CN103418389A - Visible-light-response photocatalyst BaFe4Ti2O11 and preparation method thereof - Google Patents
Visible-light-response photocatalyst BaFe4Ti2O11 and preparation method thereof Download PDFInfo
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- CN103418389A CN103418389A CN2013103639277A CN201310363927A CN103418389A CN 103418389 A CN103418389 A CN 103418389A CN 2013103639277 A CN2013103639277 A CN 2013103639277A CN 201310363927 A CN201310363927 A CN 201310363927A CN 103418389 A CN103418389 A CN 103418389A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 title abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 7
- 230000003292 diminished effect Effects 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000013064 chemical raw material Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 17
- 230000001699 photocatalysis Effects 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910015999 BaAl Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VEUKJXRCHYAIAW-UHFFFAOYSA-N [Nb].[K] Chemical compound [Nb].[K] VEUKJXRCHYAIAW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a visible-light-response photocatalyst BaFe4Ti2O11 and a preparation method thereof. The preparation method is simple and low in cost, and the prepared photocatalyst is good in catalytic performance, capable of decomposing harmful chemical substances under visible light irradiation, good in stability, and promising in application prospect.
Description
Technical field
The present invention relates to a kind of visible light-responded photocatalyst Ba Fe
4Ti
2O
11And preparation method thereof, belong to inorganic field of photocatalytic material.
Background technology
Along with socioeconomic development, people more and more pay close attention to for the energy and ecological environment, solve energy shortage and problem of environmental pollution and be realize sustainable development, improve people's living standard and safeguard national security in the urgent need to.
From phase late 1970s, people proposed to utilize in the photochemical catalyst decomposition water and atmosphere in agricultural chemicals and the organic matter such as odorant, and application examples such as self-cleaning that scribble the surface of solids of photochemical catalyst.The principle of light-catalyzed reaction is that photochemical catalyst is after the photon absorbed higher than its band-gap energy, hole and electronics have been generated, these holes and electronics carry out respectively oxidation reaction and reduction reaction, reach the purpose of decomposing harmful chemical, organic-biological matter and sterilization.Photochemical catalyst has many kinds, and wherein most representative is titanium dioxide (TiO
2), utilized titanium dioxide in water and the agricultural chemicals in atmosphere and the organic matters such as odorant decomposed, yet the band gap of titanium dioxide is 3.2eV, only under the ultraviolet irradiation shorter than 400nm, just can show activity, can only be indoor or the local work of uviol lamp arranged, almost can not utilize visible ray, this has limited the use of titanium dioxide optical catalyst greatly.
Consider the practicality of photochemical catalyst in decomposing harmful substances, utilizing sunshine is indispensable as light source.Irradiation is near sunshine medium wavelength visible light intensity maximum 500nm on earth's surface, the energy of the visible region that wavelength is 400nm ~ 750nm is approximately 43% of sunshine gross energy, so for efficient utilization, the R and D of bismuth series photocatalyst have obtained a series of great achievements, and bismuthous compound is as BiVO
4, Bi
2MoO
6, Bi
2Mo
2O
9, Bi
2Mo
3O
12And Bi
2WO
4Be reported under visible ray and there is good absorption.A series of niobiums (tantalum) hydrochlorate photochemical catalyst is widely studied owing to having higher photocatalytic activity.For example, niobate photocatalyst Pb
3Nb
4O
13, BiNbO
4And Bi
2MNbO
7(M=Al, Ga, In, Y, rare earth element and Fe) etc. with niobium potassium compound oxide photocatalyst as KNbO
3, KNb
3O
8, K
4Nb
6O
17And K
6Nb
10.6O
30Deng all thering is photocatalysis performance preferably.
Although photocatalysis research has been carried out the several years, but at present report to have visible light-responded photochemical catalyst kind still very limited, still exist that light conversion efficiency is low, poor stability and the problem such as the spectrum respective range is narrow, so research and develop the new visible light-responded high efficiency photocatalyst that has, be very necessary.Existing document [Materials Research Bulletin, 1983,18:1543] has been reported composite oxides BaFe
4Ti
2O
11Synthetic, structure and dielectric properties, but have not yet to see the research report of relevant this compounds photocatalysis performance, we are to BaFe
4Ti
2O
11, BaCr
4Ti
2O
11And BaAl
4Ti
2O
11Deng having carried out Photocatalytic Performance Study, found that BaFe
4Ti
2O
11There is excellent visible light-responded photocatalysis performance, but the compound of other composition do not have visible light-responded photocatalysis performance.
Summary of the invention
The purpose of this invention is to provide a kind of visible light-responded photocatalyst Ba Fe that has
4Ti
2O
11And preparation method thereof.
The chemical constitution formula with visible light-responded photochemical catalyst the present invention relates to is: BaFe
4Ti
2O
11.
Preparation method's concrete steps of above-mentioned visible light-responded photochemical catalyst are:
(1) by 99.9% analytically pure chemical raw material BaCO
3, Fe
2O
3And TiO
2, press BaFe
4Ti
2O
11The chemical formula weigh batching.
(2) raw material step (1) prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 8 hours, be mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed is 1250 ~ 1280 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means, particle diameter diminished, and lower than 2 μ m, obtains BaFe
4Ti
2O
11Powder.
Preparation method of the present invention is simple, cost is low, and the photochemical catalyst of preparation has good catalytic performance, has the effect of decomposing harmful chemical, organic-biological matter and sterilization under radiation of visible light.
The specific embodiment
Below will be specifically described the present invention:
1, the composite oxides in order to obtain using in the present invention, at first used solid-phase synthesis to prepare powder, the various oxides as raw material or carbonate measured than being mixed according to the target constitutional chemistry, more synthetic in air atmosphere under normal pressure.
2, in order effectively to utilize light, the size of the photochemical catalyst in the present invention is preferably in micron level, or even nano particle, and specific area is larger.The oxide powder prepared with solid-phase synthesis, its particle is large and surface area is less, but can particle diameter be diminished by ball mill pulverizing means.
3, photocatalysis experiment of the present invention is usingd methyl orange as the simulation organic pollution, and its concentration is 20mg/L; Photocatalyst Ba Fe
4Ti
2O
11Addition be 1g/L; Light source is used the xenon lamp of 300W, and the vessel that reactive tank is used pyrex to make, obtain by wave filter the light that wavelength is greater than 420nm long wavelength, then irradiates photochemical catalyst; Catalysis time is set as 120 minutes.
Embodiment 1:
(1) by 99.9% analytically pure chemical raw material BaCO
3, Fe
2O
3And TiO
2, press BaFe
4Ti
2O
11The chemical formula weigh batching.
(2) raw material step (1) prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 8 hours, be mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed is 1250 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means, particle diameter diminished, and lower than 2 μ m, obtains BaFe
4Ti
2O
11Powder.
Prepared photochemical catalyst, be greater than at wavelength under the radiation of visible light of 420nm, the methyl orange clearance reached to 97.9% in 120 minutes.
Embodiment 2:
(1) by 99.9% analytically pure chemical raw material BaCO
3, Fe
2O
3And TiO
2, press BaFe
4Ti
2O
11The chemical formula weigh batching.
(2) raw material step (1) prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 8 hours, be mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed is 1260 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means, particle diameter diminished, and lower than 2 μ m, obtains BaFe
4Ti
2O
11Powder.
Prepared photochemical catalyst, be greater than at wavelength under the radiation of visible light of 420nm, the methyl orange clearance reached to 98.7% in 120 minutes.
Embodiment 3:
(1) by 99.9% analytically pure chemical raw material BaCO
3, Fe
2O
3And TiO
2, press BaFe
4Ti
2O
11The chemical formula weigh batching.
(2) raw material step (1) prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 8 hours, be mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed is 1280 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means, particle diameter diminished, and lower than 2 μ m, obtains BaFe
4Ti
2O
11Powder.
Prepared photochemical catalyst, be greater than at wavelength under the radiation of visible light of 420nm, and 120min reaches 98.0% to the methyl orange clearance.
The present invention never is limited to above embodiment.The bound of each temperature, interval value can realize the present invention, at this, do not enumerate embodiment.
The made photocatalyst powder of above inventive embodiments can be carried on multiple matrix surface.Matrix can be glass, pottery, active carbon or quartz sand etc., and photochemical catalyst can be carried on matrix surface with the form of film.
Claims (1)
1. composite oxides, as the application of visible light-responded photochemical catalyst, is characterized in that the chemical constitution formula of described composite oxides is: BaFe
4Ti
2O
11
Preparation method's concrete steps of described composite oxides are:
(1) by 99.9% analytically pure chemical raw material BaCO
3, Fe
2O
3And TiO
2, press BaFe
4Ti
2O
11The chemical formula weigh batching;
(2) raw material step (1) prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 8 hours, be mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves;
(3) powder step (2) mixed is 1250 ~ 1280 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means, particle diameter diminished, and lower than 2 μ m, obtains BaFe
4Ti
2O
11Powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310363927.7A CN103418389B (en) | 2013-08-20 | 2013-08-20 | Visible light-responded photocatalyst Ba Fe4Ti2O11 and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310363927.7A CN103418389B (en) | 2013-08-20 | 2013-08-20 | Visible light-responded photocatalyst Ba Fe4Ti2O11 and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103418389A true CN103418389A (en) | 2013-12-04 |
| CN103418389B CN103418389B (en) | 2015-08-19 |
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ID=49644075
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|---|---|---|---|
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| Country | Link |
|---|---|
| CN (1) | CN103418389B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289633A (en) * | 2015-11-30 | 2016-02-03 | 桂林理工大学 | Visible-light responsive photocatalyst CaFe2Ge2O8 and preparation method thereof |
| CN105478126A (en) * | 2015-12-26 | 2016-04-13 | 桂林理工大学 | Visible-light responding photocatalyst Fe2TiGe3O11 and preparation method thereof |
| CN105562015A (en) * | 2015-12-15 | 2016-05-11 | 桂林理工大学 | Visible light responding photocatalyst Ca3Fe2GeO8 and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947001A (en) * | 2010-03-12 | 2013-02-27 | 株式会社小原 | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building material and clarification material |
-
2013
- 2013-08-20 CN CN201310363927.7A patent/CN103418389B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947001A (en) * | 2010-03-12 | 2013-02-27 | 株式会社小原 | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building material and clarification material |
Non-Patent Citations (2)
| Title |
|---|
| X.OBRADORS ET AL: ""CRYSTAL STRUCTURE AND CATIONIC DISTRIBUTION OF BaFe4Ti2O11 R-TYPE HEXAGONAL FERRITE"", 《MATERIALS RESEARCH BULLETIN》 * |
| 孙萌萌: ""钙钛矿型催化剂光化学活性与其稳定性及与SiO2质材料的复合"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289633A (en) * | 2015-11-30 | 2016-02-03 | 桂林理工大学 | Visible-light responsive photocatalyst CaFe2Ge2O8 and preparation method thereof |
| CN105562015A (en) * | 2015-12-15 | 2016-05-11 | 桂林理工大学 | Visible light responding photocatalyst Ca3Fe2GeO8 and preparation method thereof |
| CN105478126A (en) * | 2015-12-26 | 2016-04-13 | 桂林理工大学 | Visible-light responding photocatalyst Fe2TiGe3O11 and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103418389B (en) | 2015-08-19 |
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