CN108745390B - Visible light photocatalyst and preparation and application thereof - Google Patents
Visible light photocatalyst and preparation and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 24
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- 239000002994 raw material Substances 0.000 claims abstract description 18
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
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- 150000001875 compounds Chemical class 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 16
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 claims description 9
- 238000006731 degradation reaction Methods 0.000 claims description 9
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- -1 phosphorus ion Chemical class 0.000 claims description 6
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- 238000010790 dilution Methods 0.000 claims description 2
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- 230000001699 photocatalysis Effects 0.000 abstract description 11
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- 230000000694 effects Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 5
- 238000010668 complexation reaction Methods 0.000 description 4
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- 241000282414 Homo sapiens Species 0.000 description 2
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- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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Abstract
The invention relates to a visible light photocatalyst preparation and application thereof, which is characterized in that the chemical formula is as follows: AlV6+xP1‑xO19(0.01<x<0.65) in the field of inorganic photocatalytic materials. The preparation method of the photocatalyst is a chemical solution method, the raw materials with chemical integral ratio are prepared into transparent solution, and a macromolecular complexing agent is added to ensure that Al in the raw materials3+Ion, V5+Ions and P3+Fully complexing ions, drying to prepare a precursor xerogel, calcining at high temperature, volatilizing organic components to obtain pure phase AlV6+xP1‑xO19(0.01<x<0.65); the material prepared by the invention can absorb light from ultraviolet to 580 nm; has photocatalysis effect under the irradiation of visible light; and the preparation process is simple and easy to operate, the sintering temperature is low, a complex sintering atmosphere is not needed, and the obtained particles are uniform in size and good in chemical stability.
Description
Technical Field
The invention belongs to the field of inorganic photocatalytic materials, relates to a photocatalyst for degrading organic dyes and other pollutants, and particularly relates to a visible light photocatalyst as well as preparation and application thereof.
Background
With the development of industry and society, environmental pollution worldwide becomes more and more serious, and becomes one of the focus problems of strong attention in the social development. For example, the industrial wastewater and the domestic sewage of people cause serious ecological environment destruction due to the continuous aggravation of environmental pollution, and pose a serious threat to the survival of all human beings. In order to solve many environmental pollution problems, people have been working on controlling and managing environmental pollution through various methods. Among them, the photocatalytic reaction is utilized to degrade pollutants, which is one of green means and has been paid more and more attention.
The photocatalytic reaction is a substance that can promote a chemical reaction without changing itself under irradiation of light, and can generate a catalytic action by converting light energy existing in the nature into energy required for the chemical reaction, so that surrounding oxygen and water molecules are excited into free negative ions having an extremely high oxidizing power. Almost all organic substances and partial inorganic substances harmful to human bodies and environment can be decomposed, not only can the reaction be accelerated, but also the natural definition can be applied, and the resource waste and the additional pollution formation are not caused. Classical photocatalysts such as TiO2The photocatalytic reaction can be realized only under the irradiation of ultraviolet light, but the proportion of the ultraviolet light in the sunlight is less than five percent, and most of the sunlight energy is mainly concentrated in the visible light range (400-700 nm), so that TiO2It does not have catalytic activity in the visible range, and thus current photocatalytic technology cannot fully utilize sunlight. Researchers have broadened their visible light response by means of doping, compounding, etc., or have turned to search for other novel photocatalytic materials. However, these modified TiO2The material still has the defects of complex preparation, instability in the application process, overhigh cost and the like.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide a visible light photocatalyst, and a preparation method and application thereof, wherein the visible light photocatalyst is a vanadic aluminate based on AlV6PO19Matrix by realizing part of V in lattice5+Substituted P5+Element, photocatalyst AlV obtained by realizing self-doping6+xP1-xO19The technique is self-doping realized in the same crystal lattice, and the preparation adopts a chemical solution synthesis methodThe method has the advantages of very mild conditions, very low calcination temperature, simple process, low cost, good stability and repeatability of experimental process, stable doping and high efficiency, greatly improves the light absorption efficiency in a visible light region, and realizes better photocatalytic efficiency. Researches find that the compound has good photocatalytic performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a visible light photocatalyst has a chemical formula: AlV6+xP1-xO19X is V in the lattice5+Self-doping of substituted P5+The molar ratio of the elements is more than or equal to 0.01 and less than or equal to 0.65.
The invention also provides a preparation method of the visible light photocatalyst, which comprises the following steps:
(1) according to the general formula AlV6+xP1-xO19The stoichiometric ratio of the elements in the alloy is respectively weighed to obtain Al containing aluminum ions3+Compound of (2), vanadium ion-containing compound V5+And a compound containing phosphorus ion P5+The compounds of (1) are respectively and completely dissolved in dilute nitric acid, and a proper amount of deionized water is added for dilution;
(2) respectively adding a complexing agent into the raw materials in the step (1), and stirring under magnetic force until the raw materials are completely dissolved to obtain a solution of the completely dissolved raw materials;
(3) slowly mixing the solutions of the raw materials obtained in the step (2), stirring until the raw materials are completely and uniformly mixed, standing and drying to obtain a fluffy precursor;
(4) and (4) placing the precursor in the step (3) in a muffle furnace, sintering in an air atmosphere, naturally cooling, grinding and uniformly mixing to obtain the powdery visible light photocatalyst.
In the step (1), Al ions are contained3+The compound of (A) may be Al (NO)3)3·9H2O or Al (OH)3Etc. containing vanadium ions V5+The compound of (D) may be NH4VO3Etc. containing phosphorus ions P5+The compound of (D) may be NH4H2PO4Or P2O5And the like.
In the step (2), the complexing agent can be citric acid or oxalic acid, and the addition amount of the complexing agent in each raw material is 10-20 wt% of the reaction substances in the raw materials. The term "reactive substance" as used herein means Al containing aluminum ions3+Compound of (2), vanadium ion-containing compound V5+And a compound containing phosphorus ion P5+The compound of (1).
In the step (3), the mixture can be stirred at a temperature of 70-90 ℃.
In the step (4), the sintering temperature is preferably 500-650 ℃, the sintering time is 3-10 hours,
the visible light photocatalyst can degrade a dye solution under the irradiation of visible light.
Compared with the prior art, the invention has the beneficial effects that:
1、AlV6+xP1-xO19(0.01<x<0.65) can be adjusted by varying the amount of V, and the resulting photocatalyst has good visible light absorption.
2. The preparation method is simple, the preparation conditions are very mild, and the calcination temperature is very low.
3. Under the irradiation of visible light, the photocatalyst can efficiently catalyze and degrade methylene blue, and has good photocatalytic activity.
Drawings
FIG. 1: the technical scheme of the embodiment 1 of the invention is used for preparing the X-ray powder diffraction pattern of the sample.
FIG. 2 is a drawing: electron micrographs of samples prepared according to the examples of the present invention.
FIG. 3: the ultraviolet-visible absorption spectrum of the sample prepared in example 1 of the present invention.
FIG. 4 is a drawing: the samples prepared in example 1 of the present invention degrade methylene blue, an organic dye, under different illumination times.
FIG. 5: the technical scheme of the embodiment 4 of the invention is used for preparing the X-ray powder diffraction pattern of the sample.
FIG. 6: ultraviolet-visible diffuse reflectance spectrum of the sample prepared in inventive example 4.
FIG. 7: the samples prepared in example 4 of the present invention degrade methylene blue, an organic dye, under different illumination times.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
Example 1
According to the chemical formula AlV6.2P0.8O19Middle Al3+Ion, V5+And P5+Respectively weighing aluminum hydroxide Al (OH)3: 0.78 g, ammonium metavanadate NH4VO3: 7.254 g of ammonium dihydrogen phosphate NH4H2PO4: 0.92 g, three reagents are respectively dissolved in dilute nitric acid; in the above-mentioned Al-containing3+Ion, V5+And P5+Adding 0.16 g, 1.45 g and 0.18 g of citric acid into the solution respectively for complexing; mixing the three solutions, stirring at 90 ℃ until the three solutions are completely and uniformly mixed, standing, and putting into an oven for drying to obtain a fluffy precursor; taking out the precursor, calcining in air atmosphere at 650 deg.C for 3 hr, taking out, and grinding to obtain AlV6.2P0.8O19A photocatalyst powder.
Referring to FIG. 1, it is an X-ray powder diffraction pattern of a sample prepared according to the embodiment of this example 1, showing that the prepared sample is a single-phase material without other impurity phases.
Referring to FIG. 2, which is an electron micrograph of a sample prepared according to this example, it can be seen that the crystal size is fine and uniform, the particles are loose, and are easily dispersed in a mortar or water;
referring to FIG. 3, which is a UV-VIS diffuse reflectance spectrum of a sample prepared according to example 1, it can be seen that the sample absorbs UV-VIS light.
See fig. 4, which is a graph showing the degradation curves of the sample prepared in this example 1 under different visible light irradiation times for the organic dye methylene blue. It can be seen that the sample has visible light photocatalytic activity.
Example 2
According to the chemical formula AlV6.1P0.9O19Medium element Al3+、V5+And P5+Respectively weighing aluminum nitrate Al (NO)3)3: 3.75 g, ammonium metavanadate NH4VO3: 7.13 g of phosphorus pentoxide P2O5: 1.28 g, three reagents are respectively dissolved in dilute nitric acid; in the above-mentioned Al-containing3+Ion, V5+And P5+Adding oxalic acid of 0.675 g, 1.28 g and 0.23 g into the solution respectively for complexation; mixing the three solutions, stirring at 70 ℃ until the three solutions are completely and uniformly mixed, standing, and putting into an oven for drying to obtain a fluffy precursor; taking out the precursor, calcining in air atmosphere at 500 deg.C for 10 hr, taking out, and grinding to obtain AlV6.1P0.9O19A photocatalyst powder.
The X-ray powder diffraction pattern of the photocatalyst obtained in example 2 was the same as that of fig. 1, and had a pure phase; the main micro-morphology, the degradation to methylene blue, is similar to example 1.
Example 3
According to the chemical formula AlV6.01P0.99O19Medium element Al3+、V5+And P5+Respectively weighing aluminum nitrate Al (NO)3)3: 3.75 g, ammonium metavanadate NH4VO3: 7.032 g, ammonium dihydrogen phosphate NH4H2PO4: : 1.138 g, three reagents are respectively dissolved in dilute nitric acid; in the above-mentioned Al-containing3+Ion, V5+And P5+Adding 0.375 g, 0.7 g and 0.114 g of citric acid into the solution respectively for complexation; mixing the three solutions, stirring at 80 ℃ until the three solutions are completely and uniformly mixed, standing, and putting into an oven for drying to obtain a fluffy precursor; taking out the precursor, calcining in air atmosphere at 550 ℃ for 8 hours, taking out and fully grinding to obtain AlV6.01P0.99O19A photocatalyst powder.
The X-ray powder diffraction pattern of the photocatalyst obtained in example 3 is the same as that of fig. 1, and has a pure phase; the main micro-morphology, the degradation to methylene blue, is similar to example 1.
Example 4
According to the chemical formula AlV6.65P0.35O19Respectively weighing aluminum nitrate Al (NO) according to the stoichiometric ratio of the medium elements Al, V and P3)3: 3.75 g, ammonium metavanadate NH4VO3: 7.78 g, ammonium dihydrogen phosphate NH4H2PO4: 0.405 g, three reagents are respectively dissolved in dilute nitric acid; in the above-mentioned Al-containing3+Ion, V5+And P5+Adding 0.75 g, 1.556 g and 0.08 g of citric acid into the solution respectively for complexation; mixing the three solutions, stirring at 80 ℃ until the three solutions are completely and uniformly mixed, standing, and putting into an oven for drying to obtain a fluffy precursor; taking out the precursor, calcining in air atmosphere at 600 deg.C for 5 hr, taking out, and grinding to obtain AlV6.65P0.35O19A photocatalyst powder.
Referring to FIG. 5, it is the X-ray powder diffraction pattern of the sample prepared according to the embodiment of this example 4, which shows that the prepared material is a single-phase material without other impurity phases.
Referring to fig. 6, the diffuse reflectance uv-vis spectrum of the sample prepared according to this example 4 is shown, and it can be seen that the sample can absorb visible light from uv to 600 nm.
Referring to fig. 7, the degradation curves of the sample prepared in this example 4 under different illumination time for methylene blue, an organic dye, are shown. It can be seen that the sample has visible light photocatalytic activity.
Example 5
According to the chemical formula AlV6.5P0.5O19Respectively weighing aluminum nitrate Al (NO) according to the stoichiometric ratio of the medium elements Al, V and P3)3: 3.75 g, ammonium metavanadate NH4VO3: 7.605 g of ammonium dihydrogen phosphate NH4H2PO4: 0.575 g, three reagents are respectively dissolved in dilute nitric acid; in the above-mentioned Al-containing3+Ions,V5+And P5+Adding 0.56 g, 1.14 g and 0.08 g of citric acid into the solution respectively for complexing; mixing the three solutions, stirring at 80 ℃ until the three solutions are completely and uniformly mixed, standing, and putting into an oven for drying to obtain a fluffy precursor; taking out the precursor, calcining in air atmosphere at 630 ℃ for 4 hours, taking out and fully grinding to obtain AlV6.5P0.5O19A photocatalyst powder.
AlV obtained in example 56.5P0.5O19The photocatalyst had a pure phase, as obtained in example 4, with an X-ray powder diffraction pattern; the light absorption and the rate of degradation of methylene blue and the kinetics of the degradation of methylene blue were similar to those of example 4.
Example 6
According to the chemical formula AlV6.3P0.3O19Respectively weighing aluminum nitrate Al (NO) according to the stoichiometric ratio of the medium elements Al, V and P3)3: 3.75 g, ammonium metavanadate NH4VO3: 7.371 g of ammonium dihydrogen phosphate NH4H2PO4: 0.081 g of three reagents are respectively dissolved in dilute nitric acid; in the above-mentioned Al-containing3+Ion, V5+And P5+Adding oxalic acid of 0.563 g, 1.105 g and 0.121 g into the solution for complexation; mixing the three solutions, stirring at 80 ℃ until the three solutions are completely and uniformly mixed, standing, and putting into an oven for drying to obtain a fluffy precursor; taking out the precursor, calcining in air atmosphere at 600 deg.C for 6 hr, taking out, and grinding to obtain AlV6.3P0.3O19A photocatalyst powder.
AlV obtained in example 56.3P0.3O19The photocatalyst had a pure phase, as obtained in example 4, with an X-ray powder diffraction pattern; the light absorption and the rate of degradation of methylene blue and the kinetics of the degradation of methylene blue were similar to those of example 4.
In conclusion, the invention adopts a chemical solution method to prepare, the raw materials with chemical integral ratio are prepared into transparent solution, and the macromolecular complexing agent is added to ensure thatAl in the raw material3+Ion, V5+Ions and P3+Fully complexing ions, drying to prepare a precursor xerogel, calcining at high temperature, volatilizing organic components to obtain pure phase AlV6+xP1-xO19(ii) a The obtained material can absorb light from ultraviolet to 580 nm; has photocatalysis effect under the irradiation of visible light; and the preparation process is simple and easy to operate, the sintering temperature is low, a complex sintering atmosphere is not needed, and the obtained particles are uniform in size and good in chemical stability.
Claims (9)
1. A visible light photocatalyst has a chemical formula: AlV6+xP1-xO19X is V in the lattice5+Self-doping of substituted P5+The molar ratio of the elements is more than or equal to 0.01 and less than or equal to 0.65.
2. The visible-light photocatalyst as set forth in claim 1, which has the chemical formula of AlV6.2P0.8O19、AlV6.1P0.9O19、AlV6.01P0.99O19、AlV6.65P0.35O19Or AlV6.5P0.5O19。
3. The method for preparing the visible light photocatalyst according to claim 1, comprising the steps of:
(1) according to the general formula AlV6+xP1-xO19The stoichiometric ratio of the elements in the alloy is respectively weighed to obtain Al containing aluminum ions3+Compound of (2), vanadium ion-containing compound V5+And a compound containing phosphorus ion P5+The compounds of (1) are respectively and completely dissolved in dilute nitric acid, and a proper amount of deionized water is added for dilution;
(2) respectively adding a complexing agent into the raw materials in the step (1), and stirring under magnetic force until the raw materials are completely dissolved to obtain a solution of the completely dissolved raw materials;
(3) slowly mixing the solutions of the raw materials obtained in the step (2), stirring until the raw materials are completely and uniformly mixed, standing and drying to obtain a fluffy precursor;
(4) and (4) placing the precursor in the step (3) in a muffle furnace, sintering in an air atmosphere, naturally cooling, grinding and uniformly mixing to obtain the powdery visible light photocatalyst.
4. The method for preparing visible light photocatalyst according to claim 3, wherein in the step (1), Al ion Al is contained3+The compound of (A) is Al (NO)3)3•9H2O, containing vanadium ions V5+Is NH4VO3Containing phosphorus ions P5+Is NH4H2PO4。
5. The method for preparing visible light photocatalyst according to claim 3, wherein in the step (2), the amount of the complexing agent added to each raw material is 10 to 20 wt% of the total amount of the reaction substance in the raw materials, and the reaction substance is Al containing aluminum ions3+Compound of (2), vanadium ion-containing compound V5+And a compound containing phosphorus ion P5+The compound of (1).
6. The method for preparing a visible light photocatalyst as claimed in claim 3 or 5, wherein in the step (2), the complexing agent is citric acid or oxalic acid.
7. The method for preparing a visible light photocatalyst according to claim 3, wherein in the step (3), the mixture is stirred at a temperature of 70 to 90 ℃.
8. The method for preparing the visible light photocatalyst according to claim 3, wherein in the step (4), the sintering temperature is 500 to 650 ℃ and the sintering time is 3 to 10 hours.
9. Use of the visible light photocatalyst according to claim 1 for the degradation of dye solutions under irradiation with visible light.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259430A (en) * | 2007-03-06 | 2008-09-10 | 福建师范大学 | Metal doped non-semiconductor visible light photocatalyst and preparation and use thereof |
| JP2009034584A (en) * | 2007-07-31 | 2009-02-19 | Univ Of Tokyo | Photocatalytic material |
| CN103447080A (en) * | 2013-09-09 | 2013-12-18 | 上海电力学院 | Silver phosphate/aluminum phosphate composite visible-light-induced photocatalyst and preparation method thereof |
| CN106431930A (en) * | 2015-08-05 | 2017-02-22 | 湘潭大学 | Method for preparing nitrobenzene from benzene |
| CN107175099A (en) * | 2017-07-21 | 2017-09-19 | 江苏师范大学 | A kind of V ion dopings BiNb5O14Photochemical catalyst and its preparation method and application |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259430A (en) * | 2007-03-06 | 2008-09-10 | 福建师范大学 | Metal doped non-semiconductor visible light photocatalyst and preparation and use thereof |
| JP2009034584A (en) * | 2007-07-31 | 2009-02-19 | Univ Of Tokyo | Photocatalytic material |
| CN103447080A (en) * | 2013-09-09 | 2013-12-18 | 上海电力学院 | Silver phosphate/aluminum phosphate composite visible-light-induced photocatalyst and preparation method thereof |
| CN106431930A (en) * | 2015-08-05 | 2017-02-22 | 湘潭大学 | Method for preparing nitrobenzene from benzene |
| CN107175099A (en) * | 2017-07-21 | 2017-09-19 | 江苏师范大学 | A kind of V ion dopings BiNb5O14Photochemical catalyst and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| F.M Bautista et al..Vanadyl–aluminum binary phosphate: Al/V ratio influence on their structure and catalytic behavior in the 2-propanol conversion.《Catalysis Today》.2002, * |
| Vanadyl–aluminum binary phosphate: Al/V ratio influence on their structure and catalytic behavior in the 2-propanol conversion;F.M Bautista et al.;《Catalysis Today》;20021205;第269页摘要 * |
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