CN107185522B - Monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material and preparation method and application thereof - Google Patents
Monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material and preparation method and application thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 50
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 68
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 18
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [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 9
- 229940043267 rhodamine b Drugs 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910002915 BiVO4 Inorganic materials 0.000 description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 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 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 bismuth vanadate Chemical class 0.000 description 1
- XOBGMVXXJIHFNI-UHFFFAOYSA-N bismuth;oxotungsten Chemical compound [Bi].[W]=O XOBGMVXXJIHFNI-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 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 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a monoclinic tungsten oxide composite bismuth vanadate photocatalytic material, a preparation method and application thereof6H8O7(citric acid) Bi (NO)3·5H2O nitric acid solution; with the addition of an appropriate amount of C6H8O7NH of (citric acid)4VO3The aqueous solution is stirred and mixed evenly by magnetic force, and proper amount of (NH) is added4)6H2W12O40(ammonium metatungstate) is used as a precursor reaction source of tungsten oxide, placed in a water bath at the temperature of 80-100 ℃ for reaction for 4 hours, dried and ground, and then is annealed by a muffle furnace; by optimizing the pH value, the reaction temperature, the amount of substances and the annealing parameters in the reaction process, the monoclinic tungsten oxide composite bismuth vanadate material with good photocatalytic performance can be prepared. The preparation method provided by the invention has the advantages of green and environment-friendly raw materials, richness, low cost, simplicity, easiness in control, easiness in realization of large-scale batch production and important application potential.
Description
Technical Field
The invention belongs to the field of photocatalytic nano materials, and particularly relates to a preparation method of a monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material.
Background
As an inorganic material with good photochemical stability, bismuth vanadate has important application value in the field of photocatalysis. In previous researches, the photocatalytic performance of the photocatalyst is mainly improved through the regulation and control of micro-morphology, crystal structure and the like. Such as octahedral bismuth vanadate, has a good degradation function on rhodamine B; (Crystal Eng Comm. 2011,13(22):6674) ellipsoidal and bicquaronic bismuth vanadate has higher degradation activity to methylene blue; (Journal of Physics and chemistry of Solids 2015, 85: 44.) for different crystal structures, monoclinic scheelite crystal form of bismuth vanadate has the best photocatalytic performance in the visible range compared to tetragonal zircon and tetragonal scheelite structures. In recent years, thanks to the breakthrough of the doped composite modification theory, science and the industry have focused on the improvement of the photocatalytic activity by regulating and controlling the performances of electron-hole separation, transmission efficiency and the like in a manner of introducing other ions or carrying out binary recombination.
In 2014, Shan and the like adopt a gel-sol technology to prepare silver-doped bismuth vanadate nano powder, and the result proves that silver doping can red shift the absorption wavelength of bismuth vanadate, so that the photocatalytic activity of the bismuth vanadate nano powder is effectively improved. The degradation rate of the methyl orange fuel is obviously improved. (Lianwei, Shan, Jinbo, et al. Enhanced Photocompatible Properties of Silver Oxide Loaded Bismuth Vanadate [ J ]. Chinese chemical engineering newspaper (English edition), 2014, 320(8):654-660.)
In 2015, Gao and the like adopt a hydrothermal method to prepare Cu-doped bismuth vanadate with a square structure, and the result proves that the activity of superoxide radical is effectively improved by Cu doping, so that phenol prepared under the condition has good degradation efficiency. (Gao X, et al. effects of pH on the structural and photocatalytic performance of Cu-ordered BiVO4, prepared via the hydrothermal method [J]. Materials Science in Semiconductor Processing, 2015, 35:197-206.）
In 2017, Zhao et al synthesized a three-dimensional structure of C-doped bismuth vanadate nanosheet by a sol-gel method, and the results show that: the three-dimensional structure formed by doping C effectively reduces the bandwidth of bismuth vanadate, and shows good photodegradation on rhodamine B under the irradiation of visible light. (Zhao D, et al. Synthesis of carbon-bonded nanosheets m-BiVO4 with three-dimensional (3D) structural by one-dimensional hydrolytic method and evaluation of the high-visible-light photocatalytic performance [ J ]. Journal of nanoparticie Research, 2017, 19(4): 124.)
However, when different ions or structures are introduced to form a doped or composite structure, the monoclinic structure is mostly destroyed, and the effective improvement of the photocatalytic performance of the bismuth vanadate is limited. Therefore, how to keep the monoclinic crystal form of the bismuth vanadate when the doped composite material is introduced has an important influence on the selectivity of the photocatalytic performance of the bismuth vanadate.
Disclosure of Invention
In order to overcome the defect that the monoclinic crystal form of a bismuth vanadate material is damaged to improve the photocatalytic performance of the bismuth vanadate material to a limited extent due to doping or composite modification in the prior art, the invention provides a monoclinic tungsten oxide composite bismuth vanadate photocatalytic material and a preparation method and application thereof. Under the condition of not influencing the crystal form of monoclinic bismuth vanadate, heterojunction is formed by compounding tungsten oxide/bismuth vanadate to improve the separation efficiency of electron holes, so that the photocatalytic performance of the tungsten oxide-bismuth vanadate composite is obviously improved compared with that of the pure bismuth vanadate, and the degradation rate of rhodamine B can reach 98.7%. The preparation method is simple and controllable, is easy to amplify and has important application value.
The invention is realized by adopting the following technical scheme:
the preparation method of the monoclinic tungsten oxide composite bismuth vanadate photocatalytic material is characterized by comprising the following steps
(1) Weighing appropriate amount of ammonium metavanadate (NH)4VO3) And citric acid (C)6H8O7) At a molar ratio of 1:2, in boiling deionized water to obtain a clear solution A, wherein NH4VO3The concentration of (A) is 0.5 mol/L;
(2) adding proper amount of pentahydrate bismuth nitrate (Bi (NO)3·5H2O) is dissolved in 1mol/L nitric acid solution to obtain the nitric acid solution with the concentration of 0.5mol/LBi(NO)3·5H2O nitric acid solution; according to Bi (NO)3·5H2O：C6H8O7(citric acid) =1:2, adding citric acid, adding deionized water with the same volume as nitric acid for dilution, placing magnetons, and magnetically stirring at room temperature for 10 minutes to obtain a clear solution B;
(3) pouring the solution B in the step (2) 2 into the solution A at a constant speed, and stirring at a high speed for 5 minutes; obtaining a mixed solution C;
(4) weighing ammonium metatungstate ((NH) with a certain mass4)6H2W12O40) Adding the mixed solution obtained in the step (3), adjusting the pH value to 8-9 by using ammonia water, and continuing stirring at a high speed for 5 minutes; reacting for 4 hours in a water bath at the temperature of 80-100 ℃, drying and grinding;
(5) and (3) the milled powder is subjected to annealing in a muffle furnace for a plurality of times to obtain the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material.
Step (2) and step (1) Bi (NO)3·5H2O and NH4VO3The mass ratio of (A) is 1.01-1.07; the optimal scheme is 1.05.
In the step (3), the speed of pouring the solution B into the solution A is controlled to be 5 ml/min.
Meta-tungstate of step (4) and Bi (NO) of step (2)3·5H2The mass ratio of O to the substance is 0.01-0.017; the optimal scheme is 0.015.
The temperature of the annealing in the step (5) is 450-550 ℃; for a period of 90 to 150 minutes; the optimal solution is 500 ℃ for 120 minutes.
A monoclinic tungsten oxide composite bismuth vanadate photocatalytic material is characterized by being prepared according to any one of the methods.
An application of a monoclinic tungsten oxide composite bismuth vanadate photocatalytic material in degradation photocatalysis of rhodamine B.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a sol-gel method, directly completes the compounding of tungsten oxide/bismuth vanadate in the reaction process, and completely maintains the monoclinic crystal form of bismuth vanadate by optimizing the reaction conditions. The tungsten oxide and the bismuth vanadate form a heterojunction structure, so that the separation efficiency of electrons and holes is effectively improved. The degradation rate of the monoclinic tungsten oxide composite bismuth vanadate photocatalytic material on rhodamine B is as high as 98.7%. The preparation method provided by the invention has the advantages of green and environment-friendly raw materials, richness, low cost, simplicity, easiness in control, easiness in realization of large-scale batch production and important application potential.
Drawings
FIG. 1: raman spectrum of example sample 1;
FIG. 2: the results of the degradation of rhodamine B by tungsten oxide composite bismuth vanadate and bismuth vanadate in example 1 were compared.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1:
1.167g of NH were weighed4VO3(10mmol) and 3.84g C6H8O7(20mmol) dissolved in 10mL boiling deionized water to give a clear solution A; 5.095g Bi (NO) were weighed out3)3·5H2O (10.5mmol) is dissolved in 20mL of 1mol/L dilute nitric acid, and 4.032g C is added6H8O7(21 mmol); adding magnetons, stirring at the rotating speed of 300r/min for 10 minutes to obtain a clear solution B; introducing the clear solution B into the clear solution A at a constant speed of 5mL/min to obtain a mixed solution C, adding ammonia water to adjust the pH value of the solution to 8, setting the rotation speed of magnetic stirring to be 800r/min, and stirring for 5 minutes; 0.456g (NH) was weighed4)6H2W12O40(0.15mmol), adding the mixed solution C; continuously stirring at high speed for 5 minutes; placing the stirred solution in a water bath condition at 90 ℃ for reaction for 4 hours; drying and grinding the reacted solution at 80 ℃; the ground sample is annealed in a muffle furnace at 500 ℃ for 120 minutes(ii) a Thus obtaining the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material; FIG. 1 is a Raman spectrum of a sample of this example; FIG. 2 is a graph comparing the degradation results of the sample and pure monoclinic bismuth vanadate on rhodamine B.
Example 2:
1.167g of NH were weighed4VO3(10mmol) and 3.84g C6H8O7(20mmol) dissolved in 10mL boiling deionized water to give a clear solution A; weighing 4.901g Bi (NO)3)3·5H2O (10.1mmol) is dissolved in 20mL of dilute nitric acid with the concentration of 1mol/L, 3.878g C is added6H8O7(20.2 mmol); adding magnetons, stirring at the rotating speed of 300r/min for 10 minutes to obtain a clear solution B; introducing the clear solution B into the clear solution A at a constant speed of 5mL/min to obtain a mixed solution C, adding ammonia water to adjust the pH value of the solution to 9, setting the rotation speed of magnetic stirring to be 800r/min, and stirring for 5 minutes; 0.456g (NH) was weighed4)6H2W12O40(0.15mmol), adding the mixed solution C; continuously stirring at high speed for 5 minutes; placing the stirred solution in a water bath at 80 ℃ for reaction for 4 hours; drying and grinding the reacted solution at 80 ℃; the ground sample is annealed in a muffle furnace at 450 ℃ for 150 minutes; thus obtaining the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material.
Example 3:
1.167g of NH were weighed4VO3(10mmol) and 3.84g C6H8O7(20mmol) dissolved in 10mL boiling deionized water to give a clear solution A; weighing 4.998gBi (NO)3)3·5H2O (10.3mmol) is dissolved in 20mL of dilute nitric acid with the concentration of 1mol/L, 3.955g C is added6H8O7(20.6 mmol); adding magnetons, stirring at the rotating speed of 300r/min for 10 minutes to obtain a clear solution B; introducing the clear solution B into the clear solution A at a constant speed of 5mL/min to obtain a mixed solution C, adding ammonia water to adjust the pH value of the solution to 8, setting the rotation speed of magnetic stirring to be 800r/min, and stirring for 5 minutes; 0.456g (NH) was weighed4)6H2W12O40(0.15mmol), adding the mixed solution C; continuously stirring at high speed for 5 minutes; placing the stirred solution in a water bath at 100 ℃ for reaction for 4 hours; drying and grinding the reacted solution at 80 ℃; the ground sample is annealed in a muffle furnace at 550 ℃ for 90 minutes; thus obtaining the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material.
Example 4:
1.167g of NH were weighed4VO3(10mmol) and 3.84g C6H8O7(20mmol) dissolved in 10mL boiling deionized water to give a clear solution A; 5.192g Bi (NO) were weighed out3)3·5H2O (10.7mmol) is dissolved in 20mL of dilute nitric acid with a concentration of 1mol/L, 4.108g C is added6H8O7(21.4 mmol); adding magnetons, stirring at the rotating speed of 300r/min for 10 minutes to obtain a clear solution B; introducing the clear solution B into the clear solution A at a constant speed of 5mL/min to obtain a mixed solution C, adding ammonia water to adjust the pH value of the solution to 8, setting the rotation speed of magnetic stirring to be 800r/min, and stirring for 5 minutes; 0.456g (NH) was weighed4)6H2W12O40(0.15mmol), adding the mixed solution C; continuously stirring at high speed for 5 minutes; placing the stirred solution in a water bath condition at 90 ℃ for reaction for 4 hours; drying and grinding the reacted solution at 80 ℃; the ground sample is annealed in a muffle furnace at 500 ℃ for 120 minutes; thus obtaining the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material.
Example 5:
1.167g of NH were weighed4VO3(10mmol) and 3.84g C6H8O7(20mmol) dissolved in 10mL boiling deionized water to give a clear solution A; 5.095g Bi (NO) were weighed out3)3·5H2O (10.5mmol) is dissolved in 20mL of 1mol/L dilute nitric acid, and 4.032g C is added6H8O7(21 mmol); adding magnetons, stirring at the rotating speed of 300r/min for 10 minutes to obtain a clear solution B; leading the clear solution B into the clear solution A at a constant speed of 5mL/min to obtain a mixed solution C,adding ammonia water to adjust the pH value of the solution to 8, setting the rotating speed of magnetic stirring to be 800r/min, and stirring for 5 minutes; 0.304g (NH) is weighed4)6H2W12O40(0.1mmol), adding the mixed solution C; continuously stirring at high speed for 5 minutes; placing the stirred solution in a water bath condition at 90 ℃ for reaction for 4 hours; drying and grinding the reacted solution at 80 ℃; the ground sample is annealed in a muffle furnace at 450 ℃ for 150 minutes; thus obtaining the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material.
Example 6:
1.167g of NH were weighed4VO3(10mmol) and 3.84g C6H8O7(20mmol) dissolved in 10mL boiling deionized water to give a clear solution A; 5.095g Bi (NO) were weighed out3)3·5H2O (10.5mmol) is dissolved in 20mL of 1mol/L dilute nitric acid, and 4.032g C is added6H8O7(21 mmol); adding magnetons, stirring at the rotating speed of 300r/min for 10 minutes to obtain a clear solution B; introducing the clear solution B into the clear solution A at a constant speed of 5mL/min to obtain a mixed solution C, adding ammonia water to adjust the pH value of the solution to 8, setting the rotation speed of magnetic stirring to be 800r/min, and stirring for 5 minutes; 0.395g (NH) was weighed4)6H2W12O40(0.13mmol), adding the mixed solution C; continuously stirring at high speed for 5 minutes; placing the stirred solution in a water bath condition at 90 ℃ for reaction for 4 hours; drying and grinding the reacted solution at 80 ℃; the ground sample is annealed in a muffle furnace at 550 ℃ for 90 minutes; thus obtaining the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material.
Example 7:
1.167g of NH were weighed4VO3(10mmol) and 3.84g C6H8O7(20mmol) dissolved in 10mL boiling deionized water to give a clear solution A; 5.095g Bi (NO) were weighed out3)3·5H2O (10.5mmol) is dissolved in 20mL of 1mol/L dilute nitric acid, and 4.032g C is added6H8O7(21 mmol); adding magneton, stirring at 300r/minStirring for 10 minutes at a rotating speed to obtain a clear solution B; introducing the clear solution B into the clear solution A at a constant speed of 5mL/min to obtain a mixed solution C, adding ammonia water to adjust the pH value of the solution to 8, setting the rotation speed of magnetic stirring to be 800r/min, and stirring for 5 minutes; weigh 0.516g (NH)4)6H2W12O40(0.17mmol), adding the mixed solution C; continuously stirring at high speed for 5 minutes; placing the stirred solution in a water bath condition at 90 ℃ for reaction for 4 hours; drying and grinding the reacted solution at 80 ℃; the ground sample is annealed in a muffle furnace at 500 ℃ for 120 minutes; thus obtaining the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material.
The degradation rate of the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material obtained in the example case to rhodamine B is shown in table 1 (the test conditions are the same as the experimental process in fig. 2):
| example samples | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Rate of degradation | 98.7% | 96.3% | 97.4% | 95.9% | 95.2% | 98.2% | 98.5% |
Claims (5)
1. A preparation method of a monoclinic tungsten oxide composite bismuth vanadate photocatalytic material is characterized by comprising the following steps:
(1) weighing appropriate amount of ammonium metavanadate (NH)4VO3) And citric acid in a molar ratio of 1:2, in boiling deionized water to obtain a clear solution A, in which NH is present4VO3The concentration of (A) is 0.5 mol/L;
(2) adding proper amount of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) was dissolved in a 1mol/L nitric acid solution to obtain Bi (NO) having a concentration of 0.5mol/L3)3·5H2O nitric acid solution; according to Bi (NO)3)3·5H2O: adding citric acid at a ratio of citric acid =1:2, adding deionized water with the volume same as that of nitric acid for dilution, adding magnetons, and magnetically stirring at room temperature for 10 minutes to obtain a clear solution B;
(3) pouring the solution B in the step (2) into the solution A at a constant speed, and stirring at a high speed for 5 minutes; obtaining a mixed solution C;
(4) weighing ammonium metatungstate ((NH) with a certain mass4)6H2W12O40) Adding the mixed solution obtained in the step (3), adjusting the pH value to 8-9 by using ammonia water, and continuing stirring at a high speed for 5 minutes; reacting for 4 hours in a water bath at the temperature of 80-100 ℃, drying and grinding;
(5) annealing the ground powder in a muffle furnace for a plurality of times to obtain the monoclinic tungsten oxide composite bismuth vanadate high-performance photocatalytic material;
in step (2), Bi (NO)3)3·5H2O and NH in step (1)4VO3The mass ratio of (A) is 1.01-1.07;
in the step (3), the speed of pouring the solution B into the solution A is controlled to be 5 ml/min;
step (4) of ammonium metatungstate and step (2) of Bi (NO)3)3·5H2The mass ratio of O to the substance is 0.01-0.017;
the annealing temperature in the step (5) is 450-550 ℃; the time period is 90 minutes to 150 minutes.
2. The monoclinic crystal of claim 1The preparation method of the tungsten oxide composite bismuth vanadate photocatalytic material is characterized in that ammonium metatungstate in the step (4) and Bi (NO) in the step (2)3)3·5H2The mass ratio of O was 0.015.
3. The method for preparing a monoclinic tungsten oxide composite bismuth vanadate photocatalytic material according to claim 1, wherein the annealing temperature in the step (5) is 500 ℃ for 120 minutes.
4. A monoclinic tungsten oxide composite bismuth vanadate photocatalytic material, which is characterized by being prepared according to the method of any one of claims 1 to 3.
5. The application of the monoclinic tungsten oxide composite bismuth vanadate photocatalytic material in photocatalysis of rhodamine B degradation according to claim 4.
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| CN107626298B (en) * | 2017-09-29 | 2020-02-04 | 盐城工学院 | Bismuth semiconductor photocatalyst and preparation method thereof |
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