CN103433049A - Visible-light-responsive photocatalyst CaCuV2O7 and preparation method thereof - Google Patents
Visible-light-responsive photocatalyst CaCuV2O7 and preparation method thereof Download PDFInfo
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- CN103433049A CN103433049A CN2013103995534A CN201310399553A CN103433049A CN 103433049 A CN103433049 A CN 103433049A CN 2013103995534 A CN2013103995534 A CN 2013103995534A CN 201310399553 A CN201310399553 A CN 201310399553A CN 103433049 A CN103433049 A CN 103433049A
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- photochemical catalyst
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011941 photocatalyst Substances 0.000 title abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 22
- 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
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000013064 chemical raw material Substances 0.000 claims description 5
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 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
- 239000011159 matrix material 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
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003205 fragrance 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
- 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
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 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
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 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
- 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
Abstract
The invention discloses a visible-light-responsive photocatalyst CaCuV2O7 and a preparation method thereof. The chemical composition formula of the photocatalyst is CaCuV2O7. The invention also discloses a preparation method of the material. The preparation method disclosed by the invention is simple and low in cost; and the prepared photocatalyst has the advantages of excellent catalytic property and high stability, has the function of decomposing harmful chemical substances under visible light irradiation, and thus, has favorable application prospects.
Description
Technical field
The present invention relates to a kind of visible light-responded photochemical catalyst
caCuV 2 o 7 and 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 or 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 [Vogt R., Mueller-Buschbaum H., The shift from planar to tetrahedal CuO4 groups in calcium copper vanadate (CaCuV2O7),
z. Anorg. Allg. Chem .,
594, 119-26 (1991)] and reported vanadate CaCuV
2o
7crystal structure, but have not yet to see the research report of relevant this compounds photocatalysis performance, we are to BaCuV
2o
7, SrCuV
2o
7and CaCuV
2o
7deng having carried out Photocatalytic Performance Study, found that CaCuV
2o
7there is excellent visible light-responded photocatalysis performance, but BaCuV
2o
7, SrCuV
2o
7but do not there is visible light-responded photocatalysis performance.
Summary of the invention
The purpose of this invention is to provide a kind of visible light-responded photochemical catalyst CaCuV that has
2o
7and preparation method thereof.
The chemical constitution formula with visible light-responded photochemical catalyst the present invention relates to is: CaCuV
2o
7.
Preparation method's concrete steps of above-mentioned visible light-responded photochemical catalyst are:
(1) by 99.9% analytically pure chemical raw material CaCO
3, CuO and V
2o
5, press CaCuV
2o
7the 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 800 ~ 850 ℃ 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 CaCuV
2o
7powder.
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; Photochemical catalyst CaCuV
2o
7addition 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 CaCO
3, CuO and V
2o
5, press CaCuV
2o
7the 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 800 ℃ 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 CaCuV
2o
7powder.
Prepared photochemical catalyst, be greater than at wavelength under the radiation of visible light of 420nm, the methyl orange clearance reached to 98.2% in 120 minutes.
Embodiment 2:
(1) by 99.9% analytically pure chemical raw material CaCO
3, CuO and V
2o
5, press CaCuV
2o
7the 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 830 ℃ 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 CaCuV
2o
7powder.
Prepared photochemical catalyst, be greater than at wavelength under the radiation of visible light of 420nm, the methyl orange clearance reached to 98.9% in 120 minutes.
Embodiment 3:
(1) by 99.9% analytically pure chemical raw material CaCO
3, CuO and V
2o
5, press CaCuV
2o
7the 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 850 ℃ 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 CaCuV
2o
7powder.
Prepared photochemical catalyst, be greater than at wavelength under the radiation of visible light of 420nm, and 120min reaches 98.5% 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. a vanadate, as the application of visible light-responded photochemical catalyst, is characterized in that the chemical constitution formula of described vanadate is: CaCuV
2o
7;
Preparation method's concrete steps of described vanadate are:
(1) by 99.9% analytically pure chemical raw material CaCO
3, CuO and V
2o
5, press CaCuV
2o
7the 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 800 ~ 850 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by pulverizing means such as ball mills, particle diameter diminished, and lower than 2 μ m, obtains CaCuV
2o
7powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310399553.4A CN103433049B (en) | 2013-09-05 | 2013-09-05 | Visible-light-responsive photocatalyst CaCuV2O7 and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310399553.4A CN103433049B (en) | 2013-09-05 | 2013-09-05 | Visible-light-responsive photocatalyst CaCuV2O7 and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103433049A true CN103433049A (en) | 2013-12-11 |
| CN103433049B CN103433049B (en) | 2015-04-15 |
Family
ID=49686818
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310399553.4A Active CN103433049B (en) | 2013-09-05 | 2013-09-05 | Visible-light-responsive photocatalyst CaCuV2O7 and preparation method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN103433049B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069866A (en) * | 2014-06-30 | 2014-10-01 | 桂林理工大学 | Photocatalyst LiCu2V3O10 in response to visible light and preparation method thereof |
| CN104275176A (en) * | 2014-10-13 | 2015-01-14 | 桂林理工大学 | Visible light responding photocatalyst Ca3Nb3V5O23 and preparation method thereof |
| CN104785241A (en) * | 2015-04-21 | 2015-07-22 | 桂林理工大学 | Visible light responsible photocatalyst CaSiV2O8 and preparation method thereof |
| CN104874403A (en) * | 2015-05-23 | 2015-09-02 | 桂林理工大学 | Visible-light responding photocatalyst BaLi2Cu2V8O24 and preparation method thereof |
| WO2023163057A1 (en) * | 2022-02-25 | 2023-08-31 | 日本化学工業株式会社 | Negative thermal expansion material and composite material |
| JP7408721B2 (en) | 2022-02-25 | 2024-01-05 | 日本化学工業株式会社 | Negative thermal expansion materials and composite materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004330047A (en) * | 2003-05-06 | 2004-11-25 | Univ Kanazawa | Metal or metal oxide-carrying bismuth vanadate photocatalyst for photodecomposition of endocrine disruptor |
| CN102557133A (en) * | 2011-12-19 | 2012-07-11 | 陕西科技大学 | Method for preparing fishbone-shaped and firewood-shaped BiVO4 powder by microwave hydrothermal method |
-
2013
- 2013-09-05 CN CN201310399553.4A patent/CN103433049B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004330047A (en) * | 2003-05-06 | 2004-11-25 | Univ Kanazawa | Metal or metal oxide-carrying bismuth vanadate photocatalyst for photodecomposition of endocrine disruptor |
| CN102557133A (en) * | 2011-12-19 | 2012-07-11 | 陕西科技大学 | Method for preparing fishbone-shaped and firewood-shaped BiVO4 powder by microwave hydrothermal method |
Non-Patent Citations (1)
| Title |
|---|
| VOGT R. ,等: "The shift from planar to tetrahedal CuO4 groups in calcium copper vanadate (CaCuV2O7)", 《Z. ANORG. ALLG. CHEM.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069866A (en) * | 2014-06-30 | 2014-10-01 | 桂林理工大学 | Photocatalyst LiCu2V3O10 in response to visible light and preparation method thereof |
| CN104275176A (en) * | 2014-10-13 | 2015-01-14 | 桂林理工大学 | Visible light responding photocatalyst Ca3Nb3V5O23 and preparation method thereof |
| CN104785241A (en) * | 2015-04-21 | 2015-07-22 | 桂林理工大学 | Visible light responsible photocatalyst CaSiV2O8 and preparation method thereof |
| CN104874403A (en) * | 2015-05-23 | 2015-09-02 | 桂林理工大学 | Visible-light responding photocatalyst BaLi2Cu2V8O24 and preparation method thereof |
| WO2023163057A1 (en) * | 2022-02-25 | 2023-08-31 | 日本化学工業株式会社 | Negative thermal expansion material and composite material |
| JP7408721B2 (en) | 2022-02-25 | 2024-01-05 | 日本化学工業株式会社 | Negative thermal expansion materials and composite materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103433049B (en) | 2015-04-15 |
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