CN104150532A - Preparation method of hollow titanium dioxide millimeter spheres consisting of nanoparticles - Google Patents
Preparation method of hollow titanium dioxide millimeter spheres consisting of nanoparticles Download PDFInfo
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Abstract
The invention discloses a preparation method of hollow titanium dioxide millimeter spheres consisting of nanoparticles and relates to the preparation method of the hollow titanium dioxide millimeter spheres. The invention aims to solve the technical problems that the existing TiO2 nano materials are difficult to separate and are low in recovery rate in photocatalysis or environmental pollution control system. The preparation method comprises the following steps: firstly, weighing a titanium source, an aqueoussolution of tetrapropylammonium hydroxide, deionized water and anion exchange resin; secondly, mixing the aqueoussolution of the tetrapropylammonium hydroxide with the deionizedwater, and then adding the titanium source and the anion exchange resin and stirring to obtain a mixture; thirdly, filling a reaction still with the mixture; fourthly, pouring out supernatant liquor to obtain small solid-phase spheres, and drying after washing the small solid-phase spheres; fifthly, placing the dried small spheres into a tube furnace to obtain small carbonized spheres; sixthly, placing the small carbonized spheres into a mufflefurnace for roasting to obtain the titanium dioxide millimeter spheres. The titanium dioxide millimeter spheres prepared through adopting the preparation method disclosed by the invention are easily separated and are high in recovery rate in the photocatalysis or environmentalpollution control system. The preparation method is used for preparing the hollow titanium dioxide millimeter spheres.
Description
Technical field
The present invention relates to a kind of preparation method of hollow titanium dioxide millimeter ball.
Background technology
Photocatalysis technology is a kind of eco-friendly green technology, has huge application potential aspect environmental pollution improvement.Titanium dioxide, because of its stable chemical nature, strong to biological nontoxic and oxidation capacity, becomes the most promising photocatalyst material.Quantity research shows greatly, and crystal formation, particle diameter, pattern and the microtexture of titanium dioxide can produce significant impact to its photocatalysis performance.In recent years, people had developed TiO
2the TiO of the different morphologies such as nano particle, nanometer ball, nanometer rod, nano thin-film, nanotube and hollow nanosphere and structure
2material.Although nano-TiO
2in environmental pollution improvement's process, show good activity, but along with going deep into of research, people also find, the particle size of these nano materials is too small, be difficult to separate from reaction mixture, cause the turnover rate of photocatalyst larger, can not effectively from reaction system, reclaim and recycle, virtually increased processing cost.
Summary of the invention
The present invention will solve existing TiO
2nano material difficult separation in photochemical catalysis or environmental pollution improvement's system, the technical problem that the rate of recovery is low, provide a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball.
The present invention, by the preparation method of the molecular hollow titanium dioxide millimeter of nanoparticle ball, carries out according to the following steps:
One, take the TPAOH aqueous solution, deionized water and the anionite-exchange resin that titanium source, concentration expressed in percentage by volume are 50%, wherein mass ratio 1:1～5 of titanium source and the TPAOH aqueous solution, mass ratio 1:5～30 of titanium source and deionized water, titanium source and anionite-exchange resin mass ratio 1:2～15;
Two, after TPAOH aqueous solution step 1 being taken and deionized water mix, obtain mixing solutions, and then under the condition of stirring at room temperature, titanium source is joined in mixing solutions, then continue to stir 1～6h, add anionite-exchange resin, stir 6～24h, obtain presoma solidliquid mixture;
Three, presoma solidliquid mixture step 2 being obtained packs in the stainless steel cauldron with teflon lined, and under the condition of 60～160 DEG C, constant temperature is processed 24～96h, obtains solidliquid mixture;
The supernatant liquid of the solidliquid mixture four, step 3 being obtained is outwelled, and obtains solid phase bead, then by the solid phase bead obtaining with after deionized water wash, be placed in the loft drier of 40～80 DEG C dry;
Five, dried bead step 4 being obtained is placed in tube furnace, under nitrogen atmosphere, rises to 900 DEG C and keep 4h, the black carbonization bead obtaining with the temperature rise rate of 1.5 DEG C/h～2 DEG C/h;
Six, black carbonization bead step 5 being obtained is placed in retort furnace, rises to 500～750 DEG C and keep 4～8h with the temperature rise rate of 1 DEG C/min～5 DEG C/min, obtains by the molecular hollow titanium dioxide millimeter of nanoparticle ball.
Beneficial effect of the present invention:
The present invention, taking tetrabutyl titanate or titanium isopropylate as titanium source, taking the TPAOH aqueous solution as alkali source, taking anionite-exchange resin as hard template, through Hydrothermal Synthesis, obtains by the molecular hollow titanium dioxide millimeter of nanoparticle ball.In the present invention, the macropore in anionite-exchange resin can limit the growth of particle, thereby is conducive to obtain the nanoparticle of titanium dioxide; Meanwhile, because these macroporous structures have connectedness, these nanoparticles can self-assembly in the duct of its connection, after the organic constituent in resin is removed in high-temperature roasting, has just obtained the molecular continuous titanium dioxide skeleton of nanoparticle.
Spherical or the elliposoidal nano particle self-assembly within the scope of 10～90nm forms hollow titanium dioxide millimeter ball prepared by the present invention by median size, and the size range of the millimeter ball being self-assembled into is at 0.1～1mm.The hollow titanium dioxide millimeter ball of preparation easily separates in photochemical catalysis or environmental pollution improvement's system, and the rate of recovery can reach more than 90%.X-ray diffraction analysis shows that titanium dioxide nano-particle in millimeter ball has the crystalline structure of anatase octahedrite or rutile-type.
Brief description of the drawings
Fig. 1 is the hollow titanium dioxide millimeter ball optical photograph of test one preparation;
Fig. 2 is hollow titanium dioxide millimeter ball scanning electron microscope Fig. 1 of test one preparation;
Fig. 3 is hollow titanium dioxide millimeter ball scanning electron microscope Fig. 2 of test one preparation;
Fig. 4 is the hollow titanium dioxide millimeter ball X-ray diffraction spectrogram of test one preparation;
Fig. 5 is the hollow titanium dioxide millimeter ball optical photograph of test two preparations;
Fig. 6 is hollow titanium dioxide millimeter ball scanning electron microscope Fig. 1 of test two preparations;
Fig. 7 is hollow titanium dioxide millimeter ball scanning electron microscope Fig. 2 of test two preparations;
Fig. 8 is the hollow titanium dioxide millimeter ball X-ray diffraction spectrogram of test two preparations;
Fig. 9 is the hollow titanium dioxide millimeter ball optical photograph of test three preparations;
Figure 10 is hollow titanium dioxide millimeter ball scanning electron microscope Fig. 1 of test three preparations;
Figure 11 is hollow titanium dioxide millimeter ball scanning electron microscope Fig. 2 of test three preparations;
Figure 12 is the hollow titanium dioxide millimeter ball X-ray diffraction spectrogram of test three preparations.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment, by the preparation method of the molecular hollow titanium dioxide millimeter of nanoparticle ball, is carried out according to the following steps:
One, take the TPAOH aqueous solution, deionized water and the anionite-exchange resin that titanium source, concentration expressed in percentage by volume are 50%, wherein mass ratio 1:1～5 of titanium source and the TPAOH aqueous solution, mass ratio 1:5～30 of titanium source and deionized water, titanium source and anionite-exchange resin mass ratio 1:2～15;
Two, after TPAOH aqueous solution step 1 being taken and deionized water mix, obtain mixing solutions, and then under the condition of stirring at room temperature, titanium source is joined in mixing solutions, then continue to stir 1～6h, add anionite-exchange resin, stir 6～24h, obtain presoma solidliquid mixture;
Three, presoma solidliquid mixture step 2 being obtained packs in the stainless steel cauldron with teflon lined, and under the condition of 60～160 DEG C, constant temperature is processed 24～96h, obtains solidliquid mixture;
The supernatant liquid of the solidliquid mixture four, step 3 being obtained is outwelled, and obtains solid phase bead, then by the solid phase bead obtaining with after deionized water wash, be placed in the loft drier of 40～80 DEG C dry;
Five, dried bead step 4 being obtained is placed in tube furnace, under nitrogen atmosphere, rises to 900 DEG C and keep 4h, the black carbonization bead obtaining with the temperature rise rate of 1.5 DEG C/h～2 DEG C/h;
Six, black carbonization bead step 5 being obtained is placed in retort furnace, rises to 500～750 DEG C and keep 4～8h with the temperature rise rate of 1 DEG C/min～5 DEG C/min, obtains by the molecular hollow titanium dioxide millimeter of nanoparticle ball.
Spherical or the elliposoidal nano particle within the scope of 10～90nm forms hollow titanium dioxide millimeter ball prepared by present embodiment by median size, and the size range of the hollow millimeter ball being self-assembled into is at 0.1～1mm.X-ray diffraction analysis shows that titanium dioxide nano-particle in bead has the crystalline structure of anatase octahedrite or rutile-type.
Embodiment two: present embodiment is different from embodiment one: described in step 1, titanium source is tetrabutyl titanate or titanium isopropylate.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: described in step 2, room temperature refers to 15 DEG C～30 DEG C.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from embodiment one or two: described in step 2, room temperature refers to 20 DEG C.Other is identical with embodiment one or two.
Embodiment five: present embodiment is different from one of embodiment one to four: add anionite-exchange resin in step 2, stir 8～20h.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: in step 3, constant temperature is processed 30～90h under the condition of 80～120 DEG C.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to five: in step 3, constant temperature is processed 48h under the condition of 100 DEG C.Other is identical with one of embodiment one to five.
Embodiment eight: present embodiment is different from one of embodiment one to seven: in step 4, be 15～22 hours time of drying.Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: rise to 520～730 DEG C and keep 5～7h with the temperature rise rate of 1.5 DEG C/min～4.5 DEG C/min in step 6.Other is identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to eight: rise to 550 DEG C and keep 6h with the temperature rise rate of 2 DEG C/min in step 6.Other is identical with one of embodiment one to eight.
With following verification experimental verification beneficial effect of the present invention:
Test one:
This test, by the preparation method of the molecular hollow titanium dioxide millimeter of nanoparticle ball, is carried out according to the following steps:
One, take the TPAOH aqueous solution, deionized water and the macroporous strong basic styrene series anionite-exchange resin that tetrabutyl titanate, concentration expressed in percentage by volume are 50%, the wherein mass ratio 1:5 of titanium source and the TPAOH aqueous solution, the mass ratio 1:20 of titanium source and deionized water, titanium source and macroporous strong basic styrene series anionite-exchange resin mass ratio 1:3;
Two, after TPAOH aqueous solution step 1 being taken and deionized water mix, obtain mixing solutions, and then under the condition of stirring at room temperature, titanium source is joined in mixing solutions, then continue to stir 3h, add macroporous strong basic styrene series anionite-exchange resin, stir 12h, obtain presoma solidliquid mixture;
Three, presoma solidliquid mixture step 2 being obtained packs in the stainless steel cauldron with teflon lined, and under the condition of 100 DEG C, constant temperature is processed 48h, obtains solidliquid mixture;
The supernatant liquid of the solidliquid mixture four, step 3 being obtained is outwelled, and obtains solid phase bead, then by the solid phase bead obtaining with after deionized water wash, be placed on dry 12h in the loft drier of 60 DEG C;
Five, dried bead step 4 being obtained is placed in retort furnace, rises to 550 DEG C and keep 4h with the temperature rise rate of 2 DEG C/min, obtains by the molecular hollow titanium dioxide millimeter of nanoparticle ball.
This test obtain by the molecular hollow titanium dioxide millimeter of nanoparticle ball optical photograph as shown in Figure 1, as can be seen from Figure 1, bead is of a size of 0.1～0.6mm.In the time using this millimeter ball as photocatalyst material, after liquid-solid phase reaction finishes, this TiO
2millimeter ball is expected to very easily from reaction system, separate, and realizes recycling.
The TiO that this test obtains
2millimeter ball hollow structure as shown in Figure 2, its inner scanning electromicroscopic photograph as shown in Figure 3, as we know from the figure, these hollow TiO
2millimeter ball is that the spherical or elliposoidal nanoparticle within the scope of 20～60nm is molecular by median size.
The X ray of the hollow titanium dioxide millimeter ball that this test obtains spreads out spectrogram as shown in Figure 4, as can be seen from Figure 4, sample is about 25.3 ° and 27.3 ° at 2 θ and locates to have occurred respectively two characteristic diffraction peaks, the diffraction peak position of other diffraction peaks and titanium dioxide crystal coincide, and shows that the nanoparticle in bead is the mixed phase of anatase octahedrite and rutile-type structure.
Test two:
This test, by the preparation method of the molecular hollow titanium dioxide millimeter of nanoparticle ball, is carried out according to the following steps:
One, take the TPAOH aqueous solution, deionized water and the macroporous strong basic styrene series anionite-exchange resin that tetrabutyl titanate, concentration expressed in percentage by volume are 50%, the wherein mass ratio 1:5 of tetrabutyl titanate and the TPAOH aqueous solution, the mass ratio 1:20 of tetrabutyl titanate and deionized water, tetrabutyl titanate and macroporous strong basic styrene series anionite-exchange resin mass ratio 1:3;
Two, after TPAOH aqueous solution step 1 being taken and deionized water mix, obtain mixing solutions, and then under the condition of stirring at room temperature, tetrabutyl titanate is joined in mixing solutions, then continue to stir 3h, add macroporous strong basic styrene series anionite-exchange resin, stir 12h, obtain presoma solidliquid mixture;
Three, presoma solidliquid mixture step 2 being obtained packs in the stainless steel cauldron with teflon lined, and under the condition of 100 DEG C, constant temperature is processed 48h, obtains solidliquid mixture;
The supernatant liquid of the solidliquid mixture four, step 3 being obtained is outwelled, and obtains solid phase bead, then by the solid phase bead obtaining with after deionized water wash, be placed on dry 12h in the loft drier of 60 DEG C, the dried bead obtaining is stand-by;
Five, after the TPAOH aqueous solution that is 50% by concentration expressed in percentage by volume and deionized water mix, obtain mixing solutions, and then under the condition of stirring at room temperature, tetrabutyl titanate is joined in mixing solutions, then continue to stir 3h, the dried bead that adds step 4 to obtain, stirs 12h, obtains presoma solidliquid mixture;
Six, presoma solidliquid mixture step 5 being obtained packs in the stainless steel cauldron with teflon lined, and under the condition of 100 DEG C, constant temperature is processed 48h, obtains solidliquid mixture;
The supernatant liquid of the solidliquid mixture seven, step 6 being obtained is outwelled, and obtains solid phase bead, then by the solid phase bead obtaining with after deionized water wash, be placed on dry 12h in the loft drier of 60 DEG C, the dried bead obtaining is stand-by;
Eight, dried bead step 7 being obtained is placed in retort furnace, rises to 550 DEG C and keep 4h with the temperature rise rate of 2 DEG C/min, obtains by the molecular hollow titanium dioxide millimeter of nanoparticle ball.
Re-filling and ion-exchange have been carried out in this test.
As shown in Figure 5, as can be seen from Figure 5, bead is of a size of 0.1～0.5mm to the hollow titanium dioxide millimeter ball optical photograph that this test obtains.In the time using this millimeter ball as photocatalyst material, after liquid-solid phase reaction finishes, this TiO
2millimeter ball is expected to very easily from reaction system, separate, and realizes recycling.
The TiO that this test obtains
2millimeter ball hollow structure as shown in Figure 6, its inner scanning electromicroscopic photograph as shown in Figure 7, as we know from the figure, these hollow TiO
2millimeter ball is that the spherical or elliposoidal nanoparticle within the scope of 15～70nm is molecular by median size.
The hollow titanium dioxide millimeter ball X ray that this test obtains spreads out spectrogram as shown in Figure 8, as can be seen from Figure 8, sample is about at 2 θ the main diffraction peak that anatase octahedrite and rutile have appearred in 25.3 ° and 27.3 places respectively, shows the mixed structure that contains anatase octahedrite and rutile in synthetic material.
Test three:
This test, by the preparation method of the molecular hollow titanium dioxide millimeter of nanoparticle ball, is carried out according to the following steps:
One, take the TPAOH aqueous solution, deionized water and the macroporous strong basic styrene series anionite-exchange resin that tetrabutyl titanate, concentration expressed in percentage by volume are 50%, the wherein mass ratio 1:5 of titanium source and the TPAOH aqueous solution, the mass ratio 1:20 of titanium source and deionized water, titanium source and macroporous strong basic styrene series anionite-exchange resin mass ratio 1:3;
Two, after TPAOH aqueous solution step 1 being taken and deionized water mix, obtain mixing solutions, and then under the condition of stirring at room temperature, titanium source is joined in mixing solutions, then continue to stir 3h, add macroporous strong basic styrene series anionite-exchange resin, stir 12h, obtain presoma solidliquid mixture;
Three, presoma solidliquid mixture step 2 being obtained packs in the stainless steel cauldron with teflon lined, and under the condition of 100 DEG C, constant temperature is processed 48h, obtains solidliquid mixture;
The supernatant liquid of the solidliquid mixture four, step 3 being obtained is outwelled, and obtains solid phase bead, then by the solid phase bead obtaining with after deionized water wash, be placed on dry 12h in the loft drier of 60 DEG C;
Five, dried bead step 4 being obtained is placed in tube furnace, under nitrogen atmosphere, rises to 900 DEG C and keep 4h, the black carbonization bead obtaining with the temperature rise rate of 1.5 DEG C/h～2 DEG C/h;
Six, black carbonization bead step 5 being obtained is placed in retort furnace, rises to 550 DEG C and keep 4h with the temperature rise rate of 2 DEG C/min, obtains by the molecular hollow titanium dioxide millimeter of nanoparticle ball.
As shown in Figure 9, as can be seen from Figure 9, bead is of a size of 0.1～0.4mm to the hollow titanium dioxide millimeter ball optical photograph that this test obtains.In the time using this millimeter ball as photocatalyst material, after liquid-solid phase reaction finishes, this TiO
2millimeter ball is expected to very easily from reaction system, separate, and realizes recycling.
The TiO that this test obtains
2millimeter ball hollow structure as shown in figure 10, its inner scanning electromicroscopic photograph as shown in figure 11, as we know from the figure, these hollow TiO
2millimeter ball is that the spherical or elliposoidal nanoparticle within the scope of 20～65nm is molecular by median size.
The hollow titanium dioxide millimeter ball X ray that this test three obtains spreads out spectrogram as shown in figure 12, and as can be seen from Figure 12, sample is only about 25.3 ° of main diffraction peaks of having located to occur anatase octahedrite at 2 θ, shows that synthetic material is anatase structured.
Claims (10)
1. by a preparation method for the molecular hollow titanium dioxide millimeter of nanoparticle ball, it is characterized in that the method carries out according to the following steps:
One, take the TPAOH aqueous solution, deionized water and the anionite-exchange resin that titanium source, concentration expressed in percentage by volume are 50%, wherein mass ratio 1:1～5 of titanium source and the TPAOH aqueous solution, mass ratio 1:5～30 of titanium source and deionized water, titanium source and anionite-exchange resin mass ratio 1:2～15;
Two, after TPAOH aqueous solution step 1 being taken and deionized water mix, obtain mixing solutions, and then under the condition of stirring at room temperature, titanium source is joined in mixing solutions, then continue to stir 1～6h, add anionite-exchange resin, stir 6～24h, obtain presoma solidliquid mixture;
Three, presoma solidliquid mixture step 2 being obtained packs in the stainless steel cauldron with teflon lined, and under the condition of 60～160 DEG C, constant temperature is processed 24～96h, obtains solidliquid mixture;
The supernatant liquid of the solidliquid mixture four, step 3 being obtained is outwelled, and obtains solid phase bead, then by the solid phase bead obtaining with after deionized water wash, be placed in the loft drier of 40～80 DEG C dry;
Five, dried bead step 4 being obtained is placed in tube furnace, under nitrogen atmosphere, rises to 900 DEG C and keep 4h, the black carbonization bead obtaining with the temperature rise rate of 1.5 DEG C/h～2 DEG C/h;
Six, black carbonization bead step 5 being obtained is placed in retort furnace, rises to 500～750 DEG C and keep 4～8h with the temperature rise rate of 1 DEG C/min～5 DEG C/min, obtains by the molecular hollow titanium dioxide millimeter of nanoparticle ball.
2. a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball according to claim 1, is characterized in that described in step 1 that titanium source is tetrabutyl titanate or titanium isopropylate.
3. a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball according to claim 1 and 2, is characterized in that described in step 2 that room temperature refers to 15 DEG C～30 DEG C.
4. a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball according to claim 1 and 2, is characterized in that described in step 2 that room temperature refers to 20 DEG C.
5. a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball according to claim 3, is characterized in that adding anionite-exchange resin in step 2, stirs 8～20h.
6. a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball according to claim 4, is characterized in that in step 3 that constant temperature is processed 30～90h under the condition of 80～120 DEG C.
7. a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball according to claim 4, is characterized in that in step 3 that constant temperature is processed 48h under the condition of 100 DEG C.
8. a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball according to claim 6, is characterized in that in step 4 that be 15～22 hours time of drying.
9. a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball according to claim 8, is characterized in that in step 6 rising to 520～730 DEG C and keep 5～7h with the temperature rise rate of 1.5 DEG C/min～4.5 DEG C/min.
10. a kind of preparation method by the molecular hollow titanium dioxide millimeter of nanoparticle ball according to claim 8, is characterized in that in step 6 rising to 550 DEG C and keep 6h with the temperature rise rate of 2 DEG C/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728055A (en) * | 2016-01-28 | 2016-07-06 | 安徽工程大学 | Preparation method of TiO2-AER composite photocatalyst |
| EP3056501A1 (en) * | 2015-02-13 | 2016-08-17 | Evonik Degussa GmbH | Titanium-containing aqueous solution and dispersion |
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| CN1749172A (en) * | 2004-09-15 | 2006-03-22 | 中国科学院合肥物质科学研究院 | The preparation method of titanium dioxide nano mesoporous balls |
| US20100266487A1 (en) * | 2007-11-05 | 2010-10-21 | E. I. Du Pont De Nemours And Company | High temperature stable anatase titanium dioxide |
| CN103073069A (en) * | 2013-02-01 | 2013-05-01 | 哈尔滨工业大学 | One-pot method for preparing iron sulfide/carbon composite mesoporous millimeter ball |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1749172A (en) * | 2004-09-15 | 2006-03-22 | 中国科学院合肥物质科学研究院 | The preparation method of titanium dioxide nano mesoporous balls |
| US20100266487A1 (en) * | 2007-11-05 | 2010-10-21 | E. I. Du Pont De Nemours And Company | High temperature stable anatase titanium dioxide |
| CN103073069A (en) * | 2013-02-01 | 2013-05-01 | 哈尔滨工业大学 | One-pot method for preparing iron sulfide/carbon composite mesoporous millimeter ball |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3056501A1 (en) * | 2015-02-13 | 2016-08-17 | Evonik Degussa GmbH | Titanium-containing aqueous solution and dispersion |
| CN105728055A (en) * | 2016-01-28 | 2016-07-06 | 安徽工程大学 | Preparation method of TiO2-AER composite photocatalyst |
| CN105728055B (en) * | 2016-01-28 | 2018-04-06 | 安徽工程大学 | A kind of TiO2The preparation method of/AER composite photo-catalysts |
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