CN106111107B - A kind of Zinc oxide nano sheet catalyst of titania additive - Google Patents
A kind of Zinc oxide nano sheet catalyst of titania additive Download PDFInfo
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- CN106111107B CN106111107B CN201610476277.0A CN201610476277A CN106111107B CN 106111107 B CN106111107 B CN 106111107B CN 201610476277 A CN201610476277 A CN 201610476277A CN 106111107 B CN106111107 B CN 106111107B
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- zinc oxide
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 96
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 239000000654 additive Substances 0.000 title claims abstract description 16
- 230000000996 additive effect Effects 0.000 title claims abstract description 16
- 239000002135 nanosheet Substances 0.000 title claims abstract description 16
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000005416 organic matter Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 abstract description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 oxygen Radical ion Chemical class 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A kind of Zinc oxide nano sheet catalyst of titania additive of the present invention uses hydro-thermal reaction method, first prepare ZnO nano piece, ZnO nano piece is reacted with isopropyl titanate with diethylenetriamine again, obtains the Zinc oxide nano sheet catalyst of titania additive, wherein Zn（NO3)2·6H2The molar ratio of O and hexamethylenetetramine is controlled 1:0.5~1:1, the molar ratio of ZnO nano piece and metatitanic acid second butyl ester is 10:1~1:1, the volume ratio of isopropyl titanate and diethylenetriamine is 6:1.The Zinc oxide nano sheet catalyst of titania additive of the present invention has good photocatalysis effect, organic matter degradation can be kept complete in 2 h.
Description
Technical field
The present invention relates to a kind of Zinc oxide nano sheet catalyst of titania additive, particularly belong to photocatalyst material skill
Art field.
Background technique
As a kind of green catalyst, huge progress is achieved in recent years.Push the enormous motivation of light-catalyzed reaction research
Value is potentially explored from the strong request, and photochemical catalyst itself of the clean source the Sheng Chan ﹑ Neng Wei Ji ﹑ environmental protection of Qing and is answered
Use potentiality.Photocatalyst of zinc oxide can exhibit one's skill to the full in environmental protection, and powerful catalytic degradation ability can allow big absolutely
Partial contamination turns materially innocuous substance, contributes for water conservation, can solve country and enterprise's sewage effluent together
Problem.Using ZnO by noxious material CN-It is degraded to innocuous substance CO2, N2, NO3-.It is right since light-catalyzed reaction meets low energy consumption
The environmental-friendly favor for having obtained numerous scholars, in recent years, scientific worker furthers investigate light-catalyzed reaction, having obtained can
Achievement is liked, thus light-catalyzed reaction has become an important method of catalysis reaction.
Surface sensitization is that photolytic activity sensitizer is adsorbed in the surface ZnO, and sensitizing molecules absorb photon and are produced under illumination
By electronics, free electron is transferred to the surface ZnO, at the same ZnO be excited after the hole that generates then be transferred to the valence band of photosensitizer, make
Its absorption spectrum is mobile to visible light direction, so that the range for extending ZnO absorbing wavelength improves visible light photocatalysis efficiency.Partly lead
Bluk recombination is to be sufficiently separated photo-generated carrier, and extend compound using the difference of conduction band and valence band between two kinds of semiconductor components
The spectral response range of system achievees the purpose that promote photocatalysis efficiency.Titanium dioxide optical catalyst is since its is safe and non-toxic, changes
It learns the advantages that property is stable, efficiency is high, pollution-free and is widely used in every field, as semiconductor material with wide forbidden band, in ring
Border pollution control field also has a good application prospect.Most of anatase TiO2It is all [101] face of better heat stability
TiO2(content is greater than 94%).But [001] face has higher activity, however [001] face anatase compared to [101] face
TiO2Surface can average out to 0.90J/m2, it is much larger than [101] face (0.44J/m2), pole is not easy to be formed in the synthesis process.
The application passes through to ZnO/TiO2The research of photochemical catalyst photochemical catalyst finds the TiO in [001] face of high exposure2Its
Body catalytic efficiency with higher and activity, therefore, the application retains this advantage when constructing hetero-junctions.Furthermore nanometer
The influence of particle size is also bigger, and activity changes with the variation of granular size.When the hetero-junctions is wide by its forbidden band is greater than
After photon irradiation with energy, photohole and light induced electron are generated on its surface, light induced electron is reacted with oxygen generates super oxygen
Radical ion O2-, many difficult organic matters decomposed can be resolved into CO2And H2The inorganic matters such as O.Based on these good characteristics, this Shen
It please find a kind of preparation method to be combined zinc oxide and titanium dioxide, produce the photochemical catalyst of function admirable.
The present invention prepares ZnO/TiO using hydro-thermal method2Photochemical catalyst, allows the TiO with [001] face2It is grown on ZnO, this
Sample makes two kinds of matter dimensions in the hetero-junctions to be formed reach a kind of size being suitble to just.Pass through catalytic degradation organic dyestuff
Show that catalyst performance of the present invention is excellent.It is in ZnO nano that hetero-junctions possessed by catalyst of the present invention, which is different from method for distinguishing,
On, allowing, there is [001] face to make TiO2It is grown on ZnO, so that two kinds of matter dimensions in the hetero-junctions of formation reach one
The size that kind is suitble to just, and TiO in the hetero-junctions2[001] face still have higher proportion, and the hetero-junctions surface shape
State it is flat and smooth and it is organic be infected with unique degradation effect, organic matter degradation can be made complete in 2h.
Summary of the invention
The Zinc oxide nano sheet catalyst of titania additive, the preparation of the catalyst include the following steps：
Step 1：The preparation of ZnO nano piece
By Zn (NO3)2·6H2O and hexamethylenetetramine are dissolved in the deionized water for being placed with magnetite, in 90 DEG C of oil bath conditions
It is cooled to room temperature after lower reaction 8h, through filtering, gained filter cake is dried in vacuo for 24 hours reaction product at 60 DEG C, obtains ZnO nano piece；
Zn (the NO3)2·6H2The control of the molar ratio of O and hexamethylenetetramine exists：1:0.5~1:1.
Step 2：The preparation of the Zinc oxide nano sheet catalyst of titania additive
ZnO nano piece made from step 1 is added in isopropanol, after ultrasonic dissolution is complete, then metatitanic acid is added dropwise respectively
Isopropyl ester and diethylenetriamine continue after being ultrasonically treated 40min, then heating is reacted for 24 hours under the conditions of 200 DEG C；Reaction product is cold
But after, through centrifugal treating, obtained sediment successively uses deionized water, ethanol washing three times respectively, and turns through 8000r/min
After fast centrifugal treating, it is dried in vacuo for 24 hours at a temperature of 60 DEG C；Thereafter by vacuum drying product in 400 DEG C of roasting temperature 2h,
Annealed processing again obtains the Zinc oxide nano sheet catalyst of titania additive；The roasting heating rate be 1 DEG C/
The molar ratio of min, ZnO nano piece and metatitanic acid second butyl ester is 10:1~1:1, the volume ratio of isopropyl titanate and diethylenetriamine is
6:1。
In the catalyst, titanium dioxide accounts for the Zinc oxide nano sheet catalyst quality percentage of titania additive
20%-80%.
Beneficial effects of the present invention：
ZnO and TiO2With similar forbidden bandwidth (Eg=3.37eV), with TiO2It compares, ZnO has direct band gap, height
Electron mobility, ZnO when a little organic pollutant difficult to degrade, have than TiO in handling waste water2Better photocatalysis effect.
It is in ZnO that the preparation for the hetero-junctions that the Zinc oxide nano sheet catalyst of titania additive of the present invention has, which is different from method for distinguishing,
In nanometer, allowing, there is [001] face to make TiO2It is grown on ZnO, so that two kinds of matter dimensions in the hetero-junctions of formation reach
To a kind of suitable size just, and TiO in the hetero-junctions2[001] face still have higher proportion, and the hetero-junctions table
Face form it is flat and smooth and it is organic be infected with unique degradation effect, organic matter degradation can be made complete in 2h.
Specific embodiment
Embodiment 1
Weigh 5.3548g Zn (NO3)2·6H2O and 2.5234g hexamethylenetetramine.Alleged acquirement drug is dissolved in
In 100mL beaker, inside there is 60mL deionized water.Magnetite is added, is put into 90 DEG C of oil bath pan reaction 8h.It is cooled to room temperature, filters
It is dried for 24 hours in 60 DEG C of vacuum oven.
Embodiment 2
It takes a beaker to 55mL isopropanol is added in beaker, adds 0.5gZnO, place the beaker in ultrasonic machine, surpass
Sound dissolution after the completion of dissolution, then 0.18mL isopropyl titanate (TIP) and 0.03mL diethylenetriamine (DETA) is added dropwise respectively and continues
Ultrasonic 40min is transferred to 50mL autoclave, is then placed in 200 DEG C of baking ovens, and heating is for 24 hours.After having reacted cooling, pour into
It marks, and is centrifuged in centrifugation Boiling tube, using deionized water and ethanol washing three times respectively, be centrifuged 8000r/min.It obtains
Product is put into 60 DEG C of vacuum drying in vacuum oven, for 24 hours.Final product is put into 400 DEG C/2h of Muffle furnace, and general 1 DEG C of rate/
Min carries out annealing quenching treatment.Prepare TiO2Doping content is 20%ZnO/TiO2Catalyst.
Embodiment 3
It takes a beaker to 55mL isopropanol is added in beaker, adds 0.5gZnO, place the beaker in ultrasonic machine, surpass
Sound dissolution after the completion of dissolution, then 0.36mL isopropyl titanate (TIP) and 0.06mL diethylenetriamine (DETA) is added dropwise respectively and continues
Ultrasonic 40min is transferred to 50mL autoclave, is then placed in 200 DEG C of baking ovens, and heating is for 24 hours.After having reacted cooling, pour into
It marks, and is centrifuged in centrifugation Boiling tube, using deionized water and ethanol washing three times respectively, be centrifuged 8000r/min.It obtains
Product is put into 60 DEG C of vacuum drying in vacuum oven, for 24 hours.Final product is put into 400 DEG C/2h of Muffle furnace, and general 1 DEG C of rate/
Min carries out annealing quenching treatment.Prepare TiO2Doping content is 40%ZnO/TiO2Catalyst.
Embodiment 4
It takes a beaker to 55mL isopropanol is added in beaker, adds 0.5gZnO, place the beaker in ultrasonic machine, surpass
Sound dissolution after the completion of dissolution, then 0.72mL isopropyl titanate (TIP) and 0.12mL diethylenetriamine (DETA) is added dropwise respectively and continues
Ultrasonic 40min is transferred to 50mL autoclave, is then placed in 200 DEG C of baking ovens, and heating is for 24 hours.After having reacted cooling, pour into
It marks, and is centrifuged in centrifugation Boiling tube, using deionized water and ethanol washing three times respectively, be centrifuged 8000r/min.It obtains
Product is put into 60 DEG C of vacuum drying in vacuum oven, for 24 hours.Final product is put into 400 DEG C/2h of Muffle furnace, and general 1 DEG C of rate/
Min carries out annealing quenching treatment.Prepare TiO2Doping content is 60%ZnO/TiO2Catalyst.
Embodiment 5
It takes a beaker to 55mL isopropanol is added in beaker, adds 0.5gZnO, place the beaker in ultrasonic machine, surpass
Sound dissolution after the completion of dissolution, then 1.44mL isopropyl titanate (TIP) and 0.24mL diethylenetriamine (DETA) is added dropwise respectively and continues
Ultrasonic 40min is transferred to 50mL autoclave, is then placed in 200 DEG C of baking ovens, and heating is for 24 hours.After having reacted cooling, pour into
It marks, and is centrifuged in centrifugation Boiling tube, using deionized water and ethanol washing three times respectively, be centrifuged 8000r/min.It obtains
Product is put into 60 DEG C of vacuum drying in vacuum oven, for 24 hours.Final product is put into 400 DEG C/2h of Muffle furnace, and general 1 DEG C of rate/
Min carries out annealing quenching treatment.Prepare TiO2Doping content is 80%ZnO/TiO2Catalyst.
Claims (2)
1. a kind of Zinc oxide nano sheet catalyst of titania additive, it is characterised in that：The preparation of the catalyst includes
Following steps：
Step 1：The preparation of ZnO nano piece
By Zn (NO3)2·6H2O and hexamethylenetetramine are dissolved in the deionized water for being placed with magnetite, anti-under the conditions of 90 DEG C of oil baths
It is cooled to room temperature after answering 8h, through filtering, gained filter cake is dried in vacuo for 24 hours reaction product at 60 DEG C, obtains ZnO nano piece；It is described
Zn (NO3)2·6H2The control of the molar ratio of O and hexamethylenetetramine exists：1:1~2:1；
Step 2：The preparation of the Zinc oxide nano sheet catalyst of titania additive
ZnO nano piece made from step 1 is added in isopropanol, after ultrasonic dissolution is complete, then metatitanic acid isopropyl is added dropwise respectively
Ester and diethylenetriamine continue after being ultrasonically treated 40min, then heating is reacted for 24 hours under the conditions of 200 DEG C；After reaction product is cooling,
Through centrifugal treating, obtained sediment respectively successively with deionized water, ethanol washing three times, and the revolving speed through 8000r/min from
After heart processing, it is dried in vacuo for 24 hours at a temperature of 60 DEG C；Thereafter it by vacuum drying product in 400 DEG C of roasting temperature 2h, then passes through
Annealing, obtains the Zinc oxide nano sheet catalyst of titania additive；The roasting heating rate is 1 DEG C/min, ZnO
Nanometer sheet and the molar ratio of isopropyl titanate are 10:1~1:1, the volume ratio of isopropyl titanate and diethylenetriamine is 6:1.
2. a kind of Zinc oxide nano sheet catalyst of titania additive according to claim 1, it is characterised in that：It is described
Catalyst in, titanium dioxide accounts for the 20%~80% of the Zinc oxide nano sheet catalyst quality percentage of titania additive.
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| CN106362722A (en) * | 2016-08-31 | 2017-02-01 | 东华理工大学 | Method for preparing photocatalyst |
| CN107233878B (en) * | 2017-01-22 | 2020-02-07 | 南昌航空大学 | Preparation method of superfine zinc oxide nanoparticle/titanium dioxide nanowire composite photocatalytic material |
| CN108548098B (en) * | 2018-04-18 | 2020-09-15 | 广东职业技术学院 | Ultraviolet LED lamp bead capable of degrading organic volatile matter of methyl-oleoresin, and preparation method and application thereof |
| CN115700145A (en) * | 2022-11-21 | 2023-02-07 | 中国人民解放军海军特色医学中心 | Photocatalyst material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4333855A (en) * | 1980-02-18 | 1982-06-08 | Phillips Petroleum Company | Promoted zinc titanate as catalytic agent |
| CN101224418A (en) * | 2008-02-15 | 2008-07-23 | 哈尔滨工业大学 | Preparing method of core-shell TiO2/ZnO photocatalyst and applications thereof |
| CN103084160A (en) * | 2012-12-31 | 2013-05-08 | 青岛信锐德科技有限公司 | TiO2 carbon nano tube air purifier material doped with ZnO, and preparation method and use thereof |
| CN103111276A (en) * | 2013-01-17 | 2013-05-22 | 河南科技大学 | Preparation method of porous array ZnO/TiO2 composite photocatalyst |
-
2016
- 2016-06-27 CN CN201610476277.0A patent/CN106111107B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4333855A (en) * | 1980-02-18 | 1982-06-08 | Phillips Petroleum Company | Promoted zinc titanate as catalytic agent |
| CN101224418A (en) * | 2008-02-15 | 2008-07-23 | 哈尔滨工业大学 | Preparing method of core-shell TiO2/ZnO photocatalyst and applications thereof |
| CN103084160A (en) * | 2012-12-31 | 2013-05-08 | 青岛信锐德科技有限公司 | TiO2 carbon nano tube air purifier material doped with ZnO, and preparation method and use thereof |
| CN103111276A (en) * | 2013-01-17 | 2013-05-22 | 河南科技大学 | Preparation method of porous array ZnO/TiO2 composite photocatalyst |
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