CN104549193B - A kind of low-density TiO2/SiO2Complex microsphere and preparation method thereof - Google Patents
A kind of low-density TiO2/SiO2Complex microsphere and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 69
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 46
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 46
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 46
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 46
- 239000011148 porous material Substances 0.000 claims abstract description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 20
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010668 complexation reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 6
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 12
- 230000007062 hydrolysis Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000000839 emulsion Substances 0.000 abstract description 5
- 230000008602 contraction Effects 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000008267 milk Substances 0.000 description 4
- 210000004080 milk Anatomy 0.000 description 4
- 235000013336 milk Nutrition 0.000 description 4
- 229950000845 politef Drugs 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
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- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- -1 Titanium alkoxides Chemical class 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to technical field prepared by inorganic functional material, particularly to a kind of low-density TiO2/SiO2Microsphere and synthetic technology thereof. With tetra-n-butyl titanate and tetraethyl orthosilicate for raw material, prepare O/W type emulsion system, by emulsion system is carried out hydrothermal treatment consists, synthesized the SiO with nucleocapsid structure2/TiO2Complex microsphere, the shell of this microsphere is SiO2With TiO2Complex, kernel is TiO2. In water-heat process, tetraethyl orthosilicate adsorbs and quickly occurs hydrolysis in the outer layer of dispersed oil droplets, form the spherical shell layer of some strength, and the formation of this shell inhibits the volume contraction that internal tetra-n-butyl titanate produces because of hydrolysis and polycondensation reaction. By control tetraethyl orthosilicate addition, the shell control ability to microspheres shrink can be regulated and controled continuously, thus the inner structural features of complex microsphere include specific surface area, hole diameter, pore volume etc. all can obtain tuning control.
Description
Technical field
The invention belongs to technical field prepared by inorganic functional material, particularly to a kind of low-density TiO2/SiO2Microsphere and synthetic technology thereof.
Background technology
TiO2Semiconductor physical chemistry stable in properties, abundant raw material source, nontoxic and photocatalytic activity advantages of higher so that it is as photocatalyst, obtain in depollution of environment field and study widely. TiO2Existing forms have amorphous, Detitanium-ore-type, brookite type and rutile-type, wherein amorphous it is generally acknowledged to catalytically inactive, brookite type is less studied due to the preparation comparatively difficulty of pure single crystal form product, and Detitanium-ore-type is a kind of crystalline state that wherein photocatalytic activity is higher. Except crystal formation, particle size also can affect TiO2Activity. The TiO of size2Particle has higher photocatalytic activity, but it in use exists the problem such as difficult separation and recycling, easy loss. Prepare low-density, there is the random network structure Ti O in size cavity2Microsphere can solve this problem well. This porous TiO2The structural characteristic parameters such as the specific surface area of microsphere, hole diameter and pore volume directly influence the photocatalysis efficiency of product. High specific surface area, pore volume have a reactivity point of relatively horn of plenty, and be conducive to low concentration in adsorption and enrichment environment treat degradation of organic substances molecule, thus the photocatalysis efficiency of product can be improved.
The sol-gel process utilizing Titanium alkoxides hydrolysis and polycondensation reaction is to prepare TiO2The common method of photocatalyst. In order to obtain desirable micro structure, available interpolation surfactant or polymer in the feed, then utilize the method that high-temperature calcination removes additive to improve specific surface area and the porosity of product.The present invention proposes a novel synthesis thinking, adopts a step water-heat process, utilizes the composite shell formed in advance to control the contraction of internal gel, it is achieved that TiO2The self-intelligent control of microsphere internal structure.
Summary of the invention
It is an object of the invention to: a kind of low-density, high-specific surface area TiO are provided2/SiO2Complex microsphere and synthetic method thereof,
Low-density TiO provided by the present invention2/SiO2The synthetic method of complex microsphere is:
First, the complex of preparation tetra-n-butyl titanate, owing to the hydrolysing activity of tetra-n-butyl titanate is higher, meet water fast hydrolyzing and form TiO2, so adopting acetylacetone,2,4-pentanedione complexation, to relax its hydrolysis rate; Secondly, preparation O/W type emulsion system, with tetra-n-butyl titanate complex for oil phase dispersion phase, deionized water is continuous phase, and DBSA is interface stability agent, preparation O/W type emulsion system, 3rd, the intervention in Si source, in dispersion, add a certain amount of tetraethyl orthosilicate and ethanol, the addition of tetraethyl orthosilicate, is intended to obtain TiO on the one hand2/SiO2Complex microsphere, is intended to the spherical shell layer utilizing the tetraethyl orthosilicate absorption in oil droplets and hydrolysis formation some strength, on the other hand with the volume contraction suppressing internal tetra-n-butyl titanate hydrolysis to produce, the low-density TiO of final acquisition2Complex microsphere, the use of ethanol is intended to the compatibility improving tetraethyl orthosilicate with water; 4th, hydrothermal treatment consists, the O/W type dispersion of preparation is proceeded in autoclave, under 150 DEG C of conditions, hydro-thermal reaction 10h can obtain TiO2/SiO2Complex microsphere.
Concrete operations are:
(1) DBSA is dissolved in deionized water, is configured to dodecylbenzenesulfonic acid solution,
Wherein, the concentration of the dodecylbenzenesulfonic acid solution of preparation is 90mg/L;
(2) tetra-n-butyl titanate and acetylacetone,2,4-pentanedione are carried out complexation, obtain tetra-n-butyl titanate complex;
(3) the tetra-n-butyl titanate complex obtained in step (2) is joined in the dodecylbenzenesulfonic acid solution obtained in step (1), be uniformly mixing to obtain dispersion system;
(4), in the dispersion system obtained in step (3), add a certain proportion of tetraethyl orthosilicate and ethanol, and stir, obtain reaction system, namely described in following embodiment " O/W type dispersion ";
(5) by the reaction system that obtains in step (4) under 150 DEG C of conditions, hydro-thermal reaction 10h, by product centrifugation, washing, dry, obtain low-density TiO2/SiO2Complex microsphere,
Wherein, product being washed according to the order of " deionized water wash, washing with alcohol ", " drying " operation is, dry 6h at 60 DEG C.
In the present invention, by low-density TiO prepared by such scheme2/SiO2Complex microsphere has nucleocapsid structure, and its spherical shell layer is TiO2/SiO2Complex, kernel is TiO2, this TiO2/SiO2The pore volume of complex microsphere is 0.33 0.63cm3��g-1, the specific surface area of microsphere is 214 293m2��g-1, average pore diameter is 5.7 12nm.
Above-mentioned complex microsphere is to be synthesized, being greatly improved of microsphere internal porosity volume by the step hydro-thermal reaction to dispersion system, the inhibitory action that is based in hydrothermal reaction process spherical shell layer ball internal volume is shunk and realize; The change of complex microsphere internal porosity diameter and pore volume is then pass through SiO2Compound quantity carry out regulating and controlling.
This synthetic method and synthesized TiO2/SiO2Complex microsphere has the following characteristics that
(1) adopting O/W type emulsion system: use water as continuous phase, the preparation cost of microsphere load low, that environment is produced is little;
(2) by a step water-heat process, obtain the complex microsphere of nucleocapsid structure: utilize tetra-n-butyl titanate complex and the capillary difference of tetraethyl orthosilicate, realize the tetraethyl orthosilicate absorption in tetra-n-butyl titanate complex oil droplets, by water-heat process, obtain the complex microsphere of nucleocapsid structure;
(3) complex microsphere has extremely low apparent density, difference due to both tetra-n-butyl titanate complex and tetraethyl orthosilicate hydrolysing activity, tetraethyl orthosilicate is initially formed the spherical shell layer gel with some strength in outer layer hydrolysis, the spherical shell layer formed suppresses the volume contraction that next internal tetra-n-butyl titanate produces because of hydrolysis, so that microsphere is internally formed substantial amounts of size space;
(4) shell of microsphere is not for pure SiO2, but SiO2With TiO2Complex, under hydrothermal conditions, be not only tetraethyl orthosilicate generation hydrolysis, the complex of tetra-n-butyl titanate equally also produces hydrolysis and polycondensation reaction, and simply the hydrolysis reaction activity of tetraethyl orthosilicate is higher, so the spherical shell layer of formation is SiO2With TiO2Complex;
(5) by changing SiO2Compound quantity, namely the addition of regulation and control tetraethyl orthosilicate, just can change the shell thickness of microsphere, regulate the shell control ability to microsphere shaped volumes, thus obtaining the microsphere of a series of different apparent density, the voidage of microsphere ranges up to and reaches 71% (with pure Detitanium-ore-type TiO2Solid density 3.89g cm-3And calculate);
(6) SiO is adopted2Compound, also improves the specific surface area of product, by pure TiO while improving microsphere porosity2193m2/ g increases to 293m2/g(SiO2Compound quantity is 30% (when feeding intake, Si accounts for the mole percent of Ti, Si total amount));
(7)SiO2Compound can improve TiO2The acidic site of photocatalyst, and then strengthen the photocatalysis performance of product, TiO2With SiO2Isoelectric point, IP respectively may be about pH=6.3 and pH=3.0, so complex microsphere is particularly suitable in neutral solution environment organic cation that a large amount of absorption is positively charged;
(8) agglomeration of crystal grain is weak, and the reunion of crystal grain has a strong impact on the performance of product and includes photocatalytic activity, surface area that complex microsphere is high and pore volume mark, it was shown that through SiO2After compound, TiO2The agglomeration of crystal grain is obviously reduced.
Accompanying drawing explanation
Fig. 1 is prepared by embodiment 1��4, SiO2The TiO of compound quantity respectively 0,10%, 20% and 30% (" 0,10%, 20%, 30% " here refers to when feeding intake, and Si accounts for the mole percent of Ti, Si total amount, lower same)2/SiO2The FESEM of complex microsphere or SEM photograph, with pure TiO2Microsphere (the corresponding product of embodiment 1) is compared, and the surface of complex microsphere is comparatively coarse;
Fig. 2 is prepared in embodiment 3, SiO2Compound quantity is the TiO of 20%2/SiO2(before tem analysis, sample is through the HCl treatment 2h of Solute mass fraction 18% for the TEM photo of complex microsphere. ), this analysis is it is shown that complex microsphere has nucleocapsid structure;
Fig. 3 is prepared by embodiment 1��4, SiO2Compound quantity respectively 0,10%, 20% and 30% TiO2/SiO2The N of complex microsphere2Isothermal adsorption result, this analysis is it is shown that work as SiO2When compound quantity is 20%, complex microsphere has maximum N2Adsorption volume;
Fig. 4 is prepared by embodiment 1��4, SiO2Compound quantity respectively 0,10%, 20% and 30% TiO2/SiO2The comparison of the pore volume of microsphere, average pore diameter and specific surface area, this analysis it is shown that with pure TiO2Microsphere is compared, SiO2The amplitude that compound quantity is the specific surface area increase of the complex microsphere of 20% is less, but pore volume and average pore diameter increase about 100% respectively;
Fig. 5 is embodiment 1 and the sample of preparation, i.e. pure TiO in embodiment 32Microsphere and SiO2Compound quantity is the XPS elementary analysis (O1s and Si2p) of the complex microsphere of 20%, and this analysis is it is shown that pass through process route of the present invention, SiO2Successfully it is compound to TiO2On microsphere,
During preparation embodiment 3 sample, it is by the atomic number of Ti and Si than 4:1 addition tetra-n-butyl titanate and tetraethyl orthosilicate, and the atomic number of Ti and the Si detected by electron probe (EPMA) and x-ray photoelectron power spectrum (XPS) is than respectively 5.6:1 and 1.1:1. The wherein signal response volume about 1 ��m of EPMA3, and XPS is a kind of surface analysis technology, its analysis depth only has several atomic layers thick, so above-mentioned analysis is it is shown that Si element is concentrated mainly on the shell of microsphere.
Detailed description of the invention
Embodiment 1:
One, the complexation of tetra-n-butyl titanate
5.0mL tetra-n-butyl titanate adds 2.0mL acetylacetone,2,4-pentanedione, stirring reaction 0.5h, obtains the complex of tetra-n-butyl titanate.
Two, the preparation of O/W type dispersion
When stirring, tetra-n-butyl titanate complex step one obtained is distributed in the DBSA aqueous solution of 40mL, 90mg/L, after stirring 1h, it is thus achieved that uniform milk yellow dispersion.
Three, hydrothermal treatment consists
The O/W type dispersion obtained in step 2 is proceeded in politef in the autoclave of cup, under 150 DEG C of conditions, hydro-thermal reaction 10h.
Four, separate, wash and dry
After the product being obtained by reacting in step 3 is performing centrifugal separation on, with deionized water and ethanol sequential purge, sample dry 6h under 60 DEG C of conditions after washing.
TiO prepared in the present embodiment2The pore volume of microsphere is 0.29cm3��g-1, the specific surface area of microsphere is 193m2��g-1, average pore diameter is 5.6nm, and relative density is 47% (with pure Detitanium-ore-type TiO2Solid density 3.89g cm-3For benchmark).
Embodiment 2:
One, the complexation of tetra-n-butyl titanate
5.0mL tetra-n-butyl titanate adds 2.0mL acetylacetone,2,4-pentanedione, stirring reaction 0.5h, obtains the complex of tetra-n-butyl titanate.
Two, the preparation of O/W type dispersion
When stirring, tetra-n-butyl titanate complex step one obtained is distributed to 40mL, in the DBSA aqueous solution of 90mg/L, after stirring 1h, obtain uniform milk yellow dispersion, in this system, add 0.34mL tetraethyl orthosilicate and 1.7mL ethanol again, continue stirring 30min.
Three, hydrothermal treatment consists
The O/W type dispersion obtained in step 2 is proceeded in politef in the autoclave of cup, under 150 DEG C of conditions, hydro-thermal reaction 10h.
Four, separate, wash and dry
After the product being obtained by reacting in step 3 is performing centrifugal separation on, with deionized water and ethanol sequential purge, sample dry 6h under 60 DEG C of conditions after washing.
TiO prepared in the present embodiment2/SiO2The pore volume of complex microsphere is 0.33cm3��g-1, the specific surface area of microsphere is 216m2��g-1, average pore diameter is 5.7nm, and relative density is 44% (with pure Detitanium-ore-type TiO2Solid density 3.89g cm-3For benchmark).
Embodiment 3:
One, the complexation of tetra-n-butyl titanate
5.0mL tetra-n-butyl titanate adds 2.0mL acetylacetone,2,4-pentanedione, stirring reaction 0.5h, obtains the complex of tetra-n-butyl titanate.
Two, the preparation of O/W type dispersion
When stirring, tetra-n-butyl titanate complex step one obtained is distributed to 40mL, in the DBSA aqueous solution of 90mg/L, after stirring 1h, obtain uniform milk yellow dispersion, in this system, add 0.76mL tetraethyl orthosilicate and 1.7mL ethanol again, continue stirring 30min.
Three, hydrothermal treatment consists
The O/W type dispersion obtained in step 2 is proceeded in politef in the autoclave of cup, under 150 DEG C of conditions, hydro-thermal reaction 10h.
Four, separate, wash and dry
After the product being obtained by reacting in step 3 is performing centrifugal separation on, with deionized water and ethanol sequential purge, sample dry 6h under 60 DEG C of conditions after washing.
TiO prepared in the present embodiment2/SiO2The pore volume of complex microsphere is 0.63cm3��g-1, the specific surface area of microsphere is 214m2��g-1, average pore diameter is 12nm, and relative density is 29% (with pure Detitanium-ore-type TiO2Solid density 3.89g cm-3For benchmark).
Embodiment 4:
One, the complexation of tetra-n-butyl titanate
5.0mL tetra-n-butyl titanate adds 2.0mL acetylacetone,2,4-pentanedione, stirring reaction 0.5h, obtains the complex of tetra-n-butyl titanate.
Two, the preparation of O/W type dispersion
When stirring, tetra-n-butyl titanate complex step one obtained is distributed to 40mL, in the DBSA aqueous solution of 90mg/L, after stirring 1h, obtain uniform milk yellow dispersion, in this system, add 1.31mL tetraethyl orthosilicate and 1.7mL ethanol again, continue stirring 30min.
Three, hydrothermal treatment consists
The O/W type dispersion obtained in step 2 is proceeded in politef in the autoclave of cup, under 150 DEG C of conditions, hydro-thermal reaction 10h.
Four, separate, wash and dry
After the product being obtained by reacting in step 3 is performing centrifugal separation on, with deionized water and ethanol sequential purge, sample dry 6h under 60 DEG C of conditions after washing.
TiO prepared in the present embodiment2/SiO2The pore volume of complex microsphere is 0.45cm3��g-1, the specific surface area of microsphere is 293m2��g-1, average pore diameter is 6.9nm, and relative density is 36% (with pure Detitanium-ore-type TiO2Solid density 3.89g cm-3For benchmark).
Embodiment 5:
In the present invention, with acetylacetone,2,4-pentanedione, tetra-n-butyl titanate being carried out complexation in advance is form O/W type dispersion and synthesis TiO2/SiO2The basis of complex microsphere.
Comparing to be formed with it, 5mL, when stirring, is dispersed directly in the DBSA aqueous solution of 40mL, 90mg/L by embodiment 5 without the tetra-n-butyl titanate of complexation. There is rapidly hydrolysis due to tetra-n-butyl titanate, system is immediately generated substantial amounts of TiO2Particle, thus stable O/W type dispersion can not be formed, also cannot synthesize TiO smoothly2/SiO2Complex microsphere.
Claims (5)
1. a low-density TiO2/SiO2Complex microsphere, it is characterised in that: described microsphere has nucleocapsid structure, and its spherical shell layer is TiO2/SiO2Complex, kernel is TiO2,
Described TiO2/SiO2The pore volume of complex microsphere is 0.33 0.63cm3��g-1, specific surface area is 214 293m2��g-1, average pore size is 5.7 12nm.
2. low-density TiO as claimed in claim 12/SiO2The preparation method of complex microsphere, it is characterised in that: described preparation method is,
(1) DBSA is dissolved in deionized water, is configured to dodecylbenzenesulfonic acid solution;
(2) tetra-n-butyl titanate and acetylacetone,2,4-pentanedione are carried out complexation, obtain tetra-n-butyl titanate complex;
(3) the tetra-n-butyl titanate complex obtained in step (2) is joined in the dodecylbenzenesulfonic acid solution obtained in step (1), be uniformly mixing to obtain dispersion system;
(4) dispersion system obtained in step (3) adds tetraethyl orthosilicate and ethanol, and stir, obtain reaction system;
(5) by the reaction system that obtains in step (4) under 150 DEG C of conditions, hydro-thermal reaction 10h, by product centrifugation, washing, dry, obtain low-density TiO2/SiO2Complex microsphere.
3. low-density TiO as claimed in claim 22/SiO2The preparation method of complex microsphere, it is characterised in that: the concentration of the dodecylbenzenesulfonic acid solution described in step (1) is 90mg/L.
4. low-density TiO as claimed in claim 22/SiO2The preparation method of complex microsphere, it is characterised in that: the washing described in step (5) is, according to the order of " deionized water wash, washing with alcohol ", described product is washed.
5. low-density TiO as claimed in claim 22/SiO2The preparation method of complex microsphere, it is characterised in that: drying described in step (5) is, dry 6h at 60 DEG C.
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| CN105836796A (en) * | 2016-03-23 | 2016-08-10 | 南京华狮化工有限公司 | Preparation method of bell-type core-shell structured nano-TiO2(at)void(at)SiO2 powder |
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