CN104437514B - Visible light-responded photocatalyst Co3znFeSbO8and preparation method thereof - Google Patents
Visible light-responded photocatalyst Co3znFeSbO8and preparation method thereof Download PDFInfo
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- CN104437514B CN104437514B CN201410825633.6A CN201410825633A CN104437514B CN 104437514 B CN104437514 B CN 104437514B CN 201410825633 A CN201410825633 A CN 201410825633A CN 104437514 B CN104437514 B CN 104437514B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- 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
- 239000002994 raw material Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000013064 chemical raw material Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract description 2
- 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 5
- 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
- 239000011159 matrix material Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction 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
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910003334 KNbO3 Inorganic materials 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution 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
- 239000012212 insulator Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- -1 pottery Substances 0.000 description 1
- 238000010298 pulverizing process Methods 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
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000035922 thirst Effects 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 the visible light responsive photocatalyst Co of a kind of high-efficient wide-frequency3ZnFeSbO8And preparation method thereof.The chemical constitution formula of this photocatalyst is Co3ZnFeSbO8.The invention also discloses the preparation method of above-mentioned material.The photocatalyst that the present invention obtains has the advantages such as spectral response range width, light conversion efficiency height and good stability.There is decomposition harmful chemical, organic-biological matter and the effect of sterilization under visible light illumination；Additionally preparation method is simple, synthesis temperature is low, low cost, is suitable for commercial production and application.
Description
Technical field
The present invention relates to a kind of visible light-responded photocatalyst Co3ZnFeSbO8And preparation method thereof, belong to inorganic field of photocatalytic material.
Background technology
Along with socioeconomic development, people increasingly pay close attention to for the energy and ecological environment, solve energy shortage and problem of environmental pollution be realize sustainable development, improve people's living standard and safeguard national security in the urgent need to.
From phase late 1970s, there has been proposed and utilize in photocatalyst decomposition water and the Organic substance such as pesticide in air and odorant, and scribble the application example such as self-cleaning of the surface of solids of photocatalyst.The principle of light-catalyzed reaction be photocatalyst after absorbing higher than the photon of its band-gap energy, generate hole and electronics, these holes and electronics carry out oxidation reaction and reduction reaction respectively, reach to decompose harmful chemical, organic-biological matter and the purpose of sterilization.Photocatalyst has many kinds, and the most most representative is titanium dioxide (TiO2), utilize titanium dioxide that the Organic substances such as the pesticide in water and in air and odorant are decomposed, but the band gap of titanium dioxide is 3.2eV, under the ultraviolet irradiation shorter than 400nm, only just can show activity, can only be at indoor or the local work having uviol lamp, being little to utilize visible ray, this greatly limits the use of titanium dioxide optical catalyst.
In view of photocatalyst practicality in decomposing harmful substances, it is indispensable for utilizing sunlight as light source.Irradiate the sunlight medium wavelength maximum intensity of visible ray near 500nm to earth's surface, wavelength is that the energy of the visible region of 400nm ~ 750nm is about the 43% of sunlight gross energy, so in order to utilize efficiently, the R and D of bismuth series photocatalyst have been achieved for a series of great achievement, bismuthous complex such as BiVO4、Bi2MoO6、Bi2Mo2O9、Bi2Mo3O12And Bi2WO4It is in the news and there is good absorption under visible light.A series of niobiums (tantalum) hydrochlorate photocatalyst is widely studied owing to having higher photocatalytic activity.Such as, niobate photocatalyst Pb3Nb4O13、BiNbO4And Bi2MNbO7(M=Al, Ga, In, Y, rare earth element and Fe) etc. and niobium potassium compound oxide photocatalyst such as KNbO3、KNb3O8、K4Nb6O17And K6Nb10.6O30Deng all having preferable photocatalysis performance, but in visible-range, its intrinsic photocatalytic effect is the most weak or does not has activity.
Although photocatalysis research has been carried out the several years, major part of exploring and develop to visible light-responded photocatalyst is the summary of experience drawn by great many of experiments at present, the most also cannot be from the crystal structure of compound, composition, its photocatalysis performance is predicted in the physicochemical properties such as molecular weight, therefore at present report to have visible light-responded photocatalyst kind the most limited, and it is low to there is light conversion efficiency, synthesis difficulty, poor stability and the problem such as spectral response range is narrow, research and develop that new preparation method is simple and to have the visible light-responded high efficiency photocatalyst of wideband be that this area scientific and technical personnel thirst for solving always but are difficult to the difficult problem succeeded all the time, which greatly limits extensively application and the development of photocatalyst.We are to consisting of Co3MgFeSbO8、Co3ZnFeSbO8And Co3ZnFeNbO8Sample carried out Photocatalytic Performance Study.Found that Co3ZnFeSbO8Band gap is 2.61eV, has the visible light-responded photocatalysis performance of excellence；Co3MgFeSbO8Band gap is 3.36eV, just shows activity under ultraviolet irradiation；Co3ZnFeNbO8For insulator, under ultraviolet irradiation, the most do not show activity.
Summary of the invention
It is an object of the invention to provide and a kind of there is visible light-responded photocatalyst Co3ZnFeSbO8And preparation method thereof.
The chemical constitution formula with visible light-responded photocatalyst that the present invention relates to is: Co3ZnFeSbO8。
The preparation method of above-mentioned visible light-responded photocatalyst concretely comprises the following steps:
(1) by 99.9% analytically pure chemical raw material CoO, ZnO, Fe2O3And Sb2O5Starting powder press Co3ZnFeSbO8Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and dehydrated alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves.
(3) by the powder of step (2) mix homogeneously 800 ~ 850 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room temperature, then pulverized by ball mill and make average diameter of particles diminish, less than 2 μm, i.e. obtain Co3ZnFeSbO8Powder.
Advantages of the present invention: Co3ZnFeSbO8The visible light-responded wide frequency range of photocatalyst, light conversion efficiency height and good stability, there is decomposition harmful chemical, organic-biological matter and the effect of sterilization under visible light illumination；Additionally preparation method is simple, synthesis temperature is low, low cost, is suitable for commercial production and application.
Detailed description of the invention
Present invention will be described in detail below:
1, in order to obtain the composite oxides used in the present invention, prepare powder first by solid-phase synthesis, i.e. various oxides or the carbonate as raw material is mixed according to target constitutional chemistry metering ratio, then synthesize in air atmosphere at ambient pressure.
2 in order to effectively utilize light, the size of the photocatalyst in the present invention preferably in micron level, even nanoparticle, and specific surface area is bigger.The oxide powder prepared with solid-phase synthesis, its particle is relatively big and surface area is less, but can be by ball mill pulverizing means and make particle diameter diminish.
3, the photocatalysis experiment of the present invention is using methyl orange as simulation organic pollution, and its concentration is 20mg/L；Photocatalyst Co3ZnFeSbO8Addition be 1g/L；Light source uses the xenon lamp of 300W, and reactive tank uses the vessel that pyrex is made, and obtains the wavelength light more than 420nm by wave filter, then irradiates photocatalyst；Catalysis time is set as 60 minutes.
Embodiment 1:
(1) by 99.9% analytically pure chemical raw material CoO, ZnO, Fe2O3And Sb2O5Starting powder press Co3ZnFeSbO8Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and dehydrated alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves.
(3) by the powder of step (2) mix homogeneously 800 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room temperature, then pulverized by ball mill and make average diameter of particles diminish, less than 2 μm, i.e. obtain Co3ZnFeSbO8Powder.
Prepared photocatalyst, under the wavelength radiation of visible light more than 420nm, reaches 97.4% to methyl orange clearance in 60 minutes.
Embodiment 2:
(1) by 99.9% analytically pure chemical raw material CoO, ZnO, Fe2O3And Sb2O5Starting powder press Co3ZnFeSbO8Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and dehydrated alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves.
(3) by the powder of step (2) mix homogeneously 830 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room temperature, then pulverized by ball mill and make average diameter of particles diminish, less than 2 μm, i.e. obtain Co3ZnFeSbO8Powder.
Prepared photocatalyst, under the wavelength radiation of visible light more than 420nm, reaches 98.3% to methyl orange clearance in 60 minutes.
Embodiment 3:
(1) by 99.9% analytically pure chemical raw material CoO, ZnO, Fe2O3And Sb2O5Starting powder press Co3ZnFeSbO8Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and dehydrated alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves.
(3) by the powder of step (2) mix homogeneously 850 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room temperature, then pulverized by ball mill and make average diameter of particles diminish, less than 2 μm, i.e. obtain Co3ZnFeSbO8Powder.
Prepared photocatalyst, under the wavelength radiation of visible light more than 420nm, 60min reaches 97.9% to methyl orange clearance.
The present invention is never limited to above example.The bound of each temperature, interval value can realize the present invention, embodiment numerous to list herein.
The made photocatalyst powder of above inventive embodiments can be carried on multiple matrix surface.Matrix can be glass, pottery, activated carbon or quartz sand etc., and photocatalyst can be carried on matrix surface in the form of a film.
Claims (1)
1. a visible light-responded photocatalyst, it is characterised in that the chemical constitution formula of described photocatalyst is Co3ZnFeSbO8；
The preparation method of described photocatalyst concretely comprises the following steps:
(1) by 99.9% chemical raw material CoO, ZnO, Fe2O3And Sb2O5Starting powder press Co3ZnFeSbO8Composition weigh dispensing；
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and dehydrated alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves；
(3) by the powder of step (2) mix homogeneously 800 ~ 850 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room temperature, then pulverized by ball mill and make average diameter of particles be less than 2 μm, i.e. obtain Co3ZnFeSbO8Powder.
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| CN105126859A (en) * | 2015-09-20 | 2015-12-09 | 桂林理工大学 | Photocatalyst Sr3Li3Fe2Sb5O20 with visible light response performance and preparation method of photocatalyst Sr3Li3Fe2Sb5O20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228836A (en) * | 2011-04-13 | 2011-11-02 | 桂林理工大学 | Composite oxide photochemical catalyst Li3Co2Nb(1-x)TaxO6 responded by visible light and preparation method thereof |
| CN103157458A (en) * | 2013-04-01 | 2013-06-19 | 桂林理工大学 | Visible-light-responsive tantalate photocatalyst LiMTa3O9 and preparation method thereof |
| CN103418390A (en) * | 2013-08-20 | 2013-12-04 | 桂林理工大学 | Visible-light-response photocatalyst Sr2Co4Ti5O36 and preparation method thereof |
| CN103521210A (en) * | 2013-10-22 | 2014-01-22 | 桂林理工大学 | Photocatalyst Bi3Sb3Zn2O14 with visible light response |
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| WO2002016026A2 (en) * | 2000-08-25 | 2002-02-28 | Apyron Technologies, Inc. | Adsorbent and/or catalyst compounds promoted with halide ions and methods of making and using thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228836A (en) * | 2011-04-13 | 2011-11-02 | 桂林理工大学 | Composite oxide photochemical catalyst Li3Co2Nb(1-x)TaxO6 responded by visible light and preparation method thereof |
| CN103157458A (en) * | 2013-04-01 | 2013-06-19 | 桂林理工大学 | Visible-light-responsive tantalate photocatalyst LiMTa3O9 and preparation method thereof |
| CN103418390A (en) * | 2013-08-20 | 2013-12-04 | 桂林理工大学 | Visible-light-response photocatalyst Sr2Co4Ti5O36 and preparation method thereof |
| CN103521210A (en) * | 2013-10-22 | 2014-01-22 | 桂林理工大学 | Photocatalyst Bi3Sb3Zn2O14 with visible light response |
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Application publication date: 20150325 Assignee: DONGTAI GAOKE TECHNOLOGY INNOVATION PARK Co.,Ltd. Assignor: Jiangsu Chuangqi Testing Technology Co.,Ltd. Contract record no.: X2023980048819 Denomination of invention: Visible light responsive photocatalyst Co3ZnFeSbO8and its preparation method Granted publication date: 20160928 License type: Common License Record date: 20231202 |
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