CN101733087A - Floating type TiO2/floating bead composite photochemical catalyst and preparation method and application thereof - Google Patents
Floating type TiO2/floating bead composite photochemical catalyst and preparation method and application thereof Download PDFInfo
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- CN101733087A CN101733087A CN200910263396A CN200910263396A CN101733087A CN 101733087 A CN101733087 A CN 101733087A CN 200910263396 A CN200910263396 A CN 200910263396A CN 200910263396 A CN200910263396 A CN 200910263396A CN 101733087 A CN101733087 A CN 101733087A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000011324 bead Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000007667 floating Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 22
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 28
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000010881 fly ash Substances 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 7
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- 239000010883 coal ash Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- -1 Methylene Chemical group 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229960003511 macrogol Drugs 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention discloses a floating type TiO2/floating bead composite photochemical catalyst and preparation method and application thereof. The floating bead in photochemical catalyst is spherical and is taken as carrier, and TiO2 forms a film on the surface of the floating bead. The preparation method includes that mixed solution of tetrabutyl titanate and absolute ethanol is added with an amount of ultrapure water, and stirring is carried out, so as to form TiO2 sol; coal ash floating bead is added into the TiO2 sol, and mixing and stirring are simultaneously carried out; impregnation is carried out for a period of time at room temperature, redundant TiO2 sol is filtered, and drying and calcinating are carried out, thus obtaining the photochemical catalyst. The floating type TiO2/floating bead composite photochemical catalyst has favourable degradation performance on methylene blue solution under the condition of UV irradiation.
Description
Technical field
The present invention relates to a kind of photochemical catalyst, particularly a kind of float type TiO
2/ float bead composite photochemical catalyst and preparation method thereof, the invention still further relates to this photochemical catalyst photocatalytic degradation performance to methylene blue under the UV-irradiation condition.
Background technology
In oxide semiconductor, anatase type nano TiO
2Photocatalytic activity is the strongest, and has good chemical stability, abrasion resistance, low cost, can directly utilize advantages such as sunshine, is applied to environmental areas such as wastewater treatment, desalt and air cleaning gradually at present.In actual applications, because nano-TiO
2Particle is tiny, separates difficulty, contains nano-TiO
2Particle suspension liquid will through filtration, methods such as centrifugal, copolymerization and sedimentation separate, processing procedure more complicated, thereby limited its industrialized application.Therefore, the research of immobilization photochemical catalyst has been subjected to people's attention.
Float pearl and be a kind of pearl particle in the flyash, wall approaches hollow, can float on the water, and has light weight, heat insulation, sound insulation, characteristic such as high temperature resistant and wear-resisting.At present, fly ash float is applied to building field more, as be used for production lightweight high temperature insulating refractory material, float the pearl filler, float pearl concrete and light weight cement etc., but its value-added content of product is low, the whole economic efficiency of comprehensive utilization is also not high, and the comprehensive utilization value that improves fly ash float has been research focus in recent years.It is more cheap relatively to float the pearl price, can float on the long period easily to accept illumination on the water surface, and the characteristic of floating pearl has also determined it to be convenient to reclaim and can repeatedly reuse, and is preparing carriers TiO to float pearl
2Composite photo-catalyst should have bigger application and development and be worth.
Summary of the invention
Technical problem solved by the invention provides a kind of can floating on the water surface long period, and is convenient to reclaim the float type TiO that can repeatedly reuse
2/ floating bead composite photochemical catalyst and preparation method thereof, this photochemical catalyst has photocatalytic degradation effect preferably to methylene blue.
Float type TiO of the present invention
2/ float bead composite photochemical catalyst, it is characterized in that being the spherical of rule, TiO as the pearl that floats of carrier
2Floating bead surface formation rete.
It is above-mentioned that to float pearl be a kind of pearl particle in the flyash.
Float type TiO among the present invention
2/ float the preparation method of bead composite photochemical catalyst, may further comprise the steps:
1) float the pearl preliminary treatment: will from flyash, extract float pearl with rare nitric acid dousing 8～12h after, use the distilled water rinsing afterwards, be neutral until the water that flows out, the oven dry back is standby;
2) be raw material with butyl titanate, absolute ethyl alcohol, acetylacetone,2,4-pentanedione and ultra-pure water, the mol ratio of butyl titanate, absolute ethyl alcohol, acetylacetone,2,4-pentanedione and ultra-pure water is 1: 22: 1: 0.5～1.5, regulate its pH to 3.5～5.5 with red fuming nitric acid (RFNA), stirring is fully reacted it, add polyethylene glycol then, the mol ratio that makes butyl titanate and polyethylene glycol is 800～1200: 1, and heating and stirring make it abundant dissolving, promptly obtain the TiO of yellow transparent
2Colloidal sol;
3) to TiO
2Add in the colloidal sol step 1) pretreated float bead carrier, making butyl titanate and the mass ratio that floats pearl is 5～10: 1, stirring makes it to mix, behind dipping 12～36h, filter out unnecessary colloidal sol, the sample oven dry with leaching places Muffle furnace in 400 ℃～600 ℃ temperature lower calcination 1.5h～2.5h again, the calcining back is cooled to room temperature in air, thereby makes the TiO of a load
2/ float bead composite photochemical catalyst;
4) loading process repeatedly: the sample that obtains with above-mentioned step 3) is a carrier, repeating step 2) and step 3), to make the TiO of secondary load
2/ float the pearly-lustre catalyst; Repeat above-mentioned experiment, to finish repeatedly load;
5) catalyst sample that step 4) is obtained distilled water rinsing, and collect floating TiO
2/ float the pearly-lustre catalyst, be placed in the baking oven and dry, promptly make float type TiO
2/ float bead composite photochemical catalyst.
Above-mentioned steps 4) TiO in
2/ load the number of times that floats pearl is 2～4 times.
In addition, the present invention also provides this float type TiO
2/ float bead composite photochemical catalyst to the application in the methylene blue solution degradation process.
Because it is more cheap relatively to float the pearl price, and can float on the long period on the water surface, easily accepts illumination, and be convenient to reclaim and can repeatedly reuse, so with floating the TiO that pearl is a carrier
2Composite photo-catalyst not only cost is lower, and lighting effect is fine, has improved the photochemical catalyst utilization rate.This photochemical catalyst is higher to the degradation efficiency of methylene blue solution, sees Table 1.In addition, this Preparation of catalysts method is simple, easy to implement, is convenient to industrialized utilization.
Description of drawings
Fig. 1 is the float type TiO that the present invention relates to
2/ float the ESEM shape appearance figure of bead composite photochemical catalyst.
Fig. 2 is the float type TiO that the present invention relates to
2/ float bead composite photochemical catalyst degradation efficiency figure to methylene blue solution under UV-irradiation.
Specific embodiment
Embodiment 1:
1) fly ash float preliminary treatment: behind the rare nitric acid dousing 8h of 10% weight ratio, with a large amount of distilled water rinsings, be neutral until the water that flows out, the oven dry back is standby.
2) be raw material with 34g butyl titanate, 71g absolute ethyl alcohol, 9.8g acetylacetone,2,4-pentanedione and 0.9g ultra-pure water, regulating its pH with red fuming nitric acid (RFNA) is 5, stirs 1h, it is fully reacted, add 2.5g Macrogol 2000 0 then, heating and stirring make it abundant dissolving, promptly obtain the TiO of yellow transparent
2Colloidal sol;
3) to step 2) in the TiO that makes
2Add in the colloidal sol 3.4g pretreated float bead carrier, stir and make it to mix, dipping 12h filters out unnecessary colloidal sol, the sample oven dry with leaching places 550 ℃ of temperature lower calcination 2.5h of Muffle furnace again, the calcining back is cooled to room temperature in air;
4) secondary load process: the sample that obtains with above-mentioned step 3) is a carrier, repeats 2), 3) step, to make the TiO of secondary load
2/ float the pearly-lustre catalyst;
5) catalyst that then step 4) is obtained distilled water rinsing, and the TiO of collection float type
2/ float the pearly-lustre catalyst, be placed in the baking oven and dry, promptly make float type TiO
2/ float bead composite photochemical catalyst.Its shape appearance figure as shown in Figure 1.
Fig. 1 is float type TiO
2/ float the sem photograph of bead composite photochemical catalyst.As can be seen from the figure: float pearl and be the spherical of rule, TiO
2Formed rete floating bead surface, film distributes more even relatively.Fig. 2 is the float type TiO that the present invention relates to
2/ float bead composite photochemical catalyst degradation efficiency figure to methylene blue solution under UV-irradiation, along with the increase of UV-irradiation time, the degradation rate of methylene blue solution increases thereupon.
Float type TiO
2/ float bead composite photochemical catalyst photocatalysis performance test process: utilize homemade photo catalysis reactor, it is 20mgL that the catalyst that makes in the 1.8g step 5) is added to 600mL concentration
-1Methylene blue solution in, air agitation reaches the adsorption equilibrium of methylene blue solution under the half-light condition, promptly carries out the test of UV-irradiation degradation of methylene blue subsequently, the degradation efficiency of methylene blue is measured in sampling at set intervals.
Listed the float type TiO that makes among the embodiment 1 in the table 1
2/ float bead composite photochemical catalyst degradation efficiency to methylene blue solution under the UV-irradiation condition.
Embodiment 2:
1) fly ash float preliminary treatment: behind the rare nitric acid dousing 10h of 10% weight ratio, with a large amount of distilled water rinsings, be neutral until the water that flows out, the oven dry back is standby.
2) be raw material with 34g butyl titanate, 71g absolute ethyl alcohol, 9.8g acetylacetone,2,4-pentanedione and 1.8g ultra-pure water, regulating its pH with red fuming nitric acid (RFNA) is 3.5, stirs 1h, it is fully reacted, add 2g Macrogol 2000 0 then, heating and stirring make it abundant dissolving, promptly obtain the TiO of yellow transparent
2Colloidal sol;
3) to step 2) in the TiO that makes
2Add in the colloidal sol 5g pretreated float bead carrier, stir and make it to mix, dipping 24h filters out unnecessary colloidal sol, the sample oven dry with leaching places 450 ℃ of temperature lower calcination 2h of Muffle furnace again, the calcining back is cooled to room temperature in air;
4) secondary load process: the sample that obtains with above-mentioned step 3) is a carrier, repeats 2), 3) step, to make the TiO of secondary load
2/ float the pearly-lustre catalyst;
5) catalyst that then step 4) is obtained distilled water rinsing, and the TiO of collection float type
2/ float the pearly-lustre catalyst, be placed in the baking oven and dry, promptly make float type TiO
2/ float bead composite photochemical catalyst.
Float type TiO
2/ float bead composite photochemical catalyst photocatalysis performance test process: utilize homemade photo catalysis reactor, it is 20mgL that the catalyst that makes in the 1.8g step 5) is added to 600mL concentration
-1Methylene blue solution in, air agitation reaches the adsorption equilibrium of methylene blue solution under the half-light condition, promptly carries out the test of UV-irradiation degradation of methylene blue subsequently, the degradation efficiency of methylene blue is measured in sampling at set intervals.
Listed the float type TiO that makes among the embodiment 2 in the table 1
2/ float bead composite photochemical catalyst degradation efficiency to methylene blue solution under the UV-irradiation condition.
Embodiment 3:
1) fly ash float preliminary treatment: behind 10% rare nitric acid dousing 12h, with a large amount of distilled water rinsings, be neutral until the water that flows out, the oven dry back is standby.
2) be raw material with 34g butyl titanate, 71g absolute ethyl alcohol, 9.8g acetylacetone,2,4-pentanedione and 2.7g ultra-pure water, regulating its pH with red fuming nitric acid (RFNA) is 5.5, stirs 1h, it is fully reacted, add 1.7g Macrogol 2000 0 then, heating and stirring make it abundant dissolving, promptly obtain the TiO of yellow transparent
2Colloidal sol;
3) to step 2) in the TiO that makes
2Add in the colloidal sol 6.8g pretreated float bead carrier, stir and make it to mix, dipping 36h filters out unnecessary colloidal sol, the sample oven dry with leaching places 600 ℃ of temperature lower calcination 1.5h of Muffle furnace again, the calcining back is cooled to room temperature in air;
4) secondary load process: the sample that obtains with above-mentioned step 3) is a carrier, repeats 2), 3) step, to make the TiO of secondary load
2/ float the pearly-lustre catalyst;
Three loading processes: the sample that obtains with above-mentioned secondary load is a carrier, repeats 2), 3) step, to make the TiO of three loads
2/ float the pearly-lustre catalyst;
5) catalyst that then step 4) is obtained distilled water rinsing, and the TiO of collection float type
2/ float the pearly-lustre catalyst, be placed in the baking oven and dry, promptly make float type TiO
2/ float bead composite photochemical catalyst.
Float type TiO
2/ float bead composite photochemical catalyst photocatalysis performance test process: utilize homemade photo catalysis reactor, it is 20mgL that the catalyst that makes in the 1.8g step 5) is added to 600mL concentration
-1Methylene blue solution in, air agitation reaches the adsorption equilibrium of methylene blue solution under the half-light condition, promptly carries out the test of UV-irradiation degradation of methylene blue subsequently, the degradation efficiency of methylene blue is measured in sampling at set intervals.
Listed the float type TiO that makes among the embodiment 3 in the table 1
2/ float bead composite photochemical catalyst degradation efficiency to methylene blue solution under the UV-irradiation condition.
Table 1:
| Float type TiO 2/ float the pearly-lustre catalyst | The degradation efficiency of methylene blue solution behind the UV- |
| Embodiment | |
| 1 | ??93.2 |
| Embodiment | |
| 2 | ??93.6 |
| Embodiment | |
| 3 | ??97.2％ |
More than be thinking of the present invention and implementation method, concrete application approach is a lot, should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make some improvement, these improvement also should be considered as protection scope of the present invention.
Claims (5)
1. float type TiO
2/ float bead composite photochemical catalyst, it is characterized in that being the spherical of rule, TiO as the pearl that floats of carrier
2Floating bead surface formation rete.
2. float type TiO according to claim 1
2/ float bead composite photochemical catalyst, it is characterized in that described to float pearl be a kind of pearl particle in the flyash.
3. float type TiO
2/ float the preparation method of bead composite photochemical catalyst, it is characterized in that may further comprise the steps:
1) float the pearl preliminary treatment: that will extract from flyash floats pearl with rare nitric acid dousing 8～12h, uses the distilled water rinsing afterwards, is neutral until the water that flows out, and the oven dry back is standby;
2) be raw material with butyl titanate, absolute ethyl alcohol, acetylacetone,2,4-pentanedione and ultra-pure water, the mol ratio of butyl titanate, absolute ethyl alcohol, acetylacetone,2,4-pentanedione and ultra-pure water is 1: 22: 1: 0.5～1.5, regulate its pH to 3.5～5.5 with red fuming nitric acid (RFNA), stirring is fully reacted it, add polyethylene glycol then, the mol ratio that makes butyl titanate and polyethylene glycol is 800～1200: 1, and heating and stirring make it abundant dissolving, promptly obtain the TiO2 colloidal sol of yellow transparent;
3) to TiO
2Add in the colloidal sol step 1) pretreated float bead carrier, making butyl titanate and the mass ratio that floats pearl is 5～10: 1, stirring makes it to mix, behind dipping 12～36h, filter out unnecessary colloidal sol, the sample oven dry with leaching places Muffle furnace in 400 ℃～600 ℃ temperature lower calcination 1.5h～2.5h again, the calcining back is cooled to room temperature in air, thereby makes the TiO of a load
2/ float bead composite photochemical catalyst;
4) loading process repeatedly: the sample that obtains with above-mentioned step 3) is a carrier, repeating step 2) and step 3), to make the TiO of secondary load
2/ float the pearly-lustre catalyst; Repeat above-mentioned experiment, to finish repeatedly load;
5) catalyst sample that step 4) is obtained distilled water rinsing, and collect floating TiO
2/ float the pearly-lustre catalyst, be placed in the baking oven and dry, promptly make float type TiO
2/ float bead composite photochemical catalyst.
4. according to the described float type TiO of claim 3
2/ float the preparation method of bead composite photochemical catalyst, it is characterized in that TiO in the step 3)
2/ load the number of times that floats pearl is 2～4 times.
5. the described float type TiO of claim 1
2/ float bead composite photochemical catalyst to the application in the methylene blue solution degradation process.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910263396A CN101733087A (en) | 2009-12-18 | 2009-12-18 | Floating type TiO2/floating bead composite photochemical catalyst and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910263396A CN101733087A (en) | 2009-12-18 | 2009-12-18 | Floating type TiO2/floating bead composite photochemical catalyst and preparation method and application thereof |
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|---|---|
| CN101733087A true CN101733087A (en) | 2010-06-16 |
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ID=42457417
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|---|---|---|---|
| CN200910263396A Pending CN101733087A (en) | 2009-12-18 | 2009-12-18 | Floating type TiO2/floating bead composite photochemical catalyst and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890358A (en) * | 2010-06-23 | 2010-11-24 | 南京大学 | Leafing type N-TiO2/cenosphere photocatalyst, preparation method thereof and use thereof |
| CN102302955A (en) * | 2011-06-22 | 2012-01-04 | 南京大学 | Floating polypyrrole-TiO2/floating bead photocatalyst, and preparation method and application thereof |
| CN102513075A (en) * | 2011-11-16 | 2012-06-27 | 黑龙江大学 | Preparation method of floating type porous crystalline state TiO2 ceramic membrane photochemical catalyst |
| CN102872846A (en) * | 2012-10-12 | 2013-01-16 | 合肥工业大学 | Coal ash microsphere loaded one-dimensional nanometer titanium dioxide (TiO2) composite photocatalyst and preparation method thereof |
| CN103084163A (en) * | 2012-12-14 | 2013-05-08 | 上海师范大学 | Process for coating Bi2O3/TiO2 photocatalysis film on surface of hollow lightweight glass sphere |
| CN104128184A (en) * | 2014-06-24 | 2014-11-05 | 安徽理工大学 | Floating type CoFe2O4/TiO2/floating bead composite photocatalyst and preparation method thereof |
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| CN101890358A (en) * | 2010-06-23 | 2010-11-24 | 南京大学 | Leafing type N-TiO2/cenosphere photocatalyst, preparation method thereof and use thereof |
| CN102302955A (en) * | 2011-06-22 | 2012-01-04 | 南京大学 | Floating polypyrrole-TiO2/floating bead photocatalyst, and preparation method and application thereof |
| CN102513075A (en) * | 2011-11-16 | 2012-06-27 | 黑龙江大学 | Preparation method of floating type porous crystalline state TiO2 ceramic membrane photochemical catalyst |
| CN102872846A (en) * | 2012-10-12 | 2013-01-16 | 合肥工业大学 | Coal ash microsphere loaded one-dimensional nanometer titanium dioxide (TiO2) composite photocatalyst and preparation method thereof |
| CN103084163A (en) * | 2012-12-14 | 2013-05-08 | 上海师范大学 | Process for coating Bi2O3/TiO2 photocatalysis film on surface of hollow lightweight glass sphere |
| CN104128184B (en) * | 2014-06-24 | 2016-05-11 | 安徽理工大学 | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof |
| CN104128184A (en) * | 2014-06-24 | 2014-11-05 | 安徽理工大学 | Floating type CoFe2O4/TiO2/floating bead composite photocatalyst and preparation method thereof |
| CN104909633A (en) * | 2015-06-05 | 2015-09-16 | 宁夏永能新材料有限公司 | Preparation method of polymer cement mortar made of TiO2-flyash composite photocatalytic material |
| CN104929283A (en) * | 2015-06-24 | 2015-09-23 | 江苏建筑职业技术学院 | Self-purifying light pollution resisting building external wall |
| CN104929283B (en) * | 2015-06-24 | 2017-03-08 | 江苏建筑职业技术学院 | The external wall of auto purification light pollution preventive |
| CN105521821A (en) * | 2015-12-16 | 2016-04-27 | 江南大学 | Preparation method of suspension type active immobilized enzyme catalyst |
| CN109967060A (en) * | 2017-12-27 | 2019-07-05 | 北京有色金属研究总院 | A kind of preparation process of cenosphere loaded photocatalyst |
| CN112264069A (en) * | 2020-10-23 | 2021-01-26 | 南京信息工程大学 | Attapulgite photocatalyst and preparation method thereof |
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