CN1114484C - Process for preparing mesopore titania photocatalyst - Google Patents
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- CN1114484C CN1114484C CN 00119748 CN00119748A CN1114484C CN 1114484 C CN1114484 C CN 1114484C CN 00119748 CN00119748 CN 00119748 CN 00119748 A CN00119748 A CN 00119748A CN 1114484 C CN1114484 C CN 1114484C
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Abstract
The present invention relates to a method for preparing mesoporous titanium dioxide photocatalysts, and belongs to the field of fine chemical industry. The present invention is characterized in that the method comprises the following steps of preparing titanium and silicon composite oxides by utilizing titanium alkoxide and ethyl orthosilicate as main raw materials and adopting inorganic acid as hydrolysts with a sol-gel method, drying, pulverizing and sieving the composite oxides, then calcining the composite oxides at high temperature to enable titanium dioxide to be crystallized, washing the crystallized composite powder by aqueous alkali, and dissolving and removing the silicon dioxide to obtain mesoporous titanium dioxide photocatalytic materials. The photocatalytic materials are aggregates formed by titanium dioxide and having meson pore diameter and grain diameter of 10 nanometers or so, and the specific surface area is larger than 100m<2>/g. The wall of the mesoporous titanium dioxide prepared with the method different from a method reported by a literature is in a crystalline state (octahedrite phases), and the synthesizing process does not use templates. Additionally, the aggregates are in a micron order, and the separation and the recovery of the aggregates are easier than those of nanometer titanium dioxide crystals in the application fields of sewage treatment, etc. The photocatalytic activity can be greatly improved by decorating meson pores with precious metal, such as silver, platinum, aurum, etc.
Description
Technical field
The present invention relates to the preparation method of mesoporous TiO 2, belong to field of fine chemical.
Background technology
In more than ten years in the past, nano material has had fast development, and its application begins to take shape.Nano-functional material is wherein to develop a very fast growing point.Nanocrystalline skin effect and dimensional effect are that it is different from the most significant character of conventional powder, have broad application prospects in heterogeneous catalysis field.In fact, the history of the existing many decades of the application of nano material aspect catalysis.The molecular sieve of petroleum catalytic cracking field extensive use is exactly a kind of nano structural material.Can obtain the homodisperse nano combined catalysis material of nano particle with molecular sieve carried noble metal and other catalyst.Be accompanied by the rise of nano material, the material of multiple structure such as nano-pore, nanocrystalline, nanometer rods, nanotube, quantum dot all successfully prepares, and catalysis has become one of topmost application of these nano structural materials.
As everyone knows, face of mankind nowadays the pressure of unprecedented environmental pollution.Photocatalysis technology will play a significant role aspect environmental protection and the resource regeneration, be the eco-friendly green catalysis technology of a class.Traditional sewage water treatment method is that pollutant is transferred to another kind of medium from a kind of medium, and the real degraded of the pollutant of being unrealized.Photocatalysis technology can be carbon dioxide, water and other inorganic molecules or ion with most mineralization of organic material in the sewage at ambient temperature, can also reduce the toxicity of the big inorganic matter of part toxicity and be used in aspects such as extracting and reclaim noble metal.Used catalysis material is a n type semiconductor now, for example: TiO
2, CdS, ZnO, WO
3, Fe
2O
3, SnO
2, SrTiO
3Deng.TiO in these semiconductors
2, CdS, ZnO catalytic activity higher, light anodic attack can take place and produces Cd in but instability when CdS and ZnO light irradiation
2+, Zn
2+, these ion pair biologies are toxic.In existing catalysis material, titanium dioxide avirulence and catalytic activity are the highest.Titanium dioxide has also that resistance to acids and bases is good in addition, chemical property is stable, characteristics such as photoetch do not take place.Its shortcoming is that quantum yield is low and need to be still the main cause that photocatalysis technology is difficult to large-scale application with ultraviolet excitation.
Nano titanium oxide be meant its crystallite dimension in 100 nanometers with interior titanium dioxide product, replace fine titanium dioxide powder can improve its quantum yield with its, but to the photocatalytic activity research of titanium dioxide nanocrystalline and insufficient.And this respect is very important for application.The mesoporous material of ordered mesoporous titanium dioxide that six sides pile up and other transition elements oxide is similar, and their heat endurance is not as good as the mesoporous material of silicon-dioxide-substrate.After the calcining of the temperature more than 350 ℃, the hole begins to cave in, and the 350 ℃ of organic formwork agents that still can not burn fully wherein also can not make the titanium dioxide crystallization.Because titanium dioxide wherein is indefiniteness, and is not suitable for photocatalyst.The aluminium oxide that recent useful anode electrolysis method is produced is that template prepares the report of aperture greater than the macroporous titanium dioxide of 50 nanometers.
Summary of the invention
The object of the present invention is to provide a kind of alkali solution technique to prepare the method for mesopore titania photocatalyst, its advantage is that technology is easy to control, can obtain the mesoporous titanium dioxide photochemical catalyst that pore-size distribution is narrow, body of wall is crystalline state.
The objective of the invention is to implement like this: it is to utilize titanium alkoxide and ethyl orthosilicate to be primary raw material, the employing inorganic acid is a hydrolyst, use the Prepared by Sol Gel Method Ti-Si composite oxide, the composite oxides drying, pulverize and sieve after, high-temperature calcination makes the titanium dioxide crystallization.Powder after the crystallization is after the aqueous slkali washing, and the molten silica that goes wherein obtains required mesoporous titanium dioxide photocatalytic material.This material is about the aggregate that the titanium dioxide of 10 nanometers is constructed by mesoporous and particle diameter, and its specific area reaches 100m
2More than/the g.The body of wall of the mesoporous TiO 2 of this method that different with reported in literature is preparation be crystalline state anatase mutually or the hybrid junctions crystalline phase of anatase and rutile phase, and in the building-up process without the template agent.
Concrete enforcement can be divided into three and go on foot greatly:
The first step prepares Ti-Si composite oxide; The second step composite oxides crystallization; Composite oxides after the 3rd step aqueous slkali washing crystallization, thus acquisition has the mesoporous titanium dioxide material of photocatalysis characteristic.Now details are as follows respectively:
One, the preparation of Ti-Si composite oxide
By bistep hydrolysis, can control the texture of Ti-Si composite oxide effectively.The mentioned titanium alkoxide of the present invention can be tetraethyl titanate, isopropyl titanate or butyl titanate.At present, butyl titanate is easy to get in the alkoxide of domestic titanium.Because the hydrolysis rate of ethyl orthosilicate is than titanium alkoxide slow (when especially using butyl titanate), thus to obtain the uniform composite granule of component should allow ethyl orthosilicate at first partial hydrolysis obtain colloidal sol.When the composite granule of the high titanium silicon ratio of preparation, in order to make the composite granule component evenly and not phenomenon of phase separation takes place, utilize acetylacetone,2,4-pentanedione and titanium formation complex, can reduce the activity of titanium alkoxide and obtain forming even gel.Acetylacetone,2,4-pentanedione is the stabilizing agent of titanium hydrolysis of alkoxide.
Concrete preparation technology is: the ethanolic solution of ethyl orthosilicate that at first with volume ratio is 1: 1 is in 50-70 ℃ of hydrolysis, make colloidal sol, the ethanolic solution that with volume ratio is 1: 1 titanium alkoxide then joins in the above-mentioned colloidal sol, the ethanolic solution that progressively adds 0.1M watery hydrochloric acid again makes the hydrolysis of alkoxide of titanium, obtain complex sol, complex sol is gelation at room temperature.The ratio of regulating two kinds of solution can obtain the composite oxides of different titanium silicon ratios.The titanium silicon of composite oxides provided by the invention is 1: 19 to 9: 1 than excursion.Specifically consist of: TiO
219SiO
2, TiO
29SiO
2, TiO
23SiO
2, TiO
2SiO
2, 4TiO
2SiO
2, 9TiO
2SiO
2Deng 6 kinds.,, prevent composite granule composition inequality and be separated than greater than 4 o'clock at titanium silicon with the hydrolysis stabilizer of acetylacetone,2,4-pentanedione as the titanium alkoxide.
Gelation time and titanium silicon are than relevant under the mixed sols room temperature, and titanium silicon ratio is 4: 1 o'clock, and gel process can be finished in 1h; Titanium silicon ratio is 1: 19 o'clock, and gelation time needed for 3 weeks just finished.Under the room temperature gelation required time from 1 hour to not waiting in several weeks.
The control of the presoma hydrolytic process of titanium and silicon is crucial in the process of two-step method making prepared silicon dioxide/titania composite oxide.The hydrolysis of ethyl orthosilicate is by the rising temperature, for example 50-70 ℃ was carried out in backflow 1-2 hour, as hydrolyst, silicon was controlled at 1: 1 with the ratio of the amount of substance of water with the ethanolic solution of 0.1M watery hydrochloric acid, and the total amount of the water that adds in the whole process remains on (Ti+Si): H
2O=1: 2 ratio, the water of reaction are that the mode with 0.1M watery hydrochloric acid ethanolic solution progressively adds.
Two, the crystallization of composite oxides
With plural gel in 120-150 ℃ of vacuum drying, grinding and sieving.Then with gel in 600-1000 ℃ of insulation 2 hours, make the titanium dioxide crystallization, crystallization temperature and titanium silicon are than relevant.Heating rate is 3 ℃/min during calcining.Titanium silicon is than higher, and the required calcining heat of crystallization is low more.Can remove residual organic effectively through vacuum drying, grinding and sieving, avoid carbon residue to make the catalyst color blackout of preparation.
In the composite granule of titania/silica, utilize the network limits of silica to be used for suppressing the quick growth of titania in the calcination process, can obtain the composite granule of crystalline state titanium dioxide and indefiniteness silica through high-temperature calcination.
Table 1 has been listed different specific area and the titanium dioxide structures of forming composite oxides after the different temperatures calcining.
Table 1
By table 1 as seen, dioxide-containing silica is high in the composite granule can suppress the titanium dioxide crystallization, makes TiO
2Exist with impalpable structure.SiO behind the gel
2/ TiO
2In the composite granule, because SiO
2Network stops transporting of titanium in calcination process, mass transport process is difficult to carry out.Thereby in the composite granule titanium dioxide grain growth than the nanocrystalline poor growth of pure titinium dioxide many.Consist of the 9TiO of face army
2SiO
2And 4TiO
2SiO
2Composite granule is through 800 ℃ of calcinings, and titanium dioxide all exists mutually with anatase, and average grain diameter is respectively 13.4nm and 9.5nm.And be that presoma begins phase transformation with the titanium dioxide powder that Hydrolyze method makes equally with the butyl titanate when calcining for 525 ℃, 650 ℃ become rutile substantially mutually.So SiO
2/ TiO
2SiO in the composite oxide powder
2Content is to TiO
2Particle diameter and crystallization, phase transformation all have a significant impact.Table 2 has been listed different temperatures calcining back TiO
2Particle diameter and phase composition.Through 1000 ℃ of calcinings, TiO
2Primary particle size all less than 50 nanometers, along with crystallization temperature improves, in the composite granule of high titanium silicon ratio, anatase begins to change mutually to rutile mutually.
Table 2
A: anatase phase; R: rutile phase; X: rutile phase fraction.
Three, the composite oxides after the aqueous slkali washing crystallization
From the transmission electron microscope photo of Ti-Si composite oxide powder as can be seen, titanium dioxide is dispersed in the silica substrate.With the molten silica that goes in the composite granule of chemical method, then can obtain mesoporous TiO 2.Alternative chemical substance has highly basic and hydrofluoric acid.But fluorine ion in the hydrofluoric acid and Ti
4+Form [TiF
6]
2-Complex ion, the result makes and moltenly titanium dioxide is partly dissolved when removing silica, and is therefore not ideal enough.
Highly basic such as selection NaOH or potassium hydroxide can moltenly effectively remove silica and can not make the titanium dioxide dissolving.Its reaction expression is:
(R
+Be Na
+, K
+Ion)
The R that generates
2SiO
3For the metasilicate of monovalent ion, soluble in water, remove by washing.The rate of removing of silica depends on concentration, reaction temperature and the time of the strong base solution of use.General alkali cleaning condition be the 10M strong base solution under temperature 50-80 ℃ alkali cleaning 12-72 hour.Optimized conditions is that the concentration of aqueous slkali is that 10M, reaction temperature are that 60 ℃, reaction time are 20 hours.The prolongation reaction time can be removed more silica, makes the powder of gained have higher porosity and bigger specific area.But overlong time can make the titanium dioxide aggregate size diminish, and is difficult for separating with the method for filtering from liquid phase.So it is important selecting the suitable reaction time.After for example the alkali cleaning time was 72 hours, the size of aggregation reduced, and the part granule only is the 100-200 nanometer, was difficult to make its separation and recovery with the method for filtering.And through alkali cleaning in 20 hours, it is little that aggregate size changes, and size is several microns, 24 hours molten SiO of 91% that go of energy of alkali cleaning
2
The mesoporous titanium dioxide material that obtains according to the method that the invention provides has heat endurance preferably, as table 3 and shown in Figure 4, is example with Ti/Si than=4: 1 component, its aperture mesoporous scope and through alkali cleaning after 72 hours in 110 ℃ of oven dry with through after 400 ℃ or the 500 ℃ of calcinings, specific area, pore volume and pore-size distribution all illustrate to have heat endurance preferably.
Table 3
| Calcining heat (℃) | 110 | 400 | 500 |
| Specific area (m 2/g) | 150.2 | 132.8 | 78.2 |
| Pore volume (cm 3/g) | 0.102 | 0.107 | 0.096 |
| Average pore size (nm) | 2.71 | 3.24 | 3.98 |
By table 3 as seen, 400 ℃ the calcining 2 hours specific areas only descend 10%, and 500 ℃ the calcining 2 hours after, its specific area still can reach 80m
2About/g.
The Ti-Si composite oxide photocatalytic activity after alkali cleaning that makes from three above big one step preparation methods is improved, this is because anatase all has higher photocatalytic activity with rutile titanium dioxide mutually mutually, but catalytic activity is still low than titanium dioxide nanocrystalline.The method of photoactivation deposition, deposit noble metal island (cluster) in the mesoporous TiO 2 nanocrystal surface, as clusters such as platinum, gold, silver, these clusters help the migration of light induced electron, can suppress the compound of light induced electron and photohole effectively, thereby improve the photocatalysis productive rate.
The platinum source can be selected chloroplatinic acid (H for use
2PtCl
6) solution.The platinum acid chloride solution of preparation debita spissitudo is dispersed in mesoporous TiO 2 powder in the solution, and ultrasonic dispersion is poured this solution in the Photoreactor into then, the illumination certain hour.Along with the carrying out of reaction, the suspension that can be observed white becomes brown.The primary particle size of body of wall titanium dioxide only is about 10 nanometers in the mesoporous TiO 2, and the light induced electron that produces after the illumination is moved to the reduction reaction that nanocrystalline surface participates in chloroplatinic acid very soon:
Show that with the HRTEM observation platinum that the photoactivation deposition process obtains is deposited on the surface of titanium dioxide nanocrystalline equably, crystallite dimension is 2～3 nanometers.Fig. 5 is for carrying the curve that photocatalytic activity improves behind the platinum in the phenol photocatalytic degradation reaction.
Mesopore titania photocatalyst preparation method's provided by the invention outstanding characteristics are:
1, body of wall titanium dioxide is crystalline state (anatase phase) in Zhi Bei the mesoporous TiO 2, is that unbodied titanium dioxide mesoporous material is compared with body of wall, can produce light induced electron and photohole effectively behind ultraviolet excitation, is suitable for using photocatalyst.
2, mesoporous pore-size distribution is narrow, is the 2-5 nanometer, and the most probable aperture is 4 nanometers, and heat endurance is preferably arranged.
The primary particle size of the titanium dioxide in 3, mesoporous changes process conditions and can obtain the different titanium dioxide nanocrystalline mesoporous material of primary particle size still at nanoscale.These nanocrystalline mesoporous materials had not only kept that the characteristics of nanocrystalline high catalytic activity but also ratio nano crystalline substance are easier to be separated and reclaim from liquid phase.
4, this mesoporous material is easy to separate and reclaim, and the photocatalytic activity that makes carried noble metal improve titanium dioxide has Practical significance.
Description of drawings
Fig. 1 is the XRD figure of earth silicon/titanic oxide composite granule after 1000 ℃ of calcinings.A, b, c, d represent that respectively the Ti/Si ratio is the composite granule of 1: 3,1: 1,4: 1 and 9: 1 among the figure, and A is an anatase phase diffraction maximum, and R is a rutile phase diffraction maximum.
Fig. 2 is the X-ray diffractogram of the mesoporous TiO 2 for preparing behind 800 ℃, alkali cleaning for crystallization temperature, and each main diffraction maximum is all corresponding to the anatase phase among the figure.
Fig. 3-1,3-2 are that white portion is mesoporous in Fig. 3-2 photo with the transmission electron microscope photo of the mesoporous TiO 2 that obtains after the composite granule of method preparation provided by the invention and the alkali cleaning.
Fig. 4 is a mesoporous TiO 2 through 110 ℃ of oven dry, 400 ℃ of calcinings two hours and two hours graph of pore diameter distribution of 500 ℃ of calcinings, and ordinate is the differential in pore volume/aperture, and unit is centimetre
3Gram
-1, nanometer
-1Abscissa is the aperture, and unit is a nanometer.As seen from the figure, pore-size distribution is in the 2-5 nanometer, and the most probable aperture is 4 nanometers.
Fig. 5 is that three kinds of photochemical catalysts are used for phenol degrading reaction degradation rate with the situation of change in reaction time, and abscissa is the reaction time, and unit is for dividing; Ordinate is a phenol concentration, and unit is millimeter/liter.A is 800 ℃ of 4TiO after the calcining among the figure
2SiO
2Composite oxides, b are mesoporous TiO after the alkali cleaning
2, c is for carrying the mesoporous TiO of 0.22wt% platinum
2
Fig. 6 is that three kinds of photochemical catalysts are used for chromate degradation reaction degradation rate with the situation of change in reaction time, and abscissa is the reaction time, and unit is for dividing; Ordinate is a chromate concentration, and unit is millimeter/liter.A is 800 ℃ of 4TiO after the calcining among the figure
2SiO
2Composite oxides, b are mesoporous TiO after the alkali cleaning
2, c is for carrying the mesoporous TiO of 0.22wt% platinum
2
The specific embodiment
Further specify embodiment and effect with following non-limiting embodiment.
Embodiment 1
Past volume ratio is the ethanolic solution that the ethanolic solution of 1: 1 ethyl orthosilicate adds 0.1M hydrochloric acid, and making the silicon and the ratio of the amount of substance of water is 1: 1, and 70 ℃ were refluxed 1 hour, and were cooled to room temperature.Add the ethanolic solution that volume ratio is 1: 1 a butyl titanate then, making the Ti/Si ratio is 4: 1.The ethanolic solution that progressively adds 0.1M hydrochloric acid again, the amount of substance that makes water are the twice of the amount of substance sum of titanium and silicon.Form gel after 1 hour.Dry, pulverize, sieve, 800 ℃ of calcinings two hours, back 110 ℃ of oven dry are washed in 60 ℃ of washings of 20% sodium hydroxide solution 20 hours.Its X-ray diffraction (XRD) is schemed as shown in Figure 2, and the composite granule transmission electron microscope photo before the alkali cleaning is shown in Fig. 3-1, and the transmission electron microscope photo of the mesoporous TiO 2 that alkali cleaning obtains is shown in Fig. 3-2, and pore-size distribution is shown in 1 among Fig. 4.Titanium dioxide primary particle size wherein is 9.5nm.Resulting mesoporous titanium dioxide photocatalytic material was through 110 ℃ of oven dry, 400 ℃ or 500 ℃ of calcinings two hours, and mesoporous pore-size distribution is shown in 1 among Fig. 4,2,3.
Embodiment 2
The ethanolic solution of 1: 1 ethyl orthosilicate of volume ratio adds the ethanolic solution of 0.1M hydrochloric acid, and silicon is 1: 1 with the ratio of the amount of substance of water, and 50 ℃ were refluxed 2 hours, and were cooled to room temperature.Add volume ratio then and be 1: 1 butyl titanate, make Ti/Si=9: 1, texture is all even to be avoided being separated in order to keep, and needs to add an amount of acetylacetone,2,4-pentanedione and titanium formation complex.Acetylacetone,2,4-pentanedione is as the stabilizing agent of titanium hydrolysis of alkoxide, and mixed sols can be preserved the long time behind the adding stabilizing agent.All the other are with embodiment 1.
Embodiment 3
Mesoporous TiO 24 gram of embodiment gained is dispersed in the water that is dissolved with chloroplatinic acid, and 400W high voltage mercury lamp radiation 2 hours is with metal platinum photocatalytic deposition nanocrystalline surface in mesoporous TiO 2.X-ray fluorescence analysis has deposited 0.22wt% platinum, and XPS shows that platinum all is simple substance.Its photocatalytic activity is three times of mesoporous TiO 2 before the load platinum in the degradation reaction of chromate.
Claims (10)
1, a kind of mesoporous TiO 2 Preparation of catalysts method, comprise the washing of sol-gel process and aqueous slkali, it is characterized in that: (1) utilizes tetraethyl titanate, butyl titanate or isopropyl titanate and ethyl orthosilicate to be primary raw material, employing hydrochloric acid is hydrolyst, prepare Ti-Si composite oxide with sol-gel process, the titanium silicon ratio of composite oxides is 9: 1 to 1: 4; Than greater than 4: 1 o'clock, need to use the acetylacetone,2,4-pentanedione used as stabilizers at titanium silicon; (2) composite oxides through vacuum drying, pulverize and sieve after made the titanium dioxide crystallization in 2 hours in 600～1000 ℃ of high-temperature calcinations; (3) composite granule after the crystallization through NaOH or potassium hydroxide solution in 50～80 ℃ of washings after 12～72 hours, the molten silica that goes wherein, obtaining by mesoporous and particle diameter is the aggregate that the titanium dioxide of 10 nanometers is constructed.
2,, it is characterized in that Ti-Si composite oxide is the bistep hydrolysis preparation by the described preparation method of claim 1:
(a) in volume ratio is 1: 1 the ethanolic solution of ethyl orthosilicate, add the ethanolic solution of 0.1M watery hydrochloric acid, silicon is 1: 1 with the ratio of the amount of substance of water, makes teos hydrolysis become colloidal sol;
(b) be that the ethanolic solution of 1: 1 titanium alkoxide joins in above-mentioned (a) colloidal sol with volume ratio, the ethanolic solution that adds 0.1M watery hydrochloric acid then makes the hydrolysis of alkoxide of titanium, obtains complex sol, and the total amount that adds entry in the whole hydrolytic process remains on (Ti+Si): H
2O=1: 2 ratio;
(c) complex sol gelation at room temperature.
3. by claim 1 or 2 described preparation methods, the ethanolic solution hydrolysis that it is characterized in that ethyl orthosilicate is carried out at 50-70 ℃ of backflow 1-2 hour by the rising temperature; The water of hydrolysis is progressively to add in the mode of 0.1M diluted hydrochloric acid dissolution in ethanol.
4. by claim 1 or 2 described preparation methods, it is characterized in that the gelation time of complex sol is at the Ti/Si ratio at 4: 1 o'clock, gelation time is 1 hour.
5. by the described preparation method of claim 1, it is characterized in that gelation composite oxides vacuum drying temperature is 120-150 ℃.
6. by the described preparation method of claim 1, it is characterized in that the aqueous slkali that adopts is that the concentration of NaOH or potassium hydroxide is 10M, 24 hours molten silica total amounts 91% of going of alkali cleaning.
7, by the described preparation method of claim 6, it is characterized in that the alkali cleaning condition is 60 ℃, 20 hours.
8. by the described preparation method of claim 1, it is characterized in that available light catalytic deposition method goes out precious metal atom bunch at the mesoporous TiO 2 surface deposition, improves photocatalytic activity; Wherein pt atom bunch be by chloroplatinic acid photo-reduction condition deposit on the mesoporous TiO 2 surface, grain size is the 2-3 nanometer.
9. by the described preparation method of claim 8, it is characterized in that described precious metal atom bunch is platinum, gold, silver or palladium.
10. by the described preparation method of claim 1, the body of wall that it is characterized in that prepared mesoporous TiO 2 is that the anatase phase or the anatase of crystalline state mixes crystalline phase with rutile, and building-up process is without the template agent.
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2000
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296131C (en) * | 2004-09-23 | 2007-01-24 | 武汉理工大学 | In-situ preparation of Ag and TiOz multi-phase nanometer crystal composite thin-membrane light catalyst |
| CN102824931A (en) * | 2012-09-11 | 2012-12-19 | 复旦大学 | Three-dimensional pore intercommunicated nano crystal mesoporous photocatalyst and preparation method thereof |
| CN102824931B (en) * | 2012-09-11 | 2015-03-11 | 复旦大学 | Three-dimensional pore intercommunicated nano crystal mesoporous photocatalyst and preparation method thereof |
| CN103059634A (en) * | 2013-01-15 | 2013-04-24 | 雅安百图高新材料有限公司 | Titanium dioxide silicon dioxide composite oxide powder and preparation method thereof |
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| CN1287878A (en) | 2001-03-21 |
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