CN114558573A - Titanium dioxide/silver metavanadate composite photocatalyst and preparation method and application thereof - Google Patents
Titanium dioxide/silver metavanadate composite photocatalyst and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 102
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000006731 degradation reaction Methods 0.000 claims abstract description 25
- 230000015556 catabolic process Effects 0.000 claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 238000013329 compounding Methods 0.000 claims abstract 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 19
- 229940043267 rhodamine b Drugs 0.000 claims description 19
- 239000002351 wastewater Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000013032 photocatalytic reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 6
- 239000003054 catalyst Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 239000008204 material by function Substances 0.000 abstract description 2
- 229910017988 AgVO3 Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
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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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- B01J35/61—Surface area
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- C02—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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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention belongs to the field of functional materials, and particularly relates to a preparation method and application of a titanium dioxide/silver metavanadate composite photocatalyst. The composite photocatalyst is formed by compounding titanium dioxide nanosheets on one-dimensional banded silver metavanadate, and the titanium dioxide/silver metavanadate composite photocatalyst is synthesized by a two-step hydrothermal method in the preparation process. Compared with titanium dioxide and silver metavanadate, the photocatalytic activity of the titanium dioxide/silver metavanadate composite photocatalyst is obviously improved. The titanium dioxide/silver metavanadate composite photocatalyst has the advantages of simple preparation method, easily controlled conditions, good photocatalytic activity and the like, is a novel photocatalyst and is successfully applied to dye degradation.
Description
Technical Field
The invention belongs to the field of functional materials, particularly relates to the field of photocatalysis, and relates to a titanium dioxide/silver metavanadate composite photocatalyst as well as a preparation method and application thereof.
Background
Titanium dioxide is one of the widely used photocatalysts because of its advantages of optical, physicochemical stability, environmental friendliness, low cost effectiveness, easy availability, etc. But the photocatalytic activity of titanium dioxide is low due to its narrow photoresponse range, high electron-hole recombination rate and relatively small quantum efficiency. In order to improve the photocatalytic activity of titanium oxide, a heterojunction structure can be formed by recombination with other semiconductors, and the electron-hole recombination efficiency can be reduced, thereby improving the photocatalytic activity.
Silver metavanadate has a narrow band gap and good visible light absorption capacity, and is an ideal photocatalyst, so that the silver metavanadate and titanium dioxide are compounded to form a heterojunction structure, and the visible light absorption capacity and the electron-hole separation efficiency are improved, so that the photocatalytic activity is improved.
Disclosure of Invention
The invention aims to provide a titanium dioxide/silver metavanadate composite photocatalyst and a preparation method and application thereof, wherein the obtained titanium dioxide/silver metavanadate composite photocatalyst is compounded on one-dimensional banded silver metavanadate through a titanium dioxide nanosheet to form a p-n heterojunction structure, and the separation efficiency of photo-generated electrons and holes is improved to effectively degrade dye wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a titanium dioxide/silver metavanadate composite photocatalyst is characterized in that a titanium dioxide nanosheet is compounded on one-dimensional banded silver metavanadate.
Further, the titanium dioxide accounts for 4-10% of the silver metavanadate by mass.
The preparation method of the titanium dioxide/silver metavanadate composite photocatalyst comprises the following steps:
(1) the titanium-containing compound and the fluorine-containing compound are sufficiently stirred to form a solution A.
(2) And (3) carrying out hydrothermal reaction on the solution A, after the reaction is finished and cooling is carried out, washing the precipitate, washing away redundant ions, and drying to obtain the titanium dioxide nanosheet.
(3) Adding a certain content of titanium dioxide nanosheets and a silver-containing compound into a dispersing agent, and uniformly mixing the titanium dioxide nanosheets and the silver-containing compound through ultrasonic treatment to form a solution B; adding a vanadium-containing compound into a dispersant, and stirring to form a solution C; and adding the solution C into the solution B, continuously stirring for a period of time, transferring the solution B into a hydrothermal reaction kettle for hydrothermal reaction, cooling to room temperature, carrying out centrifugal washing, and drying to obtain the titanium dioxide/silver metavanadate composite photocatalyst.
Further, in the step (1), the titanium-containing compound is tetrabutyl titanate, the dosage of which is 5 mL, and the fluorine-containing compound is hydrofluoric acid, and the dosage of which is 0.4-0.8 mL. The hydrothermal reaction condition of the step (2) is 180 ℃ and 24 hours. The using amount of the titanium dioxide nanosheets in the step (3) is 0.005 g-0.02 g, the silver-containing compound is silver nitrate, the dispersing agent is ultrapure water, and the content of silver nitrate in the solution B is 0.05 mol/L. The vanadium-containing compound is sodium metavanadate, and the content of silver metavanadate in the solution C is 0.05 mol/L. The continuous stirring time is 30 min, the hydrothermal reaction temperature is 150-180 ℃, and the time is 6-24 h.
The application of the titanium dioxide/silver metavanadate composite photocatalyst in degrading dye wastewater specifically comprises the steps of mixing the titanium dioxide/silver metavanadate composite photocatalyst with the dye wastewater, stirring in the dark, and carrying out adsorption balance. And carrying out photocatalytic reaction under the condition of illumination to finish the degradation of the dye wastewater.
Further, the adding amount of the titanium dioxide/silver metavanadate composite photocatalyst is 0.4 g/L, the dye wastewater is rhodamine B wastewater, and the concentration of rhodamine B is 15 mg/L. The stirring time is 1h, the illumination condition is a xenon lamp of 500W, and the photocatalytic reaction time is 80 min.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the nano-sheet titanium dioxide is compounded on the one-dimensional banded silver metavanadate, so that the agglomeration phenomenon of the titanium dioxide is solved, the specific surface area of the silver metavanadate is increased, and the photocatalytic reaction active sites are increased, thereby improving the photocatalytic activity. Titanium dioxide is an n-type semiconductor and can form a titanium dioxide/silver vanadate p-n heterojunction with a p-type semiconductor silver metavanadate. Under the action of an internal electric field, the positions of a conduction band and a valence band of titanium dioxide and silver metavanadate can deviate, and electron-hole pairs can be rapidly transferred and separated, so that the recombination probability of the electron-hole pairs is reduced. Therefore, the photocatalytic activity of the titanium dioxide/silver metavanadate composite material is further improved, and compared with the prior art, the titanium dioxide/silver metavanadate composite material has the advantages that:
(1) the invention provides a titanium dioxide/silver metavanadate composite photocatalyst, which takes one-dimensional banded silver metavanadate as a carrier, modifies the one-dimensional banded silver metavanadate by using titanium dioxide nanosheets, has the advantages of high photoproduction electron-hole separation efficiency, high photocatalytic activity, strong light absorption capacity and the like, and can efficiently degrade dye wastewater.
(2) The invention also provides a preparation method of the titanium dioxide/silver metavanadate composite photocatalyst, which has the advantages of simple and convenient synthesis method, easily controlled conditions, no by-product generated in the preparation process, small environmental pollution and the like.
(3) The titanium dioxide/silver metavanadate composite photocatalyst can be used for dye wastewater, has the advantages of stable photocatalytic performance, high pollutant degradation efficiency and the like, and has good application prospect.
Drawings
FIG. 1 shows a titanium dioxide/silver metavanadate composite photocatalyst (6 wt% TiO) prepared in example 2 of the present invention2/AgVO3) SEM images of titanium dioxide prepared in comparative example 1 and silver metavanadate prepared in comparative example 2, wherein (a) is titanium dioxide, (b) is silver metavanadate, and (c) is 6 wt% TiO2/AgVO3；
FIG. 2 is a degradation diagram of the titanium dioxide/silver metavanadate composite photocatalyst prepared in examples 1 to 4 of the present invention, and the corresponding degradation diagrams of the titanium dioxide prepared in comparative example 1 and the corresponding degradation diagram of the silver metavanadate photocatalytic degradation rhodamine B dye wastewater prepared in comparative example 2;
fig. 3 is a corresponding kinetic diagram of the titanium dioxide/silver metavanadate composite photocatalyst prepared in embodiments 1 to 4 of the present invention, the titanium dioxide prepared in comparative example 1, and the silver metavanadate prepared in comparative example 2 when photocatalytic degradation of rhodamine B dye wastewater is performed.
Detailed Description
The invention is further illustrated by the following specific examples in conjunction with the accompanying drawings.
Example 1
A titanium dioxide/silver metavanadate composite photocatalyst takes one-dimensional banded silver metavanadate as a carrier, and a titanium dioxide nanosheet is used for modifying the silver metavanadate.
In this embodiment, the titanium dioxide/silver metavanadate composite photocatalyst contains 4wt% of titanium dioxide in the silver metavanadate.
In this embodiment, the titanium dioxide is a nanosheet, an n-type semiconductor, and the silver metavanadate is a one-dimensional strip, and is a p-type semiconductor.
The preparation method of the titanium dioxide/silver metavanadate composite photocatalyst comprises the following steps:
measuring 5 mL of tetrabutyl titanate and 0.8 mL of HF solution in polytetrafluoroethylene to form a solution A, stirring for 5 min, then placing the solution A into a hydrothermal reaction kettle, and placing the hydrothermal reaction kettle into an oven at 180 ℃ for hydrothermal reaction for 24 h. And cooling to room temperature after the reaction is finished, respectively carrying out centrifugal washing on precipitates in the polytetrafluoroethylene by using water and ethanol, and finally drying to obtain the titanium dioxide nanosheet.
0.005 g of titanium dioxide nanosheet and 0.170 g of silver nitrate are weighed and dissolved in 20 mL of ultrapure water to form solution B through ultrasonic treatment. 0.1219 g of sodium metavanadate is weighed and dissolved in 20 mL of ultrapure water to form a solution C, the solution C is poured into the solution B and is continuously stirred for 30 min, and the solution B is transferred into a hydrothermal reaction kettle to carry out hydrothermal reaction under the hydrothermal reaction condition of 150 ℃ for 6 h. Cooling to room temperature after the reaction is finished, and precipitating in the reaction kettleAnd (4) centrifugally washing the product with water and ethanol respectively, and drying to obtain the titanium dioxide/silver metavanadate composite photocatalyst. Named 4wt% TiO2/AgVO3。
Comparative example 1
A preparation method of titanium dioxide nanosheets comprises the following steps: measuring 5 mL of tetrabutyl titanate and 0.8 mL of HF solution in polytetrafluoroethylene to form a solution A, stirring for 5 min, then placing the solution A into a hydrothermal reaction kettle, and placing the hydrothermal reaction kettle into an oven at 180 ℃ for hydrothermal reaction for 24 h. And cooling to room temperature after the reaction is finished, respectively carrying out centrifugal washing on precipitates in the polytetrafluoroethylene by using water and ethanol, and finally drying to obtain the titanium dioxide nanosheet.
Comparative example 2
A preparation method of silver metavanadate comprises the following steps: 0.170 g of silver nitrate was dissolved in 20 mL of ultrapure water and sonicated to form solution B. Weighing 0.122 g of sodium metavanadate, dissolving in 20 mL of ultrapure water to form a solution C, pouring the solution C into the solution B, continuously stirring for 30 min, transferring the solution B into a hydrothermal reaction kettle for hydrothermal reaction at 150 ℃ for 6 h. And cooling to room temperature after the reaction is finished, respectively carrying out centrifugal washing on the precipitate in the reaction kettle by using water and ethanol, and drying to obtain the silver metavanadate.
Example 2
A titanium dioxide/silver metavanadate composite photocatalyst is basically the same as that in embodiment 1, and is different from the titanium dioxide/silver metavanadate composite photocatalyst only in that: in the titanium dioxide/silver metavanadate composite photocatalyst of example 2, the mass percentage of titanium dioxide in silver metavanadate is 6%.
The preparation method of the titanium dioxide/silver metavanadate composite photocatalyst in the embodiment is substantially the same as the preparation method in embodiment 1, and the differences are only that: the mass of titanium dioxide used in example 2 was 0.01 g.
The titanium dioxide/silver metavanadate composite photocatalyst prepared in example 2 was named 6 wt% TiO2/AgVO3。
Example 3
A titanium dioxide/silver metavanadate composite photocatalyst is basically the same as that in embodiment 1, and is different from the titanium dioxide/silver metavanadate composite photocatalyst only in that: in the titanium dioxide/silver metavanadate composite photocatalyst of example 3, the mass percentage of titanium dioxide in silver vanadate is 8%.
The preparation method of the titanium dioxide/silver metavanadate composite photocatalyst in the embodiment is substantially the same as the preparation method in embodiment 1, except that: the mass of titanium dioxide used in example 3 was 0.015 g.
The titanium dioxide/silver metavanadate composite photocatalyst prepared in example 3 was named 8 wt% TiO2/AgVO3。
Example 4
A titanium dioxide/silver metavanadate composite photocatalyst is basically the same as that in embodiment 1, and is different from the titanium dioxide/silver metavanadate composite photocatalyst only in that: in the titanium dioxide/silver metavanadate composite photocatalyst of example 4, the mass percentage of titanium dioxide in silver metavanadate is 10%.
A preparation method of the titanium dioxide/silver metavanadate composite photocatalyst in this embodiment is substantially the same as the preparation method in embodiment 1, except that: the mass of titanium dioxide used in example 4 was 0.02 g.
The titanium dioxide/silver metavanadate composite photocatalyst prepared in example 4 was named 10 wt% TiO2/AgVO3。
Example 5:
the application of the titanium dioxide/silver metavanadate composite photocatalyst in degradation of dye wastewater comprises the following steps:
0.02g of AgVO was weighed3Comparative example 1, TiO2Comparative example 2, 4wt% TiO2/AgVO3
Example 1 6 wt% TiO2/AgVO3、Example 2 8 wt% TiO2/AgVO3Example 3) 10 wt% TiO2/AgVO3. (example 4), adding the rhodamine B dye wastewater with the concentration of 15 mg/L into 50 mL respectively, magnetically stirring for 60 min under a dark condition to achieve adsorption balance, turning on a light source, and irradiating for 80 min under visible light (lambda is more than or equal to 420 nm) to finish degradation of the dye wastewater.
Determination of degradation efficiency: 2.5 mL reaction vessel was aspirated every 20 min with a syringeFiltering the photocatalytic degradation solution by using a filter head, and detecting by using an ultraviolet-visible spectrophotometer. FIG. 3 shows 4wt% TiO in examples 1 to 5 of the present invention2/AgVO3、6wt% TiO2/AgVO3、8 wt% TiO2/AgVO3、10 wt% TiO2/AgVO3TiO in comparative example 12And AgVO in comparative example 23A corresponding time-degradation efficiency diagram when the rhodamine B dye wastewater is degraded by photocatalysis. C in FIG. 3 represents the concentration of degraded rhodamine B, C0Indicating the initial concentration of rhodamine B.
As can be seen from fig. 1:
the invention synthesizes titanium dioxide nano-sheets in comparative example 1, silver metavanadate in one-dimensional strip in comparative example 2, and the 6 wt% TiO prepared in the invention in example 2 is in the form of TiO nano-sheets2/AgVO3Is silver metavanadate compounded by titanium dioxide nanosheets in one-dimensional strip shape.
As can be seen from fig. 2:
the titanium dioxide/silver metavanadate composite photocatalyst in example 1 of the present invention (4 wt% TiO)2/AgVO3) The degradation efficiency of rhodamine B after 80 min of photocatalytic reaction is 81.6 percent.
The titanium dioxide/silver metavanadate composite photocatalyst in example 2 of the invention (6 wt% TiO)2/AgVO3) The degradation efficiency of rhodamine B after 80 min of photocatalytic reaction is 91.2%.
The titanium dioxide/silver metavanadate composite photocatalyst in example 3 of the invention (8 wt% TiO)2/AgVO3) The degradation efficiency of rhodamine B after 80 min of photocatalytic reaction is 88.1 percent.
The titanium dioxide/silver metavanadate composite photocatalyst in example 4 of the present invention (10 wt% TiO)2/AgVO3) The degradation efficiency of rhodamine B after 80 min of photocatalytic reaction is 82.5 percent.
In the comparative example 1, the degradation efficiency of titanium dioxide (TiO 2) on rhodamine B after 80 min of photocatalytic reaction is 32.2%.
Silver metavanadate (AgVO) in comparative example 23) Degrading efficiency of rhodamine B after 80 min of photocatalytic reactionThe content was 49.5%.
As can be seen from fig. 3:
comparative example 1, comparative example 2, 4wt% TiO2/AgVO3、6 wt%TiO2/AgVO3、8 wt%TiO2/AgVO3And 10 wt% TiO2/AgVO3Has a degradation rate of 0.00467min-1、0.00838min-1、0.02103min-1、0.03035min-1、0.02615min-1And 0.02143min-1。
The above results show that: the titanium dioxide/silver metavanadate composite photocatalyst in the embodiment 2 has the best effect of removing rhodamine B, the degradation efficiency is 91.2%, and the degradation rate is 0.03035 min-1. The degradation efficiency of titanium dioxide on rhodamine B is 32.2 percent, and the degradation rate is 0.00467min-1. The degradation efficiency of the silver metavanadate on rhodamine B is 49.5 percent, and the degradation rate is 0.00838min-1. By comparison, it can be seen that: compared with silver metavanadate and titanium dioxide, the degradation rate of the titanium dioxide/silver metavanadate composite photocatalyst in example 2 is increased by 3.62 times and 6.50 times respectively. The main reasons for the phenomenon are that the titanium dioxide nanosheet is compounded with the one-dimensional banded silver metavanadate, so that the specific surface area of the silver metavanadate is increased, and the photocatalytic activity sites are increased, and a p-n heterojunction is formed between the titanium dioxide and the silver metavanadate, so that the separation efficiency of electrons and holes is improved under the action of an internal electric field, and the photocatalytic activity is improved.
The preferred embodiments of the present invention described above are only for illustrating the present invention and are not to be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present application shall fall within the scope of the present invention without creative efforts.
Claims (9)
1. A titanium dioxide/silver metavanadate composite photocatalyst is characterized in that: the catalyst is formed by compounding titanium dioxide nanosheets on one-dimensional banded silver metavanadate, and the mass percentage of titanium dioxide in the silver metavanadate is 4% -10%.
2. A method for preparing the titanium dioxide/silver metavanadate composite photocatalyst according to claim 1, which is characterized in that: the method comprises the following steps:
fully stirring a titanium-containing compound and a fluorine-containing compound to form a solution A;
carrying out hydrothermal reaction on the solution A, after the reaction is finished and cooling is carried out, washing the precipitate, washing away redundant ions, and drying to obtain a titanium dioxide nanosheet;
(3) adding titanium dioxide nanosheets and silver-containing compounds into a dispersing agent, and uniformly mixing the titanium dioxide nanosheets and the silver-containing compounds through ultrasonic treatment to form a solution B; adding a vanadium-containing compound into a dispersing agent, and stirring to form a solution C; and adding the solution C into the solution B, continuously stirring, transferring the solution B into a hydrothermal reaction kettle for hydrothermal reaction, cooling to room temperature, carrying out centrifugal washing, and drying to obtain the titanium dioxide/silver metavanadate composite photocatalyst.
3. The method of claim 2, wherein: in the step (1), the titanium-containing compound is tetrabutyl titanate, the dosage of which is 5 mL, and the fluorine-containing compound is hydrofluoric acid, and the dosage of which is 0.4-0.8 mL.
4. The method of claim 2, wherein: the hydrothermal reaction condition in the step (2) is 180 ℃ and 24 hours.
5. The method of claim 2, wherein: in the step (3), the using amount of the titanium dioxide nanosheets is 0.005 g-0.02 g, the silver-containing compound is silver nitrate, the dispersing agent is ultrapure water, and the silver nitrate content of the solution B is 0.05 mol/L; the vanadium-containing compound is silver metavanadate, and the content of the silver metavanadate in the solution C is 0.05 mol/L.
6. The method of claim 2, wherein: the hydrothermal reaction temperature in the step (3) is 150-180 ℃, and the time is 6-24 h.
7. The use of the titanium dioxide/silver metavanadate composite photocatalyst according to claim 1 in degradation of dye wastewater.
8. Use according to claim 7, characterized in that: mixing the titanium dioxide/silver metavanadate composite photocatalyst with the dye wastewater, stirring in the dark to obtain adsorption balance, and then carrying out photocatalytic reaction under the illumination condition to finish the degradation of the dye wastewater.
9. Use according to claim 8, characterized in that: the adding amount of the titanium dioxide/silver metavanadate composite photocatalyst is 0.4 g/L, the dye wastewater is rhodamine B wastewater, the concentration of rhodamine B is 15 mg/L, the stirring time is 1h, the illumination condition is a xenon lamp of 500W, and the photocatalytic reaction time is 80 min.
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| CN103657619A (en) * | 2013-10-16 | 2014-03-26 | 江苏大学 | Preparation method of titanium dioxide nanosheet photocatalytic material with controllable size |
| CN106238043A (en) * | 2016-07-28 | 2016-12-21 | 北京科技大学 | The preparation of titanium dichloride load high dispersive platinum composite photocatalyst material and application process |
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| CN103657619A (en) * | 2013-10-16 | 2014-03-26 | 江苏大学 | Preparation method of titanium dioxide nanosheet photocatalytic material with controllable size |
| CN106238043A (en) * | 2016-07-28 | 2016-12-21 | 北京科技大学 | The preparation of titanium dichloride load high dispersive platinum composite photocatalyst material and application process |
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| Title |
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| JYOTSNA ET AL.，: "β-AgVO3 nanowires/TiO2 nanoparticles heterojunction assembly with improved visible light driven photocatalytic decomposition of hazardous pollutants and mechanism insight" * |
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