepare single shell layer microsphere;the multi-layer hollow microsphere can be prepared, the technique is simple, the cost is low and the preparation method of the invention is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of sol-gel process for preparing the hollow hybrid microspheres of earth silicon/titanic oxide, can be used for photocatalysis, environmental protection, photonic crystal, medicine control release etc., belong to nanometer scale tiny balloon field.
Background technology
In recent years, tiny balloon is one of focus of material science research always, because it discharges at controlled medicine, and the low-density filler, photocatalysis, chromatogram, the confinement reactor, there is important application in fields such as photonic crystal.Titanium dioxide is because its nontoxic, high chemical stability, low cost, thereby used the shell material as core-shell particles and hollow-core construction widely.
Present existing synthetic method mainly is by template, comprises hard template (for example, inorganic metal and polymeric colloid particle) and soft template (for example, the molecular template of surfactant and polymer), and does not have template.Hard template method usually on the template particles surface by self-assembly method or sol-gel process form nucleocapsid structure and tiny balloon layer by layer.Wherein, self-assembly method (LbL) (F.Caruso.Chem.Eur.J, 6 (2000), pp.413 layer by layer; F.Caruso etal.Science, 282 (1998), be exactly that the electrolyte that has the xenogenesis electric charge alternately is adsorbed on the template particles PP.1111), form the nucleocapsid compound particle.The titanium precursor body that employings such as Caruso are water-soluble and stability is good has prepared template-titanic oxide composite microsphere by the LbL method, removes template by calcining and makes hollow titanium dioxide microballoon sphere.Yet this method complex process need relate to the polyelectrolyte that repeatedly uses band xenogenesis electric charge.Sol-gel process (Z.Zhongetal.Adv.Mater.12 (2000), pp.206; A.Imhof.Langmuir, 17 (2001), pp.3579; A.Syoufian etal.Catal.Commun.8 (2007) is directly to form core-shell type complex particle at template particles surface deposition inorganic molecule by the hydrolysis presoma pp.755).Xia etc. have reported with the polystyrene microsphere to be template, prepare titanic oxide hollow microballoon by sol-gel process, the surface of the polystyrene microsphere of on glass baseplate, arranging, drip the titania precursor body, hydrolysis by presoma, polymerization forms gel, obtains the titanium dioxide core-shell compound particle, re-uses toluene solvant selective dissolution polystyrene microsphere and obtains titanic oxide hollow microballoon.Yet this method is difficult to control the formation speed of TiOx nano particle, can cause a large amount of gatherings of offspring, influences the dispersiveness of microballoon.No template is synthesized (C.W.Guoetal.Chem.Comm.2003, pp.700; H.G.Yang etal.J.Phys.Chem.B 108 (2004), pp.3492) then are to prepare nucleocapsid structure or tiny balloon by hydro-thermal or one step of solvent-thermal method.Though the technology of this method is simple, quick, it is wide to be difficult to overcome the product Size Distribution, the shortcoming that impurity is more.The most important thing is that the synthetic method majority of having reported is used for preparing the nuclear be made up of a kind of inorganic particle or the microballoon of shell, the research of seldom relevant preparation multilayer tiny balloon.Titanium oxide multilayer tiny balloon is because its unique reflection multilayer, high specific area, the internal structure of hollow and high light utilization efficiency, so under light irradiation situation, the generation rate of shell surface photoproduction electron-hole pair can significantly rise, thereby has improved its photocatalytic degradation ability significantly.Titanium oxide multilayer tiny balloon also provides new application platform for industry developments such as catalysis, microelectronic components simultaneously.Therefore seek low cost, simple and effective preparation multilayer tiny balloon structure has important theory and realistic meaning.
Summary of the invention
The object of the present invention is to provide a kind of improved sol-gel process to prepare the method for earth silicon/titanic oxide hollow microballoon, being intended to overcome existing process method is confined to prepare the shortcoming of being made of the microballoon shell a kind of inorganic particle, a kind of method of simple two step sol-gel process synthesizing multilayer earth silicon/titanic oxide hollow microballoons is provided, and equipment is simple, safe in utilization, environmental friendliness.
The present invention implements like this: at first prepare cationic polystyrene microsphere as template, then, use for twice sol-gel process to prepare the nucleocapsid structure microballoon of single dispersion, and can repeat repeatedly to obtain the multi-layer core-shell structure microballoon, remove the macromolecule template by calcining at last and obtain hollow silicon dioxide/titanic oxide hollow microballoon.Concrete steps are:
(1) preparation of polystyrene (PS) microsphere template: have the 300mL of 200mL deionized water to be equipped with in three mouthfuls of round-bottomed flasks of condenser pipe and logical protective gas gas port in 10～30mL styrene joins; add respectively then and account for the azo diisobutyl ether hydrochloride (AIBA) of total solution weight 0.3% and account for 1.2% polyvinylpyrrolidone k30 (PVP); the use magnetic agitation mixes; and logical nitrogen purge oxygen continues 1h in reactor; use water-bath to be heated to 70-80 ℃ then, insulation 24h.High speed centrifugation is isolated white depositions, uses deionized water and absolute ethanol washing respectively 3-5 time, removes remaining styrene monomer and surfactant.
(2) polystyrene/silica dioxide (PS/SiO
2) preparation of complex microsphere particle: after being distributed to 1mL polystyrene microsphere suspension (3wt%) in 15mL deionized water and the 50mL isopropyl alcohol mixture, solution is joined in the reactor of step 1, add 0.1～0.6g silester (TEOS) behind the magnetic agitation 15min, and use the pH value extremely～10 of ammoniacal liquor (4-6vol%) the solution regulator solution of dilution, at room temperature magnetic agitation 2h.High speed centrifugation is isolated white depositions, uses washed with isopropyl alcohol 3 times, makes PS/SiO
2The complex microsphere particle.
(3) polystyrene/silica dioxide/titanium dioxide (PS/SiO
2/ TiO
2) the complex microsphere preparation of hybrid inorganic-organic: 0.03g PS/SiO
2The complex microsphere powder join in 0.15g deionized water and the 24mL absolute ethyl alcohol blending agent and ultrasonic dispersion 15min after, solution is joined in the reactor of step 1, add 0～0.03g PVP and 0.06～0.18g TBOT then, 70-80 ℃ of water bath heat preservation 1-3h, high speed centrifugation is isolated precipitation, uses deionized water and absolute ethanol washing respectively 3-5 time, and sediment is put into baking oven, 60-70 ℃ of drying 6～10 hours, obtain PS/SiO
2/ TiO
2Hybrid inorganic-organic complex microsphere powder.
(4) PS/SiO
2/ TiO
2Hybrid inorganic-organic complex microsphere powder sample is put into Muffle furnace 550～650 ℃ of calcinings 2-4 hour, obtains the earth silicon/titanic oxide hollow microballoon powder.
The method of a kind of sol-gel process synthetic silica/titanic oxide hollow microballoon provided by the invention is characterized in:
(1) prepare cationic PS particle by emulsion method, obtain regular spherical, monodispersity is good, and average grain diameter is the microsphere template of 250-270nm; By at first at PS particle surface coated Si O
2Layer will help TiO
2The perfection of particle coats.The spherical shell internal layer white layer of prepared earth silicon/titanic oxide hollow microballoon is SiO
2Phase, outer coversheet are TiO
2Phase.
(2) production technology flexibly, simply.By changing the content of butyl titanate, can adjust TiO flexibly
2The thickness of shell and density.The content that changes surfactant PVP can be optimized the distribution situation of microballoon, thereby obtains the core-shell particles structure of single dispersion;
(3) do not need use polyelectrolyte repeatedly to change the electric charge of microsphere surface, thereby directly realize the synthetic of composite hybridization microballoon.And overcome the shortcoming that existing test method can only prepare the microballoon of the nuclear be made up of a kind of inorganic particle or shell, for realizing that the microballoon with labyrinth provides a brand-new synthesis path;
(4) change the size that calcination time can be controlled titanium oxide shell crystal grain flexibly, thereby optimize the photocatalysis performance of tiny balloon.Calcination time changes to 650 ℃, then outer TiO from 500
2The thickness of phase changes to 20nm from 10nm.
(5) raw material is cheap and easy to get, and required production equipment is simple, is easy to realize suitability for industrialized production.
Description of drawings
The TEM photo of the cationic PS template microsphere shown in Fig. 1 embodiment 1.
Fig. 2 (a) and (b) be respectively the PS/SiO of embodiment 2 and 3
2Hybrid inorganic-organic microballoon TEM photo.
Fig. 3 PS/SiO
2/ TiO
2Hybrid inorganic-organic complex microsphere particle TEM photo (a) embodiment 4, (b) embodiment 5, and (c) embodiment 6, and (d) embodiment 7.
The SiO of Fig. 4 embodiment 8 preparations
2/ TiO
2The TEM photo of tiny balloon; Inserting figure is outer nano-TiO
2SEAD figure.
Fig. 5 SiO
2/ TiO
2The X-ray diffractogram of tiny balloon (a) embodiment 8, (b) embodiment 9, and (c) embodiment 10.
The SiO of Fig. 6 embodiment 10 preparations
2/ TiO
2The TEM photo of tiny balloon; Insertion figure is SiO
2/ TiO
2The amplification SEM figure of double-deck shell.
Fig. 7 SiO
2/ TiO
2The photocatalytic degradation ability of tiny balloon and the comparison diagram of P-25 powder.
The specific embodiment
Further specify embodiment and effect with following non-limiting embodiment:
In joining, 20mL styrene have the 300mL of 200mL deionized water to be equipped with in three mouthfuls of round-bottomed flasks of condenser pipe and logical protection gas gas port; add 0.6g azo diisobutyl ether hydrochloride (AIBA) and 2.5g polyvinylpyrrolidone k30 (PVP) then; the use magnetic agitation mixes; and logical nitrogen purge oxygen continues 1h in reactor; use water-bath to be heated to 70 ℃ then; insulation 24h. high speed centrifugation is isolated white depositions (PS), uses deionized water and absolute ethanol washing respectively 3 times.Fig. 1 is the TEM photo of the PS microsphere template of present embodiment preparation, and from photo as can be seen, microsphere template is very even, and diameter is about 262nm.
After being distributed to 1mL polystyrene microsphere suspension (3wt%) in 15mL deionized water and the 50mL isopropyl alcohol mixture; solution is joined in three mouthfuls of round-bottomed flasks of 300mL that condenser pipe and logical protection gas gas port are housed; add 0.15g silester (TEOS) behind the magnetic agitation 15min again; and use the pH value extremely～10 of ammoniacal liquor (5vol%) the solution regulator solution of dilution, at room temperature magnetic agitation 2h.High speed centrifugation is isolated white depositions, uses washed with isopropyl alcohol 3 times, makes PS/SiO
2The complex microsphere particle.Fig. 2 (a) is the described PS/SiO of present embodiment
2The TEM photo of hybrid inorganic-organic microballoon, the SiO of gained complex microsphere
2The thickness of shell is about 8nm, and shell thickness is even, the microballoon favorable dispersibility.
Embodiment 3
After being distributed to 1mL polystyrene microsphere suspension (3wt%) in 15mL deionized water and the 50mL isopropyl alcohol mixture; solution is joined in three mouthfuls of round-bottomed flasks of 300mL that condenser pipe and logical protection gas gas port are housed; add 0.6g silester (TEOS) behind the magnetic agitation 15min again; and use the pH value extremely～10 of ammoniacal liquor (5vol%) the solution regulator solution of dilution, at room temperature magnetic agitation 2h.High speed centrifugation is isolated white depositions, uses washed with isopropyl alcohol 3 times, makes PS/SiO
2The hybrid inorganic-organic microsphere particles.When silester content increases SiO
2The thickness of shell also increases thereupon, but the dispersed variation of microballoon, and this is because more SiO
2The generation of offspring has caused the gathering of microballoon.The PS/SiO that present embodiment is prepared
2The TEM photo of organic and inorganic microballoon shown in Fig. 2 (b), the SiO of complex microsphere
2The thickness of shell is 55nm, and thickness is even.
Embodiment 4
At room temperature, 0.03g PS/SiO
2The complex microsphere powder join in 0.15g deionized water and the 24mL absolute ethyl alcohol blending agent and ultrasonic dispersion 15min after; solution is joined in three mouthfuls of round-bottomed flasks of 300mL that condenser pipe and logical protection gas gas port are housed; add 0.06g TBOT then, form suspension after 300 rev/mins of magnetic agitation.This suspension is heated and insulation 2h 80 ℃ of water-baths.Subsequently the reactant liquor high speed centrifugation is isolated precipitation, use deionized water and absolute ethanol washing respectively 3 times, obtain PS/SiO
2/ TiO
2The hybrid inorganic-organic complex microsphere.The SiO of the complex microsphere of gained
2/ TiO
2The thickness of double-deck shell is 16nm, and shell thickness is (Fig. 3 (a)) evenly.
Embodiment 5
At room temperature, 0.03g PS/SiO
2The complex microsphere powder join in 0.15g deionized water and the 24mL absolute ethyl alcohol blending agent and ultrasonic dispersion 15min after; solution is joined in three mouthfuls of round-bottomed flasks of 300mL that condenser pipe and logical protection gas gas port are housed; add 0.12g TBOT then, form suspension after 300 rev/mins of magnetic agitation.This suspension is heated and insulation 2h 80 ℃ of water-baths.Subsequently the reactant liquor high speed centrifugation is isolated precipitation, use deionized water and absolute ethanol washing respectively 3 times, obtain PS/SiO
2/ TiO
2The hybrid inorganic-organic complex microsphere.The SiO of the complex microsphere of gained
2/ TiO
2The thickness of double-deck shell increases to some extent than embodiment 4, increases to 30nm, and shell thickness is (Fig. 5 (b)) evenly.
Embodiment 6
At room temperature, 0.03g PS/SiO
2The complex microsphere powder join in 0.15g deionized water and the 24mL absolute ethyl alcohol blending agent and ultrasonic dispersion 15min after; solution is joined in three mouthfuls of round-bottomed flasks of 300mL that condenser pipe and logical protection gas gas port are housed; add 0.18g TBOT then, form suspension after 300 rev/mins of magnetic agitation.This suspension is heated and insulation 2h 80 ℃ of water-baths.Subsequently the reactant liquor high speed centrifugation is isolated precipitation, use deionized water and absolute ethanol washing respectively 3 times, obtain PS/SiO
2/ TiO
2The hybrid inorganic-organic complex microsphere.The SiO of the complex microsphere of gained
2/ TiO
2The thickness of double-deck shell increases to some extent than embodiment 5, increases to 66nm, and shell thickness is (Fig. 3 (c)) evenly.
Embodiment 7
At room temperature, 0.03g PS/SiO
2The complex microsphere powder join in 0.15g deionized water and the 24mL absolute ethyl alcohol blending agent and ultrasonic dispersion 15min after; solution is joined in three mouthfuls of round-bottomed flasks of 300mL that condenser pipe and logical protection gas gas port are housed; add 0.01g PVP and 0.12g TBOT then, form suspension after 300 rev/mins of magnetic agitation.This suspension is heated and insulation 2h 80 ℃ of water-baths.Subsequently the reactant liquor high speed centrifugation is isolated precipitation, use deionized water and absolute ethanol washing respectively 3 times, obtain PS/SiO
2/ TiO
2The hybrid inorganic-organic complex microsphere.The PS/SiO of present embodiment preparation
2/ TiO
2Hybrid inorganic-organic complex microsphere dispersiveness more obviously improves, and shell thickness is approximately 31nm (Fig. 3 (d)).
Embodiment 8
Step according to embodiment 7 prepares PS/SiO
2/ TiO
2The hybrid inorganic-organic complex microsphere is put into product Muffle furnace then 550 ℃ of calcinings 2 hours, naturally cools to room temperature, obtains the earth silicon/titanic oxide hollow microballoon powder.Fig. 4 shows that for the transmission electron microscope photo of the earth silicon/titanic oxide hollow microballoon powder of present embodiment preparation shell is by tiny nano-TiO
2Particle is formed, the shell even compact.Insertion SEAD figure in the drawings is well corresponding to nano-TiO
2The diffraction ring of polycrystalline shows that the shell skin is really by nano-TiO
2Particle is formed.Fig. 5 (a) is the X-ray diffractogram of the prepared earth silicon/titanic oxide hollow microballoon powder of present embodiment, and visible gained powder is anatase phase TiO
2Structure, diffraction maximum is successively corresponding to the crystal face diffraction maximum of (101), (103), (004), (112), (200), (105), (211), (204), (116), (220) and (215) in the spectrum; Do not find the diffraction maximum of rutile phase in the spectrogram.Because SiO
2Be amorphous phase mutually, so in X-ray diffractogram and fail to reflect.Calculate outer shell TiO according to the Schrerrer formula
2Particle size is 11.1nm.
Embodiment 9
Step according to embodiment 7 prepares PS/SiO
2/ TiO
2The hybrid inorganic-organic complex microsphere is put into product Muffle furnace then 600 ℃ of calcinings 2 hours, naturally cools to room temperature, obtains the earth silicon/titanic oxide hollow microballoon powder.Fig. 5 (b) is the X-ray diffractogram of the prepared earth silicon/titanic oxide hollow microballoon powder of present embodiment, calculates outer shell TiO according to the Schrerrer formula
2Particle size is 13.7nm.
Step according to embodiment 7 prepares PS/SiO
2/ TiO
2The hybrid inorganic-organic complex microsphere is put into product Muffle furnace then 650 ℃ of calcinings 2 hours, naturally cools to room temperature, obtains the earth silicon/titanic oxide hollow microballoon powder.Fig. 5 (c) is the X-ray diffractogram of the prepared earth silicon/titanic oxide hollow microballoon powder of present embodiment, and visible gained powder is anatase phase TiO
2Account for primary structure, have the part rutile to occur mutually.Diffraction peak intensity is high and sharp-pointed, has as seen obtained the earth silicon/titanic oxide hollow microballoon of complete crystallization, calculates outer shell TiO according to the Schrerrer formula
2Particle size is 17.3nm.Fig. 6 is the transmission electron microscope photo of the earth silicon/titanic oxide hollow microballoon powder of present embodiment preparation.The SEM photo that inserts has confirmed that hollow ball shell is made up of two parts, i.e. SiO
2And TiO
2Two phase compositions, spherical shell internal layer white layer is SiO
2Phase, outer coversheet are TiO
2Phase.Photocatalytic degradation methylene blue test (Fig. 7) shows that the catalytic activity of earth silicon/titanic oxide hollow microballoon powder improves 2-3 doubly than the P-25 powder.
Claims (10)
1. the process for preparing sol-gel of an earth silicon/titanic oxide hollow microballoon is characterized in that: at first prepare cationic polystyrene microsphere as template; Then, use sol-gel process to prepare the nucleocapsid structure microballoon of single dispersion, remove the macromolecule template by calcining at last and obtain earth silicon/titanic oxide hollow microballoon for twice;
Step of preparation process is:
1. the preparation of polystyrene microsphere template: have in 10～30mL styrene joins in three mouthfuls of round-bottomed flasks that condenser pipe and logical protective gas gas port are housed of 200mL deionized water, add respectively then and account for the azo diisobutyl ether hydrochloride (AIBA) of total solution weight 0.3% and account for 1.2% polyvinylpyrrolidone k30, the use magnetic agitation mixes, and logical nitrogen purge oxygen continues 1h in reactor, uses water-bath to be heated to 70-80 ℃ then; High speed centrifugation is isolated white depositions, uses deionized water and absolute ethanol washing respectively, removes remaining styrene monomer and surfactant;
2. the preparation of polystyrene/silica dioxide complex microsphere particle: with mass percentage concentration is after 3% polystyrene microsphere suspension 1ml is distributed in 15ml deionized water and the 50ml isopropyl alcohol mixture, solution is joined in the step reactor 1., after magnetic agitation, add 0.1～0.6g silester, and the pH value to 10 of the ammonia spirit regulator solution of use dilution, at room temperature magnetic force stirs again, high speed centrifugation is isolated white depositions, uses washed with isopropyl alcohol 3 times, makes PS/SiO
2The complex microsphere particle;
3. the complex microsphere of polystyrene/silica dioxide/titanium dioxide hybrid inorganic-organic preparation: the 0.03g PS/SiO that 2. step is made
2The complex microsphere powder join in 0.15g deionized water and the 24mL absolute ethyl alcohol blending agent and ultrasonic dispersion 15min after, solution is joined in the step reactor 1., add 0～0.03g polyvinylpyrrolidone K then
30With 0.06～0.18g butyl titanate, 70-80 ℃ of water bath heat preservation 1-3h, high speed centrifugation is isolated precipitation, uses deionized water and absolute ethanol washing respectively 3-5 time, and sediment is put into baking oven, 60-70 ℃ of drying, obtains PS/SiO
2/ TiO
2The complex microsphere powder of hybrid inorganic-organic;
4. the PS/SiO that 3. step is prepared
2/ TiO
2The complex microsphere powder sample of hybrid inorganic-organic is put into Muffle furnace 550～650 ℃ of calcinings, obtains the earth silicon/titanic oxide hollow microballoon powder.
2. by the process for preparing sol-gel of the described earth silicon/titanic oxide hollow microballoon of claim 1, it is characterized in that 1. water-bath heat tracing time 20-24h of step.
3. by the process for preparing sol-gel of the described earth silicon/titanic oxide hollow microballoon of claim 1, it is characterized in that 1. step is 3-5 time with deionized water and absolute ethanol washing number of times.
4. by the process for preparing sol-gel of the described earth silicon/titanic oxide hollow microballoon of claim 1, it is characterized in that the concentration expressed in percentage by volume of the weak ammonia that uses during step 2. is 4-6%.
5. by the process for preparing sol-gel of the described earth silicon/titanic oxide hollow microballoon of claim 1, it is characterized in that step 3. sediment to put into the oven drying time be 6-10 hour.
6. by the process for preparing sol-gel of the described earth silicon/titanic oxide hollow microballoon of claim 1, it is characterized in that step 4. in the Muffle furnace calcination time be 2-4 hour.
7. by the process for preparing sol-gel of the described earth silicon/titanic oxide hollow microballoon of claim 1, it is characterized in that the little 250-270nm of average grain diameter of microsphere template.
8. by the process for preparing sol-gel of claim 1 or 6 described earth silicon/titanic oxide hollow microballoons, the internal layer white layer that it is characterized in that prepared earth silicon/titanic oxide hollow microballoon is SiO
2Phase, outer shell are TiO
2Phase.
9. by the process for preparing sol-gel of the described earth silicon/titanic oxide hollow microballoon of claim 8, it is characterized in that calcining heat is raised to 600 ℃ from 550 ℃, makes TiO
2The size of shell changes to 20nm from 10nm.
10. by the process for preparing sol-gel of the described earth silicon/titanic oxide hollow microballoon of claim 1, it is characterized in that 3. 2. step repeat repeatedly to obtain the polytrope shell structure with step.
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Citations (2)
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| CN1454924A (en) * | 2003-05-15 | 2003-11-12 | 复旦大学 | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof |
| CN1546225A (en) * | 2003-12-17 | 2004-11-17 | 同济大学 | TiO2/SiO2 aerogel globule and method for making same |
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| CN1454924A (en) * | 2003-05-15 | 2003-11-12 | 复旦大学 | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof |
| CN1546225A (en) * | 2003-12-17 | 2004-11-17 | 同济大学 | TiO2/SiO2 aerogel globule and method for making same |
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