CN103433049B - 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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- CN103433049B CN103433049B CN201310399553.4A CN201310399553A CN103433049B CN 103433049 B CN103433049 B CN 103433049B CN 201310399553 A CN201310399553 A CN 201310399553A CN 103433049 B CN103433049 B CN 103433049B
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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
- 238000002156 mixing 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
- 230000003292 diminished effect Effects 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
- 239000011159 matrix material Substances 0.000 description 3
- 230000005855 radiation Effects 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
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical class [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 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
- 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-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 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 to utilize in photochemical catalyst decomposition water and the organic matter such as agricultural chemicals in air and odorant, and scribble the application example such as self-cleaning of the surface of solids of photochemical catalyst.The principle of light-catalyzed reaction is that photochemical catalyst is after absorbing the photon higher than its band-gap energy, generate hole and electronics, these holes and electronics carry out oxidation reaction and reduction reaction respectively, reach the object of decomposing harmful chemical, organic-biological matter and sterilization.Photochemical catalyst has many kinds, and wherein most representative is titanium dioxide (TiO
2), titanium dioxide has been utilized to decompose organic matters such as the agricultural chemicals in water and in air and odorants, but the band gap of titanium dioxide is 3.2eV, only under the ultraviolet irradiation shorter than 400nm, just activity can be shown, can only at indoor or the local work having uviol lamp, almost can not utilize visible ray, this limits the use of titanium dioxide optical catalyst greatly.
Consider the practicality of photochemical catalyst in decomposing harmful substances, utilize sunshine to be indispensable as light source.Irradiate maximum to sunshine medium wavelength intensity of visible ray near 500nm on earth's surface, wavelength is the energy of the visible region of 400nm ~ 750nm is approximately 43% of sunshine gross energy, so in order to efficient utilization, the R and D of bismuth series photocatalyst have achieved a series of great achievement, and bismuthous compound is as BiVO
4, Bi
2moO
6, Bi
2mo
2o
9, Bi
2mo
3o
12and Bi
2wO
4be in the news and there is good absorption under visible light.A series of niobium (tantalum) hydrochlorate photochemical catalyst is widely studied owing to having higher photocatalytic activity.Such as, 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 there is good photocatalysis performance.
Although photocatalysis research has carried out the several years, but at present report to have visible light-responded photochemical catalyst kind still very limited, still also exist that light conversion efficiency is low, poor stability and the problem such as spectrum respective range is narrow, so it is very necessary for researching and developing the new visible light-responded high efficiency photocatalyst that has.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 report vanadate CaCuV
2o
7crystal structure, but the research had not yet to see about this compounds photocatalysis performance is reported, we are to BaCuV
2o
7, SrCuV
2o
7and CaCuV
2o
7etc. 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 not there is visible light-responded photocatalysis performance.
Summary of the invention
The object of this invention is to provide and a kind of there is visible light-responded photochemical catalyst CaCuV
2o
7and preparation method thereof.
The chemical constitution formula with visible light-responded photochemical catalyst that 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, by CaCuV
2o
7chemical formula weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 800 ~ 850 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then pulverizes means by ball mill and particle diameter is diminished, lower than 2 μm, namely obtain CaCuV
2o
7powder.
Preparation method of the present invention is simple, cost is low, and the photochemical catalyst of preparation has excellent catalytic performance, has the effect of decomposing harmful chemical, organic-biological matter and sterilization under visible light illumination.
Detailed description of the invention
To be specifically described the present invention below:
1, in order to obtain the composite oxides used in the present invention, first use solid-phase synthesis to prepare powder, namely using as the various oxide of raw material or carbonate according to the metering of target constitutional chemistry than mixing, then to synthesize in air atmosphere at ambient pressure.
2, in order to effectively 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.With oxide powder prepared by solid-phase synthesis, its particle is comparatively large and surface area is less, but can pulverize means by ball mill makes particle diameter diminish.
3, photocatalysis experiment of the present invention is using methyl orange as simulation organic pollution, and its concentration is 20mg/L; Photochemical catalyst CaCuV
2o
7addition be 1g/L; Light source uses the xenon lamp of 300W, the vessel that reactive tank uses pyrex to make, and obtains the light that wavelength is greater than 420nm long wavelength, then irradiate photochemical catalyst by wave filter; 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, by CaCuV
2o
7chemical formula weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 800 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then pulverizes means by ball mill and particle diameter is diminished, lower than 2 μm, namely obtain CaCuV
2o
7powder.
Prepared photochemical catalyst, under being greater than the radiation of visible light of 420nm, reaches 98.2% to methyl orange clearance in 120 minutes at wavelength.
Embodiment 2:
(1) by 99.9% analytically pure chemical raw material CaCO
3, CuO and V
2o
5, by CaCuV
2o
7chemical formula weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 830 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then pulverizes means by ball mill and particle diameter is diminished, lower than 2 μm, namely obtain CaCuV
2o
7powder.
Prepared photochemical catalyst, under being greater than the radiation of visible light of 420nm, reaches 98.9% to methyl orange clearance in 120 minutes at wavelength.
Embodiment 3:
(1) by 99.9% analytically pure chemical raw material CaCO
3, CuO and V
2o
5, by CaCuV
2o
7chemical formula weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 850 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then pulverizes means by ball mill and particle diameter is diminished, lower than 2 μm, namely obtain CaCuV
2o
7powder.
Prepared photochemical catalyst, be greater than the radiation of visible light of 420nm at wavelength under, 120min reaches 98.5% to methyl orange clearance.
The present invention is never limited to above embodiment.Bound, the interval value of each temperature can realize the present invention, do not enumerate embodiment at this.
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 in the form of a film.
Claims (1)
1. vanadate is as an application for visible light-responded photochemical catalyst, it 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, by CaCuV
2o
7chemical formula weigh batching;
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves;
(3) powder step (2) mixed 800 ~ 850 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then pulverizes means by ball mill and particle diameter is diminished, lower than 2 μm, namely obtain 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 |
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| Publication Number | Publication Date |
|---|---|
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| CN103433049B true CN103433049B (en) | 2015-04-15 |
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| 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 |
| CN104275176B (en) * | 2014-10-13 | 2016-06-29 | 桂林理工大学 | Visible light-responded photocatalyst Ca3Nb3V5O23And 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 |
| TW202340097A (en) * | 2022-02-25 | 2023-10-16 | 日商日本化學工業股份有限公司 | 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.》.2004, * |
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